CN111129632B - Method for recycling anode and cathode mixed materials of waste ternary lithium ion battery - Google Patents
Method for recycling anode and cathode mixed materials of waste ternary lithium ion battery Download PDFInfo
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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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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01D—COMPOUNDS OF ALKALI METALS, i.e. LITHIUM, SODIUM, POTASSIUM, RUBIDIUM, CAESIUM, OR FRANCIUM
- C01D15/00—Lithium compounds
- C01D15/08—Carbonates; Bicarbonates
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- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G53/00—Compounds of nickel
- C01G53/006—Compounds containing, besides nickel, two or more other elements, with the exception of oxygen or hydrogen
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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
- C22B21/00—Obtaining aluminium
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- 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
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- 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 a positive-negative electrode mixed material of a waste ternary lithium ion battery, which comprises the following steps: discharging and disassembling the waste lithium ion battery to obtain nickel cobalt lithium manganate anode and silicon carbon cathode mixed powder, a battery shell, copper foil, aluminum foil and a diaphragm; mixing the mixed powder with carbonate, ball milling, roasting, and recovering CO generated in the reaction process2(ii) a Placing the mixture after roasting into dilute alkali solution for filtering, and introducing CO2Separating silicon and aluminum in the filtrate, dissolving the filter residue in acid, leaching Li in the filter residue+、Ni2+、Co2+、Mn2+And Cu2+Filtering to remove graphite, and recovering the negative electrode material carbon by a solid phase method; adding sulfide into the leaching solution, adjusting the pH value to remove impurity copper, and preparing a nickel-cobalt-manganese hydroxide ternary precursor by a coprecipitation method; introducing CO2And introducing the lithium carbonate into the filtrate, and heating, concentrating and crystallizing to prepare the lithium carbonate. The method has the advantages of simple process, low cost, high recovery rate and cyclic utilization of resources, and can realize the full-component recovery of the mixed material of the nickel cobalt lithium manganate positive electrode and the silicon carbon negative electrode.
Description
Technical Field
The invention belongs to the technical field of waste lithium ion battery recovery, and particularly relates to a method for recovering a positive-negative electrode mixed material of a waste ternary lithium ion battery with a silicon-carbon negative electrode.
Background
Since 2014, new energy automobiles in China are rapidly developed, and the production and sales volume shows a high-speed growth trend. According to the gasoline coordination data, the new energy automobiles are sold in 125.6 thousands of cars in 2018 all the year round, the sales volume is 16.8 times of the sales volume in 2014, and the sales volume is expected to reach 230 thousands of cars in 2020. The scrapping period of the lithium iron phosphate battery is generally 5 years, the scrapping period of the ternary lithium battery is 6 years, the power battery is expected to enter the scale scrapping period at the end of 2019 years, the scrapping and loading amount of the power battery reaches 24.7GWH in 2020, and the scrapping amount of the power battery is expected to reach 126GWH in 2025 times of the scrapping scale in 2020. If the waste lithium ions cannot be effectively treated, not only is environmental pollution caused, but also valuable metal elements in the waste lithium ions cannot be reasonably utilized, and thus, resources are wasted. Therefore, the recycling of the waste lithium ion battery is urgent.
At present, the common negative electrode material of the lithium ion battery in the market is graphite, and the graphite material is used as the traditional negative electrode material of the lithium ion battery, although the lithium ion battery has the advantages of long cycle life, abundant resources and low cost, the theoretical specific capacity of the lithium ion battery is only 372mAh/g which is relatively low, and the requirement of further development of the lithium ion battery cannot be met. Therefore, researchers are constantly searching for new anode materials to achieve significant improvements in battery capacity, energy density, and rate capability, with silicon-based materials being the most attractive anode material for lithium ion batteries and gradually replacing traditional graphite anodes. Silicon formation of Li at room temperature15Si4The theoretical capacity of the catalyst is 3580m Ah/g, and it forms Li at high temperature22Si4The theoretical capacity is 4200m Ah/g, which is more than 10 times of the current known negative electrode material with the highest theoretical specific capacity, and the specific capacity of the commercial graphite negative electrode is achieved. The discharge potential of the silicon cathode is relatively low, so that the lithium ion battery can output relatively high voltage. In future, the silicon-based negative electrode material ternary lithium ion battery will gradually enter a large-scale retirement period.
At present, the problems existing in the wet recovery of waste ternary lithium ion batteries in the industry are as follows:
1) the cost for recycling the silicon-carbon cathode material is high; 2) the conventional method has narrow applicability range, only single positive electrode or negative electrode active material can be recovered, and the front-end disassembly and crushing process is complicated due to the recovery of the single positive electrode or negative electrode active material; 3) the common reducing agents for leaching comprise reducing agents such as liquid-phase hydrogen peroxide, solid sodium sulfite and gaseous hydrogen sulfide, however, the addition of the reducing agents can introduce new impurity elements and increase a recovery route on one hand, and increase the storage and management costs of the reducing agents on the other hand; 4) the impurity removal method is usually extraction and neutralization reaction, the extraction process has large equipment investment and high cost, a large amount of sewage is generated, and colloidal precipitates generated by the neutralization reaction are difficult to filter. 5) The traditional recovery process is difficult to realize the recycling of the added raw materials.
The Chinese patent office discloses some waste ternary lithium ion battery recovery process methods, and in the published documents, some processes can only recover a single anode material and can only be completed through multiple times of precipitation; in some processes, a method of reducing copper by using iron powder is adopted during impurity removal, then iron is filtered by using an iron ore method, and then alkaline liquid is added for removing aluminum, the more times of precipitation in the solution, the more serious the loss of valuable metals can be caused, and because Ni ions can be separated out when the pH value is about 3, the more the method is carried, the impurity phases are easy to generate, the phase and the electrochemical performance of the recovered material are difficult to ensure, in addition, acid and alkali are continuously used for dissolution and extraction in the process, the acid and alkali consumption is large, a large amount of waste water is generated, and the three wastes are difficult to treat; the waste lithium batteries are disassembled and then are roasted through sulfate, aluminum impurities generated by the waste lithium batteries can enter leaching liquid during acid leaching, and due to the fact that the pH value of the aluminum is high, a large amount of nickel and cobalt are lost, and the recovery rate is reduced.
However, the recovery methods of the used lithium ion batteries disclosed in the above patent documents are all innovations made for the negative electrode material being graphite, and do not relate to the recovery of the negative electrode material being silicon carbon.
Therefore, there is a need to address the above-mentioned deficiencies of the prior art.
Disclosure of Invention
The invention aims to overcome the defects of the prior art, provides the method for recycling the silicon-carbon negative electrode material and the nickel cobalt lithium manganate positive electrode material of the waste ternary lithium ion battery, and has the advantages of simple process, shorter process flow, low cost, less wastewater discharge, cyclic utilization of resources and capability of realizing industrial production.
The invention provides a method for recovering a positive-negative electrode mixed material of a waste ternary lithium ion battery, which comprises the following steps:
s1, performing discharge treatment on the waste lithium ion battery, crushing by a physical method, and disassembling and separating out nickel cobalt lithium manganate positive electrode and silicon carbon negative electrode mixed powder, a battery shell, copper foil, aluminum foil and a diaphragm;
s2, mixing and ball-milling the separated positive and negative electrode mixed powder with carbonate, roasting the mixture in a furnace for a certain time under the condition of inert gas to enable the carbonate to react with silicon compounds in the positive and negative electrode mixed powder and residual aluminum oxide which is difficult to dissolve in acid and alkali after disassembly to generate CO2、Na2O·SiO2And Na2O·Al2O3Said CO2Reacting with graphite in the positive and negative electrode mixed powder at high temperature in inert atmosphere to generate reductive gas CO, and recovering gas carbon dioxide generated in the reaction process, wherein the carbonate is sodium carbonate or sodium bicarbonate, and the molar ratio of the sodium carbonate or sodium bicarbonate to the nickel cobalt lithium manganate is 0.11-0.30;
s3, placing the mixture after roasting into a dilute alkali solution for filtering to obtain a filtrate which is a mixture of an aluminum compound and a silicon compound, and introducing carbon dioxide generated in roasting into the filtrate to separate silicon and aluminum in the filtrate;
s4, dissolving the filter residue processed in the step S3 in acid with certain concentration, and leaching Li in the filter residue+、Ni2+、Co2+、Mn2+And Cu2+The acid is inorganic acid or organic acid, the concentration is 0.5-2.5mol/L, the solid-to-liquid ratio of the filter residue to the acid solution is 50-100g/L, the temperature is 50-90 ℃, and the reaction time is 2-3 h; filtering to remove graphite, separating the positive active material and the negative active material, and recovering the negative material by a solid phase method;
s5, adding a certain amount of sulfide into the filtrate obtained in the step S4, and adjusting the pH value to remove impurity copper;
s6, preparing a nickel-cobalt-manganese hydroxide ternary precursor from the filtrate treated in the step S5 by a coprecipitation method;
s7, introducing the carbon dioxide generated in the step S2 into the solution obtained after the coprecipitation method in the step S6, and heating, concentrating and crystallizing to prepare lithium carbonate.
The invention has the following technical effects:
(1) according to the invention, when the waste lithium ion battery is disassembled, the battery core is directly crushed to obtain the positive and negative electrode mixed powder, so that the disassembling mode is greatly simplified, the disassembling time is shortened, the disassembling and sorting cost of the waste battery is reduced, and the automatic mechanical disassembling industrial production of the battery can be realized.
(2) The invention aims at the recovery treatment of the waste lithium ion battery of the waste nickel cobalt lithium manganate anode and the silicon carbon cathode, solves the problems of complex silicon element recovery process, high cost and low recovery rate of the Si/C cathode lithium ion battery in the current industry, realizes the deep separation of the positive active substance and the silicon carbon cathode active substance of the waste lithium ion battery, the separation of silicon and elements, the deep removal of copper and aluminum, and the preparation of the nickel cobalt manganese hydroxide ternary precursor and the lithium carbonate, comprehensively recovers the positive active material and the negative active material of the waste lithium ion battery, has high recovery rate under the condition of low cost, and realizes the effective cyclic utilization of resources.
(3) The invention selects carbonate to be roasted with anode and cathode active materials in inert atmosphere, so that the carbonate reacts with the disassembled anode and cathode mixed powder at high temperature to generate Na which is very soluble in dilute alkali2O·SiO2And Na2O·Al2O3Is beneficial to removing the insoluble Al in the mixed powder2O3And the silicon compound can ensure the recovery of aluminum and silicon, the impurity removal is simple, efficient and quick, and the problems that the leaching rate is reduced because the silicon compound enters acid to form silicic acid colloid during the subsequent acid leaching of the nickel-cobalt lithium manganate and valuable metal elements are carried in the colloid removal to cause valuable metal loss can be avoided. At the same time, CO is generated by carbonate through reaction at high temperature2With graphite in inert gasCO is generated by reaction under the high-temperature condition in the atmosphere and can be used as a reducing agent for leaching the ternary cathode material, so that the mixed recovery of the cathode active material and the anode active material can be realized without adding an additional reducing agent, and the material cost used in the recovery process is greatly reduced.
(4) The invention selects carbonate to realize the separation of silicon and aluminum elements, and the reaction product can be used as a reducing agent of ternary material high-valence elements to reduce CO generated by the reaction2Li can be prepared by introducing gas into filtrate after coprecipitation of ternary hydroxide2CO3And the residual sodium carbonate can be recycled, so that the recovery cost is further reduced.
(5) The alkali used in the invention is dilute alkali, the acid and alkali loss is less, the production cost can be reduced, the waste water discharge is less, and the waste gas only contains CO2And the recycling is realized, the ecological environment is protected, and the economic benefit is high.
(6) The method has the advantages of simple process, short flow, no need of additionally adding a reducing agent in the reduction reaction, simple treatment of three wastes, contribution to industrial large-scale production, accordance with the requirements of the current industry and very wide application prospect.
Drawings
FIG. 1 is a flow chart of a method of an embodiment of the present invention;
FIG. 2 is an XRD (X-ray diffraction) diagram of mixed powder of a silicon-carbon negative electrode and a nickel-cobalt lithium manganate positive electrode of a waste battery in example 1 of the invention;
FIG. 3 is an XRD (X-ray diffraction) pattern of the mixed powder regenerated ternary hydroxide of the silicon-carbon cathode of the waste battery and the anode of the NCM523 in the embodiment 1 of the invention;
FIG. 4 is an SEM image of the ternary NCM hydroxide regenerated from the mixed powder of the silicon-carbon negative electrode of the waste battery and the positive electrode of the NCM523 in the embodiment 1 of the invention.
Detailed Description
In order to make the objects, technical solutions and advantages of the present invention more apparent, the present invention is further described in detail with reference to the following 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.
Referring to fig. 1, the method for recovering positive and negative active materials of a waste ternary lithium ion battery provided by the embodiment of the invention comprises the following steps:
s1, performing discharge treatment on the waste lithium ion battery, and disassembling and separating the mixed powder of the nickel-cobalt lithium manganate anode and the silicon-carbon cathode, the battery shell, the copper foil, the aluminum foil and the diaphragm by a physical method.
In the step, the waste lithium ion battery is subjected to discharge treatment, the voltage of the battery is ensured to be lower than 1-2V, the discharge treatment can be completed in a saline water soaking or charging and discharging machine mode, then the nickel-cobalt lithium manganate anode and silicon-carbon cathode mixed powder (anode and cathode mixed powder), the battery shell, the copper foil, the aluminum foil and the diaphragm are automatically disassembled and separated through physical methods such as crushing, magnetic separation, screening and the like, and the disassembled battery shell, the copper foil, the aluminum foil and the diaphragm are directly recycled.
The anode and cathode mixed powder disassembled in the step is a silicon-carbon anode material and a nickel cobalt lithium manganate anode material. The disassembly mode is to mechanically crush the discharged battery cell and physically separate the battery cell to obtain the positive and negative electrode mixed powder. Compared with the existing disassembling mode, the disassembling process is relatively simple, the positive pole piece and the negative pole piece do not need to be separated, the disassembling time is short, the requirement on equipment is low, the disassembling cost and the complexity of the waste battery are reduced, and the industrial production can be realized.
S2, mixing and ball-milling the separated positive and negative electrode mixed powder and carbonate, then placing the mixture in a high-temperature furnace for roasting for a certain time, and recovering carbon dioxide generated in the reaction process.
According to the step, the mixed powder of the positive electrode and the negative electrode is mixed with the carbonate and then is subjected to ball milling by using a ball mill, so that the mixed powder of the positive electrode and the negative electrode can be further refined, and the separation of valuable elements in the subsequent reaction process is facilitated. The carbonate used for mixing is preferably sodium carbonate or sodium bicarbonate, and the molar ratio of the sodium carbonate or the sodium bicarbonate to the nickel cobalt lithium manganate is 0.11-0.30. The molar ratio is calculated according to the oxidation-reduction reaction, and the excessive sodium carbonate or sodium bicarbonate can cause the loss of a large amount of graphite, because the generated carbon dioxide can react with the graphite in the positive and negative electrode mixed powder, if the sodium carbonate or sodium bicarbonate is too little, the nickel cobalt lithium manganate material can not be reduced, the leaching rate of the nickel cobalt lithium manganate is reduced during the later acid leaching, and the recovery rate of a large amount of valuable metal elements is low.
The step adopts the mixing of carbonate and the anode and cathode mixed powder, and the carbonate is not used as a precipitator in the traditional mode, but is used as a silicon compound (SiO) in the anode and cathode mixed powder2) And residual aluminum oxide (Al) which is difficult to dissolve in acid and alkali after disassembly2O3) Reaction to CO2、Na2O·SiO2And Na2O·Al2O3And CO2The carbon monoxide can further react with graphite in the mixed powder of the positive electrode and the negative electrode at high temperature in inert atmosphere to generate gas carbon monoxide (CO) with reducibility, the carbon monoxide can be used as a reducing agent to reduce the high valence state of valuable metal elements in the nickel cobalt lithium manganate, and the acid leaching is facilitated. Thus, Na is obtained by adopting a roasting reaction2O·SiO2And Na2O·Al2O3When the separation and recovery of silicon and aluminum in the subsequent steps are realized, the defects that the leaching rate is reduced due to the fact that silicon compounds enter acid to form silicic acid colloid when the nickel cobalt lithium manganate is subjected to acid leaching, and the recovery rate of valuable metals is reduced due to the fact that a large amount of valuable metal elements are carried in the colloid removal process can be avoided.
The specific reaction formula is as follows:
Na2CO3+SiO2＝Na2O·SiO2+CO2，
Na2CO3+Al2O3＝Na2O·Al2O3+CO2，
CO2+C＝2CO
after the ball milling is finished, placing the mixture of the anode and cathode mixed powder and the carbonate in a high-temperature furnace, roasting under the condition of inert gas (at least one of nitrogen, argon or helium), at the temperature of 600-900 ℃, after the roasting time is 0.8-1.5h, cooling along with the furnace.
In the step, inert gas is introduced during the mixed roasting of the anode mixed powder and the cathode mixed powder and the carbonate, on one hand, the CO is favorable for generating CO, and the CO can provide reducing atmosphere for the recovery of the nickel cobalt lithium manganate so as to achieve the aim of reductionOn the other hand, the graphite can be prevented from being greatly lost in an air state at high temperature. When the temperature is lower than 500 ℃ during roasting, Na cannot be generated2O·SiO2And Na2O·Al2O3The leaching effect will not be achieved during the subsequent leaching process. If the temperature is higher than 1000 ℃, Na is quickly generated2O·Al2O3·2SiO2The substance is not dissolved in dilute alkali solution, and silicon and aluminum elements will remain in the mixed powder, thus the purpose of separating silicon and aluminum compounds can not be achieved.
S3, placing the mixture after roasting into a dilute alkali solution for filtering to obtain a filtrate which is a mixed solution of an aluminum-containing compound and a silicon-containing compound, wherein filter residues contain nickel-cobalt lithium manganate, graphite and impurity element copper, introducing carbon dioxide generated in roasting into the mixed solution of the aluminum-containing compound and the silicon-containing compound to obtain an aluminum hydroxide precipitate, introducing excessive carbon dioxide to obtain a silicic acid precipitate, and separating silicon and aluminum in the mixed solution by using sodium bicarbonate as the filtrate.
In the step, the alkali in the dilute alkali solution is NaOH or LiOH, the concentration is 0.05-2mol/L, the solid-liquid ratio (the ratio of the solid mass of the mixture after roasting to the volume of the dilute alkali solution) is 50-150g/L, the reaction time is 2-3h, the temperature is between normal temperature and 50 ℃, and the pH value is adjusted to 6.5-8.5.
Due to Na2O·Al2O3And Na2O·SiO2The mixture is very easy to dissolve in weak base solution, the mixture after roasting is placed into the alkali solution with the concentration for filtration, carbon dioxide is introduced into the filtrate of the compound containing aluminum and the compound containing silicon, the pH value of the solution can be reduced to 6.5-8.5, aluminum hydroxide can be precipitated, then excessive carbon dioxide is introduced, silicic acid precipitation can be generated according to the principle of strong acid and weak acid preparation, the remaining filtrate is sodium bicarbonate solution and can be recycled, and the filtrate can be concentrated and crystallized to obtain sodium bicarbonate crystals.
Through the step, the anode and cathode mixed powder is easy to dissolve in a dilute alkali solution after being roasted in the earlier stage, so that the silicon and the aluminum in the aluminum compound and silicon compound mixed solution can be effectively separated, the recovery of the silicon and the aluminum in the anode and cathode mixed powder is realized, the silicon and the aluminum are removed simultaneously in the step, and the method is one-step, quick and simple; and because the solution is alkalescent solution, the use cost is low, the nickel, cobalt and manganese in the positive and negative electrode mixed powder are not lost in the process, the recovery effect can be effectively ensured, and the sodium bicarbonate can be recycled in the recovery process of the positive and negative electrode active materials of the next waste lithium battery, so that the recovery cost can be further reduced.
S4, dissolving the filter residue containing the nickel cobalt lithium manganate, the graphite and the impurity element copper after the treatment in the step S3 in acid with a certain concentration, and leaching Li+、Ni2+、Co2+、Mn2+And Cu2+The graphite was removed by filtration to separate the positive electrode active material and the negative electrode active material, and the negative electrode material carbon was recovered by a solid phase method.
In the step, the acid can be inorganic acid or organic acid, wherein the inorganic acid can be at least one of hydrochloric acid, dilute sulfuric acid, nitric acid, carbonic acid and the like, the organic acid can be at least one of tartaric acid, oxalic acid, malic acid, citric acid and the like, the acid concentration is 0.5-2.5mol/L, and the solid-to-liquid ratio of the filter residue to the acid is 50-100 g/L.
Because the graphite is insoluble in acid, when the filter residue is dissolved in acid with certain concentration, the positive active substance Li can be separated out from the leached solution+、Ni2+、Co2+、Mn2+And Cu2+Thus, the graphite insoluble in acid can be removed to separate the graphite in the positive and negative electrode mixed powder. After being separated, the graphite can be placed in a ball mill, calcined at the high temperature of 600 ℃ under inert gas, and recycled and regenerated after annealing, so that the negative active materials of silicon and carbon in the waste ternary lithium ion battery are completely recycled.
The step is carried out under the condition of certain temperature, the temperature can be 50-90 ℃, and the reaction time is 2-3 h. In the temperature range, the Li is favorably improved+、Ni2+、Co2+、Mn2+And Cu2+The leaching rate of (A).
S5 adding a certain amount of sulfide into the step S4 to obtain a solution containing Li+、Ni2+、Co2+、Mn2+And Cu2+Filter (2)In the solution, the pH value is adjusted to remove impurity copper.
The sulfide in the step is sodium sulfide or ammonium sulfide, and the pH value is adjusted to-2-1.
Since the filtrate of the step S4 also contains impurity element Cu2+After sodium sulfide or ammonium sulfide is added, copper sulfide, cobalt sulfate, manganese sulfate and nickel sulfate can be obtained, the copper sulfide can be precipitated by adjusting the pH value of the solution to be lower, and the copper sulfide is separated after filtration, so that impurity copper is removed.
S6, preparing the ternary precursor of the nickel-cobalt-manganese hydroxide from the filtrate treated in the step S5 by a coprecipitation method.
Before the step, firstly, an inductively coupled plasma emission spectrometer (ICP-OES) is adopted to measure the contents of nickel, cobalt and manganese in the leachate treated in the step S5, and then missing cobalt sulfate, manganese sulfate and nickel sulfate are added in proportion, so that the molar ratio of manganese sulfate, nickel sulfate and cobalt sulfate is 2.98-3.02: 4.97-5.1: 1.98-2.01; to ensure the purity of the nickel-cobalt-manganese phase, and then adopting a coprecipitation method to prepare the nickel-cobalt-manganese hydroxide ternary precursor.
In the step, a peristaltic pump can be adopted to mix the mixed solution of ammonia water and sodium hydroxide and the Li contained in the S5 step+、Ni2+、Co2+、Mn2+Pumping the filtrate into a coprecipitation reaction kettle for coprecipitation reaction, and adding NH4 in ammonia water and sodium hydroxide+The concentration of the sodium hydroxide is 0.3-0.5mol/L, the concentration of the sodium hydroxide is 0.5-2.0mol/L, the pH value is controlled to be 10-11.5 in the reaction process, and the temperature is controlled to be 75-95 ℃ and the rotating speed is 800-one-step at 1000 r/min. And after the coprecipitation reaction is finished, continuously mechanically stirring the obtained slurry, aging for 24h at the temperature of 75-95 ℃, washing with deionized water, drying in an air drying oven (80 ℃) for 10-12h, and sieving by a 200-mesh sieve to obtain the precursor of the ternary cathode material (nickel-cobalt-manganese hydroxide) with extremely low impurity content.
S7, introducing the carbon dioxide generated in the S2 step into the solution coprecipitated in the S6 step, and heating, concentrating and crystallizing to prepare lithium carbonate.
In the step, the temperature is increased to 80-90 ℃ for concentration, and the crystal of lithium carbonate can be obtained.
The present invention will be described in further detail with reference to examples.
Example 1:
s1, discharging the waste lithium ion battery for about 4 hours (discharging for many times to ensure that the battery voltage is lower than 1V) through a charging and discharging machine, then automatically disassembling and separating out positive and negative electrode mixed powder, a battery shell, copper foil, aluminum foil and a diaphragm through methods of mechanical crushing, magnetic separation, screening and the like, and directly recovering the disassembled battery shell, copper foil, aluminum foil and diaphragm;
s2, mixing the positive and negative electrode mixed powder separated in the step S1 and sodium carbonate according to the molar ratio of the sodium carbonate to the nickel cobalt lithium manganate of 0.3, placing the mixture in a ball mill, roasting for 2 hours under the condition of nitrogen at the roasting temperature of 800 ℃, simultaneously recovering carbon dioxide generated by reaction, and cooling along with the furnace.
S3, placing 800g of the mixture roasted in the step S2 into 8L of dilute alkali solution with the concentration of 0.07mol/L, reacting for 2 hours at normal temperature, filtering to obtain a compound mixed solution of aluminum and silicon, introducing carbon dioxide generated by roasting in the step S2 into the mixed solution, adjusting the pH value to 7 to obtain aluminum hydroxide precipitate, introducing excessive carbon dioxide to obtain silicic acid precipitate, wherein the filtrate is sodium bicarbonate, and the sodium bicarbonate is recycled.
S4, placing 600g of filter residue treated in the step S3 in 10L of hydrochloric acid solution with the concentration of 1mol/L, reacting for 2 hours at the temperature of 80 ℃, and leaching Li+、Ni2+、Co2+、Mn2+And Cu2+Filtering to obtain graphite matter insoluble in acid, separating the positive and negative active matters, calcining in ball mill at 600 deg.c in nitrogen, annealing and recovering.
S5 adding 5.6g of sodium sulfide into the filtrate treated in the step S4, adjusting the pH to 1 to obtain copper sulfide precipitate, and filtering to remove the precipitate.
And S6, detecting the filtrate treated in the step S5 by adopting ICP-OES, wherein the contents of nickel, cobalt and manganese are determined according to the molar ratio of manganese sulfate, nickel sulfate and cobalt sulfate being 3: 2: 5, adding missing cobalt sulfate, manganese sulfate and nickel sulfate, and pumping NH4 by a peristaltic pump+0.4mol/L ammonia water and 1mol/L sodium hydroxide pumpPutting the mixture into a coprecipitation reaction kettle, controlling the pH value to be 10.5, the temperature to be 80 ℃ and the rotating speed to be 1000 r/min. And after the coprecipitation reaction is finished, continuously mechanically stirring the slurry, aging for 24h at 80 ℃, then washing with deionized water, drying for 12h in an air drying oven (80 ℃), and sieving by a 200-mesh sieve to obtain the precursor of the ternary cathode material.
S7 reaction of CO generated in S22And introducing the lithium carbonate into the filtrate subjected to S6 coprecipitation, heating to 90 ℃, adjusting the pH value to 11, and concentrating and crystallizing to obtain the lithium carbonate.
The change situation of the impurity content before and after treatment in the embodiment is shown in table 1, the recovery rate of each component is shown in table 2, and the performance of the ternary cathode material precursor after recovery is shown in table 3.
Table 1: example 1 Change in impurity content before and after treatment
| Composition (I) | Si | Al | Cu |
| Before treatment (%) | 10.5 | 0.6 | 0.58 |
| After treatment (%) | 0.025 | 0.0021 | 0.0045 |
As can be seen from Table 1, by adopting the recovery method of the embodiment 1 of the invention, the separation effect of impurities Si, Al and Cu in the mixed powder of the positive electrode and the negative electrode of the waste lithium ion battery is better, and the content of the impurities remained in the recovered materials is very low.
Table 2: example 1 recovery of each component
As can be seen from Table 2, by adopting the recovery method of the embodiment 1 of the invention, the recovery rate of Ni, Co, Mn, Al, Cu, Si and graphite in the mixed powder of the positive electrode and the negative electrode of the waste lithium ion battery is up to more than 98.5%, and the recovery rate of Li is more than 85%, so that the recovery method has a better recovery effect.
Table 3: example 1 performance test result of recovered ternary cathode material precursor
| Serial number | Test value | General market demand |
| Na(ppm) | 87 | ≤200 |
| SO4 2-Mass fraction (%) | 0.1 | 0.4 |
| Average particle diameter D50(μm) | 10.5 | —— |
| Tap density (g/cm)3) | 2.3 | ≥2 |
As can be seen from table 3, the ternary cathode material precursor obtained by the recovery method of embodiment 1 of the present invention has satisfactory impurity content, average particle size, and tap density.
The XRD pattern of the regenerated ternary hydroxide obtained by the process of this embodiment can be seen in fig. 3, comparing the XRD patterns of the mixed powder of the silicon-carbon negative electrode of the waste battery and the nickel-cobalt lithium manganate positive electrode shown in fig. 2, it can be seen that the phase of the regenerated NCM ternary precursor is NCM hydroxide as a pure phase, and there is no other impurity phase. Meanwhile, as can be seen from the SEM image of the regenerated ternary NCM hydroxide shown in fig. 4, the material phase is nickel cobalt manganic oxide hydroxide, and has no other impurity phase and higher purity.
Example 2:
s1, discharging the waste lithium ion battery for about 3 hours in a brine soaking mode, then automatically disassembling and separating out positive and negative electrode mixed powder, a battery shell, copper foil, aluminum foil and a diaphragm by methods of mechanical crushing, magnetic separation, screening and the like, and directly recovering the disassembled battery shell, copper foil, aluminum foil and diaphragm;
s2, mixing the positive and negative electrode mixed powder separated in the step S1 and sodium carbonate according to the molar ratio of the sodium carbonate to the nickel cobalt lithium manganate of 0.2, then placing the mixture in a ball mill, roasting for 1h under the condition of nitrogen at the roasting temperature of 850 ℃, simultaneously recovering carbon dioxide generated by the reaction, and cooling along with the furnace.
S3, 1.2kg of the mixture roasted in the step S2 is placed into 10L of dilute alkali solution with the concentration of 0.1mol/L to react for 2 hours at normal temperature, the mixture is filtered to obtain a compound mixed solution of aluminum and silicon, carbon dioxide generated by roasting in the step S2 is introduced into the mixed solution, the pH value is adjusted to 8.5 to obtain aluminum hydroxide precipitate, then excessive carbon dioxide is introduced to obtain silicic acid precipitate, the filtrate is sodium bicarbonate, and the sodium bicarbonate is recycled.
S4, placing 700g of filter residue treated in the step S3 in 10L of sulfuric acid solution with the concentration of 2mol/L, reacting for 2 hours at the temperature of 90 ℃, and leaching Li+、Ni2+、Co2+、Mn2+And Cu2+Filtering to obtain graphite matter insoluble in acid, separating the positive and negative active matters, calcining in ball mill at 600 deg.c in nitrogen, annealing and recovering.
S5 adding 6g of sodium sulfide into the filtrate treated in the step S4, adjusting the pH to-0.5 to obtain a copper sulfide precipitate, and filtering to remove the precipitate.
And S6, detecting the filtrate treated in the step S5 by adopting ICP-OES, wherein the contents of nickel, cobalt and manganese are determined according to the molar ratio of manganese sulfate, nickel sulfate and cobalt sulfate being 3: 5: 2, adding missing cobalt sulfate, manganese sulfate and nickel sulfate, and pumping NH4 by a peristaltic pump+Pumping 0.5mol/L ammonia water and 2mol/L sodium hydroxide into a coprecipitation reaction kettle, controlling the pH value to be 10, the temperature to be 85 ℃, and the rotating speed to be 1000 r/min. And after the coprecipitation reaction is finished, continuously mechanically stirring the slurry, aging for 24h at 85 ℃, then washing with deionized water, drying in an air drying oven (80 ℃) for 10h, and sieving by 200 meshes to obtain a ternary cathode material precursor (a nickel-cobalt-manganese hydroxide ternary precursor).
S7 reaction of CO generated in S22And introducing into the filtrate subjected to S6 coprecipitation, heating to 80 ℃, adjusting the pH value to 11, and concentrating and crystallizing to obtain lithium carbonate.
The change situation of the impurity content before and after the treatment in the embodiment is shown in table 4, the recovery rate of each component is shown in table 5, and the performance of the ternary cathode material precursor after the recovery is shown in table 6.
Table 4: example 2 Change in impurity content before and after treatment
| Composition (I) | Si | Al | Cu |
| Before treatment (%) | 9.8 | 0.67 | 0.57 |
| After treatment (%) | 0.035 | 0.0025 | 0.0043 |
As can be seen from Table 4, by adopting the recovery method of the embodiment 2 of the invention, the separation effect of impurities Si, Al and Cu in the mixed powder of the positive electrode and the negative electrode of the waste lithium ion battery is better, and the content of the impurities remained in the recovered materials is very low.
Table 5: example 2 recovery of each component
As can be seen from Table 5, by adopting the recovery method of the embodiment 2 of the invention, the recovery rate of Ni, Co, Mn, Al, Cu, Si and graphite in the mixed powder of the positive electrode and the negative electrode of the waste lithium ion battery is up to more than 98.5%, the recovery rate of Li is more than 85%, and the recovery effect is better.
Table 6: example 2 performance test result of recovered ternary cathode material precursor
| Serial number | Test value | General market demand |
| Na(ppm) | 56 | ≤200 |
| SO4 2-Mass fraction (%) | 0.24 | 0.4 |
| Average particle diameter D50(μm) | 11 | —— |
| Tap density (g/cm)3) | 2.14 | ≥2 |
As can be seen from table 6, the ternary precursor of the positive electrode material obtained by the recovery method in example 1 of the present invention has impurity content, average particle size, and tap density that meet the general market requirements.
Example 3:
s1, discharging the waste lithium ion battery for about 4 hours (discharging for many times to ensure that the battery voltage is lower than 1V) through a charging and discharging machine, then automatically disassembling and separating out positive and negative electrode mixed powder, a battery shell, copper foil, aluminum foil and a diaphragm through methods of mechanical crushing, magnetic separation, screening and the like, and directly recovering the disassembled battery shell, copper foil, aluminum foil and diaphragm;
s2, mixing the positive electrode mixed powder and the negative electrode mixed powder separated in the step S1 with sodium carbonate according to the molar ratio of the sodium bicarbonate to the nickel cobalt lithium manganate of 0.12, then placing the mixture in a ball mill, roasting the mixture for 1 hour under the condition of nitrogen at the roasting temperature of 860 ℃, simultaneously recovering carbon dioxide generated by reaction, and cooling the mixture along with the furnace.
S3, putting 1.5kg of the mixture roasted in the step S2 into 10L of dilute alkali solution with the concentration of 0.09mol/L, reacting for 3 hours at normal temperature, filtering to obtain a compound mixed solution of aluminum and silicon, introducing carbon dioxide generated by roasting in the step S2 into the mixed solution, adjusting the pH value to 6.5 to obtain aluminum hydroxide precipitate, and then introducing excessive carbon dioxide to obtain silicic acid precipitate, wherein the filtrate is sodium bicarbonate, and the sodium bicarbonate is recycled.
S4, placing 1kg of filter residue treated in the step S3 in 20L of citric acid solution with the concentration of 2mol/L, reacting for 3h at the temperature of 90 ℃, and leaching Li+、Ni2+、Co2+、Mn2+And Cu2+Filtering to obtain graphite matter insoluble in acid, separating the positive and negative active matters, calcining in ball mill at 600 deg.c in nitrogen, annealing and recovering.
S5 adding 8g of sodium sulfide into the filtrate processed in the step S4, adjusting the pH to 0.5 to obtain copper sulfide precipitate, and removing the precipitate after filtration.
S6 passing NH4 through peristaltic pump+Pumping 0.5mol/L ammonia water and 1mol/L sodium hydroxide into a coprecipitation reaction kettle, controlling the pH value to be 11, the temperature to be 85 ℃, and the rotating speed to be 900 r/min. And after the coprecipitation reaction is finished, continuously mechanically stirring the slurry, aging for 24h at 85 ℃, then washing with deionized water, drying in an air drying oven (80 ℃) for 12h, and sieving by a 200-mesh sieve to obtain the precursor of the ternary cathode material.
S7 reaction of CO generated in S22And introducing the lithium carbonate into the filtrate subjected to S6 coprecipitation, heating to 90 ℃, adjusting the pH value to 11, and concentrating and crystallizing to obtain the lithium carbonate.
Table 7: example 3 Change in impurity content before and after treatment
| Composition (I) | Si | Al | Cu |
| Before treatment (%) | 9.85 | 0.58 | 0.57 |
| After treatment (%) | 0.047 | 0.0035 | 0.0036 |
As can be seen from Table 7, by adopting the recovery method of the embodiment 2 of the invention, the separation effect of impurities Si, Al and Cu in the mixed powder of the positive electrode and the negative electrode of the waste lithium ion battery is good, the content of the impurities remained in the recovered materials is very low, and the regeneration requirement is met.
Table 8: example 3 recovery of each component
According to table 8, it can be seen that by adopting the recovery method of the embodiment 3 of the present invention, the recovery rate of Ni, Co, Mn, Al, Cu, Si and graphite in the mixed powder of the positive electrode and the negative electrode of the waste lithium ion battery is as high as more than 98.5%, and the recovery rate of Li is close to 85%, so that a good recovery effect is achieved.
The above-described embodiments of the present invention are merely exemplary and not intended to limit the present invention, and those skilled in the art may make various modifications, substitutions and improvements without departing from the spirit of the present invention.
Claims (8)
1. A method for recycling a mixed anode and cathode material of a waste ternary lithium ion battery is characterized by comprising the following steps:
s1, performing discharge treatment on the waste lithium ion battery, crushing by a physical method, and disassembling and separating out nickel cobalt lithium manganate positive electrode and silicon carbon negative electrode mixed powder, a battery shell, copper foil, aluminum foil and a diaphragm;
s2, mixing and ball-milling the separated positive and negative electrode mixed powder with carbonate, roasting the mixture in a furnace for a certain time under the condition of inert gas to enable the carbonate to react with silicon compounds in the positive and negative electrode mixed powder and residual aluminum oxide which is difficult to dissolve in acid and alkali after disassembly to generate CO2、Na2O·SiO2And Na2O·Al2O3Said CO2Reacting with graphite in the positive and negative electrode mixed powder at high temperature in inert atmosphere to generate reductive gas CO, and recovering gas carbon dioxide generated in the reaction process, wherein the carbonate is sodium carbonate or sodium bicarbonate, and the molar ratio of the sodium carbonate or sodium bicarbonate to the nickel cobalt lithium manganate is 0.11-0.30;
s3, placing the mixture after roasting into a dilute alkali solution for filtering to obtain a filtrate which is a mixture of an aluminum compound and a silicon compound, and introducing carbon dioxide generated in roasting into the filtrate to separate silicon and aluminum in the filtrate;
s4, dissolving the filter residue processed in the step S3 in acid with certain concentration, and leaching Li in the filter residue+、Ni2+、Co2+、Mn2+And Cu2+The acid is inorganic acid or organic acid, the concentration is 0.5-2.5mol/L, the solid-to-liquid ratio of the filter residue to the acid solution is 50-100g/L, the temperature is 50-90 ℃, and the reaction time is 2-3 h; filtering to remove graphite, separating the positive active material and the negative active material, and recovering the negative material by a solid phase method;
s5, adding a certain amount of sulfide into the filtrate obtained in the step S4, and adjusting the pH value to remove impurity copper;
s6, preparing a nickel-cobalt-manganese hydroxide ternary precursor from the filtrate treated in the step S5 by a coprecipitation method;
s7, introducing the carbon dioxide generated in the step S2 into the solution obtained after the coprecipitation method in the step S6, and heating, concentrating and crystallizing to prepare lithium carbonate.
2. The method for recycling the anode and cathode mixed materials of the waste ternary lithium ion battery as claimed in claim 1, wherein before the step S6, the nickel, cobalt and manganese contents in the filtrate processed in the step S5 are detected, then the missing cobalt sulfate, manganese sulfate and nickel sulfate are added in proportion, and then a nickel-cobalt-manganese hydroxide ternary precursor is prepared by adopting a coprecipitation method.
3. The method for recycling the anode and cathode mixed materials of the waste ternary lithium ion battery as claimed in claim 1 or 2, wherein in the step S2, the anode and cathode mixed powder and carbonate are mixed and ball-milled, and then are calcined at the temperature of 600-900 ℃ for 0.8-1.5h under the inert gas condition.
4. The method for recycling the anode and cathode mixed materials of the waste ternary lithium ion batteries according to claim 1 or 2, wherein in the step S3, the alkali in the dilute alkali solution is NaOH or LiOH, the concentration is 0.05 to 2mol/L, the solid-to-liquid ratio of the calcined mixture to the dilute alkali solution is 50 to 150g/L, the reaction time is 2 to 3 hours, the temperature is between normal temperature and 50 ℃, and the pH is adjusted to 6.5 to 8.5.
5. The method for recycling the anode-cathode mixed material of the waste ternary lithium ion battery according to claim 1, wherein the inorganic acid in the step S4 is at least one of hydrochloric acid, sulfuric acid, nitric acid or carbonic acid, and the organic acid is at least one of tartaric acid, oxalic acid, malic acid or citric acid.
6. The method for recycling the anode-cathode mixed material of the waste ternary lithium ion battery according to claim 1 or 2, wherein in the step S5, the sulfide is sodium sulfide or ammonium sulfide, and the pH value is adjusted to-2-1.
7. The method for recycling the positive-negative electrode mixed material of the waste ternary lithium ion battery according to claim 1 or 2, wherein in the step S7, the crystallization temperature for preparing the lithium carbonate by heating, concentrating and crystallizing is 80-90 ℃.
8. The method for recycling the anode-cathode mixed material of the waste ternary lithium ion battery as claimed in claim 2, wherein before the step of S6, the molar ratio of manganese sulfate, nickel sulfate and cobalt sulfate is 2.98-3.02: 4.97-5.1: 1.98-2.01, and then preparing the nickel-cobalt-manganese hydroxide ternary precursor by adopting a coprecipitation method.
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| US11932554B2 (en) | 2022-04-11 | 2024-03-19 | American Hyperform, Inc. | Method of recovering high nickel content cathode material from recycled lithium ion and nickel metal hydride batteries |
| CN115161483B (en) * | 2022-07-05 | 2023-08-08 | 广西师范大学 | Method for fully recycling waste lithium ion batteries and realizing metal separation |
| CN115642330A (en) * | 2022-10-11 | 2023-01-24 | 华南理工大学 | Recovery method and application of waste positive pole piece of lithium ion battery |
| CN116722253B (en) * | 2023-08-09 | 2023-12-01 | 深圳市杰成镍钴新能源科技有限公司 | Polar material leaching method and device for retired ternary lithium battery |
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Address after: C709-1, 7 / F, Institute of Tsinghua University, 019 Gaoxin South 7th Road, high tech Zone community, Yuehai street, Nanshan District, Shenzhen, Guangdong 518000 Patentee after: Shenzhen Qingyan Lithium Industry Technology Co.,Ltd. Address before: C709-1, 7 / F, Institute of Tsinghua University, 019 Gaoxin South 7th Road, high tech Zone community, Yuehai street, Nanshan District, Shenzhen, Guangdong 518000 Patentee before: Shenzhen Qingyan Equipment Technology Co.,Ltd. |