CN112095000A - Method for recovering cobalt and lithium metals from waste lithium cobalt oxide batteries - Google Patents
Method for recovering cobalt and lithium metals from waste lithium cobalt oxide batteries Download PDFInfo
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Abstract
The invention provides a method for recovering cobalt and lithium from waste lithium cobalt oxide batteries, which is characterized by comprising the following steps of: the method comprises the following specific steps: (1) performing discharge treatment on the waste lithium cobaltate battery, and obtaining black lithium cobaltate powder after disassembling, crushing, pyrolyzing and screening; (2) mixing the black lithium cobaltate powder obtained in the step (1) with ammonium salt according to the molar ratio of 1: 1.5-4, placing the mixture in a high-temperature ball mill for carrying out enhanced ammonia roasting to convert lithium cobaltate into sulfate, and soaking in waterObtaining rich Co2+、Li+The leaching solution is used for recovering ammonia gas generated in the process, and the ammonia gas is recovered in the form of ammonium sulfate and recycled; (3) the Co-rich obtained in the step (2)2+、Li+The leaching solution is used for selectively recovering cobalt and lithium components, an organic extractant is used for recovering cobalt, a precipitation method is used for recovering lithium in residual liquid, and the lithium is recovered in a lithium carbonate form. The method meets the requirements of recovering valuable metals of the waste lithium ion battery in a green, low-consumption, high-efficiency and short process.
Description
Technical Field
The invention relates to a method for treating waste lithium ion batteries, in particular to a method for recovering cobalt and lithium from waste lithium cobalt oxide batteries.
Background
In recent years, due to energy shortage and environmental protection requirements, chemical fuel energy is being transformed and developed into new energy, and therefore lithium ion batteries have been rapidly developed since the commercialization in 1991. Compared with the commonly used lead-acid battery, nickel-copper battery and other traditional batteries, the lithium ion battery has higher theoretical capacity and volume energy density, and also has a series of advantages of long working time, high safety performance, no memory effect, environmental friendliness and the like, so that the lithium ion battery can be widely applied to electronic equipment as an excellent energy storage device, such as mobile phones, computers, digital cameras, power batteries and the like. The lithium ion battery mainly comprises a positive electrode material, a negative electrode material, a diaphragm, a binder, a conductive agent and the like, wherein the positive electrode material mainly comprises lithium cobaltate, lithium manganate, lithium nickelate, lithium iron phosphate, a ternary material and the like. Lithium cobaltate is a typical positive electrode material, is widely used in daily life due to high capacity and strong cycling stability, and cobalt and lithium in the lithium cobaltate have high recovery value as rare metal elements.
In China, cobalt resources and lithium resources are deficient, the existence proportion of cobalt in the lithium cobaltate anode material is far higher than the occurrence degree of a natural mineral phase, and the cost of obtaining a metal raw material through resource recovery is lower than the cost of directly smelting and preparing the metal raw material from the natural mineral phase. In addition, cobalt has wide application in the industrial and military fields, is the most valuable element in the main heavy metals used in the lithium ion battery, and has important strategic significance in cobalt resource recovery; according to the information of the Shanghai nonferrous metal net in 2020 and 4 months, the average price of Li is 54 ten thousand per ton, and the average price of Co is 24 ten thousand per ton. In addition, with the development of industries such as 5G, intelligent terminals and the like, the demand and market value of cobalt resources can further rise, and the recovery of lithium and cobalt from waste lithium ion batteries has obvious economic benefits. Moreover, cobalt belongs to heavy metal elements, and if the waste lithium cobalt oxide is not reasonably treated, the problem of serious environmental pollution is caused, and the life health of human beings is influenced. Therefore, the recovery of cobalt and lithium in the waste lithium ion battery can relieve the resource pressure and eliminate the hidden pollution danger, and the economic benefit, the social benefit and the environmental benefit are outstanding.
After the lithium ion battery is charged and discharged for a period of time, the electrode material can generate different degrees of volume expansion and material denaturation, so that the specific capacity is gradually attenuated, when the capacity is attenuated to 50%, the lithium ion battery becomes a retired lithium ion battery, and the lithium ion battery becomes a waste lithium ion battery after cascade utilization. With the rapid development of new energy power automobiles and large-scale energy storage markets, the number of lithium ion batteries is increased in a well-jet manner, at present, the service life of the lithium ion batteries is generally 3-5 years, which means that the number of the waste lithium ion batteries is increased in an explosive manner, and a large number of waste lithium ion batteries inevitably cause environmental pollution and resource waste if not processed, so how to process the waste lithium ion batteries is a common problem facing current new energy enterprises.
According to the composition and proportion of valuable components in the lithium ion battery, the current treatment mode for resource recovery of the lithium cobalt oxide battery mainly comprises the following steps:
(1) wet recovery
Chinese patent (CN 101269889A) discloses a method for recovering cobalt from waste lithium cobalt oxide batteries, which comprises pretreating positive electrode material containing lithium cobalt oxide to remove binder and conductive agent, stripping active substance from current collector, and recovering cobalt from the current collector with sulfurAcid and reducing agent (H)2O2Or Na2S2O3·5H2O) reductive acid leaching of active material containing lithium cobaltate to leach Co2+And Li+Then recovering cobalt and lithium metal by precipitation treatment. Chinese patent (CN 101509071A) discloses a method for recovering valuable metals from lithium batteries containing Co, Ni and Mn, which adopts hydrochloric acid with the concentration of more than 250g/L or sulfuric acid with the concentration of 200g/L and hydrogen peroxide solution with the concentration of 20g/L to extract Co by reductive acid leaching at the temperature of 80 DEG C2+、Ni2+、Mn2+And Li+. Chinese patent (CN 10906320A) describes a method for recovering Co and Li from waste lithium battery by using ethanol as reducing agent, and the main research of the method is that lithium cobaltate powder is added into leaching solution (sulfuric acid and ethanol mixed solution) in the pretreatment stage, mechanical stirring is added under the condition of 80-90 ℃ for leaching, and Co is added2+And Li+The precipitation extraction is carried out respectively. In the above technology, although the leaching method for recovering valuable components in lithium ion batteries has a high leaching rate, the method also has the disadvantages that the leaching is not negligible, for example, a large amount of acid is introduced in the leaching process, so that the treatment cost and the treatment difficulty of tail liquid are greatly increased, wherein when hydrochloric acid is adopted to dissolve lithium cobaltate cathode materials, toxic and harmful gases (chlorine) are released, and the environment is seriously polluted; although the sulfuric acid + reducing agent process is feasible, the treatment cost is high due to the large consumption of the reducing agent.
(2) Recovery by pyrogenic process
Chinese patent (CN 101054631A) discloses a method for recovering valuable components from a failed lithium ion battery, and mainly introduces the treatment of discharging, high-temperature roasting, crushing, magnetic separation and recovery of the failed lithium ion battery, wherein the roasting temperature range is 400-1000 ℃, the granularity after crushing is 0.5-5 mm, and the separation and recovery of the sieved materials are realized under the action of a strong magnetic field.
Chinese patent (CN 103178315A) discloses a resource recovery technology of waste lithium ion batteries, after the waste batteries are discharged and treated at high temperature, ammonium sulfate and active substances are added according to a certain proportion for roasting, roasting reaction is carried out at the roasting temperature of 400 ℃, valuable metal elements exist in the form of sulfate, and then hydrochloric acid is used for dissolving and filtering to obtain filtrate for extraction, precipitation and collection. The method can reduce the consumption of acid during dissolution, but sulfate obtained after roasting is consolidated to different degrees, and the obtained material has large granularity and uneven distribution, which greatly reduces the subsequent leaching efficiency.
In summary, the common problems faced by the extraction and recovery of valuable components in the waste lithium ion battery materials at present include: (1) chemical reagents such as acid and alkali are consumed greatly in the leaching and recycling process, and the generated waste liquid is difficult to treat; (2) the energy consumption caused by the high temperature condition in the pyrogenic process recovery process is large, and the selective extraction rate is low; (3) the process flow is long and the operation is complex. Therefore, it is highly desirable to develop an efficient, green, low-cost, short-flow treatment process.
Disclosure of Invention
Aiming at the defects of the prior art, the invention provides a method for recovering cobalt and lithium metals from waste lithium cobalt acid batteries, which comprises the steps of treating lithium cobalt acid cathode materials by adopting an enhanced ammonia roasting method to obtain sulfate which is easy to dissolve in water, carrying out enhanced ammonia roasting by relying on a high-temperature ball mill, recycling ammonia gas generated in the enhanced ammonia roasting process, and carrying out high-recognition separation and resource recovery on the lithium cobalt acid cathode materials by an extraction method and a precipitation method.
The technical scheme of the invention is realized as follows:
a method for recovering cobalt and lithium metal from waste lithium cobalt oxide batteries comprises the following specific steps:
(1) performing discharge treatment on the waste lithium cobaltate battery, and obtaining black lithium cobaltate powder after disassembling, crushing, pyrolyzing and screening;
(2) black obtained in the step (1)Mixing lithium cobaltate powder and ammonium salt according to the molar ratio of 1: 1.5-4, placing the mixture in a high-temperature ball mill for carrying out enhanced ammonia roasting at the ball milling speed of 70-90 rpm, the ball milling heat preservation temperature of 280-550 ℃, the ball milling heat preservation time of 2-6 h and the ball material mass ratio of 10-20: 1 to convert lithium cobaltate into sulfate, and soaking in water to obtain the Co-rich cobalt2+、Li+The leaching solution is used for recovering ammonia gas generated in the process, and the ammonia gas is recovered in the form of ammonium sulfate and recycled;
(3) the Co-rich obtained in the step (2)2+、Li+The leaching solution is used for selectively recovering cobalt and lithium components, firstly, an organic extracting agent is used for recovering cobalt, then, a precipitation method is used for recovering lithium in residual liquid, and the lithium is recovered in a lithium carbonate form.
Preferably, in the step (1), the waste lithium cobalt oxide battery is immersed into a NaCl solution with a concentration of 10% -40% for self-discharge treatment, the discharged waste lithium cobalt oxide battery is manually disassembled or mechanically crushed to obtain a positive electrode material, the positive electrode material is placed in a muffle furnace for calcination treatment, the calcination temperature is 500-700 ℃, the calcination time is 2-4 h, the calcination process is to pyrolyze the binder, the conductive agent and the electrolyte on the positive electrode material under a high temperature condition to peel the lithium cobalt oxide active substance from the current collector, and then the black lithium cobalt oxide powder is obtained by screening.
Preferably, the ammonium salt in the step (2) is (NH)4)2SO4And or NH4HSO4The ball milling speed is 80 rpm.
Preferably, in the step (2), ammonia gas is generated in the roasting process of the enhanced ammonia process, 3% -7% of dilute sulfuric acid is used for absorbing the ammonia gas to obtain a solution of ammonium sulfate and ammonium bisulfate, the solution of ammonium sulfate and ammonium bisulfate obtained by capturing the ammonia gas is concentrated and crystallized to obtain ammonium sulfate and ammonium bisulfate crystals, and the ammonium sulfate and ammonium bisulfate crystals are used as an ammonia source to be applied to the roasting process of the enhanced ammonia process, so that the closed-loop cyclic utilization of the ammonia gas is realized.
Preferably, in the step (2), the sulfate product after the ammonia-strengthening roasting is immersed in distilled water for dissolution, and the temperature of the immersion is 40 DEGLeaching for 1-5 h at-90 ℃, selecting the solid-liquid mass ratio of 1: 6-20, performing ultrasonic treatment simultaneously in the water leaching process, wherein the ultrasonic frequency is 100Hz, so that sulfate is completely dissolved, and the obtained leaching solution mainly comprises Co2+、Li+、SO4 2-、H+、OH-、NH4 +。
Preferably, in the step (3), the pH of the leaching solution is controlled to be 4.2, and an organic extractant is added to extract Co2+The volume ratio of the leaching solution to the organic extractant is 1: 1-2, and then the Co in the organic extractant is back extracted by adopting a dilute acid solution2+The volume ratio of the organic extractant to the dilute acid solution is 1: 5-8, and cobalt is precipitated in the form of cobalt sulfate through concentration treatment; and then adding an alkali solution into the extracted residual solution to adjust the pH value of the residual solution to 8-10, simultaneously adding a precipitator to react with lithium ions to generate lithium carbonate precipitate, wherein the molar ratio of the precipitator to the lithium ions is 1.5:1, filtering, washing and drying to obtain lithium carbonate crystals, performing ICP-OES detection on the filtrate obtained after filtering to detect that the residual cobalt concentration and the residual lithium concentration meet the national sewage discharge standard, adjusting the filtrate to be neutral, and discharging the filtrate, thus finishing the operation.
Preferably, the organic extractant in the step (3) is one or more of P204, Cyanex272, P507 and sulfonated kerosene.
Preferably, the diluted acid solution in the step (3) is a diluted sulfuric acid solution or a diluted hydrochloric acid solution.
Preferably, the alkali solution in the step (3) is one or more of a NaOH solution, ammonia water and urea.
Preferably, the precipitant in step (3) is one or more of sodium carbonate solution, sodium bicarbonate solution and potassium carbonate solution.
The invention has the following beneficial effects:
(1) according to the method, the sulfate which is easy to dissolve in water is obtained by treating the lithium cobaltate positive electrode material by using the enhanced ammonia roasting method, so that the use of a large amount of acid solution in the leaching process can be avoided, the recovery cost is reduced, and the problem of environmental pollution caused by the leaching solution is solved.
Compared with the prior art, the method comprises the steps of firstly obtaining the anode material through discharging, disassembling, crushing, pyrolyzing and screening; compared with the prior art, the valuable components of cobalt and lithium are fully extracted by adopting an enhanced ammonia roasting method and water leaching, so that the secondary pollution is avoided while the high extraction efficiency is ensured; the selective recovery of cobalt and lithium can be ensured by the organic combination of the extraction method and the precipitation method. The invention has obvious innovation, feasibility and foresight, has outstanding economic, social and environmental benefits, and can be widely applied to the fields of metallurgy, waste lithium ion battery recovery, resource recycling and the like.
(2) The invention relies on a high-temperature ball mill to carry out the roasting by the intensified ammonia method, can reduce the roasting temperature, refine the particle size, improve the roasting capability under the coupling action of a mechanical force field and a thermal field, reduce the reaction energy consumption and realize the integration of short flow.
Compared with the prior art, the invention provides a pyrogenic process treatment method with additional mechanical force, which is characterized in that a positive electrode material is obtained by pretreating waste lithium cobaltate batteries, and the high-temperature ball mill is used for carrying out enhanced ammonia roasting treatment, so that valuable components in the positive electrode material exist in a sulfate form, and the valuable components are extracted and recovered after water immersion, extraction and precipitation treatment.
(3) The invention recycles the ammonia gas generated in the roasting process of the ammonia strengthening method, constructs the closed loop circulation of ammonium sulfate and avoids the pollution to the environment.
Compared with the prior art, the invention carries out resource utilization on cobalt and lithium elements in the anode material of the lithium cobalt oxide lithium ion battery. Firstly, performing discharge treatment on a waste lithium ion battery, and then performing disassembly, breaking, pyrolysis and screening to obtain a black powdery positive electrode material lithium cobaltate; then mixing the obtained waste lithium cobaltate material and ammonium salt according to a certain proportion, transferring the mixture into a ball milling tank, placing the ball milling tank into a high-temperature ball mill, roasting the mixture by an enhanced ammonia method, and endowing the mixture with valuable elements in lithium cobaltateIn the corresponding sulfate, the sulfate is soaked in water to obtain the product rich in Co2+、Li+In addition, ammonia gas generated after the ammonia-strengthening roasting is synchronously recovered to prepare ammonium sulfate, so that closed-loop circulation of the ammonium sulfate is realized.
(4) And performing high-recognition separation and resource recovery on the lithium cobaltate cathode material by an extraction method and a precipitation method.
Compared with the prior art, the method selectively recovers the cobalt and lithium components by utilizing an extraction method and a coprecipitation method, and meets the requirements of recovering valuable metals of the waste lithium ion battery with low consumption, high efficiency and short flow.
Drawings
FIG. 1 is a process flow diagram of the present invention for recovering cobalt and lithium from waste lithium cobalt oxide batteries.
Detailed Description
For a more clear understanding of the technical features, objects and advantages of the present invention, reference is now made to the following detailed description of the embodiments of the present invention taken in conjunction with the accompanying drawings, which are included to illustrate and not to limit the scope of the present invention.
The test methods described in the following examples are all conventional methods unless otherwise specified; the reagents and materials are commercially available, unless otherwise specified.
The ball mill used in the following examples is called a high temperature ball mill, which is obtained by winding a heating resistance wire around the outside of a commercially available ball mill crucible, and is equipped with a corresponding power supply and a temperature control device, and has a heating function and a temperature control function. The high-temperature ball mill has two functions of heating and calcining and mechanical ball milling, a heating body is introduced to the outer side of the ball mill tank body to serve as a heat source, the ball milling heat preservation temperature is controlled through a temperature control program, and the ball milling rotating speed is controlled and adjusted by changing the current frequency. The high temperature ball mill can be selected from a vibration type ball mill and a rotary type ball mill, and the material of the ball milling tank is at least one of alumina, zirconia and calcium carbide. The ball-to-feed ratio refers to the ratio of the mass of the grinding balls to the mass of the raw material.
Example 1
A method for recovering cobalt and lithium metal from waste lithium cobalt oxide batteries comprises the following specific steps:
(1) the method comprises the steps of immersing a waste lithium cobalt oxide battery (in the field of electronic communication) into a NaCl solution with the concentration of 10% for self-discharge treatment, preventing explosion caused by short circuit of the battery in subsequent operation, manually disassembling or mechanically crushing the discharged waste lithium cobalt oxide battery to obtain different parts including a positive electrode, a negative electrode, a diaphragm and a battery shell, placing a positive electrode material in a muffle furnace for calcination treatment under the conditions of air atmosphere, calcination temperature of 500 ℃ and calcination time of 2 hours, wherein in the calcination process, a binder, a conductive agent and an electrolyte on the positive electrode material are pyrolyzed under the high-temperature condition, so that active substances of lithium cobalt oxide can be stripped from a current collector, and then screening to obtain black lithium cobalt oxide powder;
(2) mixing the black lithium cobaltate powder obtained in the step (1) with (NH)4)2SO4Mixing according to the molar ratio of 1:2, placing the mixture into a high-temperature ball mill for low-temperature enhanced ammonia roasting at the ball milling speed of 80rpm, the ball milling heat preservation temperature of 280 ℃ and the ball milling heat preservation time of 2 hours, wherein the ball material ratio is 10:1, and realizing the enhanced ammonia roasting reaction under the actions of calcining, grinding and uniform mixing of the high-temperature ball mill, so that the reaction rate is improved, the reaction energy consumption is reduced, and lithium cobaltate is converted into sulfate which is easy to dissolve in water, has small particle size and uniform components; in addition, the solution of ammonium sulfate and ammonium bisulfate obtained by trapping the ammonia gas is concentrated and crystallized to obtain ammonium sulfate and ammonium bisulfate crystals, and the ammonium sulfate and ammonium bisulfate crystals can be used as an ammonia source to be applied to the roasting process of the enhanced ammonia method, so that the closed-loop cyclic utilization of the ammonia gas is realized; soaking the sulfate product after ammonia-enhanced roasting in distilled water for dissolving, soaking for 5h at 40 deg.C, selecting solid-liquid mass ratio of 1:8, simultaneously performing ultrasonic treatment in water soaking process at 100Hz to completely dissolve the sulfate, wherein the obtained leaching solution mainly comprises Co2+、Li+、SO4 2-、H+、OH-、NH4 +And analyzing to obtain the leaching rates of the valuable elements as follows: 95.66% of cobalt and 90.12% of lithium;
(3) will obtain a Co-rich product from step (2)2+、Li+The leaching solution is a mother liquor, and ions contained in the leaching solution comprise Co2 +、Li+、SO4 2-、H+、OH-、NH4 +Controlling the pH value of the leaching solution to be 4.2 and adding an organic extractant P204 with strong selectivity to extract Co2 +The volume ratio of the leaching solution to the organic extractant is 1:1, and then the Co in the organic extractant P204 is back extracted by adopting dilute sulfuric acid solution2+The volume ratio of the organic extracting agent to the dilute sulfuric acid solution is 1:5, and cobalt is precipitated in a cobalt sulfate form through concentration treatment; and then adding an alkali solution (NaOH solution) into the extracted residual solution to adjust the pH value of the residual solution to 8, simultaneously adding a precipitator sodium carbonate solution to react with lithium ions to generate lithium carbonate precipitate, wherein the molar ratio of the precipitator to the lithium ions is 1.5:1, filtering, washing and drying to obtain lithium carbonate crystals, and performing ICP-OES detection on the filtered filtrate to detect that the concentration of residual cobalt is 1.5mg/L and the concentration of residual lithium is 0.56mg/L, so that the national sewage discharge standard is met, and the filtrate is adjusted to be neutral and then discharged, so that the cobalt and lithium metals in the waste lithium cobaltate ion battery can be selectively recovered at low cost, in a short process, and in a green environment.
Example 2
A method for recovering cobalt and lithium metal from waste lithium cobalt oxide batteries comprises the following specific steps:
(1) the method comprises the steps of immersing a waste lithium cobalt oxide battery (in the field of power automobiles) into a NaCl solution with the concentration of 20% for self-discharge treatment, preventing explosion caused by short circuit of the battery in subsequent operation, manually disassembling or mechanically crushing the discharged waste lithium cobalt oxide battery to obtain different parts including a positive electrode, a negative electrode, a diaphragm and a battery shell, placing a positive electrode material in a muffle furnace for calcination treatment under the conditions of air atmosphere, calcination temperature of 600 ℃ and calcination time of 3 hours, wherein in the calcination process, a binder, a conductive agent and an electrolyte on the positive electrode material are pyrolyzed under the high-temperature condition, so that active substances of lithium cobalt oxide can be stripped from a current collector, and then screening to obtain black lithium cobalt oxide powder;
(2) mixing the black lithium cobaltate powder obtained in the step (1) with (NH)4)2SO4(mixing according to the proportion of 1:3, placing the mixture in a high-temperature ball mill for low-temperature enhanced ammonia roasting with the ball milling speed of 80rpm, the ball milling heat preservation temperature of 320 ℃, the ball milling heat preservation time of 4 hours and the ball material ratio of 15: 1. realizing the enhanced ammonia roasting reaction under the actions of calcining, grinding and uniform mixing of the high-temperature ball mill, improving the reaction rate, reducing the reaction energy consumption, converting lithium cobaltate into sulfate which is easy to dissolve in water and has small granularity and uniform components, generating a certain amount of ammonia gas in the enhanced ammonia roasting process, absorbing the ammonia gas by using 5 percent of dilute sulfuric acid to obtain a solution of ammonium sulfate and ammonium bisulfate, preventing the environment from being polluted, concentrating and crystallizing the solution of the ammonium sulfate and the ammonium bisulfate obtained by capturing the ammonia gas to obtain ammonium sulfate and ammonium bisulfate crystals, and applying the ammonium sulfate and ammonium bisulfate crystals as an ammonia source to the enhanced ammonia roasting process, realizing closed-loop cyclic utilization of ammonia gas; soaking the sulfate product after ammonia-enhanced roasting in distilled water for dissolving, soaking at 50 deg.C for 3 hr, selecting solid-liquid mass ratio of 1:10, simultaneously performing ultrasonic treatment in water soaking process at 100Hz to completely dissolve the sulfate, wherein the obtained leaching solution mainly comprises Co2+、Li+、SO4 2-、H+、OH-、NH4 +And analyzing to obtain the leaching rates of the valuable elements as follows: 97.5% of cobalt and 91.22% of lithium;
(3) will obtain a Co-rich product from step (2)2+、Li+The leaching solution is a mother liquor, and ions contained in the leaching solution comprise Co2 +、Li+、SO4 2-、H+、OH-、NH4 +Controlling the pH value of the leaching solution to be 4.2 and adding an organic extractant Cyanex272 with strong selectivity to extract Co2+The volume ratio of the leaching solution to the organic extractant is 1:1.2, and then dilute sulfuric acid solution is adopted for back extractionCo in organic extractant Cyanex2722+The volume ratio of the organic extracting agent to the dilute sulfuric acid solution is 1:6, and cobalt is precipitated in a cobalt sulfate form through concentration treatment; and then adding an alkali solution (ammonia water) into the extracted residual liquid to adjust the pH value of the residual liquid to 9, simultaneously adding a precipitator (a sodium carbonate solution and a sodium bicarbonate solution react with lithium ions according to a volume ratio of 2:1) to generate a lithium carbonate precipitate, wherein the molar ratio of the precipitator to the lithium ions is 1.5:1, filtering, washing and drying to obtain lithium carbonate crystals, and performing ICP-OES detection on the filtered filtrate to detect that the residual cobalt concentration is 1.03mg/L and the residual lithium concentration is 0.55mg/L, so that the national sewage discharge standard is met, and the filtrate is adjusted to be neutral and then discharged, so that the cobalt and lithium metals in the waste lithium cobaltate ion battery can be selectively recovered with low cost, short flow, green and high efficiency.
Example 3
A method for recovering cobalt and lithium metal from waste lithium cobalt oxide batteries comprises the following specific steps:
(1) the method comprises the steps of immersing a waste lithium cobalt oxide battery (in the field of infrastructure) into a NaCl solution with the concentration of 30% for self-discharge treatment, preventing explosion caused by short circuit of the battery in subsequent operation, manually disassembling or mechanically crushing the discharged waste lithium cobalt oxide battery to obtain different parts including a positive electrode, a negative electrode, a diaphragm and a battery shell, placing a positive electrode material in a muffle furnace for calcination treatment, wherein the calcination temperature is 650 ℃ and the calcination time is 4 hours, and the calcination process leads a binder, a conductive agent and an electrolyte on the positive electrode material to be pyrolyzed under the high-temperature condition, so that the active substances of lithium cobalt oxide can be stripped from a current collector, and then screening to obtain black lithium cobalt oxide powder;
(2) mixing the black lithium cobaltate powder obtained in the step (1) with (NH)4)2SO4Mixing according to the molar ratio of 1:3.5, placing the mixture into a high-temperature ball mill for low-temperature ammonia-enhanced roasting at the ball-milling speed of 90rpm and the ball-milling heat preservation temperature of 400 ℃ for 4h, wherein the ball-material ratio is 20:1, and realizing the enhanced ammonia-enhanced roasting reaction under the actions of calcining, grinding and uniform mixing of the high-temperature ball mill to improve the reverse reactionThe reaction rate is increased, the reaction energy consumption is reduced, and lithium cobaltate is converted into sulfate which is easily dissolved in water, has small granularity and uniform components; in addition, the solution of ammonium sulfate and ammonium bisulfate obtained by trapping the ammonia gas is concentrated and crystallized to obtain ammonium sulfate and ammonium bisulfate crystals, and the ammonium sulfate and ammonium bisulfate crystals can be used as an ammonia source to be applied to the roasting process of the enhanced ammonia method, so that the closed-loop cyclic utilization of the ammonia gas is realized; soaking the sulfate product after ammonia-enhanced roasting in distilled water for dissolving, soaking at 70 deg.C for 4 hr, selecting solid-liquid mass ratio of 1:15, simultaneously performing ultrasonic treatment in water soaking process at 100Hz to completely dissolve the sulfate, wherein the obtained leaching solution mainly comprises Co2+、Li+、SO4 2-、H+、OH-、NH4 +And analyzing to obtain the leaching rates of the valuable elements as follows: 98.76% of cobalt and 95.33% of lithium;
(3) will obtain a Co-rich product from step (2)2+、Li+The leaching solution is a mother liquor, and ions contained in the leaching solution comprise Co2 +、Li+、SO4 2-、H+、OH-、NH4 +Controlling the pH value of the leaching solution to be 4.2, and adding an organic extracting agent with strong selectivity (Cyanex272 and sulfonated kerosene are mixed according to the volume ratio of 1: 1) to extract Co2+The volume ratio of the leaching solution to the organic extractant is 1:1.4, and then dilute hydrochloric acid solution is adopted to back extract Co in the organic extractant2+The volume ratio of the organic extracting agent to the dilute sulfuric acid solution is 1:7, and cobalt is precipitated in a cobalt sulfate form through concentration treatment; then adding alkali solution (urea) into the extracted residual solution to adjust the pH value of the residual solution to 10, simultaneously adding precipitator potassium carbonate solution to react with lithium ions to generate lithium carbonate precipitate, wherein the molar ratio of the precipitator to the lithium ions is 1.5:1, filtering, washing and drying to obtain lithium carbonate crystals, carrying out ICP-OES detection on the filtrate obtained after filtering to detect that the concentration of residual cobalt is 0.87mg/L,the concentration of residual lithium is 0.27mg/L, and meets the national sewage discharge standard, so that the filtrate is adjusted to be neutral and then discharged, and thus the low-cost, short-flow, green and efficient selective recovery of cobalt and lithium metals in the waste lithium cobaltate ion battery can be realized.
Example 4
A method for recovering cobalt and lithium metal from waste lithium cobalt oxide batteries comprises the following specific steps:
(1) the method comprises the steps of immersing a waste lithium cobalt oxide battery (in the field of information engineering) into a NaCl solution with the concentration of 40% for self-discharge treatment, preventing explosion caused by short circuit of the battery in subsequent operation, manually disassembling or mechanically crushing the discharged waste lithium cobalt oxide battery to obtain different parts including a positive electrode, a negative electrode, a diaphragm and a battery shell, placing a positive electrode material in a muffle furnace for calcination treatment under the conditions of air atmosphere, calcination temperature of 700 ℃ and calcination time of 3 hours, wherein in the calcination process, a binder, a conductive agent and an electrolyte on the positive electrode material are pyrolyzed under the high-temperature condition, so that active substances of lithium cobalt oxide can be stripped from a current collector, and then screening to obtain black lithium cobalt oxide powder;
(2) mixing the black lithium cobaltate powder obtained in the step (1) with NH4HSO4Mixing according to the molar ratio of 1:4, placing the mixture into a high-temperature ball mill for low-temperature enhanced ammonia roasting at the ball milling speed of 70rpm, the ball milling heat preservation temperature of 500 ℃ for 3h, wherein the ball milling heat preservation time is 15:1, and realizing the enhanced ammonia roasting reaction under the actions of calcining, grinding and uniform mixing of the high-temperature ball mill to improve the reaction rate and reduce the reaction energy consumption so that lithium cobaltate is converted into sulfate which is easy to dissolve in water and has small particle size and uniform components; in addition, the solution of ammonium sulfate and ammonium bisulfate obtained by trapping the ammonia gas is concentrated and crystallized to obtain ammonium sulfate and ammonium bisulfate crystals, and the ammonium sulfate and ammonium bisulfate crystals can be used as an ammonia source to be applied to the roasting process of the enhanced ammonia method, so that the closed-loop cyclic utilization of the ammonia gas is realized; the sulfate product after the roasting by the enhanced ammonia method is immersed in distilled water for dissolving,leaching for 4h at 90 deg.C, selecting solid-liquid mass ratio of 1:15, performing ultrasonic treatment simultaneously in water leaching process at 100Hz to completely dissolve sulfate, wherein the obtained leaching solution mainly comprises Co2+、Li+、SO4 2-、H+、OH-、NH4 +And analyzing to obtain the leaching rates of the valuable elements as follows: 98.90% of cobalt and 96.12% of lithium;
(3) will obtain a Co-rich product from step (2)2+、Li+The leaching solution is a mother liquor, and ions contained in the leaching solution comprise Co2 +、Li+、SO4 2-、H+、OH-、NH4 +Controlling the pH value of the leaching solution to be 4.2, and adding an organic extracting agent with strong selectivity (P507 and sulfonated kerosene are mixed according to the volume ratio of 1: 2) to extract Co2+The volume ratio of the leaching solution to the organic extractant is 1:1.6, and then the Co in the organic extractant is back extracted by adopting dilute sulfuric acid solution2+The volume ratio of the organic extracting agent to the dilute sulfuric acid solution is 1:7.5, and cobalt is precipitated in a cobalt sulfate form through concentration treatment; then, adding an alkali solution (20% of NaOH solution and industrial ammonia water are added according to the volume ratio of 2:1) into the extracted residual solution to adjust the pH value of the residual solution to 9, simultaneously adding a precipitator sodium carbonate solution to react with lithium ions to generate lithium carbonate precipitate, wherein the molar ratio of the precipitator to the lithium ions is 1.5:1, filtering, washing and drying to obtain lithium carbonate crystals, and performing ICP-OES detection on the filtered filtrate to detect that the concentration of residual cobalt is 0.85mg/L and the concentration of residual lithium is 0.25mg/L, so that the national sewage discharge standard is met, and the filtrate is adjusted to be neutral and then discharged, so that the low-cost, short-flow, green and efficient selective recovery of cobalt and lithium metals in the waste lithium cobalt oxide ion battery can be realized.
Example 5
A method for recovering cobalt and lithium metal from waste lithium cobalt oxide batteries comprises the following specific steps:
(1) the method comprises the steps of immersing a waste lithium cobalt oxide battery (in the aerospace field) into a NaCl solution with the concentration of 25% for self-discharge treatment, preventing explosion caused by short circuit of the battery in subsequent operation, manually disassembling or mechanically crushing the discharged waste lithium cobalt oxide battery to obtain different parts including a positive electrode, a negative electrode, a diaphragm and a battery shell, placing a positive electrode material in a muffle furnace for calcination treatment, wherein the calcination temperature is 550 ℃ and the calcination time is 2 hours, and the calcination process leads a binder, a conductive agent and an electrolyte on the positive electrode material to be pyrolyzed under the high-temperature condition, so that active substances of lithium cobalt oxide can be stripped from a current collector, and then screening to obtain black lithium cobalt oxide powder;
(2) mixing the black lithium cobaltate powder obtained in the step (1) with ammonium salt ((NH)4)2SO4And NH4HSO4Mixing according to the mass ratio of 1: 1) according to the molar ratio of 1:3, placing the mixture into a high-temperature ball mill for low-temperature enhanced ammonia roasting at the ball-milling speed of 80rpm and the ball-milling heat preservation temperature of 550 ℃ for 3 hours, wherein the ball-milling heat preservation time is 20:1, and under the actions of calcining, grinding and uniform mixing of the high-temperature ball mill, the enhanced ammonia roasting reaction is realized, so that the reaction rate is increased, the reaction energy consumption is reduced, and lithium cobaltate is converted into sulfate which is easily soluble in water and has small particle size and uniform components; in addition, the solution of ammonium sulfate and ammonium bisulfate obtained by trapping the ammonia gas is concentrated and crystallized to obtain ammonium sulfate and ammonium bisulfate crystals, and the ammonium sulfate and ammonium bisulfate crystals can be used as an ammonia source to be applied to the roasting process of the enhanced ammonia method, so that the closed-loop cyclic utilization of the ammonia gas is realized; soaking the sulfate product after ammonia-enhanced roasting in distilled water for dissolving, soaking at 75 deg.C for 3 hr, selecting solid-liquid mass ratio of 1:20, simultaneously performing ultrasonic treatment in water soaking process at 100Hz to completely dissolve the sulfate, wherein the obtained leaching solution mainly comprises Co2+、Li+、SO4 2-、H+、OH-、NH4 +And analyzing to obtain the leaching rates of the valuable elements as follows: 95.69% of cobalt and 93.30% of lithium;
(3) will obtain a Co-rich product from step (2)2+、Li+The leaching solution is a mother liquor, and ions contained in the leaching solution comprise Co2 +、Li+、SO4 2-、H+、OH-、NH4 +Controlling the pH value of the leaching solution to be 4.2, and adding an organic extracting agent with strong selectivity (P204, P507 and sulfonated kerosene are mixed according to the volume ratio of 1:1: 1) to extract Co2+The volume ratio of the leaching solution to the organic extractant is 1:1.8, and then the Co in the organic extractant is back extracted by adopting dilute sulfuric acid solution2+The volume ratio of the organic extracting agent to the dilute sulfuric acid solution is 1:8, and cobalt is precipitated in a cobalt sulfate form through concentration treatment; then, adding an alkali solution (a 20% NaOH solution and industrial ammonia water are added according to the volume ratio of 3: 1) into the extracted residual solution to adjust the pH value of the residual solution to 10, simultaneously adding a precipitator sodium carbonate solution to react with lithium ions to generate lithium carbonate precipitate, wherein the molar ratio of the precipitator to the lithium ions is 1.5:1, filtering, washing and drying to obtain lithium carbonate crystals, and performing ICP-OES detection on the filtered filtrate to detect that the concentration of residual cobalt is 0.10mg/L and the concentration of residual lithium is 0.86mg/L, so that the national sewage discharge standard is met, and the filtrate is adjusted to be neutral and then discharged, so that the low-cost, short-flow, green and efficient selective recovery of cobalt and lithium metals in the waste lithium cobalt oxide ion battery can be realized.
Comparative example 1
With the raw materials and method of example 2, the only difference is that step (2) the mix is placed in a muffle furnace for (non-intensified) ammonia roasting, unlike a high temperature ball mill, in which the muffle furnace only provides the roasting function during the ammonia roasting process, without the introduction of mechanical forces, which reduces the roasting efficiency to some extent. The leaching rate of each valuable element obtained by analysis is respectively as follows: 82.5 percent of cobalt and 75.62 percent of lithium, and the leaching rates are lower than those of 97.5 percent of cobalt and 91.22 percent of lithium in example 2.
The above embodiments are merely provided to help understand the method and core principle of the present invention, and the main steps and embodiments of the present invention are described in detail by using specific examples. To those skilled in the art, the various conditions and parameters may be varied as desired in a particular implementation in accordance with the principles of the invention, and in view of the foregoing, the description is not to be taken as limiting the invention.
Claims (10)
1. A method for recovering cobalt and lithium metal from waste lithium cobalt oxide batteries is characterized by comprising the following steps: the method comprises the following specific steps:
(1) performing discharge treatment on the waste lithium cobaltate battery, and obtaining black lithium cobaltate powder after disassembling, crushing, pyrolyzing and screening;
(2) mixing the black lithium cobaltate powder obtained in the step (1) with ammonium salt according to the molar ratio of 1: 1.5-4, placing the mixture in a high-temperature ball mill for roasting by an enhanced ammonia method, wherein the ball milling speed is 70-90 rpm, the ball milling heat preservation temperature is 280-550 ℃, the ball milling heat preservation time is 2-6 h, the ball material mass ratio is 10-20: 1, so that lithium cobaltate is converted into sulfate, and obtaining Co-rich cobalt after water immersion2+、Li+The leaching solution is used for recovering ammonia gas generated in the process, and the ammonia gas is recovered in the form of ammonium sulfate and recycled;
(3) the Co-rich obtained in the step (2)2+、Li+The leaching solution is used for selectively recovering cobalt and lithium components, firstly, an organic extracting agent is used for recovering cobalt, then, a precipitation method is used for recovering lithium in residual liquid, and the lithium is recovered in a lithium carbonate form.
2. The method for recovering cobalt and lithium metal from waste lithium cobaltate batteries as claimed in claim 1, wherein the method comprises the following steps: in the step (1), the waste lithium cobalt oxide battery is immersed into a NaCl solution with the concentration of 10% -40% for self-discharge treatment, the discharged waste lithium cobalt oxide battery is manually disassembled or mechanically crushed to obtain a positive electrode material, the positive electrode material is placed in a muffle furnace for calcination treatment, the calcination temperature is 500-700 ℃, the calcination time is 2-4 h, the calcination process is used for pyrolyzing a binder, a conductive agent and an electrolyte on the positive electrode material under the high-temperature condition to strip lithium cobalt oxide active substances from a current collector, and then the black lithium cobalt oxide powder is obtained by screening.
3. The method for recovering cobalt and lithium metal from waste lithium cobaltate batteries as claimed in claim 1, wherein the method comprises the following steps: the ammonium salt in the step (2) is (NH)4)2SO4And or NH4HSO4(ii) a The ball milling speed was 80 rpm.
4. The method for recovering cobalt and lithium metal from waste lithium cobaltate batteries as claimed in claim 1, wherein the method comprises the following steps: and (3) ammonia gas is generated in the roasting process of the enhanced ammonia method in the step (2), 3% -7% of dilute sulfuric acid is used for absorbing the ammonia gas to obtain a solution of ammonium sulfate and ammonium bisulfate, the solution of the ammonium sulfate and the ammonium bisulfate obtained by trapping the ammonia gas is concentrated and crystallized to obtain ammonium sulfate and ammonium bisulfate crystals, and the ammonium sulfate and the ammonium bisulfate crystals are used as an ammonia source to be applied to the roasting process of the enhanced ammonia method, so that the closed-loop cyclic utilization of the ammonia gas is realized.
5. The method for recovering cobalt and lithium metal from waste lithium cobaltate batteries as claimed in claim 1, wherein the method comprises the following steps: in the step (2), the sulfate product after the ammonia-enhanced roasting is immersed in distilled water for dissolving, the sulfate product is immersed for 1 to 5 hours at the immersion temperature of 40 to 90 ℃, the solid-liquid mass ratio is 1:6 to 20, ultrasonic treatment is simultaneously carried out in the immersion process, the ultrasonic frequency is 100Hz, so that the sulfate is completely dissolved, and the obtained immersion liquid mainly comprises Co2+、Li+、SO4 2-、H+、OH-、NH4 +。
6. The method for recovering cobalt and lithium metal from waste lithium cobaltate batteries as claimed in claim 1, wherein the method comprises the following steps: controlling the pH value of the leaching solution to be 4.2 in the step (3) and adding an organic extractant to extract Co2+The volume ratio of the leaching solution to the organic extractant is 1: 1-2, and then the Co in the organic extractant is back extracted by adopting a dilute acid solution2+The organic extractant and the dilute acid solution are mixed according to the volume ratio of 1: 5-8The cobalt is separated out in the form of cobalt sulfate through the over-concentration treatment; and then adding an alkali solution into the extracted residual solution to adjust the pH value of the residual solution to 8-10, simultaneously adding a precipitator to react with lithium ions to generate lithium carbonate precipitate, wherein the molar ratio of the precipitator to the lithium ions is 1.5:1, filtering, washing and drying to obtain lithium carbonate crystals, carrying out ICP-OES detection on the filtrate obtained after filtering to detect that the concentration of residual cobalt and the concentration of residual lithium meet the national sewage discharge standard, adjusting the filtrate to be neutral, and discharging the filtrate, thus finishing the operation.
7. The method for recovering cobalt and lithium metal from waste lithium cobaltate batteries as claimed in claim 6, wherein the method comprises the following steps: the organic extracting agent in the step (3) is one or more of P204, Cyanex272, P507 and sulfonated kerosene.
8. The method for recovering cobalt and lithium metal from waste lithium cobaltate batteries as claimed in claim 6, wherein the method comprises the following steps: and (4) in the step (3), the dilute acid solution is dilute sulfuric acid solution or dilute hydrochloric acid solution.
9. The method for recovering cobalt and lithium metal from waste lithium cobaltate batteries as claimed in claim 6, wherein the method comprises the following steps: and (3) the alkali solution is one or more of NaOH solution, ammonia water and urea.
10. The method for recovering cobalt and lithium metal from waste lithium cobaltate batteries as claimed in claim 6, wherein the method comprises the following steps: and (3) the precipitator is one or more of a sodium carbonate solution, a sodium bicarbonate solution and a potassium carbonate solution.
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