CN112591806A - Method for recovering and regenerating anode active material of waste lithium ion battery - Google Patents
Method for recovering and regenerating anode active material of waste lithium ion battery Download PDFInfo
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- C01G53/42—Nickelates containing alkali metals, e.g. LiNiO2
- C01G53/44—Nickelates containing alkali metals, e.g. LiNiO2 containing manganese
- C01G53/50—Nickelates containing alkali metals, e.g. LiNiO2 containing manganese of the type [MnO2]n-, e.g. Li(NixMn1-x)O2, Li(MyNixMn1-x-y)O2
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Abstract
The invention discloses a method for efficiently recovering and regenerating a waste lithium ion battery anode material, which comprises the following steps: completely discharging, disassembling, stripping, calcining and grinding the recycled waste lithium ion battery to obtain LiNi0.6Co0.2Mn0.2O2An active material; leaching the active material with a leaching agent to obtain a leaching solution rich in lithium and a precipitate containing nickel, cobalt and manganese; dispersing the obtained precipitate in water, adding alkali liquor, and adjusting the pH value to obtain nickel cobalt manganese hydroxide precipitate; filtering the nickel cobalt manganese hydroxide precipitate to obtain a ternary precursor, matching the ternary precursor with an excessive lithium source according to the amount of the ternary precursor, carrying out lithiation, grinding, mixing and calcining to obtain a positive active material; adding inorganic acid into the filtrate obtained after filtration to generate new organic acid, thereby realizing the recycling of the organic acid; the method can realize the cyclic utilization of the ternary cathode material, has simple process and can effectively reduce the additionThe labor cost is low, and the recycling of the organic acid can be realized.
Description
Technical Field
The invention relates to the technical field of valuable metal recovery of waste lithium ion batteries, in particular to a method for recovering and regenerating a positive active material of a waste lithium ion battery.
Background
The lithium ion battery plays an important role in production and life of people, the output of the lithium ion battery is increased year by year due to high demand, however, the service life of the lithium ion battery is limited, and the production amount of waste lithium ion batteries is also increased year by year. With the increasing of energy mineral crisis and environmental awareness, various countries actively develop resource recycling of waste lithium batteries, and the method becomes a research hotspot in the field of solid waste treatment and resource in recent years. For a lithium battery, the energy density, rate capability and working voltage of the lithium battery are mainly determined by the limited theoretical capacity and thermodynamic characteristics of a positive electrode material, so that a positive electrode active substance accounts for 30% -50% of the manufacturing cost of the whole battery, and currently, recovery research is mainly focused on rare and precious metals such as lithium, nickel, cobalt and the like in the positive electrode active material.
At present, methods for recovering valuable metals of positive active materials can be mainly classified into pyrometallurgical processes, biometallurgical processes and hydrometallurgical processes. The pyrometallurgical process is simple, is suitable for large-scale treatment of batteries with complex components, but has high energy consumption, and waste residues and waste gases generated by high-temperature combustion pollute the environment, and metal lithium cannot be effectively recovered. The wet metallurgy is relatively mature, the raw material of the waste lithium ion battery is required to be single in component, the requirement on equipment is not high, the operation is simple, the efficiency is high, the selective recovery is good, the treatment cost is low, and the product purity is high. The acid leaching method is the most common method for recovering metal elements in the anode waste, and compared with inorganic acid, the organic acid has weak acidity, has the advantages of cyclic utilization, easy degradation, environmental friendliness and the like, and is used as a leaching agent to have higher leaching rate on metals such as cobalt, lithium, nickel, manganese and the like in the anode active material of the waste lithium ion battery, so that the simple, economic and environment-friendly organic acid leaching process is very important for recovering valuable metals in the waste lithium ion battery. Chen et al use tartaric acid as a leaching agent to recover valuable metals in LCO cells, and under optimal leaching conditions, can recover about 98% Co and 97% Li (X. Chen, D. kang, L. Cao, et al Separation and recovery of viable metals from space sites: simple recovery of Li and Co in a single step [ J ] Separation and Purification Technology,2019,210: 690-. Li et al use citric acid and hydrogen peroxide as leaching agents to recover Co and Li from waste lithium ion batteries. The metal can be efficiently recovered within 30min of a treatment time of 90 ℃ by using 1.25 mol/L-1 citric acid and 1.0 vol.% hydrogen peroxide and stirring and leaching at 300rpm when the solid-to-liquid ratio is 20 g/L-1. The results show that more than 90% Co and about 100% Li are recovered under the combined action of citric acid and hydrogen peroxide (L.Li, J.Ge, F.Wu, et al.recovery of cobalt and lithium from particulate matters using organic citric acid as a raw [ J ]. Journal of halogenated materials,2010,176: 288-.
The organic acid is adopted to recover valuable metals in the lithium ion battery, the leaching rate of the valuable metals is low due to the weak acidity of the organic acid, and the purity of products is reduced due to different chelating capacities on metal ions in the selective lithium extraction process, so that the selection of the proper organic acid is particularly important.
Disclosure of Invention
Based on the technical problems in the prior art, the organic phosphoric acid is selected to efficiently and selectively extract the valuable metals in the lithium ion battery, and the valuable metal ions can be effectively chelated, so that the purity of the lithium ions in the leaching solution is higher than 98%, and secondary extraction and impurity removal of the transition metals are avoided.
In order to achieve the purpose, the technical scheme of the invention is as follows:
a method for recovering and regenerating a positive active material of a waste lithium ion battery comprises the following steps:
s1, completely discharging, disassembling, stripping, calcining and grinding the recycled waste lithium ion battery to obtain the required LiNi0.6Co0.2Mn0.2O2A positive electrode active material;
s2, preparing the LiNi0.6Co0.2Mn0.2O2Leaching the positive active material by using a leaching agent to obtain a leaching solution rich in lithium and a precipitate containing nickel, cobalt and manganese; filtering and separating the leachate and the precipitate, drying the precipitate in an oven,grinding and storing for later use; the leaching agent consists of a reducing agent and an organic acid, the concentration of the organic acid is 0.5-5mol/L, the dosage of the reducing agent is 1-10% of the volume of the leaching agent, and the dosage ratio of the positive electrode active material to the leaching agent is 5-60 g/L; wherein the organic acid is at least one of methyl phosphoric acid, benzene phosphoric acid, naphthalene phosphoric acid, methylene diphosphonic acid, diphenyl phosphoric acid, benzyl hypophosphorous acid, trimethyl phosphoric acid, aminophosphoric acid, toluene phosphoric acid or 1, 4-benzene diphosphonic acid; the reducing agent is at least one of hydrogen peroxide, sodium persulfate, glucose, sucrose and ascorbic acid;
s3, dispersing the precipitate obtained in the step S2 in deionized water, adding 0.5-5mol/L alkali liquor, adjusting the pH to 6-9, and performing displacement precipitation and coprecipitation reaction on the precipitate and the alkali liquor to obtain nickel cobalt manganese hydroxide precipitate;
s4, filtering the nickel cobalt manganese hydroxide precipitate generated in the step S3 to obtain a ternary precursor nickel cobalt manganese hydroxide, determining the content of metal ions in the nickel cobalt manganese hydroxide according to ICP-OES, adjusting the ratio of the nickel cobalt manganese metal ions to be 6:2:2, matching the nickel cobalt manganese metal ions and an excessive 1-5% lithium source according to the amount of the ternary precursor, carrying out lithiation, grinding, mixing and calcining to obtain the ternary LiNi with good performance0.6Co0.2Mn0.2O2A positive electrode active material;
s5, adding inorganic acid into the filtrate obtained by filtering in the step S4, wherein the concentration of the inorganic acid is 0.5-5mol/L, generating new organic acid, and adding the reducing agent into the organic acid, namely generating the leaching agent; wherein the volume of the reducing agent is 1-10% of the total volume of the organic acid and the reducing agent (namely the volume of the leaching agent).
In the above technical solution, in the step S2, LiNi is leached by using organic phosphoric acid and a reducing agent0.6Co0.2Mn0.2O2The reaction principle of the material is as follows:
in the following reaction formula, Me represents transition metal (Ni, Co, Mn), HA is organic phosphoric acid, and hydrogen peroxide is used as a reducing agent, and the following reactions occur in the leaching process: 2LiMeO2(s)+6HA(aq)+H2O2(aq)＝2LiA(aq)+2MeA2(s)+4H2O(l)+O2(g)
In the course of the reaction, H+Is consumed, A-With Me2-Formation of precipitate MeA2；
In the step S3, the alkali solution and the precipitate undergo a displacement precipitation and a coprecipitation reaction to generate a nickel cobalt manganese hydroxide precipitate, wherein the reaction process is as follows:
MeA2(s)+2NaOH(aq)＝Me(OH)2(s)+2NaA(aq)
in step S4, the principle of the lithiation reaction between the ternary precursor and the lithium source is as follows:
specifically, a lithium source is taken as lithium hydroxide, and a transition metal precipitate (nickel cobalt manganese hydroxide precipitate) and the lithium source are calcined to generate the ternary LiNi0.6Co0.2Mn0.2O2Positive electrode active material:
Me(OH)2(s)+LiOH(s)→LiMeO2(s)
after solid-liquid separation is performed by filtering in the step S4, the solution is rich in NaA, the solution rich in NaA is collected, and an inorganic acid is added to regenerate the organic acid, so that recycling of the organic acid is realized, and the reaction for regenerating the organic acid by adding the inorganic acid is as follows:
NaA(aq)+HNO3(aq)＝HA(aq)+NaNO3(aq)
in some embodiments, in step S2, the leaching temperature is 20-90 ℃ and the leaching time is 5-30 min.
In some embodiments, in step S3, the alkali solution is one or a mixture of two or more of sodium hydroxide, potassium hydroxide and lithium hydroxide.
In some embodiments, in step S4, the lithium source is at least one of lithium hydroxide, lithium carbonate, and lithium formate.
In some embodiments, in the step S4, the calcination temperature is 700-900 ℃, and the calcination time is 8-12 h.
In some embodiments, in step S5, the inorganic acid is one or a mixture of two or more of sulfuric acid, nitric acid, phosphoric acid, and hydrochloric acid.
In some embodiments, the inorganic acid is added in step S5 at a concentration of 0.5 to 5 mol/L.
Compared with the prior art, the invention has the following beneficial effects:
1. according to the invention, the organic phosphoric acid and the reducing agent are mixed to be used as the leaching agent, so that lithium ions can be leached on one hand, and coordination precipitation can be formed between the organic phosphoric acid and the transition metal in the anode material of the waste lithium ion battery on the other hand, nickel, cobalt and manganese metal ions in a lithium-rich solution can be effectively removed, and the leaching agent and the LiNi to be leached are strictly controlled0.6Co0.2Mn0.2O2The proportion of the solid of the positive electrode active material effectively recovers transition metal through chelating precipitation and reduces the generation of other impurities in the lithium-rich solution;
2. the leached coordination precipitate can be subjected to displacement precipitation and coprecipitation reaction by adding alkali liquor to generate nickel cobalt manganese hydroxide precipitate, the quantity ratio of metal ion substances in the nickel cobalt manganese hydroxide is adjusted to be 6:2:2, and then the nickel cobalt manganese hydroxide precipitate is matched with an excessive lithium source according to the quantity of the metal substances in the nickel cobalt manganese hydroxide precipitate to directly regenerate a precursor by lithiation, so that the leaching process of the coordination precipitate by using acid and a reducing agent is not needed, the step of forming a salt solution by chelating the precipitate is saved, the process operation is reduced, and the use of a leaching agent is reduced; calcining the precipitate generated by displacement precipitation and coprecipitation according to the amount of precursor substances and the proportion of a lithium source to obtain a positive electrode material with good electrochemical performance;
3. the organic acid salt solution generated in the invention can be regenerated by adding inorganic acid, new organic acid can be regenerated by adding a proper amount of inorganic acid, then a certain amount of reducing agent can be added into the new organic acid to form a new leaching agent for leaching the anode active material in a circulating manner, and short-path closed cycle for recycling the waste lithium ion battery can be established.
Drawings
FIG. 1 is a process flow diagram of the present invention;
FIG. 2 is a ternary LiNi synthesized in example 30.6Co0.2Mn0.2O2Testing the electrochemical performance of the positive active material; wherein, the graph (a) is a battery cycle performance test graph; (b) the figure is a multipleRate performance test charts.
Detailed Description
In the following description, numerous specific details are set forth in order to provide a thorough understanding of the present invention. This invention may, however, be embodied in many different forms and should not be construed as limited to the embodiments set forth herein, but rather should be construed as broadly as the present invention is capable of modification in various respects, all without departing from the spirit and scope of the present invention.
Unless defined otherwise, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs. The terminology used in the description of the invention herein is for the purpose of describing particular embodiments only and is not intended to be limiting of the invention.
Example 1
As shown in fig. 1, the method for recovering and regenerating the positive active material of the waste lithium ion battery comprises the following steps:
s1, firstly, completely discharging the waste lithium ion battery, disassembling and stripping to obtain a positive pole piece, soaking the positive pole piece in N-methyl pyrrolidone solution for ultrasonic treatment to accelerate the separation of positive active substances from a current collector aluminum foil, drying and calcining solid powder after separation to obtain the waste battery LiNi0.6Co0.2Mn0.2O2And grinding the positive active material for later use.
S2, weighing a proper amount of naphthalene phosphoric acid, placing the naphthalene phosphoric acid in a three-neck flask, wherein the concentration of the naphthalene phosphoric acid is 0.5mol/L, then adding a certain amount of hydrogen peroxide into the three-neck flask to prepare a leaching agent, wherein the volume of the hydrogen peroxide is 3% of that of the leaching agent, and the LiNi obtained in the step S1 is subjected to LiNi leaching0.6Co0.2Mn0.2O2Adding a positive electrode active material into the three-neck flask for leaching, wherein the leaching temperature is 50 ℃, the solid-to-liquid ratio is 50g/L, the stirring speed is 400rpm, the leaching time is 10min, and after the reaction is finished, obtaining a suspension of a mixture of a lithium-rich solution and nickel-cobalt-manganese precipitates;
s3, filtering and separating the suspension obtained in the step S2 by vacuum filtration, repeatedly washing the obtained nickel, cobalt and manganese precipitate with distilled water, drying the washed precipitate in an oven at the temperature of 80 ℃ for 10 hours, grinding and storing for later use, and collecting and storing the leachate;
s4, dispersing the precipitate obtained in the step S3 in deionized water, adding 1mol/L of sodium hydroxide solution, adjusting the pH value to 7, carrying out displacement precipitation and coprecipitation reaction on the precipitate and the sodium hydroxide solution, and converting the precipitate into a ternary precursor hydroxide precipitate (nickel cobalt manganese hydroxide); filtering and separating nickel cobalt manganese hydroxide precipitate, determining the content of metal ions in nickel cobalt manganese hydroxide according to ICP-OES, adjusting the quantity ratio of nickel cobalt manganese metal ion substances in nickel cobalt manganese hydroxide to be 6:2:2, proportioning and lithiating the nickel cobalt manganese metal ion substances with the content of 3% lithium hydroxide according to the quantity of the metal ion substances in the ternary precursor, grinding and mixing, putting the mixture into a tubular furnace for high-temperature calcination at 850 ℃ for 10 hours to obtain the ternary LiNi with good performance0.6Co0.2Mn0.2O2A positive electrode active material;
s5, adding nitric acid with the concentration of 0.5mol/L into the filtrate obtained after filtering and separating in the step S4 to realize regeneration of the naphthalene phosphoric acid, and adding a reducing agent (hydrogen peroxide) into the regenerated naphthalene phosphoric acid to form a new leaching agent, wherein the volume of the reducing agent is 3% of the total volume of the naphthalene phosphoric acid and the reducing agent, and the new leaching agent can be used for circularly leaching the LiNi of the lithium ion battery0.6Co0.2Mn0.6O2The positive electrode active material realizes the recycling of organic acid.
Example 2
As shown in fig. 1, the method for recovering and regenerating the positive active material of the waste lithium ion battery comprises the following steps:
s1, firstly, completely discharging the waste lithium ion battery, disassembling and stripping to obtain a positive pole piece, soaking the positive pole piece in N-methyl pyrrolidone solution for ultrasonic treatment to accelerate the separation of positive active substances from a current collector aluminum foil, drying and calcining solid powder after separation to obtain the waste battery LiNi0.6Co0.2Mn0.2O2And grinding the positive active material for later use.
S2, weighing a proper amount of methyl phosphoric acid solution, placing the methyl phosphoric acid solution into a three-neck flask, wherein the concentration of the methyl phosphoric acid is 2mol/L, and then adding a certain amount of methyl phosphoric acid into the three-neck flaskHydrogen peroxide is prepared into a leaching agent, wherein the volume of the hydrogen peroxide is 5 percent of that of the leaching agent, and the LiNi obtained in the step S1 is treated0.6Co0.2Mn0.2O2Adding a positive electrode active material into the three-neck flask for leaching, wherein the leaching temperature is 70 ℃, the solid-to-liquid ratio is 40g/L, the stirring speed is 600rpm, the leaching time is 20min, and after the reaction is finished, obtaining a suspension of a mixture of a lithium-rich solution and nickel-cobalt-manganese precipitates;
s3, filtering and separating the suspension obtained in the step S2 by vacuum filtration, repeatedly washing the obtained nickel, cobalt and manganese precipitate with distilled water, drying the washed precipitate in an oven at the temperature of 80 ℃ for 10 hours, grinding and storing for later use, and collecting and storing the leachate;
s4, dispersing the precipitate obtained in the step S3 in deionized water, adding 3mol/L of sodium hydroxide solution, adjusting the pH value to 9, carrying out displacement precipitation and coprecipitation reaction on the precipitate and the sodium hydroxide solution, and converting the precipitate into a ternary precursor hydroxide precipitate (nickel cobalt manganese hydroxide); filtering and separating nickel cobalt manganese hydroxide precipitate, determining the content of metal ions in nickel cobalt manganese hydroxide according to ICP-OES, adjusting the mass ratio of nickel cobalt manganese metal ion substances in nickel cobalt manganese hydroxide to be 6:2:2, matching lithium hydroxide with 5% of excessive lithium hydroxide according to the mass ratio of a ternary precursor, grinding and mixing, putting into a tubular furnace for high-temperature calcination at the calcination temperature of 750 ℃ for 12h, and obtaining the ternary LiNi with good performance0.6Co0.2Mn0.2O2A positive electrode active material;
s5, adding nitric acid with the concentration of 3mol/L into the filtrate obtained after filtering and separating in the step S4 to realize regeneration of methyl phosphoric acid, and adding a reducing agent (hydrogen peroxide) into the regenerated methyl phosphoric acid to form a new leaching agent, wherein the volume of the reducing agent is 3% of the total volume of the methyl phosphoric acid and the reducing agent, and the new leaching agent can be used for circularly leaching LiNi of the lithium ion battery0.6Co0.2Mn0.6O2The anode active material realizes the recycling of the methyl phosphoric acid.
Example 3
As shown in fig. 1, the method for recovering and regenerating the positive active material of the waste lithium ion battery comprises the following steps:
s1, firstly, completely discharging the waste lithium ion battery, disassembling and stripping to obtain a positive pole piece, soaking the positive pole piece in N-methyl pyrrolidone solution for ultrasonic treatment to accelerate the separation of positive active substances from a current collector aluminum foil, drying and calcining solid powder after separation to obtain the waste battery LiNi0.6Co0.2Mn0.2O2And grinding the positive active material for later use.
S2, weighing a proper amount of phenylphosphoric acid, placing the phenylphosphoric acid in a three-neck flask, wherein the concentration of the phenylphosphoric acid is 5mol/L, then adding a certain amount of hydrogen peroxide into the three-neck flask to prepare a leaching agent, wherein the volume of the hydrogen peroxide is 8% of that of the leaching agent, and the LiNi obtained in the step S1 is subjected to0.6Co0.2Mn0.2O2Adding a positive electrode active material into the three-neck flask for leaching, wherein the leaching temperature is 40 ℃, the solid-to-liquid ratio is 30g/L, the stirring speed is 800rpm, the leaching time is 30min, and after the reaction is finished, obtaining a suspension of a mixture of a lithium-rich solution and nickel-cobalt-manganese precipitates;
s3, filtering and separating the suspension obtained in the step S2 by vacuum filtration, repeatedly washing the obtained nickel, cobalt and manganese precipitate with distilled water, drying the washed precipitate in an oven at the temperature of 100 ℃ for 8 hours, grinding and storing for later use, and collecting and storing the leachate;
s4, dispersing the precipitate obtained in the step S3 in deionized water, adding 5mol/L of sodium hydroxide solution, adjusting the pH value to 6, carrying out displacement precipitation and coprecipitation reaction on the precipitate and the sodium hydroxide solution, and converting the precipitate into a ternary precursor hydroxide precipitate (nickel cobalt manganese hydroxide); filtering and separating nickel cobalt manganese hydroxide precipitate, determining the content of metal ions in nickel cobalt manganese hydroxide according to ICP-OES, adjusting the mass ratio of nickel cobalt manganese metal ion substances in nickel cobalt manganese hydroxide to be 6:2:2, matching lithium hydroxide with excess 1% by mass according to the mass ratio of a ternary precursor substance for lithiation, grinding and mixing, putting into a tubular furnace for high-temperature calcination at the calcination temperature of 950 ℃ for 10h to obtain the ternary LiNi with good performance0.6Co0.2Mn0.2O2A positive electrode active material;
s5, filtering and separating in step S4Sulfuric acid with the concentration of 2mol/L is added into the obtained filtrate, the regeneration of phenylphosphoric acid can be realized, a reducing agent (hydrogen peroxide) is added into the regenerated phenylphosphoric acid, a new leaching agent can be formed, wherein the volume of the reducing agent is 5% of the total volume of the phenylphosphoric acid and the reducing agent, and the new leaching agent can be used for circularly leaching LiNi of the lithium ion battery0.6Co0.2Mn0.6O2The positive electrode active material realizes the recycling of the phenylphosphoric acid.
LiNi prepared in example 30.6Co0.2Mn02O2The lithium ion battery is prepared from the positive active material by a conventional method in the battery field, and the cycle and rate performance of the lithium ion battery are tested, wherein the test result is shown in fig. 2.
As can be seen from FIG. 2, LiNi prepared by the method of the present invention0.6Co0.2Mn02O2The positive active material has high specific discharge capacity and excellent cycling and multiplying power performance in a charge-discharge cycle of 0.5C within a voltage range of 2.7-4.3v and under different multiplying powers.
The technical features of the embodiments described above may be arbitrarily combined, and for the sake of brevity, all possible combinations of the technical features in the embodiments described above are not described, but should be considered as being within the scope of the present specification as long as there is no contradiction between the combinations of the technical features.
The above-mentioned embodiments only express several embodiments of the present invention, and the description thereof is more specific and detailed, but not construed as limiting the scope of the invention. It should be noted that, for a person skilled in the art, several variations and modifications can be made without departing from the inventive concept, which falls within the scope of the present invention. Therefore, the protection scope of the present patent shall be subject to the appended claims.
Claims (7)
1. A method for recovering and regenerating a positive active material of a waste lithium ion battery is characterized by comprising the following steps:
s1, discharging the recovered waste lithium ion battery completely, and disassemblingDissolving, stripping, calcining and grinding to obtain the required LiNi0.6Co0.2Mn0.2O2A positive electrode active material;
s2, preparing the LiNi0.6Co0.2Mn0.2O2Leaching the positive active material by using a leaching agent to obtain a leaching solution rich in lithium and a precipitate containing nickel, cobalt and manganese; filtering and separating the leachate and the precipitate, drying the precipitate in an oven, grinding and storing for later use; the leaching agent consists of a reducing agent and an organic acid, the concentration of the organic acid is 0.5-5mol/L, the using amount of the reducing agent is 1-10% of the volume of the leaching agent, and the using amount ratio of the positive electrode active material to the leaching agent is 5-60 g/L; wherein the organic acid is at least one of methyl phosphoric acid, benzene phosphoric acid, naphthalene phosphoric acid, methylene diphosphonic acid, diphenyl phosphoric acid, benzyl hypophosphorous acid, trimethyl phosphoric acid, aminophosphoric acid, toluene phosphoric acid or 1, 4-benzene diphosphonic acid; the reducing agent is at least one of hydrogen peroxide, sodium persulfate, glucose, sucrose and ascorbic acid;
s3, dispersing the precipitate obtained in the step S2 in deionized water, adding 0.5-5mol/L alkali liquor, adjusting the pH to 6-9, and performing displacement precipitation and coprecipitation reaction on the precipitate and the alkali liquor to obtain nickel cobalt manganese hydroxide precipitate;
s4, filtering the nickel cobalt manganese hydroxide precipitate generated in the step S3 to obtain a ternary precursor nickel cobalt manganese hydroxide, determining the content of metal ions in the nickel cobalt manganese hydroxide according to ICP-OES, adjusting the ratio of the nickel cobalt manganese metal ions to be 6:2:2, matching the nickel cobalt manganese metal ions and an excessive 1-5% lithium source according to the amount of the ternary precursor, carrying out lithiation, grinding, mixing and calcining to obtain the ternary LiNi with good performance0.6Co0.2Mn0.2O2A positive electrode active material;
s5, adding inorganic acid into the filtrate obtained by filtering in the step S4, wherein the concentration of the inorganic acid is 0.5-5mol/L, generating new organic acid, and adding a reducing agent into the organic acid to generate the leaching agent; wherein the volume of the added reducing agent accounts for 1-10% of the volume of the newly generated leaching agent.
2. The method for recovering and regenerating the positive active material of the waste lithium ion battery according to claim 1, wherein in the step S2, the leaching temperature is 20 to 90 ℃ and the leaching time is 5 to 30 min.
3. The method for recovering and regenerating the positive active material of the waste lithium ion battery according to claim 1, wherein in the step S3, the alkali solution is one or a mixture of two or more of sodium hydroxide, potassium hydroxide and lithium hydroxide.
4. The method for recovering and regenerating the waste lithium ion battery positive active material according to claim 1, wherein in the step S4, the lithium source is at least one of lithium hydroxide, lithium carbonate and lithium formate.
5. The method for recycling and regenerating the anode active material of waste lithium ion batteries as claimed in claim 1, wherein the calcination temperature in step S4 is 700-.
6. The method for recovering and regenerating the positive active material of the waste lithium ion battery according to claim 1, wherein in the step S5, the inorganic acid is one or a mixture of two or more of sulfuric acid, nitric acid, phosphoric acid and hydrochloric acid.
7. The method for recycling and regenerating the positive active material of the waste lithium ion battery according to claim 6, wherein the concentration of the inorganic acid added in the step S5 is 0.5-5 mol/L.
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| CN114875238A (en) * | 2022-05-20 | 2022-08-09 | 北京化工大学 | Method for recycling nickel, manganese, cobalt and lithium in waste lithium battery ternary cathode material |
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