CN113046559B - Method for recovering lithium, cobalt, nickel and manganese from retired lithium ion battery anode material - Google Patents
Method for recovering lithium, cobalt, nickel and manganese from retired lithium ion battery anode material Download PDFInfo
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- CN113046559B CN113046559B CN202110243721.5A CN202110243721A CN113046559B CN 113046559 B CN113046559 B CN 113046559B CN 202110243721 A CN202110243721 A CN 202110243721A CN 113046559 B CN113046559 B CN 113046559B
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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
- C22B7/007—Wet processes by acid leaching
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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
- C22B23/0415—Leaching processes with acids or salt solutions except ammonium salts solutions
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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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- 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
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P10/00—Technologies related to metal processing
- Y02P10/20—Recycling
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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 provides a method for recovering lithium, cobalt, nickel and manganese from an anode material of a retired lithium ion battery, which comprises the following steps: leaching the lithium ion battery positive electrode material by using a leaching agent, wherein heating and stirring are carried out in the leaching process, and the leaching agent comprises an inorganic acid, a reducing agent and a chelating agent; wherein the concentration of the inorganic acid is 0.2-4 mol/L; the concentration of the reducing agent is 0.2-2 mol/L; the concentration of the chelating agent is 0.1-2 mol/L; the method does not include a complex pretreatment process for the lithium ion battery positive electrode material. Compared with the traditional acid leaching method, the method has high leaching efficiency and large leaching capacity, the traditional acid leaching method can reach more than 95 percent of leaching rate in a plurality of hours, the method can greatly improve the leaching efficiency, the dehydroascorbic acid is used as a chelating agent to form a synergistic coordination effect with transition metal and chloride ions, the leaching rate is effectively accelerated, the use of an inorganic reducing agent is avoided, and the influence of a leached solvent on the environment is reduced.
Description
Technical Field
The invention relates to the technical field of recycling of retired battery materials, in particular to a method for recycling lithium, cobalt, nickel and manganese from a retired lithium ion battery positive electrode material.
Background
The lithium ion battery has the advantages of high working voltage, small volume, high energy density, no memory effect, long service life, wide working temperature range and the like, so the lithium ion battery is widely applied to portable electronic equipment products such as mobile phones, mobile power supplies, notebooks and the like. Meanwhile, with the continuous development of the new energy automobile industry, the demand of the market for the lithium ion battery is also continuously expanded. With the increasing demand of lithium ion batteries, the number of retired lithium batteries is inevitably increasing. It is expected that by 2023 the annual discard capacity of lithium ion batteries will reach 101GWh, about 116 million tons/year. The retired lithium battery contains a large amount of heavy metal elements and corrosive or strongly corrosive organic solvents, and if the retired lithium battery is discarded at will, the retired lithium battery can cause great pollution and damage to the natural environment. Therefore, the recycling of the retired lithium ion battery not only has positive effects on environmental protection and sustainable development, but also can fully utilize urban mine resources by recycling valuable elements in the retired lithium ion battery anode, and relieves the pressure of natural resource shortage.
The negative active material of the lithium ion battery is graphite, and the positive active material is mainly LiCoO2、LiNixCOyMnzO2(wherein x + y + z is 1) and LiMn2O4And the like. The positive electrode of the lithium ion battery is configured as follows: the positive electrode is formed by uniformly mixing a positive electrode active material (lithium transition metal oxide), a small amount of conductive agent (usually acetylene black) and an organic binder, and coating the mixture on an aluminum foil current collector.
The traditional method for recovering the retired lithium ion battery anode material is a leaching method, and the leaching method mainly comprises two steps of pretreatment and acid leaching for leaching. Firstly, after a series of operations such as disassembling, crushing, screening, sorting, magnetic separation, primary grinding, sorting of positive electrode materials, secondary grinding and the like, the retired lithium ion battery can use inorganic acid (such as strong acid such as hydrochloric acid, nitric acid, sulfuric acid and the like) as a leaching agent, and simultaneously, partial reducing agent (such as hydrogen peroxide and the like) is added to leach lithium, cobalt, nickel and manganese elements from positive electrode active materials. The leaching process of the traditional method is that the transition metal element with high valence state is reduced into low valence state by inorganic reducing agent, and the inorganic acid provides hydrogen ions to react with lithium transition metal oxide. The leaching process mainly depends on the dissolution of hydrogen ions to materials, and the leaching kinetics depend on the concentration of the hydrogen ions. The reaction rate of the traditional acid leaching method is not fast, and the leaching rate of more than 95 percent can be achieved generally within 2 to 5 hours. Therefore, a method for recovering the retired lithium ion battery anode material, which has the advantages of higher reaction rate, higher leaching rate, simplicity, economy, high efficiency, and suitability for large-scale and industrialization, is needed at present.
Disclosure of Invention
Aiming at the problems in the prior art, the invention aims to provide a method for simply and rapidly leaching lithium, cobalt, nickel and manganese from an anode of a retired lithium ion battery, and compared with the traditional leaching method of inorganic acid and inorganic reducing agent, the leaching rate and the operability of the method are greatly improved.
The invention adopts the following technical scheme:
as a specific embodiment, the present application provides a method for recovering lithium, cobalt, nickel, and manganese from a decommissioned lithium ion battery cathode material, comprising the steps of:
the lithium ion battery anode material (anode material disassembled from the lithium ion battery) is directly leached by using a leaching agent, so that a complex pretreatment process before leaching is avoided, wherein the leaching agent comprises inorganic acid, a reducing agent and a chelating agent; the lithium ion battery anode material and the leaching agent form a solid-liquid system;
wherein heating and stirring are carried out in the leaching process.
Alternatively, the leaching agent consists of an inorganic acid, a reducing agent, a chelating agent, as an example.
The recovery method of the present application is not particularly limited, and the anode material obtained by disassembling the lithium ion battery by the recovery method of the present application does not need to be further subjected to a series of operations such as disassembling, crushing, sieving, sorting, magnetic separation, grinding, primary grinding, anode material sorting, secondary grinding, and the like, unlike the conventional recovery method. The term "disassembly" as used herein is to disassemble a decommissioned lithium ion battery into a positive electrode, a negative electrode, and a separator for the decommissioned lithium ion battery, and not to disassemble further the positive electrode material of the decommissioned lithium ion battery for the positive electrode material of the decommissioned lithium ion battery.
The term "decommissioned lithium ion battery" as used herein may be used interchangeably with "spent lithium ion battery".
For example, the negative electrode active material of the lithium ion battery in the present disclosure is graphite, and the positive electrode active material is mainly LiCoO2、LiNixCOyMnzO2(wherein x + y + z is 1) and LiMn2O4And the like. As an example, the positive electrode of the lithium ion battery in the present disclosure is configured to: positive electrode active material (lithium transition metal oxide), small amount of conductive agent (acetylene black in general) and organic binderAnd the binding agent is uniformly mixed and then coated on an aluminum foil current collector to form the anode.
Without being particularly limited, the recycling method of the present invention includes a simple pretreatment, specifically, fully discharging the retired lithium ion battery, disassembling and removing the housing (for example, manual or mechanical operation may be performed in a glove box), separating the separator and the negative electrode, and taking out the positive electrode sheet (i.e., the positive electrode material); the anode plate is dried, so that organic solvents such as electrolyte and the like are volatilized, and the complex pretreatment process before leaching is avoided in the simple pretreatment process.
Further, leaching lithium, nickel, cobalt, manganese: after the positive electrode (active material and conductive agent) is dried, a leaching solution is added to carry out a leaching reaction.
Further, the concentration of the inorganic acid (concentration of the inorganic acid in the formulated leaching agent) is 0.2 to 4mol/L, such as 0.2mol/L, 0.3mol/L, 0.4mol/L, 0.5mol/L, 0.6mol/L, 0.7mol/L, 0.8mol/L, 0.9mol/L, 1.0mol/L, 1.1mol/L, 1.2mol/L, 1.3mol/L, 1.4mol/L, 1.5mol/L, 1.6mol/L, 1.7mol/L, 1.8mol/L, 1.9mol/L, 2.0mol/L, 2.1mol/L, 2.2mol/L, 2.3mol/L, 2.4mol/L, 2.5mol/L, 2.6mol/L, 2.7mol/L, 2.8mol/L, 2.3mol/L, 2.4mol/L, 2.5mol/L, 2.6mol/L, 2.7mol/L, 2.8mol/L, 3mol/L, 3.3mol/L, 2.3mol/L, 2.4mol/L, 2.8mol/L, 2.6mol/L, 2.8mol/L, 2.3mol/L, or more, 3.3mol/L, 3.4mol/L, 3.5mol/L, 3.6mol/L, 3.7mol/L, 3.8mol/L, 3.9mol/L, 4.0 mol/L.
Further, the concentration of the reducing agent (concentration of the reducing agent in the formulated leaching agent) is 0.2 to 2mol/L, such as 0.2mol/L, 0.3mol/L, 0.4mol/L, 0.5mol/L, 0.6mol/L, 0.7mol/L, 0.8mol/L, 0.9mol/L, 1.0mol/L, 1.1mol/L, 1.2mol/L, 1.3mol/L, 1.4mol/L, 1.5mol/L, 1.6mol/L, 1.7mol/L, 1.8mol/L, 1.9mol/L, 2.0mol/L, preferably 0.5 to 1 mol/L.
Further, the concentration of the chelating agent (concentration of chelating agent in the formulated leaching agent) is 0.1-2 mol/L, such as 0.1mol/L, 0.2mol/L, 0.3mol/L, 0.4mol/L, 0.5mol/L, 0.6mol/L, 0.7mol/L, 0.8mol/L, 0.9mol/L, 1.0mol/L, 1.1mol/L, 1.2mol/L, 1.3mol/L, 1.4mol/L, 1.5mol/L, 1.6mol/L, 1.7mol/L, 1.8mol/L, 1.9mol/L, 2.0mol/L, preferably 0.2-1 mol/L. For example, the chelating agent is dehydroascorbic acid. The dehydroascorbic acid as a chelating agent forms a synergistic coordination effect with the transition metal and chloride ions to effectively accelerate the leaching rate.
As an example, the chelating agent comprises dehydroascorbic acid.
Further, the method does not comprise the steps of carrying out pretreatment such as crushing, ultrasonic oscillation and roasting on the lithium ion battery positive electrode material. Wherein the ultrasonic oscillation can separate PVDF (polyvinylidene fluoride) from the positive active material. Wherein the roasting can remove acetylene black, carbon black and the like in the electrode material. Wherein the temperature of the roasting is not less than 130 ℃, preferably not less than 140 ℃, not less than 150 ℃, not less than 160 ℃, not less than 170 ℃, not less than 180 ℃, not less than 190 ℃, not less than 200 ℃, not less than 210 ℃, not less than 220 ℃, not less than 230 ℃, not less than 240 ℃, not less than 250 ℃, not less than 260 ℃, not less than 270 ℃, not less than 280 ℃, not less than 290 ℃, not less than 300 ℃, not less than 310 ℃, not less than 320 ℃, not less than 330 ℃, not less than 340 ℃, not less than 350 ℃, not less than 360 ℃, not less than 370 ℃, not less than 380 ℃, not less than 390 ℃, not less than 400 ℃, not less than 410 ℃, not less than 420 ℃, not less than 430 ℃, not less than 440 ℃, not less than 450 ℃, not less than 460 ℃, not less than 470 ℃, not less than 480 ℃, not less than 490 ℃, not less than 500 ℃, not less than 510 ℃, not less than 520 ℃, not less than 530 ℃, not less than 540 deg.C, not less than 550 deg.C, not less than 560 deg.C, not less than 570 deg.C, not less than 580 deg.C, not less than 590 deg.C, not less than 600 deg.C, not less than 610 deg.C, not less than 620 deg.C, not less than 630 deg.C, not less than 640 deg.C, not less than 650 deg.C, not less than 670 deg.C, not less than 680 deg.C, not less than 690 deg.C, not less than 700 deg.C, not less than 720 deg.C, not less than 730 deg.C, not less than 740 deg.C, not less than 750 deg.C, not less than 760 deg.C, not less than 770 deg.C, not less than 790 deg.C, not less than 800 deg.C, for example, may be 600 deg.C to 800 deg.C, may be 700 deg.C to 800 deg.C, for example may be about 650 deg.C, for example about 700 deg.C, and about 750 deg.C.
In a preferred embodiment, the inorganic acid includes at least one of hydrochloric acid, nitric acid, and sulfuric acid.
As a preferred embodiment, the mineral acid is hydrochloric acid and has a concentration (in the leaching agent already prepared) of 0.2 to 4mol/L, such as 0.2mol/L, 0.3mol/L, 0.4mol/L, 0.5mol/L, 0.6mol/L, 0.7mol/L, 0.8mol/L, 0.9mol/L, 1.0mol/L, 1.1mol/L, 1.2mol/L, 1.3mol/L, 1.4mol/L, 1.5mol/L, 1.6mol/L, 1.7mol/L, 1.8mol/L, 1.9mol/L, 2.0mol/L, 2.1mol/L, 2.2mol/L, 2.3mol/L, 2.4mol/L, 2.5mol/L, 2.6mol/L, 2.7mol/L, 2.8mol/L, 2.3mol/L, 3mol/L, 2.4mol/L, 2.5mol/L, 2.6mol/L, 2.7mol/L, 2.8mol/L, 3mol/L, 1.3mol/L, 1.8mol/L, 1mol/L, 1.6mol/L, 2.7mol/L, 2.3mol/L, 2.7mol/L, 2.4mol/L, 2.8mol/L, 2.6mol/L, 2.3mol/L, 2.7mol/L, 2.8mol/L, 2mol/L, 2.8mol/L, 2.4mol/L, 2.6mol/L, 2.7mol/L, 2.4mol/L, 2.8mol/L, 2.7mol/L, 2.8mol/L, 2.3mol/L, 2.7mol/L, 2.3mol/L, 2.4mol/L, 2.6mol/L, 2.4mol/L, 2.8mol/L, 2.3mol/L, 2.6mol/L, 2mol/L, 2.6mol/L, 2.3mol/L, 2.6mol/L, 2, 3.2mol/L, 3.3mol/L, 3.4mol/L, 3.5mol/L, 3.6mol/L, 3.7mol/L, 3.8mol/L, 3.9mol/L, 4.0mol/L, preferably 0.5-2 mol/L. The hydrochloric acid can provide hydrogen ions for reaction with the lithium transition metal oxide while providing a portion of the Cl-The concentration of hydrogen ions as a ligand for synergistic coordination with chelating agents (e.g., dehydroascorbic acid) and transition metal elements primarily affects the reaction rate, i.e., the leaching rate, but if the concentration is too high, an excess of acid is caused, resulting in subsequent adverse effects.
As a preferred embodiment, the mineral acid comprises hydrochloric acid.
As a preferred embodiment, the inorganic acid further comprises at least one of nitric acid, sulfuric acid, perchloric acid, hydrobromic acid, hydroiodic acid, phosphoric acid.
As an exemplary embodiment, the reducing agent is at least one of ascorbic acid, citric acid, oxalic acid, formic acid.
As a preferred embodiment, the reducing agent comprises ascorbic acid, preferably the reducing agent is ascorbic acid. The reducing agent is used for reducing the valence state of the transition metal element, and is more beneficial to leaching of lithium and transition metal oxide. Common inorganic reducing agents such as hydrogen peroxide have strong oxidizing properties and cause environmental hazards, while hydrogen peroxide has some carcinogenic effects on the human body. The ascorbic acid is used as a reducing agent, which is beneficial to acid leaching of the anode material, the ascorbic acid is natural organic acid, and the subsequent waste liquid is easy to biodegrade and has simple treatment process.
As an example, chelating agents (e.g., dehydroascorbic acid) can coordinate transition metal elements as well as chloride ions to increase the leaching rate. Specifically, the hydrochloric acid, the ascorbic acid and the dehydroascorbic acid system do not increase the concentration of hydrogen ions for the rapid leaching of the cathode material of the retired lithium battery, but chlorine ions provided by the hydrochloric acid and the dehydroascorbic acid generate a synergistic coordination effect with transition metal elements. Compared with the traditional system of inorganic acid and inorganic reducing agent, the leaching agent can effectively accelerate the leaching rate and simultaneously effectively reduce the dosage of acid.
As a preferred embodiment, the reducing agent is an organic reducing agent.
In various embodiments, the reducing agent is not an inorganic reducing agent.
As a preferred embodiment, the inorganic reducing agent includes at least one of hydrogen peroxide, sodium sulfite, and sodium thiosulfate. For example, the inorganic reducing agent is hydrogen peroxide.
As a preferred embodiment, the reaction time of the leaching process is 7 to 60min, alternatively 10 to 20min, for example 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, 20, 21, 22, 23, 24, 25, 26, 27, 28, 29, 30, 31, 32, 33, 34, 35, 36, 37, 38, 39, 40, 41, 42, 43, 44, 45, 46, 47, 48, 49, 50, 51, 52, 53, 54, 55, 56, 57, 58, 59, or 60min, more preferably in the range of 8 to 20 min.
In a preferred embodiment, the heating temperature is 50 to 95 ℃ or alternatively a leaching temperature, such as 50 ℃, 51 ℃, 52 ℃, 53 ℃, 54 ℃, 55 ℃, 56 ℃, 57 ℃, 58 ℃, 59 ℃, 60 ℃, 61 ℃, 62 ℃, 63 ℃, 64 ℃, 65 ℃, 66 ℃, 67 ℃, 68 ℃, 69 ℃, 70 ℃, 71 ℃, 72 ℃, 73 ℃, 74 ℃, 75 ℃, 76 ℃, 77 ℃, 78 ℃, 79 ℃, 80 ℃, 81 ℃, 82 ℃, 83 ℃, 84 ℃, 85 ℃, 86 ℃, 87 ℃, 88 ℃, 89 ℃, 90 ℃, 91 ℃, 92 ℃, 93 ℃, 94 ℃, 95 ℃ or the like. The temperature and the economic benefit have certain conflicting effects, the higher the temperature is, the higher the energy consumption is, and the economic benefit may be reduced.
In a preferable embodiment, the solid-to-liquid ratio of the leaching agent to the lithium ion battery positive electrode material is 10-200 g/L, for example, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, 20, 21, 22, 23, 24, 25, 26, 27, 28, 29, 30, 31, 32, 33, 34, 35, 36, 37, 38, 39, 40, 41, 42, 43, 44, 45, 46, 47, 48, 49, 50, 51, 52, 53, 54, 55, 56, 57, 58, 59, 60, 61, 62, 63, 64, 65, 66, 67, 68, 69, 70, 71, 72, 73, 74, 75, 76, 77, 78, 79, 80, 81, 82, 83, 84, 85, 86, 87, 88, 89, 90, 91, 92, 93, 94, 95, 96, 97, 98, 99, 100, 110, 120, 130, 140, 150, 160, 170, 180, 190, 200g/L, more preferably 10 to 20 g/L. The solid-liquid ratio can ensure the full contact of solid and liquid, and avoid the excessive solid from causing the leaching reaction time to be overlong.
Compared with the traditional inorganic acid and inorganic reducing agent leaching method, the method is characterized in that the combination of the inorganic acid, the reducing agent (such as ascorbic acid) and the chelating agent (such as dehydroascorbic acid) is adopted to form a synergistic leaching effect as a high-efficiency and quick leaching agent. The reason for the high efficiency and fast leaching is that during the active leaching reaction of the positive electrode, a reducing agent (such as ascorbic acid) reduces a high-valence transition metal element, so that the positive electrode material is easier to be leached by acid, and for example, dehydroascorbic acid can form a synergistic coordination effect (formation of (C) with the transition metal element6H6O6)2Co2+). Thereby strengthening the leaching effect and greatly improving the leaching speed. The leaching reaction equation of the lithium cobaltate positive electrode material is (1):
similarly, the leaching reaction equation of the lithium manganate cathode material is (2):
the method of the invention is different from the method which adopts ascorbic acid as a leaching agent alone or mixed leaching with hydrochloric acid, nitric acid and sulfuric acid: the process of using ascorbic acid as a leaching agent alone or mixing with hydrochloric acid, nitric acid and sulfuric acid for leaching is essentially a single leaching process of the ascorbic acid, the reaction mechanism is shown in reaction equations (3) - (6), firstly, the ascorbic acid undergoes two-step ionization to make the solution weakly acidic (reaction equations (3) - (4)), the non-ionized ascorbic acid can then be oxidized to dehydroascorbic acid by losing two electrons (reaction equation (5) reacts with the high-valence metal ions in the electrode material to reduce the positive active material (reaction equation (6), and the ionized ascorbic acid forms a coordination with lithium and cobalt, the slower kinetics of the prior art processes is due to the ascorbic acid acting as a weak acid, the acidity coefficient is large, so that the dissociation is difficult and the leaching speed of the whole system is low.
By way of example, the leaching agent in the leaching process is a combination of mineral acids (hydrochloric acid, nitric acid, sulfuric acid), ascorbic acid and dehydroascorbic acid.
The invention relates to a method for recovering lithium, cobalt, nickel and manganese from an anode material of an retired lithium ion battery, wherein the leaching rate of lithium is more than 98%, for example, under the condition that the leaching time is not more than 30min, preferably not more than 20min, more preferably not more than 10min, the leaching rate is not less than 98.0%, not less than 98.1%, not less than 98.2%, not less than 98.3%, not less than 98.4%, not less than 98.5%, not less than 98.6%, not less than 98.7%, not less than 98.8%, not less than 98.9%, not less than 99.0%, not less than 99.1%, not less than 99.2%, not less than 99.3%, not less than 99.4%, not less than 99.5%, not less than 99.6%, not less than 99.7%, not less than 99.8% and not less than 99.9%.
The invention relates to a method for recovering lithium, cobalt, nickel and manganese from an anode material of an retired lithium ion battery, wherein the leaching rate of nickel is more than 98%, for example, under the condition that the leaching time is not more than 30min, preferably not more than 20min, more preferably not more than 10min, the leaching rate is not less than 98.0%, not less than 98.1%, not less than 98.2%, not less than 98.3%, not less than 98.4%, not less than 98.5%, not less than 98.6%, not less than 98.7%, not less than 98.8%, not less than 98.9%, not less than 99.0%, not less than 99.1%, not less than 99.2%, not less than 99.3%, not less than 99.4%, not less than 99.5%, not less than 99.6%, not less than 99.7%, not less than 99.8% and not less than 99.9%.
The invention relates to a method for recovering lithium, cobalt, nickel and manganese from an anode material of an retired lithium ion battery, wherein the leaching rate of cobalt reaches more than 98%, for example, under the condition that the leaching time is not more than 30min, preferably not more than 20min, more preferably not more than 10min, the leaching rate is not less than 98.0%, not less than 98.1%, not less than 98.2%, not less than 98.3%, not less than 98.4%, not less than 98.5%, not less than 98.6%, not less than 98.7%, not less than 98.8%, not less than 98.9%, not less than 99.0%, not less than 99.1%, not less than 99.2%, not less than 99.3%, not less than 99.4%, not less than 99.5%, not less than 99.6%, not less than 99.7%, not less than 99.8% and not less than 99.9%.
The invention relates to a method for recovering lithium, cobalt, nickel and manganese from an anode material of an retired lithium ion battery, wherein the leaching rate of manganese is more than 98%, for example, under the condition that the leaching time is not more than 30min, preferably not more than 20min, more preferably not more than 10min, the leaching rate is not less than 98.0%, not less than 98.1%, not less than 98.2%, not less than 98.3%, not less than 98.4%, not less than 98.5%, not less than 98.6%, not less than 98.7%, not less than 98.8%, not less than 98.9%, not less than 99.0%, not less than 99.1%, not less than 99.2%, not less than 99.3%, not less than 99.4%, not less than 99.5%, not less than 99.6%, not less than 99.7%, not less than 99.8% and not less than 99.9%.
The terms "leach" and "leach" are used interchangeably herein. As used herein, the terms "Leaching efficiency" and "Leaching efficiency" are used interchangeably. The leaching rate is calculated as follows:
in the above formula, M is the content of the metal element in the leaching solution, and M is the total content of the metal element in the retired anode material.
The purity grade of the substance purchased or used herein is chemically pure, analytically pure or guaranteed, preferably analytically pure, more preferably guaranteed, unless otherwise specified herein.
As used herein, "and/or" includes any and all combinations of one or more of the associated listed items. The terminology used herein is for the purpose of describing particular embodiments only and is not intended to be limiting of the invention. As used herein, the singular forms "a", "an" and "the" are intended to include the plural forms as well, unless the context clearly indicates otherwise. It will be further understood that the terms "comprises" and/or "comprising," when used in this specification, specify the presence of stated features, integers, steps, operations, elements, and/or components, but do not preclude the presence or addition of one or more other features, integers, steps, operations, elements, components, and/or groups thereof.
Unless defined otherwise, all terms (including 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. It will be further understood that terms, such as those defined in commonly used dictionaries, should be interpreted as having a meaning that is consistent with their meaning in the context of the relevant art and will not be interpreted in an idealized or overly formal sense unless expressly so defined herein.
All methods described herein can be performed in any suitable order unless otherwise indicated herein or otherwise clearly contradicted by context.
The use of any and all examples, or exemplary language (such as, "for example") provided herein, is intended merely to better illuminate the invention and does not pose a limitation on the scope of the invention unless otherwise claimed. No language in the specification should be construed as indicating any element as essential to the practice of the invention unless explicitly described as such.
The exemplary invention described herein may suitably lack any one or more of the element limitations, which are not specifically disclosed herein. Thus, the terms "comprising," "including," "containing," and the like are to be construed broadly and in a non-limiting sense. Furthermore, the terms used herein are used as terms of description and not of limitation, and there is no intention in the use of such terms to describe only some of their characteristics but, in the light of the claims, various modifications are possible within the scope of the invention. Thus, while the present invention has been particularly disclosed in terms of preferred embodiments and optional features, modification of the invention herein disclosed to embody it may be noted by those skilled in the art, and such modifications and variations are considered to be within the scope of the invention.
Compared with the prior art, the invention has the beneficial effects that:
(1) compared with the traditional acid leaching method, the method has high leaching efficiency and large leaching capacity, the traditional acid leaching method can reach more than 95 percent of leaching rate in a plurality of hours, the leaching efficiency can be greatly improved, the whole leaching reaction process is controlled within ten minutes, the leaching capacity and the leaching speed of the leaching solution to the Co element are larger than those of equal aqua regia, and the leaching effect is obvious;
(2) the dehydroascorbic acid is used as a chelating agent to form a synergistic coordination effect with transition metal and chloride ions, so that the leaching rate is effectively accelerated;
(3) the system of the invention not only can accelerate the leaching rate, but also can effectively reduce the usage amount of acid;
(4) the invention avoids using inorganic reducing agent, reduces the damage of the solvent to the environment and the influence to human body after leaching;
(5) the method does not need to carry out pretreatment operations such as crushing, ultrasonic oscillation (separation of PVDF and positive active materials), roasting (removal of acetylene black, carbon black and the like in the electrode materials) and the like on the retired lithium ion battery positive electrode materials;
(6) compared with the traditional leaching method of acid and inorganic reducing agent, the method of the invention has simpler operation, faster speed and better effect.
Drawings
FIG. 1 shows a roadmap for the recovery method of the present invention;
FIG. 2 is an SEM image of a decommissioned lithium ion battery positive plate prior to leaching in accordance with the present invention;
FIG. 3 is a diagram of the reaction mechanism of the hydrochloric acid, ascorbic acid and dehydroascorbic acid system with lithium cobaltate;
FIG. 4 shows the leaching efficiencies of Mn, Li, Co, Ni elements at different leaching times;
fig. 5 is a graph of leaching kinetics of Co element at different temperatures.
Detailed Description
For better explanation of the present invention, the following specific examples are further illustrated, but the present invention is not limited to the specific examples.
Example 1
A method for recovering lithium, cobalt, nickel and manganese from an anode material of a retired lithium ion battery is realized by the following steps:
(1) simple pretreatment:
fully discharging the retired lithium ion battery, manually disassembling the retired lithium ion battery in a glove box to remove a shell, separating a diaphragm from a negative electrode, and taking out a positive plate (namely a positive electrode material); and drying the positive plate to volatilize organic solvents such as electrolyte and the like, wherein the process does not need a complex pretreatment process before leaching.
(2) Leaching lithium, nickel, cobalt and manganese:
after the positive electrode (active material and conductive agent) was dried, a mixed solution of 1M hydrochloric acid, 0.5M dehydroascorbic acid and 1M ascorbic acid (each in concentration in the formulated leaching agent) was added to carry out the leaching reaction. The reaction temperature is 90 ℃, the reaction time is 10min, and the solid-to-liquid ratio is 20 g/L; and after the reaction is finished, carrying out suction filtration and separation on the solid-liquid mixture to obtain leaching solution rich in metal and the conductive agent. ICP analysis is adopted to analyze the concentration of metal ions in the leaching solution, and the leaching rates of lithium, nickel, cobalt and manganese are calculated to be 99.85%, 99.26%, 98.35% and 98.78% respectively.
FIG. 1 shows a scheme of the recovery method of the present invention. FIG. 2 is an SEM image of a decommissioned lithium ion battery positive plate prior to leaching in accordance with the present invention; FIG. 3 is a diagram showing the reaction mechanism of the hydrochloric acid, ascorbic acid and dehydroascorbic acid system of the present invention with lithium cobaltate.
The recovery method does not need to carry out a series of operations such as disassembling, crushing, sieving, sorting, magnetic separation, grinding, primary grinding, sorting of the positive electrode material, secondary grinding, crushing, ultrasonic oscillation, roasting and the like on the positive electrode material.
This example tests the leaching efficiency of Mn, Li, Co, Ni elements at different leaching times, as shown in FIG. 4. The test result shows that the recovery method of the invention has high leaching efficiency and large leaching capacity, while the traditional acid leaching method needs hours to reach more than 95 percent of leaching rate. The invention can greatly improve the leaching efficiency, and the whole leaching reaction process is controlled within ten minutes. In addition, tests show that the leaching solution of the invention has a leaching capacity and a leaching speed for Co element which are larger than those of equal aqua regia.
The dehydroascorbic acid is used as a chelating agent to form a synergistic coordination effect with transition metal and chloride ions, so that the leaching rate is effectively increased. Therefore, the leaching rate can be accelerated and the use amount of acid can be effectively reduced under the system.
In addition, the leaching kinetics of the Co element at different temperatures were also tested, as shown in fig. 5.
The recovery method of the invention avoids using inorganic reducing agent, and reduces the damage of the leached solvent to the environment and the influence to human body.
In addition, similar technical effects can be obtained by adjusting the reaction temperature to 90 ℃ to 85 ℃, 86 ℃, 87 ℃, 88 ℃, 89 ℃, 91 ℃, 92 ℃, 93 ℃, 94 ℃ or 95 ℃. Similar technical effects can be obtained by adjusting the reaction time to 10min to 8, 9, 11, 12, 13, 14, 15, 16, 17, 18, 19 or 20min, and the like. Similar technical effects can be obtained by adjusting the solid-to-liquid ratio of 20g/L to 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, 21 or 22 g/L.
The above description is only exemplary of the present invention and is not intended to limit the scope of the present invention, which is defined by the claims appended hereto, as well as the appended claims.
For those not specified in the examples, the procedure was carried out under the conventional conditions or conditions recommended by the manufacturer. The reagents and instruments used are not specified by the manufacturer, but are all conventional products commercially available.
Claims (8)
1. The method for recovering lithium, cobalt, nickel and manganese from the anode material of the retired lithium ion battery is characterized by comprising the following steps of:
leaching the lithium ion battery positive electrode material by using a leaching agent, wherein heating and stirring are carried out in the leaching process, and the leaching agent comprises an inorganic acid, a reducing agent and a chelating agent;
wherein the concentration of the inorganic acid is 0.2-4 mol/L; the concentration of the reducing agent is 0.2-2 mol/L; the concentration of the chelating agent is 0.1-2 mol/L;
the method does not comprise the processes of crushing, ultrasonic oscillation, roasting, screening, magnetic separation, grinding and sorting of the anode material of the lithium ion battery;
the inorganic acid comprises at least one of hydrochloric acid, nitric acid and sulfuric acid;
the chelating agent comprises dehydroascorbic acid;
the reducing agent comprises at least one of ascorbic acid, citric acid, oxalic acid and formic acid.
2. The method of claim 1, wherein the mineral acid is hydrochloric acid; the chelating agent is dehydroascorbic acid.
3. The method of claim 1, wherein the inorganic acid comprises hydrochloric acid.
4. The method of claim 1, wherein the inorganic acid further comprises at least one of nitric acid, sulfuric acid, perchloric acid, hydrobromic acid, hydroiodic acid, phosphoric acid.
5. The method of claim 1, wherein the reducing agent is not an inorganic reducing agent.
6. The method of claim 5, wherein the inorganic reducing agent comprises at least one of hydrogen peroxide, sodium sulfite, and sodium thiosulfate.
7. The method as claimed in claim 1, wherein the reaction time of the leaching process is 7-60 min, and the heating temperature is 50-95 ℃.
8. The method according to claim 1, wherein the solid-to-liquid ratio of the leaching agent to the lithium ion battery positive electrode material is 10-200 g/L.
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