CN116837213A - Method for comprehensively utilizing valuable metals in waste ternary lithium ion battery electrode powder - Google Patents

Method for comprehensively utilizing valuable metals in waste ternary lithium ion battery electrode powder Download PDF

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Publication number
CN116837213A
CN116837213A CN202310587465.0A CN202310587465A CN116837213A CN 116837213 A CN116837213 A CN 116837213A CN 202310587465 A CN202310587465 A CN 202310587465A CN 116837213 A CN116837213 A CN 116837213A
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roasting
nickel
manganese
ion battery
lithium ion
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Inventor
顾剑锋
缪永华
靳志会
刘信辉
谭清武
孙仲
陆毅
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Zhongtian Energy Storage Technology Co Ltd
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Zhongtian Energy Storage Technology Co Ltd
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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
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
    • C22B1/00—Preliminary treatment of ores or scrap
    • C22B1/02—Roasting processes
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
    • C22B1/00—Preliminary treatment of ores or scrap
    • C22B1/02—Roasting processes
    • C22B1/06—Sulfating roasting
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
    • C22B23/00—Obtaining nickel or cobalt
    • C22B23/02—Obtaining nickel or cobalt by dry processes
    • 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
    • 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
    • C22B23/043—Sulfurated acids or salts thereof
    • 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
    • C22B23/0453—Treatment or purification of solutions, e.g. obtained by leaching
    • C22B23/0461—Treatment or purification of solutions, e.g. obtained by leaching by chemical methods
    • 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
    • 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
    • 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
    • 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

Abstract

The invention provides a method for comprehensively utilizing valuable metals in waste ternary lithium ion battery electrode powder, which comprises the following steps: (1) Premixing waste ternary lithium ion battery electrode powder with concentrated sulfuric acid, and roasting under a mixed atmosphere of sulfur dioxide and air; (2) Soaking the roasting material in water, and carrying out solid-liquid separation to obtain a sulfate solution containing cobalt, nickel, manganese and lithium and graphite filter residues; (3) Adding manganese sulfide into the sulfate solution containing cobalt, nickel, manganese and lithium for reaction, and carrying out solid-liquid separation to obtain filtrate and precipitation slag; (4) oxidizing and roasting the precipitate slag; (5) Leaching the roasting product with water and acid to obtain a nickel cobalt sulfate solution, and removing impurities from the nickel cobalt sulfate solution to obtain a battery grade nickel cobalt sulfate solution; (6) And (3) carrying out sulfuration and manganese precipitation on the filtrate, and carrying out solid-liquid separation after the reaction to obtain crude manganese sulfide and lithium-rich solution. The method has the advantages of low cost, high reduction rate of the metal in the counter electrode powder, capability of realizing the recycling of sulfur by the whole process, pollution avoidance and high metal recovery rate.

Description

Method for comprehensively utilizing valuable metals in waste ternary lithium ion battery electrode powder
Technical Field
The invention belongs to the technical field of recovery methods of waste lithium ion batteries, and particularly relates to a method for comprehensively utilizing valuable metals in electrode powder of waste ternary lithium ion batteries.
Background
Lithium ion batteries have an unprecedented high energy density and excellent cycling stability, and have become the energy storage device of choice for portable electronic devices and power transmission systems. According to statistics of China light industry information center (CNLIC), 2021, the sales of new energy automobiles in China reach 354.5 thousands; according to the requirements of the Ministry of industrial development of new energy automobiles (2021-2035), the new energy automobiles occupy 20% of the automobile production and marketing in 2035, and are expected to reach tens of millions of grades; the retired lithium battery in 2025 China can reach 80 ten thousand tons according to the prediction of the resource forced recovery industry technology innovation strategy alliance. The waste lithium ion battery contains a large amount of valuable metals, and the content of the valuable metals is far higher than that of the original natural ore, so that an efficient and clean recovery process needs to be developed to recover the valuable metals in the waste lithium ion battery, thereby ensuring the sustainable development of the lithium ion battery industry and relieving the problem of current shortage of resources.
The waste lithium ion battery electrode powder comprises waste lithium ion battery anode powder and waste lithium ion battery cathode powder, and contains organic matters, electrolyte salt, nickel, cobalt, manganese, copper, aluminum, carbonaceous materials and the like. At present, the technology for recovering valuable metals from waste lithium ion battery electrode powder in China mainly comprises two major types of pyrometallurgy and hydrometallurgy.
The pyrometallurgical recovery process is represented by the company of the beauty, firstly, the waste lithium ion battery is subjected to reduction smelting to obtain Co-Ni-Cu-Fe alloy, and then high-purity single metal and compound are obtained in a hydrometallurgical mode, and the pyrometallurgical process has the advantages of short process flow, low equipment requirement, strong operability and the like, but also has the defects of low process throughput, high energy consumption, high environmental pollution, low product purity and the like.
The wet recovery process is to leach all valuable metals in the electrode powder of the waste lithium ion battery into the solution, and then to recover the metal elements step by adopting purification methods such as precipitation or extraction. The wet recovery factory in China generally adopts an extraction process route to recover valuable metals in the waste lithium ion batteries, and the extraction method has the advantages of high recovery purity, but also has the defects of large reagent consumption, high operation and maintenance cost, low comprehensive recovery rate of lithium, complex flow, easiness in secondary pollution and the like.
The method of Chinese patent CN111333123A is characterized in that sulfuric acid is mixed with a positive electrode material in a wet mode and then baked at a high temperature, sulfate solution of cobalt, nickel, manganese and lithium and graphite slag are obtained through water leaching, and the solution is further subjected to hydrothermal reaction to prepare a ternary precursor. Chinese patent CN114085997A, CN110760686A is similar to CN111333123A in that waste battery anode material is roasted with concentrated sulfuric acid, but after water immersion, lithium sulfate solution, cobalt-containing nickel-manganese oxide and graphite slag phase are obtained, only lithium enters liquid phase, but the sulfuric acid consumption is large in the treatment process of the metal slag phase, high-valence metal cannot be leached completely, and the impurity removal difficulty is great. In chinese patent CN111254294a, lithium sulfate and manganese sulfate solutions, cobalt-nickel oxide and graphite slag phases are obtained by leaching with water through a sulfuric acid curing roasting method, so that metals Li and Mn enter a liquid phase, and manganese dioxide is further ionized through an electrolysis method.
In the technology of the patent, the selective leaching of cobalt nickel manganese lithium metal is realized by a sulfating roasting method, and in the roasting process, graphite plays a role of a reducing agent to reduce high-valence metal in the waste ternary cathode material into low-valence metal, however, the graphite is extremely easy to cause oxidation reaction of oxygen in the atmosphere, so that the reduction effect of the graphite on the high-valence metal in the roasting process is not ideal, and the leaching efficiency is influenced.
Disclosure of Invention
In order to solve the problems, the invention provides a method for comprehensively utilizing valuable metals in waste ternary lithium ion battery electrode powder.
To achieve the above object, the following solutions are proposed:
a method for comprehensively utilizing valuable metals in waste ternary lithium ion battery electrode powder comprises the following steps:
(1) Premixing waste ternary lithium ion battery electrode powder with concentrated sulfuric acid, transferring into a furnace body, and roasting under the mixed atmosphere of sulfur dioxide and air to obtain a roasting material;
in this step, the following reaction mainly occurs:
4SO 2 +2Me 2 O 3 +O 2 →4MeSO 4
SO 2 +Me 2 O 3 →2MeO+SO 3
C+2Me 2 O 3 →CO 2 +4MeO
H 2 SO 4 +2Al 2 O 3 → 2Al 2 (SO 4 ) 3 +H 2 O
H 2 SO 4 +2Me’O → 2Me’SO 4 +H 2 O
wherein Me represents Ni, co, mn, me' represents Cu, mg, ca, fe, ni, co, mn.
(2) Soaking the roasting material in water, and carrying out solid-liquid separation to obtain a sulfate solution containing cobalt, nickel, manganese and lithium and graphite filter residues;
(3) Adding manganese sulfide into a sulfate solution containing cobalt, nickel, manganese and lithium to carry out double decomposition displacement reaction, and carrying out solid-liquid separation after the reaction is finished to obtain filtrate and sulfide precipitate slag of nickel and cobalt, wherein the main double decomposition displacement reaction has the following formula:
MnS + CoSO 4 →CoS↓ + MnSO 4
MnS + NiSO 4 →NiS↓ + MnSO 4
the following side reactions also occur:
MnS + CuSO 4 →CuS↓ + MnSO 4
MnS + FeSO 4 →FeS↓ + MnSO 4
(4) Oxidizing and roasting the sulfide precipitate slag of nickel and cobalt to obtain roasting products, wherein the roasting products are sulfate of nickel and cobalt and oxide of nickel and cobalt;
(5) Leaching the roasting product by water, carrying out solid-liquid separation to obtain a nickel-cobalt sulfate solution and oxide slag, carrying out acid leaching on the oxide slag to obtain a nickel-cobalt sulfate solution, removing impurities from the nickel-cobalt sulfate solution obtained by water leaching and acid leaching to obtain a battery-grade nickel-cobalt sulfate solution, wherein the molar ratio of metal cobalt to metal nickel in the subsequent cobalt-nickel sulfate solution can be adjusted arbitrarily according to the requirements of customers;
(6) And (3) carrying out sulfuration and manganese precipitation on the filtrate obtained in the step (3), and carrying out solid-liquid separation after the reaction to obtain crude manganese sulfide and lithium-rich solution.
Preferably, in the step (6), part of the crude manganese sulfide is returned to the step (3) for reaction, and the rest part is washed by absolute ethyl alcohol, dried in vacuum, sieved and removed by an electromagnetic iron remover to obtain a high-purity manganese sulfide product. Wherein the absolute ethyl alcohol is washed for multiple times, the vacuum drying temperature is 85-150 ℃ and the time is 2-12h. The purity of MnS in the obtained high-purity manganese sulfate product is not lower than 99.5 percent.
Removing impurities from the lithium-rich solution in the step (6), carbonizing, precipitating lithium, and centrifugally separating to obtain industrial-grade lithium carbonate; the reaction temperature of the carbonized precipitated lithium is 70-90 ℃ and the reaction time is 2-3h; the carbonization lithium precipitation is to add saturated sodium carbonate solution into the lithium-rich solution after impurity removal for precipitation reaction; the impurity removal comprises the steps of adding sodium carbonate into a lithium-rich solution to remove calcium, then adding sodium hydroxide to remove magnesium, wherein the pH value of the solution after the calcium removal is 8-9, the pH value of the solution after the magnesium removal is 10-11, and the impurity ion content in the solution after the impurity removal can reach the industrial level.
Preferably, in the step (1), the concentrated sulfuric acid is added in a molar ratio of n (H) 2 SO 4 ): n (Co+Ni+Mn+2Li) is 0.7 to 0.9.
Preferably, in the step (1), the roasting process controls the sulfur dioxide partial pressure to be 0.2-0.8atm; the mixed atmosphere of sulfur dioxide and air is provided by the flue gas of the oxidizing roasting in the step (4).
Preferably, in the step (1), the roasting is two-stage roasting, and the first-stage roasting temperature is 80-350 ℃, and more preferably 100-200 ℃; the heat preservation time of the first stage roasting is 1-2h; the second stage roasting temperature is 280-600 ℃, and further preferably 300-450 ℃; the heat preservation time of the second stage roasting is 2-3h.
Preferably, in the step (2), the water immersion is wet ball milling water immersion of the sintering material, wherein the liquid-solid ratio is 1-6L/kg, and the time of the wet ball milling water immersion is 5-60min.
Preferably, in the step (3), the manganese sulfide excess coefficient is 105-115%, and the manganese sulfide is recycled as a product and is obtained from the step (6) of vulcanizing and precipitating manganese; the reaction temperature is 90-98 ℃, and the reaction time is 5-6h.
Preferably, in the step (4), the oxidizing roasting is realized by a roller kiln or a rotary kiln; the oxidizing roasting is two-stage roasting, wherein one-stage roasting is carried out at the temperature of 350-550 ℃ for 1-3h, and the second-stage roasting is carried out at the temperature of 600-850 ℃ for 8-10h; the oxidizing roasting is performed in an air atmosphere; the flue gas generated by the oxidizing roasting is used as a roasting atmosphere for the roasting process in step (1).
Preferably, in the step (5), the liquid-solid ratio of the water immersion is 1-6mL/g, and the water immersion time is 20-120min; the acid leaching time is 60-120min, and the acid concentration of the acid leaching is 3-6mol/L.
Preferably, in the step (6), the reaction temperature of the sulfurized manganese is 20-50 ℃, the reaction time is 2-3h, and the pH value of the solution at the end point of the sulfurized manganese is 6.5-13; the manganese sulfide precipitation comprises adding one or more sulfides of sodium sulfide, sodium hydrosulfide and potassium sulfide into sulfate filtrate containing cobalt, nickel, manganese and lithium; the excess coefficient of the sulfide is 100-120%.
Preferably, in the step (5), the impurity removal is to remove iron, aluminum and copper ions in the solution, and the method comprises the steps of firstly adding a small amount of hydrogen peroxide to oxidize ferrous ions into ferric ions, and then adding a small amount of Co (OH) 2 Or Ni (OH) 2 The pH value of the nickel cobalt sulfate solution is adjusted to 4-5,5-6 in sequence, the impurity metals (Fe, al and Cu) are precipitated in the form of hydroxide precipitation, and then the precipitate is removed by filtering through a precision filter.
Compared with the prior art, the invention has the following beneficial effects:
the method has low cost and high reduction rate of the metal in the electrode powder, so that the cobalt, nickel, manganese, lithium and other metals in the electrode powder form stable sulfate MSO 4 (M is Co, ni and Mn), so that the sulfur can be leached into the solution through water leaching with high efficiency, the metal recovery rate is high, the consumption of concentrated sulfuric acid is low, and sulfur dioxide in the atmosphere is a system intermediate product and is recycled to make the sulfur element be utilized with high efficiency; in the method, cobalt sulfide and nickel sulfide are directly oxidized into cobalt sulfate and nickel sulfate at high temperature, the cobalt sulfate and nickel sulfate are leached out by water leaching, a small amount of sulfuric acid solution is added into the leached residual phase, namely the cobalt oxide and nickel oxide, to be acidized and dissolved, and finally, the impurity is removed to obtain the battery-grade cobalt-nickel sulfate solution.
On the premise of safety and environmental protection, in order to reduce the recovery cost of the manganese metal, the method comprises the following steps ofThe invention recovers and prepares the high-purity manganese sulfide product by a precipitation method, and the coarse manganese sulfide material is used as the raw material to lead MnS and Co to be 2+ 、Ni 2+ The method has the advantages that the metal Mn is recovered by a precipitation method, the cost is low, the procedure is simple, the manganese sulfide is used as a product and an intermediate product, the manganese sulfide is recycled in a system, outsourcing is not needed, and the problems of low metal Mn precipitation rate and high recovery cost are solved.
The whole process of the method is that inorganic matters participate in the reaction, organic matters such as an extractant and the like are not needed, the recovery cost of the electrode powder is reduced, and secondary pollution is reduced.
In summary, the invention provides a novel process route for comprehensively utilizing valuable metals in the waste ternary lithium ion battery electrode powder, and the process of combining a wet method and a fire method is adopted, and meanwhile, manganese sulfide is used as a system intermediate circulating product, so that the recovery cost of the manganese metal is reduced, the comprehensive recovery rate of the lithium metal is improved, the utilization rate of sulfur is greatly improved, and the problems of low recovery rate of lithium ions, high recovery cost, secondary pollution and the like in an industrial production line are solved on the premise of safety and environmental protection.
Drawings
FIG. 1 is a process flow diagram of the method of the invention for comprehensively utilizing valuable metals in waste ternary lithium ion battery electrode powder.
Detailed Description
The present invention will be further described with reference to specific examples and drawings, but the present invention is not limited to the following examples. Unless defined otherwise, all technical and scientific terms used hereinafter have the same meaning as commonly understood by one of ordinary skill in the art. The terminology used herein is for the purpose of describing particular embodiments only and is not intended to be limiting of the scope of the present invention.
The experimental methods described in the following examples are all conventional methods unless otherwise specified; the reagents and materials, unless otherwise specified, are commercially available.
Example 1:
(1) Acidifying and premixing: 1000kg of waste ternary lithium ion battery electrode powder (W Co ：5.6%，W Ni ：13.6%，W Mn ：28.2%，W Li : 4.8%) is added into a horizontal spiral ribbon mixer, and then 925.8kg of 98% concentrated sulfuric acid is slowly and uniformly added, and the mixing time is 60min.
(2) Roasting: and (3) putting the evenly mixed premix into a push boat type steel high-temperature reduction furnace, charging 3kg of the premix per boat, and roasting under a mixed atmosphere of sulfur dioxide and air, wherein in the step, the mixed atmosphere of sulfur dioxide and air is provided by flue gas generated by roasting in the step (8), the partial pressure of sulfur dioxide is 0.3atm, the temperature of a first area of the high-temperature furnace is 120 ℃, the material stays for 1h, the temperature of a second area of the high-temperature furnace stays for 2.5h, and the temperature of the second area of the high-temperature furnace stays for 350 ℃.
(3) Soaking in water: the sintered material is transferred into a gap ball mill for wet ball milling and water leaching, the liquid-solid ratio is 3:1L/kg, and the mixture is fully ball milling and stirring is carried out for 30min, so that metal sulfide wrapped by carbon or other impurities can be better dissolved into water, and the slurry is subjected to solid-liquid separation by a plate-and-frame filter press after water leaching to obtain solution A and waste graphite residue. The leaching rate of the main metal elements is shown in table 1.
(4) Metathesis: adding 311.3kg of manganese sulfide into the solution A, wherein the excess coefficient is 110%, the reaction temperature is 95 ℃, the reaction time is 5.5h, and obtaining the solution B and cobalt nickel sulfide slag after solid-liquid separation by a filter press.
(5) And (3) vulcanizing and precipitating manganese: 873.6kg of sodium sulfide with the purity of 50 percent and the excess coefficient of 110 percent are added into the solution B, the reaction temperature is 30 ℃, the reaction time is 2 hours, and crude MnS and lithium-rich filtrate are obtained through filter pressing and separation.
(6) MnS purification: 311.3kg of crude MnS is returned to the step (4), the rest 75.9kg is added into absolute ethyl alcohol, the absolute ethyl alcohol is washed for three times and then is transferred into a vacuum drying oven, the temperature is set to 105 ℃, the time is 4 hours, after cooling to room temperature, 80-mesh screen mesh is selected for screening, the screen discharging material is subjected to iron removal by an electromagnetic iron remover and then is packaged, the obtained MnS components are shown in the table 1, and the screen discharging material is returned to the step (4) of double decomposition replacement process to be used as a double decomposition reaction raw material.
(7) Carbonizing and precipitating lithium: adding carbon to the lithium-containing filtrate obtained in the step (6)Reacting sodium acid, precipitating with sodium hydroxide at pH of 8.6 after calcium precipitation for 30min, precipitating with sodium hydroxide at pH of 11 after magnesium precipitation, filtering, and adding 800kg saturated Na into the filtrate 2 CO 3 Solution (Na) 2 CO 3 The molar quantity is about 0.5 times of the molar quantity of lithium element in the electrode powder), and Li is precipitated 2 CO 3 Filtering to obtain solid Li 2 CO 3 Washing with hot water to remove residual sodium ions to obtain industrial grade Li 2 CO 3 。
(8) Oxidizing and roasting: transferring cobalt sulfide nickel slag obtained in the step (4) into a roller hearth furnace, oxidizing and roasting in an air atmosphere, controlling the temperature of a first area of the roller hearth furnace to be 400 ℃ and preserving heat for 2 hours, and controlling the temperature of a second area of the roller hearth furnace to be 650 ℃ and preserving heat for 8 hours, wherein the main components of a sintered product are cobalt sulfate and nickel sulfate, and the sintered product also contains a small amount of cobalt oxide and nickel oxide and contains SO generated by oxidizing and roasting 2 、SO 3 And (3) conveying the flue gas to the steel reduction furnace in the step (2) through a pipeline.
(9) Soaking in water: and (3) transferring the roasting product in the step (8) into a gap ball mill for leaching, wherein the liquid-solid ratio is 3:1mL/g, the leaching time is 30min, and then, carrying out solid-liquid separation by a plate-and-frame filter press to obtain cobalt sulfate, nickel sulfate solution and cobalt nickel oxide slag.
(10) Acid dissolution: adding 50kg of 3mol/L sulfuric acid solution into the cobalt nickel oxide slag in the step (8), stirring and dissolving, leaching for 60-120min, mixing with the cobalt sulfate and nickel sulfate solution in the step (9), adding 1.5kg of hydrogen peroxide to oxidize ferrous ions into ferric ions, and then adding a small amount of Co (OH) 2 And sequentially regulating the pH value of the solution to 4-5 and 5-6, precipitating the impurity metal in a hydroxide precipitation form, filtering by a precision filter, removing the precipitate, and supplementing battery-grade cobalt sulfate or battery-grade nickel sulfate into the solution according to the requirements of customers after removing impurities to obtain the battery-grade cobalt-nickel mixed sulfate solution.
TABLE 1 high purity MnS composition table
As is clear from Table 1, the purity of high purity MnS is more than 99.5%.
TABLE 2 lithium carbonate composition Table
As is clear from Table 2, according to lithium carbonate (GB/T11075-2013), the purity of lithium carbonate exceeds Li 2 CO 3 98.5% as specified in-2 and approaching Li 2 CO 3 The purity of 99.0% specified in-1, the recovered lithium carbonate belongs to technical grade lithium carbonate, but the purity also belongs to higher level in technical grade, which reduces the difficulty for the subsequent processing to battery grade lithium carbonate.
TABLE 3 leaching rate of main metallic elements after water leaching
Calculated, the comprehensive recovery rates of Li and Mn in the embodiment reach 91.58% and 98.06% respectively; the comprehensive recovery rates of Ni and Co respectively reach 99.12 percent and 99.01 percent.
Example 2:
the difference compared to example 1 is that the temperature of calcination in step (2) is changed, specifically:
and (3) putting the evenly mixed premix into a push boat type steel high-temperature reduction furnace, wherein each boat is filled with 3kg, the temperature of a first area of the high-temperature furnace is 100 ℃, the heat preservation time is 1h, the temperature of a second area of the high-temperature furnace is 450 ℃, and the heat preservation time is 2.5h.
The leaching rate of the main metal elements after water leaching in the step (3) is shown in table 2.
TABLE 4 leaching rate of main metallic elements after water leaching
Calculated, the comprehensive recovery rates of Li and Mn in the embodiment reach 91.04% and 85.82% respectively; the comprehensive recovery rates of Ni and Co reach 98.75% and 98.54% respectively.
Example 3:
the difference compared to example 1 is that the temperature of calcination in step (2) is changed, specifically:
and (3) putting the evenly mixed premix into a push boat type steel high-temperature reduction furnace, wherein each boat is filled with 3kg, the temperature of a first area of the high-temperature furnace is 100 ℃, the heat preservation time is 1h, the temperature of a second area of the high-temperature furnace is 550 ℃, and the heat preservation time is 2.5h.
Calculated, the comprehensive recovery rates of Li and Mn in the embodiment reach 90.13% and 85.82% respectively; the comprehensive recovery rates of Ni and Co reach 90.53% and 91.56% respectively. The main reason is that part of Mn 2+ 、Co 2+ And Ni 2+ Converted to oxide form during calcination, the oxide is insoluble in water, resulting in reduced leaching rate and recovery.
Comparative example 1:
the only difference compared to example 1 is that the firing temperature in step (8) is different, specifically:
(8) Oxidizing and roasting: transferring the obtained cobalt nickel sulfide slag into a roller hearth furnace, controlling the temperature of a first area of the roller hearth furnace to be 200 ℃, the heat preservation time to be 2 hours, and controlling the temperature of a second area to be 350 ℃ and the heat preservation time to be 8 hours.
Calculated, the comprehensive recovery rates of Li and Mn in the embodiment reach 91.44% and 98.54% respectively; the comprehensive recovery rates of Ni and Co reach 35.2% and 46.8% respectively. The reason is that more cobalt nickel sulfide is converted into cobalt nickel oxide, and a large amount of sulfuric acid is needed to be supplemented for acid dissolution.
Comparative example 2:
the difference from example 1 is that the amount of the premixed concentrated sulfuric acid in the step (1) is larger, the roasting atmosphere in the step (2) is only an air atmosphere, and the oxygen generated in the step (8) is not used for the roasting atmosphere in the step (1), and the addition amount of the 98% concentrated sulfuric acid is n (H) 2 SO 4 ): n (Co+Ni+Mn+2Li) is about 1.1, specifically:
(1) Acidifying and premixing: 1000kg of waste ternary lithium ion battery electrode powder (W Co ：5.6%，W Ni ：13.6%，W Mn ：28.2%，W Li : 4.8%) is added into a horizontal spiral mixer, then 1273kg of 98% concentrated sulfuric acid is slowly added at a constant speed, and the mixing time is 60min.
(2) Roasting: and (3) putting the evenly mixed premix into a push boat type steel high-temperature reduction furnace, loading 3kg per boat, roasting in an air atmosphere, setting the temperature of the first area of the high-temperature furnace to 120 ℃, keeping the material for 1h, and keeping the temperature of the second area to 350 ℃ and keeping the material for 2.5h.
The leaching rate of the main metal elements after water leaching is shown in table 5.
TABLE 5 leaching rate of main metallic element after water leaching
Through calculation, the comprehensive recovery rates of Li and Mn in the comparative example reach 91.36% and 90.34%, respectively; the comprehensive recovery rates of Ni and Co reach 95.35% and 96.67% respectively.
The foregoing is merely a preferred embodiment of the present invention and it should be noted that modifications and adaptations to those skilled in the art may be made without departing from the principles of the present invention, which are intended to be comprehended within the scope of the present invention.

Claims (10)

1. The method for comprehensively utilizing valuable metals in the electrode powder of the waste ternary lithium ion battery is characterized by comprising the following steps of:
(1) Premixing waste ternary lithium ion battery electrode powder with concentrated sulfuric acid, transferring into a furnace body, and roasting under the mixed atmosphere of sulfur dioxide and air to obtain a roasting material;
(2) Soaking the roasting material in water, and carrying out solid-liquid separation to obtain a sulfate solution containing cobalt, nickel, manganese and lithium and graphite filter residues;
(3) Adding manganese sulfide into a sulfate solution containing cobalt, nickel, manganese and lithium for reaction, and carrying out solid-liquid separation after the reaction is finished to obtain filtrate and sulfide precipitation slag of nickel and cobalt;
(4) Oxidizing and roasting the sulfide precipitate slag of nickel and cobalt to obtain a roasting product;
(5) Leaching the roasting product with water, performing solid-liquid separation to obtain nickel-cobalt sulfate solution and oxide slag, performing acid leaching on the oxide slag to obtain nickel-cobalt sulfate solution, and removing impurities from the nickel-cobalt sulfate solution obtained by leaching with water and acid to obtain battery-grade nickel-cobalt sulfate solution;
(6) And (3) carrying out sulfuration and manganese precipitation on the filtrate obtained in the step (3), and carrying out solid-liquid separation after the reaction to obtain crude manganese sulfide and lithium-rich solution.
2. The method for comprehensively utilizing valuable metals in the waste ternary lithium ion battery electrode powder according to claim 1, wherein in the step (6), one part of crude manganese sulfide is returned to the step (3) for reaction, and the other part of crude manganese sulfide is subjected to absolute ethyl alcohol washing, vacuum drying, sieving and iron removal to obtain a high-purity manganese sulfide product;
removing impurities from the lithium-rich solution in the step (6), carbonizing, precipitating lithium, and centrifugally separating to obtain industrial-grade lithium carbonate; the reaction temperature of the carbonized precipitated lithium is 70-90 ℃ and the reaction time is 2-3h; the carbonization lithium precipitation is to add saturated sodium carbonate solution into the lithium-rich solution after impurity removal for precipitation reaction; the impurity removal comprises the steps of adding sodium carbonate to the lithium-rich solution to remove calcium and then adding sodium hydroxide to remove magnesium.
3. The method for comprehensively utilizing valuable metals in waste ternary lithium ion battery electrode powder according to claim 1, wherein in the step (1), the concentrated sulfuric acid is added according to a molar ratio n (H 2 SO 4 ): n (Co+Ni+Mn+2Li) is added in the range of 0.7 to 0.9.
4. The method for comprehensively utilizing valuable metals in the electrode powder of the waste ternary lithium ion battery according to claim 1, wherein in the step (1), the roasting process controls the sulfur dioxide partial pressure to be 0.2-0.8atm; the mixed atmosphere of sulfur dioxide and air is provided by the flue gas generated by oxidizing roasting in the step (4);
the roasting is two-stage roasting, the first-stage roasting temperature is 80-350 ℃, the heat preservation time of the first-stage roasting is 1-2h, the second-stage roasting temperature is 280-600 ℃, and the heat preservation time of the second-stage roasting is 2-3h.
5. The method for comprehensively utilizing valuable metals in the electrode powder of the waste ternary lithium ion battery according to any one of claims 1-4, wherein in the step (2), the water leaching is wet ball milling water leaching of a sintered material, the liquid-solid ratio is 1-6L/kg, and the time of the wet ball milling water leaching is 5-60min.
6. The method for comprehensively utilizing valuable metals in the electrode powder of the waste ternary lithium ion battery according to any one of claims 1-4, wherein in the step (3), the amount of manganese sulfide is 105-115% of the theoretical amount; the reaction temperature is 90-98 ℃, and the reaction time is 5-6h.
7. The method for comprehensively utilizing valuable metals in the electrode powder of the waste ternary lithium ion battery according to any one of claims 1-4, wherein in the step (4), the oxidizing roasting is realized by a roller kiln or a rotary kiln; the oxidizing roasting is two-stage roasting, wherein one-stage roasting is carried out at the temperature of 350-550 ℃ for 1-3h, and the second-stage roasting is carried out at the temperature of 600-850 ℃ for 8-10h; the oxidizing roasting is carried out in an air atmosphere; the flue gas produced by the oxidative roasting is used as the roasting atmosphere in step (1).
8. The method for comprehensively utilizing valuable metals in the electrode powder of the waste ternary lithium ion battery according to any one of claims 1-4, wherein in the step (5), the liquid-solid ratio of water immersion is 1-6mL/g, and the water immersion time is 20-120min; the acid leaching time is 60-120min, and the acid concentration of the acid leaching is 3-6mol/L.
9. The method for comprehensively utilizing valuable metals in the electrode powder of the waste ternary lithium ion battery according to any one of claims 1-4, wherein in the step (6), the reaction temperature of the sulfurization and manganese precipitation is 20-50 ℃ and the reaction time is 2-3h; the manganese sulfide precipitation comprises adding one or more sulfides of sodium sulfide, sodium hydrosulfide and potassium sulfide into sulfate filtrate containing cobalt, nickel, manganese and lithium; the addition amount of the sulfide is 100-120% of the theoretical dosage.
10. The method for comprehensively utilizing valuable metals in waste ternary lithium ion battery electrode powder according to any one of claims 1-4, wherein in step (5), the impurity removal comprises: firstly adding hydrogen peroxide to oxidize ferrous ions into ferric ions, and then adding a small amount of Co (OH) 2 Or Ni (OH) 2 The pH is adjusted to 4-5,5-6 in order to precipitate the impurity metals, and then the precipitate is removed by filtration through a filter.
CN202310587465.0A 2023-05-24 2023-05-24 Method for comprehensively utilizing valuable metals in waste ternary lithium ion battery electrode powder Pending CN116837213A (en)

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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN117448577A (en) * 2023-10-11 2024-01-26 江西江铼新材料科技有限公司 Process for recycling lithium sulfate and ferric phosphate based on waste lithium iron phosphate battery

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN117448577A (en) * 2023-10-11 2024-01-26 江西江铼新材料科技有限公司 Process for recycling lithium sulfate and ferric phosphate based on waste lithium iron phosphate battery

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