CN114480845B - Method for recovering valuable metals in retired lithium ion battery anode material - Google Patents
Method for recovering valuable metals in retired lithium ion battery anode material Download PDFInfo
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- CN114480845B CN114480845B CN202111495836.XA CN202111495836A CN114480845B CN 114480845 B CN114480845 B CN 114480845B CN 202111495836 A CN202111495836 A CN 202111495836A CN 114480845 B CN114480845 B CN 114480845B
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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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- 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
- C22B3/00—Extraction of metal compounds from ores or concentrates by wet processes
- C22B3/20—Treatment or purification of solutions, e.g. obtained by leaching
- C22B3/44—Treatment or purification of solutions, e.g. obtained by leaching by chemical 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 invention belongs to the technical field of recycling of electronic waste lithium ion batteries, and particularly relates to a method for recycling valuable metals in a retired lithium ion battery anode material. The method is a method for recovering metals in the anode material of the retired lithium ion battery by using an oxidant and organic acid, wherein the crystal structure of the anode material of the retired lithium ion battery is damaged at an accelerated speed by using free radicals generated by activating with an oxidant persulfate or a hydrogen peroxide aqueous solution under a subcritical condition, and the complexation effect of the organic acid and a reducing agent are combined to promote the valuable metals to be converted into a soluble state. The invention utilizes a green and safe method, takes the anode material of the retired lithium ion battery as the raw material, destroys the crystal structure in the anode material of the retired lithium ion battery by using free radicals generated by persulfate activation under subcritical conditions, can realize high-efficiency recovery of valuable metal resources, avoids secondary pollution to the environment, and has the advantages of low cost, simple process, easy expanded production and industrialization realization.
Description
Technical Field
The invention belongs to the technical field of recycling of electronic waste lithium ion batteries, and particularly relates to a method for recycling valuable metals in a retired lithium ion battery anode material.
Background
As a novel energy storage device, a lithium ion battery has the characteristics of high power capacity, flexible and wide working conditions, high energy density, good safety and the like, and is widely applied to a plurality of fields including renewable energy storage, new energy vehicles, portable electronic devices and the like. With the development of science and technology, more and more electronic products sold in the market adopt lithium ion batteries as energy storage units, and in addition, the usage amount of the lithium ion batteries is facing a sudden rise in consideration of the demand of the electric automobile industry which is rapidly developing at present on the lithium ion batteries. In 2020, the annual output of lithium ion batteries in China breaks through 180 hundred million. In view of the current battery yield and consumption, which are still in a rapidly growing situation, the number of retired lithium ion batteries will continue to increase, and if they are not properly disposed of, they will cause serious ecological problems.
At present, the method for recovering the anode material in the waste lithium ion battery mainly comprises a pyrometallurgical process and a hydrometallurgical process, wherein the hydrometallurgical process comprises the following steps: after the anode material is separated and disassembled, the metal oxide is completely dissolved by using concentrated acid under the heating condition to obtain a metal-rich solution, and then various metals are separated and recovered through the steps of pH regulation, precipitant addition, extraction and the like for secondary utilization. The method has the defects of harsh reaction conditions, high safety risk, high reagent consumption, serious secondary pollution and the like.
The critical point parameters for water in engineering thermodynamics are defined as pressure =22.115Mpa and temperature t =374.15 ℃. Water is heated to a temperature higher than the boiling point and lower than the critical point, and the system pressure is controlled so that the water is kept in a liquid state, and water in this state is called subcritical water. At present, a hydrothermal method is adopted to recover waste lithium ion batteries in some processes, but water has strong polarity under the conditions of normal temperature and normal pressure, so that a large amount of strong acid and strong oxidant are additionally added for auxiliary leaching in the reaction to obtain a considerable leaching rate. For example, patent document CN110724820A discloses a method for recovering a retired lithium ion battery positive electrode material by using a hydrothermal method, in which the retired lithium ion battery positive electrode material is used as a raw material, and a saccharide reducing agent is used to reduce an oxide in the lithium ion battery positive electrode material, so that although valuable metals in the lithium ion positive electrode material can be recovered at a high leaching rate, the amount of organic acid and reducing agent to be added is large, or the hydrothermal reaction temperature is high, the reaction time is long, and the recovery efficiency of valuable metals in the retired lithium ion positive electrode material needs to be further improved.
Disclosure of Invention
Aiming at the defects of the prior art, the invention provides a method for recovering valuable metals in a retired lithium ion battery anode material, which takes an oxidant and organic acid as auxiliary additives, and obtains a leaching solution rich in the valuable metals through subcritical reaction treatment in a hydrothermal reaction kettle, and the introduction of an oxidant persulfate or a hydrogen peroxide aqueous solution is matched with the organic acid and a reducing agent, so that the leaching efficiency of the valuable metals is greatly improved, the using amount of the additives is reduced, and the technical problems of large additive using amount, long reaction time, high temperature, low leaching efficiency of the valuable metals and the like in the method for recovering the retired lithium ion battery anode material in the prior art are solved.
In order to achieve the aim, the invention provides a method for recovering valuable metals in a retired lithium ion battery anode material, which comprises the following steps:
(1) Mixing the anode material of the retired lithium ion battery with organic acid, oxidant and reductant to obtain a reaction precursor solution; the oxidant is persulfate or aqueous hydrogen peroxide;
(2) Carrying out hydrothermal reaction on the reaction liquid obtained in the step (1) to obtain a reaction liquid; in the reaction process, the oxidant generates free radicals to destroy the crystal structure of the anode material of the retired lithium ion battery and release valuable metal ions; meanwhile, carboxylic acid groups in the organic acid and released valuable metal ions are subjected to a complex reaction, so that leaching of valuable metals is promoted;
(3) And (3) carrying out solid-liquid separation on the reaction liquid obtained by the reaction in the step (2), and taking supernatant to obtain leachate containing valuable metal ions.
Preferably, the organic acid is one or more of acetic acid, malic acid, tartaric acid, citric acid, lactic acid, and ascorbic acid; the molar concentration of the organic acid is 0.1mol/L to 6mol/L, and more preferably 1mol/L to 3mol/L.
Preferably, the mass ratio of the dosage of the oxidant to the anode material of the retired lithium ion battery is (0.5-5): 1, preferably (0.8-3): 1.
Preferably, the oxidizing agent is a persulfate; the persulfate is one or the combination of more of potassium persulfate, sodium persulfate, ammonium persulfate, potassium hydrogen persulfate and potassium hydrogen peroxymonosulfate composite salt.
Preferably, the reducing agent is one or more of glucose, sucrose, fructose, lactose, ascorbic acid, hydrogen peroxide and sodium thiosulfate; the mass ratio of the using amount of the reducing agent to the anode material of the retired lithium ion battery is (0.5-5): 1, and more preferably (1-3): 1.
Preferably, the mass volume concentration of the retired lithium ion battery positive electrode material in the liquid before reaction is 10g/L-50g/L, and further preferably 20g/L-30g/L.
Preferably, the temperature of the hydrothermal reaction in the step (2) is 105-374 ℃, the pressure is 0.11-22.0Mpa, and the reaction time is 15-500 min.
Preferably, the temperature of the hydrothermal reaction in the step (2) is 150-200 ℃, the pressure is 2-10 Mpa, and the reaction time is 30-90 min.
Preferably, the solid-liquid separation in step (3) is centrifugal separation.
Generally, compared with the prior art, the above technical solution conceived by the present invention has the following beneficial effects:
(1) The invention provides a method for recovering metal in an anode material of a retired lithium ion battery by using an oxidant (persulfate or aqueous hydrogen peroxide) and organic acid, aiming at the defects of difficult damage of a metal crystal structure, low metal ion recovery rate, high reagent consumption and serious secondary pollution in the anode material of the retired lithium ion battery in the prior art, wherein the crystal structure of the anode material of the retired lithium ion battery is damaged at a high speed by using free radicals generated by the activation of the oxidant under a subcritical condition, and the complexation effect of an organic acid and a reducing agent are combined to promote valuable metals to be converted into a soluble state. The invention utilizes a green and safe method, takes the anode material of the retired lithium ion battery as the raw material, uses free radicals generated by the activation of an oxidant under subcritical conditions to destroy the crystal structure in the anode material of the retired lithium ion battery, can realize the high-efficiency recovery of valuable metal resources, avoids the secondary pollution to the environment, and has the advantages of low cost, simple process, easy expanded production and industrialization realization.
(2) According to the invention, the crystal structure of the anode material of the retired lithium ion battery is destroyed by adopting free radicals generated by activating persulfate or hydrogen peroxide water, so that secondary pollution and danger caused by using a large amount of high-concentration strong acid and high temperature are avoided, the traditional high-concentration inorganic acid is replaced by low-concentration organic acid, the emission of harmful waste gas and waste liquid is avoided, and the process cost is reduced. In addition, the carboxyl group of the organic acid has a strong complexing effect on the valuable metal ions, and can promote the dissolution of the valuable metal and stabilize the form of the valuable metal. In the presence of a reducing agent, valuable metals can be converted from a difficultly soluble high valence state to a low valence state, and the leaching reaction process is effectively accelerated. Meanwhile, valuable metals in the retired lithium ion battery anode material and the persulfate can be activated to generate free radicals in the heating process in the reaction, so that an additional activation step is avoided, and the recovery process is simplified.
(3) According to the invention, the oxidant persulfate or aqueous hydrogen peroxide is added to leach with the organic acid, and the reducing agent is added, so that the method has the advantages of high recovery efficiency, high reaction speed, simplicity in operation, low cost, no pollution and the like; meanwhile, the invention can recover valuable metals in the lithium ion battery anode material in a time limit retired mode, and solves the problems that the crystal structure in the lithium ion battery anode material is difficult to damage and the recovery rate of the valuable metals is low. Especially, in the preferred embodiment, the leaching rate of the valuable metals is over 90 percent under the condition that persulfate is adopted as the oxidant, the leaching time is shortened from 300 minutes without adding the oxidant to 75 minutes, and the leaching efficiency is greatly improved.
(4) The method disclosed by the invention adopts a hydrothermal method to leach under subcritical conditions, is wide in working temperature range, is suitable for various organic acids and reducing agents, is short in reaction time, and can realize high-efficiency recovery of valuable metals under low energy consumption.
(5) The invention realizes a new method for recycling the retired lithium ion battery anode material, recovers and obtains the high-concentration valuable metal ion leachate, can be used as the precursor solution of the recycled lithium ion battery anode material after simple component regulation and control, and has considerable potential in the field of electronic waste recycling.
(6) The recovery method provided by the invention has the advantages of no pollution, no potential safety hazard, simple and convenient operation, wide application range, low cost and good popularization prospect.
Drawings
Fig. 1 is a flow chart of the method for recovering metals in the anode material of the retired lithium ion battery by using persulfate and organic acid.
FIG. 2 shows the detection result of electron paramagnetic resonance spectrometer (EPR) of the leachate of the anode material of the retired lithium ion battery.
FIG. 3 is a comparison graph of the leaching rates of valuable metal elements of the retired lithium ion battery anode material under different conditions.
Detailed Description
In order to make the objects, technical solutions and advantages of the present invention more apparent, the present invention is described in further detail below with reference to the accompanying drawings and embodiments. It should be understood that the specific embodiments described herein are merely illustrative of the invention and are not intended to limit the invention.
The invention firstly separates the anode material of the retired lithium ion battery according to the conventional method, and then recovers the valuable metals in the retired lithium ion battery anode material according to the following method, wherein the method comprises the following steps:
(1) Mixing the anode material of the retired lithium ion battery with organic acid, oxidant and reductant to obtain a reaction precursor solution; the oxidant is persulfate or aqueous hydrogen peroxide;
(2) Carrying out hydrothermal reaction on the liquid before reaction obtained in the step (1) to obtain a reaction liquid; in the reaction process, the oxidant generates free radicals to destroy the crystal structure of the anode material of the retired lithium ion battery and release valuable metal ions; meanwhile, carboxylic acid groups in the organic acid and released valuable metal ions are subjected to a complex reaction, so that leaching of valuable metals is promoted;
(3) And (3) carrying out solid-liquid separation on the reaction liquid obtained by the reaction in the step (2), and taking supernatant to obtain leachate containing valuable metal ions.
The retired lithium ion battery positive electrode material can be various waste lithium ion battery positive electrode materials, including but not limited to ternary lithium ion positive electrode materials, and the main component of the retired lithium ion battery positive electrode material is at least one of lithium cobaltate, lithium nickelate, lithium manganate and lithium nickel cobalt manganese.
In some embodiments, the organic acid is a combination of one or more of acetic acid, malic acid, tartaric acid, citric acid, lactic acid, ascorbic acid; the organic acid is an aqueous solution of an organic acid having a molar concentration of 0.1 to 6mol/L, preferably 1 to 3mol/L.
In some embodiments, the mass ratio of the amount of the oxidant to the material of the anode of the retired lithium ion battery is (0.5-5): 1, preferably (0.8-3): 1; the persulfate is one or the combination of more of potassium persulfate, sodium persulfate, ammonium persulfate, potassium monopersulfate and potassium monopersulfate composite salt; the percentage by volume of the aqueous hydrogen peroxide solution was 30%.
The free radical acting on the crystal structure of the lithium ion anode material is a free radical generated under the activation action of high temperature and metal ions, and can be one or more of hydroxyl free radical, sulfate free radical, superoxide anion free radical, singlet oxygen, hydrogen free radical and surface persistent free radical.
In some embodiments, the reducing agent is one or more of glucose, sucrose, fructose, lactose, ascorbic acid, hydrogen peroxide, sodium thiosulfate; the mass ratio of the dosage of the reducing agent to the anode material of the retired lithium ion battery is (0.5-5): 1, and preferably (1-3): 1.
In some embodiments, the mass volume concentration of the retired lithium ion battery positive electrode material in the pre-reaction solution is 10g/L to 50g/L, preferably 20g/L to 30g/L.
In some embodiments, the hydrothermal reaction in step (2) is performed at 105-374 deg.C, preferably 150-200 deg.C, under 0.11-22.0MPa, preferably 2-10 MPa, for 15-500 min, preferably 30-90 min.
In some embodiments, the solid-liquid separation of step (3) is centrifugation.
Example 1
The embodiment provides a method for recovering metal in a decommissioned lithium ion battery anode material by using persulfate and organic acid cooperatively under subcritical conditions, and fig. 1 is a flow chart of recovering valuable metal in the decommissioned lithium ion battery anode material by using persulfate and organic acid, which is provided by the embodiment, and includes the following steps:
(1) Mixing 0.2g of an out-of-service lithium ion battery anode material, 0.4g of potassium persulfate, 0.4g of glucose and 10ml of 1.5mol/L acetic acid aqueous solution, wherein the mass volume concentration of the anode material is 20g/L, and carrying out hydrothermal reaction at 175 ℃ for 75min to obtain brown turbid liquid;
(2) And centrifuging the brown turbid liquid by using a high-speed centrifuge, and then taking supernatant liquid to filter by using filter paper to obtain leachate rich in valuable metals. The leaching rate of lithium in the leaching solution is 90%, the leaching rate of cobalt is 98%, the leaching rate of nickel is 97%, and the leaching rate of manganese is 92%.
Example 2
(1) Mixing 0.2g of an out-of-service lithium ion battery anode material, 0.4g of potassium peroxymonosulfate, 0.2g of glucose and 20 ml of 1.5mol/L acetic acid aqueous solution, wherein the mass volume concentration of the anode material is 10g/L, and carrying out hydrothermal reaction at 175 ℃ for 75min to obtain brown turbid liquid;
(2) And centrifuging the brown turbid liquid by using a high-speed centrifuge, and then taking supernatant liquid to filter by using filter paper to obtain leachate rich in valuable metals. The leaching rate of lithium in the leaching solution is 94%, the leaching rate of cobalt is 95%, the leaching rate of nickel is 94%, and the leaching rate of manganese is 89%.
Example 3
(1) Mixing 0.2g of an out-of-service lithium ion battery anode material, 0.4g of potassium persulfate, 0.2g of glucose and 10ml of 1.5mol/L acetic acid aqueous solution, wherein the mass volume concentration of the anode material is 20g/L, and carrying out hydrothermal reaction at 175 ℃ for 75min to obtain brown turbid liquid;
(2) Centrifuging the brown turbid liquid by using a high-speed centrifuge, then filtering supernate by using filter paper, adding 50 mu L of dimethyl pyridine N-oxide serving as a free radical trapping agent into 3ml of filtered supernate, uniformly mixing, and then detecting free radicals by using an electron paramagnetic resonance spectrometer.
Fig. 2 is a diagram showing the detection result of free radicals in the leachate obtained after the retired lithium ion battery anode material is leached by using the method, and as can be seen from fig. 2, an electron paramagnetic resonance spectrometer detects paramagnetic substances contained in a sample by generating microwaves and changing the absorption of magnetic field detection microwaves, so that specific substances are identified by characteristics, and the mass is judged according to the fluctuation intensity. Because the anode material of the waste lithium ion battery has certain ferromagnetism, the characteristic spectrum of the anode material is in regular wave shape, and the fluctuation of the spectrum base line is large. The radicals show distinct absorption peaks at magnetic field strengths of 3410-3440B. As can be seen from fig. 2, the leachate spectrogram also presents a wave-shaped spectrogram similar to the anode material of the waste lithium ion battery, but the baseline fluctuation is obviously slowed down, which indicates that the content of the ferromagnetic anode material in the leachate is greatly reduced, and the side surface proves the modification function of the method on the anode material. In addition, a characteristic vibration spectrum with the same position as a free radical spectrum and a similar structure appears in the leachate spectrum within the range of the magnetic field intensity of 3410-3440B, which shows that the leachate contains free radicals generated after persulfate activation and reacts with the anode material of the waste lithium ion battery.
Example 4
(1) Mixing 0.2g of the retired lithium ion battery cathode material, 0.15ml of 30% aqueous hydrogen peroxide (the amount can generate the same amount of free radicals as that of example 1), 0.2g of glucose and 10ml of 1.5mol/L aqueous acetic acid, wherein the mass volume concentration of the cathode material is 20g/L, and carrying out hydrothermal reaction at 175 ℃ for 75min to obtain brown turbid liquid;
(2) And centrifuging the brown turbid liquid by using a high-speed centrifuge, and filtering the supernatant by using filter paper to obtain a leaching solution rich in valuable metals. The leaching rate of lithium in the leaching solution is 73 percent, the leaching rate of cobalt is 57 percent, the leaching rate of nickel is 70 percent, and the leaching rate of manganese is 74 percent.
This example demonstrates that the leaching rate is slightly reduced when persulfate is replaced with hydrogen peroxide. The reason may be that although hydrogen peroxide can be activated to generate radicals, it is slightly less thermally stable than persulfate and generates less radical species than persulfate, resulting in a weakening of radical action ability.
In order to facilitate comparison of the necessity of the method of the present invention, the advantages of the present invention will be described with reference to comparative examples.
Comparative example 1
(1) Mixing 0.2g of waste ternary lithium ion battery anode material, 0.4g of glucose and 10ml of 1.5mol/L acetic acid aqueous solution, wherein the mass volume concentration of the anode material is 20g/L, and carrying out hydrothermal reaction at 175 ℃ for 75min to obtain brown turbid liquid;
(2) And centrifuging the brown turbid liquid by using a high-speed centrifuge, and filtering the supernatant by using filter paper to obtain a leaching solution rich in valuable metals. The leaching rate of lithium in the leaching solution was 56%, the leaching rate of cobalt was 29%, the leaching rate of nickel was 40%, and the leaching rate of manganese was 56% (fig. 3).
The comparative example shows that the leaching effect of valuable metals in the anode material of the retired lithium ion battery can be effectively improved by using the persulfate additive; the persulfate can generate free radicals under the double activation of high temperature and metal ions to destroy the crystal structure of the anode material of the retired lithium ion battery and release valuable metal ions.
Comparative example 2
(1) Mixing 0.2g of a waste ternary lithium ion battery anode material, 0.4g of potassium persulfate, 0.4g of glucose and sulfuric acid with the pH =2, wherein the solid-to-liquid ratio of the anode material to the mixed solution of the sulfuric acid and the glucose is 20g/L, and carrying out hydrothermal reaction at 175 ℃ for 75min to obtain brown turbid liquid;
(2) And centrifuging the brown turbid liquid by using a high-speed centrifuge, and then taking supernatant liquid to filter by using filter paper to obtain leachate rich in valuable metals. The leaching rate of lithium, cobalt, nickel and manganese in the leaching solution was 43%, 8%, 12% and 7%, respectively (fig. 3).
This comparative example demonstrates that the reaction carried out with persulfate and reductant alone without organic acid (sulfuric acid with pH =2 added) is less effective in leaching out of the spent lithium ion battery cathode material. In the prior art, the anode material of the retired lithium ion battery is treated and recycled by using sulfuric acid with larger concentration, but the recycling effect can be better only by using a large amount of sulfuric acid, and the sulfuric acid causes serious pollution.
Comparative example 3
(1) Mixing 0.2g of a waste ternary lithium ion battery anode material, 0.4g of potassium persulfate and 10ml of 1.5mol/L acetic acid aqueous solution, wherein the mass volume concentration of the anode material is 20g/L, and carrying out hydrothermal reaction at 175 ℃ for 75min to obtain brown turbid liquid;
(2) And centrifuging the brown turbid liquid by using a high-speed centrifuge, and filtering the supernatant by using filter paper to obtain a leaching solution rich in valuable metals. The leaching rate of lithium in the leaching solution was 60%, the leaching rate of cobalt was 26%, the leaching rate of nickel was 41%, and the leaching rate of manganese was 49% (fig. 3).
This comparative example illustrates that the reaction carried out with persulfate and organic acid added alone without reducing agent has a poor leaching effect on the out-of-service lithium ion battery cathode material.
In the valuable metal recovery process of the lithium ion cathode material, although the persulfate with oxidability and the reducing agent with reducibility are added at the same time, experiments prove that the persulfate and the reducing agent do not react to cause internal consumption, but mutually promote to improve the leaching efficiency of the valuable metal. The possible reasons are that the persulfate activation site is on the surface of the metal, most of the generated free radicals are also present on the metal, and the free radicals are difficult to enter the solution in large quantity to react with the sucrose considering that the existence time of the free radicals is short.
Comparative example 4
(1) 0.2g of the spent lithium ion battery positive electrode material, 0.4g of potassium persulfate, 0.4g of glucose and 10ml of a 1.5mol/L aqueous acetic acid solution were mixed, followed by addition of 1ml of a radical quencher (isopropanol, tert-butanol). Wherein the mass volume concentration of the anode material is 20g/L, and the hydrothermal reaction is carried out for 75min at 175 ℃ to obtain brown turbid liquid;
(2) And centrifuging the brown turbid liquid by using a high-speed centrifuge, and filtering the supernatant by using filter paper to obtain a leaching solution rich in valuable metals. Wherein, the leaching rate of lithium in the reaction leaching solution without adding the free radical quenching agent is 63 percent, the leaching rate of cobalt is 34 percent, the leaching rate of nickel is 52 percent, and the leaching rate of manganese is 46 percent; the leaching rates of lithium, cobalt, nickel and manganese in the reaction leaching solution added with the free radical quenching agent are as follows in sequence: 53%, 30%, 33%, 23% and 61%, 26%, 47%, 33% (fig. 3).
The comparison example shows that the free radicals generated by the activation of the persulfate have a key effect on improving the leaching effect of the anode material of the waste lithium ion battery.
Comparative example 5
(1) 0.2g of the retired lithium ion battery anode material, 0.4g of potassium persulfate, 0.4g of glucose and 10ml of 1.5mol/L acetic acid aqueous solution are mixed. Wherein the mass volume concentration of the anode material is 20g/L, and the anode material reacts in water bath at 80 ℃ for 75min (under normal pressure) to obtain brown turbid liquid;
(2) And centrifuging the brown turbid liquid by using a high-speed centrifuge, and filtering the supernatant by using filter paper to obtain a leaching solution rich in valuable metals. Among them, the leaching rate of lithium was 13%, the leaching rate of cobalt was 3%, the leaching rate of nickel was 2%, and the leaching rate of manganese was 0% in the reaction leachate to which the radical quencher was not added (fig. 3).
The comparative example shows that the subcritical reaction condition plays a key role in improving the leaching effect of the waste lithium ion battery anode material.
Fig. 3 is a comparison graph of valuable metal element leaching rates of the anode material of the waste lithium ion battery under different conditions. As can be seen from fig. 3, the leaching effect of the valuable metals in the material of the cathode of the retired lithium ion battery can be effectively improved by using the persulfate additive. The reaction under subcritical conditions has a decisive effect on the improvement of the leaching rate. Free radicals generated by persulfate activation play a key role in improving the leaching effect of the anode material of the waste lithium ion battery. In addition, the organic acid and the reducing agent must be added simultaneously to achieve a significant leaching effect, and the addition of any one of persulfate, organic acid and reducing agent alone cannot achieve a significant leaching effect.
Comparative example 6
(1) 0.2g of the retired lithium ion battery positive electrode material, 2g of glucose and 10ml of a 1.5mol/L acetic acid aqueous solution were mixed. Wherein the mass volume concentration of the anode material is 20g/L, and the hydrothermal reaction is carried out for 300min at 175 ℃ to obtain brown turbid liquid.
(2) And centrifuging the brown turbid liquid by using a high-speed centrifuge, and then taking supernatant liquid to filter by using filter paper to obtain leachate rich in valuable metals. The leaching rate of lithium, cobalt, nickel and manganese in the leaching solution is 97%, 94%, 92% and 86%.
This comparative example demonstrates that significant leaching can be achieved with greatly increased organic reducing agent usage and reaction time, but that the use of persulfate can greatly reduce the usage of other additives or reduce reaction time.
It will be understood by those skilled in the art that the foregoing is only an exemplary embodiment of the present invention, and is not intended to limit the invention to the particular forms disclosed, since various modifications, substitutions and improvements within the spirit and scope of the invention are possible and within the scope of the appended claims.
Claims (10)
1. A method for recovering valuable metals in a retired lithium ion battery anode material is characterized by comprising the following steps:
(1) Mixing a retired lithium ion battery anode material with an organic acid, an oxidant and a reducing agent to obtain a reaction precursor solution; the oxidant is persulfate or aqueous hydrogen peroxide; the organic acid is one or more of acetic acid, malic acid, tartaric acid, citric acid and lactic acid; the reducing agent is one or the combination of more of glucose, sucrose, fructose and lactose;
(2) Carrying out hydrothermal reaction on the reaction liquid obtained in the step (1) to obtain a reaction liquid; in the reaction process, the oxidant generates free radicals to destroy the crystal structure of the anode material of the retired lithium ion battery and release valuable metal ions; meanwhile, carboxylic acid groups in the organic acid and released valuable metal ions are subjected to a complex reaction, so that leaching of valuable metals is promoted;
(3) And (3) carrying out solid-liquid separation on the reaction liquid obtained by the reaction in the step (2), and taking supernatant to obtain leachate containing valuable metal ions.
2. The method of claim 1, wherein the organic acid has a molar concentration of 0.1mol/L to 6mol/L.
3. The method of claim 1, wherein the organic acid has a molar concentration of 1mol/L to 3mol/L.
4. The method of claim 1, wherein the mass ratio of the amount of the oxidant to the retired lithium ion battery positive electrode material is (0.5-5): 1.
5. The method of claim 1, wherein the oxidizing agent is a persulfate salt that is a combination of one or more of potassium persulfate, sodium persulfate, ammonium persulfate, oxone, and potassium peroxymonosulfate complex salts.
6. The method of claim 1, wherein the mass ratio of the amount of the reducing agent to the material of the cathode of the retired lithium ion battery is (0.5-5): 1.
7. The method of claim 1, wherein the mass volume concentration of the retired lithium ion battery positive electrode material in the pre-reaction solution is 10g/L to 50g/L.
8. The method of claim 1, wherein the hydrothermal reaction in step (2) is carried out at a temperature of 105 ℃ to 374 ℃, a pressure of 0.11 to 22.0Mpa, and a reaction time of 15min to 500min.
9. The method of claim 1, wherein the hydrothermal reaction in step (2) is performed at a temperature of 150 ℃ to 200 ℃, a pressure of 2Mpa to 10Mpa, and a reaction time of 30min to 90min.
10. The method of claim 1, wherein the solid-liquid separation of step (3) is centrifugal separation.
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Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR101708149B1 (en) * | 2016-05-20 | 2017-02-20 | (주)이엠티 | A Method For Recovering Lithium Compound From An Anode Material In Spent Lithium Batteries By Wet-Milling |
| CN107815545A (en) * | 2017-10-31 | 2018-03-20 | 华中科技大学 | A kind of method that metallic copper in discarded circuit board powder is reclaimed using mechanochemical reaction |
| CN110724820A (en) * | 2019-10-31 | 2020-01-24 | 华中科技大学 | Method for recycling decommissioned lithium ion battery anode material by using hydrothermal method |
| CN110791652A (en) * | 2019-10-31 | 2020-02-14 | 华中科技大学 | Method for recovering anode material of waste lithium ion battery based on mechanochemical method |
| CN111455177A (en) * | 2020-04-08 | 2020-07-28 | 大连理工大学 | Method for recovering valuable metals of lithium battery positive electrode material by using saccharides and hydrogen peroxide |
| CN113308607A (en) * | 2021-04-22 | 2021-08-27 | 昆明理工大学 | Method for enhancing zinc oxide smoke dust leaching by ultrasonic waves and hydrogen peroxide |
-
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- 2021-12-08 CN CN202111495836.XA patent/CN114480845B/en active Active
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR101708149B1 (en) * | 2016-05-20 | 2017-02-20 | (주)이엠티 | A Method For Recovering Lithium Compound From An Anode Material In Spent Lithium Batteries By Wet-Milling |
| CN107815545A (en) * | 2017-10-31 | 2018-03-20 | 华中科技大学 | A kind of method that metallic copper in discarded circuit board powder is reclaimed using mechanochemical reaction |
| CN110724820A (en) * | 2019-10-31 | 2020-01-24 | 华中科技大学 | Method for recycling decommissioned lithium ion battery anode material by using hydrothermal method |
| CN110791652A (en) * | 2019-10-31 | 2020-02-14 | 华中科技大学 | Method for recovering anode material of waste lithium ion battery based on mechanochemical method |
| CN111455177A (en) * | 2020-04-08 | 2020-07-28 | 大连理工大学 | Method for recovering valuable metals of lithium battery positive electrode material by using saccharides and hydrogen peroxide |
| CN113308607A (en) * | 2021-04-22 | 2021-08-27 | 昆明理工大学 | Method for enhancing zinc oxide smoke dust leaching by ultrasonic waves and hydrogen peroxide |
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