CN111430830B - Method for recovering valuable components in positive electrode of waste lithium battery based on molten salt system - Google Patents
Method for recovering valuable components in positive electrode of waste lithium battery based on molten salt system Download PDFInfo
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Abstract
The invention provides a method for recovering valuable components in a waste lithium battery anode based on a molten salt system. The invention can realize that the anode aluminum current collector adopts Al (OH)3Directly recycling, and simultaneously recycling the valuable elements Li, Ni, Co and Mn in the anode in full.
Description
Technical Field
The invention belongs to the technical field of lithium battery recovery, and particularly relates to a method for selectively recovering a waste power lithium battery anode material.
Background
In the important period of rapid development of new energy vehicles in China, a power battery is a core component of the new energy vehicles, and a lithium ion battery is considered to be the first choice of the power battery of the vehicles due to the advantages of high energy density, high power density, long cycle life, environmental friendliness and the like. With the rapid industrialization of new energy vehicles, the sales volume of the new energy vehicles will be leaped forward, and the reserve volume of the lithium ion power batteries will also increase in geometric progression. Meanwhile, the environmental pollution problem and the reasonable resource recycling problem of the waste lithium ion power battery become the problems which are generally concerned and urgently needed to be solved at present and even at home and abroad in future. The solution of the problem is not only beneficial to the environmental protection, but also more beneficial to the cyclic utilization of resources, and has great practical significance.
At present, the main recovered substances in the waste lithium ion battery are copper, aluminum, positive electrode materials and negative electrode materials, wherein a positive plate of the lithium battery is an aluminum foil coated positive electrode material, and a negative plate of the lithium battery is a copper foil coated negative electrode material. In combination with the current situation of domestic and foreign research, the recovery usually comprises three main steps: firstly, performing early-stage discharge treatment and disassembly on the waste battery; second, separation of the electrode material from the current collector; thirdly, the valuable metals are recovered and utilized. In the most studied recycling of the anode material of the current waste battery, the anode is generally leached by using strong acid such as hydrochloric acid, sulfuric acid, nitric acid and the like as a leaching agent, so that impurities such as Al and the like are inevitably contained in the leaching solution besides valuable metals such as Li, Ni, Co, Mn and the like, and in addition, the conductive agent in the anode is hardly recycled; on the other hand, because strong acid is used as the leaching agent, high requirements are also put on leaching equipment.
Disclosure of Invention
Aiming at the problems that the recovery of valuable elements in the anode needs to be carried out by strong acid leaching, the impurity removal process in leachate is complex, and a conductive agent in the anode is not recovered in the traditional process, the invention provides a novel recovery method of valuable components in an anode material based on low-temperature molten salt, and by the method, aluminum in the anode can be recovered in a high-purity aluminum hydroxide form; valuable elements such as Li, Ni, Co and Mn of the positive electrode enter the solution in an ionic state to be recovered, and the impurity content of the recovered solution is low; in addition, the conductive agent in the positive electrode is also recovered. The above effect is realized by the following scheme:
a method for recovering valuable components in a waste lithium battery anode based on a molten salt system is characterized in that waste anode materials (also called waste anode powder in the invention), ammonium chloride and molten salt are mixed to prepare pellets (pelletizing), and then heat treatment is carried out; then separating the molten salt to obtain reaction slag enriched with positive valuable elements;
the melting point of the molten salt is 180-280 ℃;
the heat treatment temperature is greater than or equal to the melting point of the molten salt.
The invention innovatively carries out heat treatment on the anode material and ammonium chloride under the condition of molten salt, so that Al in the anode material can be removed and recovered in the form of AlCl3 gas, and other valuable elements (elements in the anode active material) are precipitated in the molten salt molten mass in the form of chloride solid. Moreover, the separation selectivity of Al and valuable elements can be improved, and the separation efficiency and recovery rate of the Al and the valuable elements can be improved.
The invention is beneficial to synergistically improving the selective separation of Al and the anode active material and further beneficial to the recovery of each valuable element by matching with the pelletizing treatment on the basis of the molten salt system.
Preferably, the molten salt is a complex salt of two or more of halides, nitrates, hydroxides, sulfates and acetates of alkali metals.
More preferably, the molten salt is 0.62xLiNO3-0.38xLiOH-(1-x)CH3COOLi(0.6≤x≤0.8)；0.59LiNO3-0.41LiOH；0.88LiNO3-any of 0.12 LiCl.
Preferably, the preparation steps of the molten salt are as follows: obtaining various molten salt components, then adding the molten salt components into deionized water according to a liquid-solid ratio (0.5:1) - (1:1), uniformly stirring, then placing the mixture into a reaction furnace under the protection of argon or nitrogen, firstly keeping the temperature at 80-100 ℃ for 12-24h, then heating to a temperature 20-120 ℃ higher than the theoretical melting point of a molten salt system, then preserving the heat for 2-4 h, and then cooling along with the furnace under the protection of inert gas; and (4) finely grinding the cooling material taken out of the furnace to below 200 meshes to obtain the cooling material.
In the invention, organic matters in the waste positive plate are removed to obtain the waste positive material.
The organic matter is, for example, electrolyte components and a binder adsorbed in the waste positive electrode sheet.
In the invention, the organic matters of the waste positive plate can be removed by adopting the existing method, and the organic matters in the waste positive plate are preferably removed by carrying out heat treatment on the waste positive plate at the temperature of 400-450 ℃.
In the invention, the waste positive plate can be crushed in advance and then the organic matters in the waste positive plate are removed, or the waste positive plate can be crushed after the organic matters in the waste positive plate are removed, or the waste positive plate is crushed and finely ground after the organic matters are removed. Preferably, the waste positive plate is crushed and then is subjected to heat treatment at 400-450 ℃ to obtain the waste positive material.
Preferably, the particle size of the waste cathode material is 200-400 meshes.
Preferably, the waste positive electrode material is a powder material which is obtained by subjecting a waste positive electrode plate to heat treatment at 400-450 ℃ and fine grinding to 200-400 meshes, and the main components of the powder material comprise a powder aluminum current collector, a conductive agent and a positive electrode active substance.
According to the invention, the waste anode material comprises the anode active material, the conductive agent and the anode current collector (Al), the Al in the waste anode material is not required to be separated in advance, the molten salt system can be directly adopted for heat treatment, the Al can be recovered and separated in the form of aluminum chloride gas, and the synchronous chlorination leaching and precipitation of valuable elements of the anode active material can be synergistically promoted.
The technology of the invention can theoretically perform one-step leaching and aluminum removal on valuable elements of active materials in any lithium ion anode.
The positive active material is preferably a nickel, cobalt and manganese ternary positive active material. That is, the valuable element is Li/Ni/Co/Mn.
Preferably, the mass ratio of the waste positive electrode material to the ammonium chloride to the molten salt is (1-3) to (2-4) to (4-6).
Preferably, the waste cathode material, ammonium chloride and molten salt are mixed and then pressed into pellets, and then the heat treatment is carried out.
Preferably, the pressure of the pressing process is 120-160kg/cm2。
Preferably, the pellet has a particle size of 20 to 50 mm.
Preferably, the temperature of the heat treatment is 1-2 times of the melting point temperature of the molten salt; more preferably 1.2 to 1.8 times.
Preferably, the temperature of the heat treatment process is 300-350 ℃.
Preferably, the heat treatment time is 60min to 120 min.
Preferably, in the heat treatment process, the tail gas discharged in the heat treatment process is recovered by alkali liquor; and recovering the aluminum hydroxide from the tail gas absorption liquid.
The alkali liquor is lithium hydroxide solution. The pH is preferably 5 to 6.
In the invention, the molten salt melt is separated from the system after heat treatment while the system is hot, and chloride reaction slag of valuable elements is obtained.
Preferably, the reaction slag is subjected to water leaching treatment and solid-liquid separation to obtain carbon slag and leachate enriched with valuable elements of the positive electrode.
The obtained leachate is the chloride aqueous solution of the valuable elements of the positive active material, and can be treated by the existing method, for example, extraction is carried out, or the content of the valuable elements is regulated and controlled after impurity removal to directly precipitate to obtain the positive material.
In the invention, the carbon slag is subjected to impurity removal treatment, and the method comprises the following steps: and (3) placing the carbon residue in a mixed acid solution of hydrochloric acid and nitric acid, treating, then carrying out solid-liquid separation, washing the separated solid with water, drying, sieving, and recovering to obtain the conductive agent.
The invention discloses a preferable method for recovering valuable components in a ternary positive electrode of a waste lithium battery based on a low-temperature molten salt system, which comprises the following steps of:
step (1): placing the waste positive plate in a heat treatment furnace at the temperature of 400-450 ℃ for heat treatment to remove residual organic matters including electrolyte and a binder, and finely grinding the positive plate after the heat treatment to a particle size of 200-400 meshes;
step (2): the mixing and compression of the anode after the organic matter removal, the ammonium chloride and the low-temperature molten salt powder refer to that the anode after the organic matter removal, the ammonium chloride and the low-temperature molten salt powder are mixed according to the mass ratio of (1-3) to (2-4) to (4-6) and then mixed at the temperature of 120kg/cm and 160kg/cm2Pressing under pressure to form pellets of 20-50 mm;
and (3):
step (3.1), placing the pellets in a tubular atmosphere furnace, heating to 300-350 ℃ under the protection of inert gas, and preserving heat for 60-120 min to liquefy low-temperature molten salt, thereby realizing the separation of the molten salt and the waste anode powder; simultaneously absorbing NH contained in the gas discharged from the tubular atmosphere furnace by using a lithium hydroxide solution with the pH value maintained between 5 and 63HCl and AlCl3The tail gas of (3) is obtained by dissolving aluminum in the positive electrode in an absorbing solution of Al (OH)3The precipitate is recovered.
Step (3.2), collecting the liquid state discharged by heating in the step (3.1) at low temperature, cooling and crushing the liquid state to be less than 200 meshes for processing the next batch of waste anode materials;
step (3.3), adding the powder separated and tightened by the low-temperature molten salt in the step (3.1) into deionized water according to 50-200g/L, stirring and filtering to obtain filtrate, namely chloride solution containing Li, Ni, Co and Mn ions, and recovering valuable elements in the chloride solution by adopting a conventional technology; the filter residue enters the next step;
step (3.4), adding the filter residue obtained in the step (3.3) into 1-4mol/L hydrochloric acid, nitric acid or mixed hydrochloric acid/nitric acid in any proportion according to the liquid-solid ratio (20-60), treating for 1-3h at the temperature of 20-80 ℃, and then filtering; washing the filter cake with deionized water to pH 6.8-7, and drying in an oven at 100-120 deg.C for 2-12 hr; the dried material is sieved by a 400-mesh sieve, the undersize is the conductive agent, and the oversize is discarded.
The granularity of the ternary positive pole piece of the waste lithium battery is between 120 and 200 meshes;
the recovery of the valuable components in the ternary positive electrode of the waste lithium battery refers to the recovery of Li, Ni, Co and Mn elements in the ternary positive electrode in an ionic state in a solution, and the recovery of the Li, Ni, Co and Mn elements in the ternary positive electrode is realized by using Al (OH) as a positive electrode current collector3The precipitated form is recovered, and the conductive agent in the positive electrode is also recovered.
The main reaction generated by recovering valuable components in the ternary positive electrode of the waste lithium battery is as follows:
first, NH4Cl decomposes, the reaction of which is: NH (NH)4Cl→NH3+HCl；
Secondly, the reaction between HCl and Al, Li, Ni, Co and Mn in the anode:
Al+3LiNixCoyMn(1-x-y)O2+12HCl→
AlCl3↑+3LiCl+3xNiCl2+3yCoCl2+3(1-x-y)MnCl2+6H2O↑
analysis of the above reaction reveals that the reduction of Al in the positive electrode promotes the chlorination of valuable elements in the positive electrode.
In addition, the reaction generated in the tail gas recovery is: AlCl3+3OH-→Al(OH)3↓+Cl-
Therefore, the invention can directly obtain high-purity Al (OH) in the absorption tail liquid3And (5) producing the product.
Compared with the prior art, the invention has the advantages and the characteristics as follows:
(1) through the molten salt heat treatment, the high-selectivity separation of Al in the waste anode material and the anode active material and the synergistic synchronous leaching of the anode active material are realized.
According to the method, the Al in the waste anode material is not required to be screened and separated, the Al in the waste anode material can be recovered in a gas form through the heat treatment of the molten salt pellets, the synchronous chlorination leaching of the anode active material in a molten salt system can be promoted, furthermore, the leaching product of the anode active material is precipitated in a solid state form in the molten salt, and the high-purity anode active material leachate can be recovered and obtained through simple solid-liquid separation.
Taking a ternary cathode material as an example, the scheme of the invention does not adopt strong acid, and utilizes the heat treatment of the molten salt system to realize the reduction recovery of aluminum, so that Li, Ni, Co and Mn in the cathode are changed into chlorides to be efficiently recovered, and meanwhile, the aluminum current collector is separated from active matters, thereby ensuring the high purity of subsequent Li, Ni, Co and Mn solutions;
(2) recovering aluminum in the anode in the tail gas absorption liquid by high-purity Al (OH) 3; meanwhile, the high purity of the chlorination solution containing Li, Ni, Co and Mn is ensured, and the impurity removal cost is reduced.
(3) Based on a low-temperature molten salt system, the decomposition product of the ammonium chloride reacts with the anode in a liquid phase, so that the sufficiency of chlorination of each element in the anode is ensured, and the low-energy consumption advantage of the invention is ensured;
(4) the low-temperature molten salt can be reused for many times, and the tail gas absorption liquid of the tube furnace can also be returned to the system for reuse, so that the low cost of the invention is further ensured;
(5) the recovery of the conductive agent in the positive electrode is another feature of the present invention.
Drawings
FIG. 1 Process flow diagram of the present invention
Detailed Description
The present invention will be described in further detail with reference to specific examples, but the present invention is not limited to the following examples.
Example 1: based on 0.59LiNO3Recovery of valuable components from 523 type waste anode of-0.41 LiOH molten salt system
Firstly, placing a waste positive plate in a heat treatment furnace at 450 ℃ for treatment for 60min, then finely grinding, and sieving with a 200-mesh sieve to obtain waste positive powder;
second, 0.59LiNO was prepared3-0.41LiOH molten salt (eutectic temperature 183 ℃ C.). LiNO is weighed according to molar ratio3Adding LiOH and the mixture into deionized water according to the liquid-solid ratio (mL/g) of 0.7, uniformly stirring, placing the mixture into a reaction furnace under the protection of argon, firstly keeping the temperature of 80 ℃ for 12 hours, then heating to 240 ℃ and preserving the temperature for 2 hours, and then cooling along with the furnace under the protection of inert gas; and (3) finely grinding the cooling material taken out from the furnace to below 200 meshes to obtain low-temperature molten salt powder.
And thirdly, pressing the pellets. Respectively weighing the anode powder obtained in the first step, the molten salt powder obtained in the second step and ammonium chloride according to the ratio of 2:5:3, uniformly mixing in a mixer, and then adding the mixture to a mixer to obtain the anode powder with the concentration of 120kg/cm2Pressed into pellets with the diameter of about 30mm under pressure.
Fourthly, placing the pellets in a tubular atmosphere furnace, heating to 300 ℃ under the protection of inert gas, and preserving heat for 60min to liquefy the low-temperature molten salt, thereby realizing the separation of the molten salt and the waste anode powder; collecting the heated and flowed liquid molten salt, cooling and crushing the molten salt to be below 200 meshes for treating the next batch of waste anode materials; and the waste anode powder is treated in the next step. Simultaneously absorbing NH contained in the discharged NH by lithium hydroxide solution with the pH value maintained between 5.5 and 6 in a tubular atmosphere furnace3HCl and AlCl3The tail gas of (3) is obtained by dissolving aluminum in the positive electrode in an absorbing solution of Al (OH)3The precipitate is recovered.
Fifthly, adding the powder separated from the low-temperature molten salt in the last step into deionized water according to the concentration of 50g/L, stirring and filtering to obtain filtrate, namely chloride solution containing Li, Ni, Co and Mn ions, and recovering valuable elements from the chloride solution by adopting a conventional technology; the filter residue enters the next step; by analyzing the content of Li, Ni, Co and Mn ions in the filtrate, the leaching efficiency of lithium in the positive electrode reaches 100%, and the leaching efficiencies of Ni, Co and Mn in the positive electrode are 97.2%, 97.5 and 97.7% respectively.
Sixthly, adding the filter residue in the last step into 3mol/L hydrochloric acid according to the liquid-solid ratio of 20:1, treating for 1h at 40 ℃, then filtering, and returning the filtrate to the fifth step to recover valuable elements in the filtrate; washing the filter cake with deionized water to pH 6.8-7, and drying in an oven at 120 deg.C for 2 hr; the dried material is sieved by a 400-mesh sieve, the undersize is the conductive agent, and the oversize is discarded.
In the embodiment, the filtrate obtained in the sixth step is returned, so that 100% of Li, Ni, Co and Mn elements in the waste anode can be recovered; 92% of aluminum in the positive electrode enters the tail gas absorption liquid in the fourth step, and Al (OH)3Recovering the precipitate, and introducing the rest leachate obtained in the fifth step in the form of impurities; 98% of the conductive agent in the positive electrode was recovered.
Comparative example 1:
the difference compared to example 1 is that the reaction was not carried out under molten salt, specifically:
firstly, placing a waste positive plate in a heat treatment furnace at 450 ℃ for treatment for 60min, then finely grinding, and sieving with a 200-mesh sieve to obtain waste positive powder;
and secondly, pressing the pellets. Respectively weighing the anode powder obtained in the first step and ammonium chloride according to the ratio of 2:3, uniformly mixing in a mixer, and then adding the mixture to a mixing machine at a concentration of 120kg/cm2Pressed into pellets with the diameter of about 30mm under pressure.
And thirdly, placing the pellets in a tubular atmosphere furnace, heating to 300 ℃ under the protection of inert gas, and preserving heat for 60 min. Simultaneously absorbing NH contained in the discharged NH by lithium hydroxide solution with the pH value maintained between 5.5 and 6 in a tubular atmosphere furnace3HCl and AlCl3The observation and test of the tail gas show that the aluminum content in the absorption liquid is only 18 percent of the aluminum content in the anode, namely, most of the aluminum in the anode current collector is not changed into gas to enter the absorption liquid.
And fourthly, adding the powder obtained in the previous step into deionized water according to the proportion of 50g/L, stirring and filtering, wherein the Li leaching efficiency in the positive electrode is 87%, and the Ni leaching efficiency, the Co leaching efficiency and the Mn leaching efficiency in the positive electrode are respectively 91.5%, 92.3% and 92.2% by analyzing the content of Li, Ni, Co and Mn ions in the filtrate.
As can be seen from comparative example 1, the use of the molten salt system is significantly advantageous for Al (OH) in the positive electrode3The product is recovered, and the molten salt system is adopted to obtain extremely high leaching efficiency of Li, Ni, Co and Mn valuable elements in the anode.
Comparative example 2:
this example is substantially the same as comparative example 1, except that the present example does not employ the spheronization treatment, i.e., the spheronization step of the "second step" of example 1, and it can be seen from the analysis of the leaching efficiency that the Li leaching efficiency in the positive electrode is 78% without using molten salt and without spheronization treatment, and the Ni, Co and Mn leaching efficiencies in the positive electrode are lower than those of comparative example 1 and example 1, and are only 82.7%, 83.2 and 83.6%, respectively. As can be seen from the analysis of aluminum in the exhaust gas absorbent, only 9% of aluminum in the current collector was Al (OH)3Precipitating from the absorption solution.
By analyzing example 1 and comparative examples 1 and 2, the molten salt system and the ball pressing process adopted by the technology of the invention obviously show superiority in processing the cathode material.
Example 2: based on 0.88LiNO3Recovery of valuable components from type 622 waste anodes of-0.12 LiCl molten salt system
Firstly, placing a waste positive plate in a heat treatment furnace at 450 ℃ for treatment for 60min, then finely grinding, and sieving with a 200-mesh sieve to obtain waste positive powder;
second, 0.88LiNO is prepared3-0.12LiCl molten salt (eutectic temperature 280 ℃). LiNO is weighed according to molar ratio3Adding LiCl and deionized water according to the liquid-solid ratio (mL/g) of 1, uniformly stirring, placing in a reaction furnace under the protection of argon, keeping the temperature at 120 ℃ for 12h, heating to 300 ℃, keeping the temperature for 2h, and then cooling along with the furnace under the protection of inert gas; and (3) finely grinding the cooling material taken out from the furnace to below 200 meshes to obtain low-temperature molten salt powder.
And thirdly, pressing the pellets. Respectively weighing the positive electrode obtained in the first step according to the weight ratio of 1:5.5:3.5The powder, the fused salt powder obtained in the second step and ammonium chloride are mixed evenly in a mixer and then are mixed at 160kg/cm2Pressed into pellets with the diameter of about 40mm under pressure.
Fourthly, placing the pellets in a tubular atmosphere furnace, heating to 350 ℃ under the protection of inert gas, and preserving heat for 120min to liquefy the low-temperature molten salt, thereby realizing the separation of the molten salt and the waste anode powder; collecting the heated and flowed liquid molten salt, cooling and crushing the molten salt to be below 200 meshes for treating the next batch of waste anode materials; and the waste anode powder is treated in the next step. Simultaneously absorbing NH contained in the discharged NH by lithium hydroxide solution with the pH value maintained between 5.5 and 6 in a tubular atmosphere furnace3HCl and AlCl3The tail gas of (3) is obtained by dissolving aluminum in the positive electrode in an absorbing solution of Al (OH)3The precipitate is recovered.
Fifthly, adding the powder separated from the low-temperature molten salt in the last step into deionized water according to 100g/L, stirring and filtering to obtain filtrate, namely chloride solution containing Li, Ni, Co and Mn ions, and recovering valuable elements from the chloride solution by adopting a conventional technology; the filter residue enters the next step; by analyzing the content of Li, Ni, Co and Mn ions in the filtrate, the leaching efficiency of lithium in the positive electrode reaches 100%, and the leaching efficiency of Ni, Co and Mn in the positive electrode is higher than 99%.
Sixthly, adding the filter residue in the last step into 3mol/L hydrochloric acid according to the liquid-solid ratio of 20:1, treating for 1h at 40 ℃, then filtering, and returning the filtrate to the fifth step to recover valuable elements in the filtrate; washing the filter cake with deionized water to pH 6.8-7, and drying in an oven at 100 deg.C for 12 hr; the dried material is sieved by a 400-mesh sieve, the undersize is the conductive agent, and the oversize is discarded.
In the embodiment, the filtrate obtained in the sixth step is returned, so that 100% of Li, Ni, Co and Mn elements in the waste anode can be recovered; 96% of aluminum in the anode enters the tail gas absorption liquid of the fourth step, and Al (OH)3Recovering the precipitate, and introducing the rest leachate obtained in the fifth step in the form of impurities; more than 98% of the conductive agent in the positive electrode is recovered.
Example 3: based on 0.62xLiNO3-0.38 xllioh- (1-x) CH3COOLi (x ═ 0.75) meltingRecovery of valuable components in 811 type waste anode of salt system
Firstly, placing a waste positive plate in a heat treatment furnace at 450 ℃ for treatment for 60min, then finely grinding, and sieving with a 200-mesh sieve to obtain waste positive powder;
second, 0.465LiNO is prepared3-0.285xLiOH-0.25CH3COOLi (x is more than or equal to 0.6 and less than or equal to 0.8) molten salt. LiNO is weighed according to molar ratio3Adding LiOH and CH3COOLi into deionized water according to a liquid-solid ratio (mL/g) of 1, uniformly stirring, placing in a reaction furnace under the protection of argon, firstly keeping the temperature at 120 ℃ for 12h, then heating to 260 ℃ and keeping the temperature for 2 hours, and then cooling along with the furnace under the protection of inert gas; and (3) finely grinding the cooling material taken out from the furnace to below 200 meshes to obtain low-temperature molten salt powder.
And thirdly, pressing the pellets. Respectively weighing the anode powder obtained in the first step, the molten salt powder obtained in the second step and ammonium chloride according to the ratio of 1:6:3, uniformly mixing in a mixer, and then mixing at 150kg/cm2Pressed into pellets with the diameter of about 50mm under pressure.
Fourthly, placing the pellets in a tubular atmosphere furnace, heating to 300 ℃ under the protection of inert gas, and preserving heat for 120min to liquefy the low-temperature molten salt, thereby realizing the separation of the molten salt and the waste anode powder; collecting the heated and flowed liquid molten salt, cooling and crushing the molten salt to be below 200 meshes for treating the next batch of waste anode materials; and the waste anode powder is treated in the next step. Simultaneously absorbing NH contained in the discharged NH by lithium hydroxide solution with the pH value maintained between 5.5 and 6 in a tubular atmosphere furnace3HCl and AlCl3The tail gas of (3) is obtained by dissolving aluminum in the positive electrode in an absorbing solution of Al (OH)3The precipitate is recovered.
Fifthly, adding the powder separated from the low-temperature molten salt in the last step into deionized water according to 200g/L, stirring and filtering to obtain filtrate, namely chloride solution containing Li, Ni, Co and Mn ions, and recovering valuable elements from the chloride solution by adopting a conventional technology; the filter residue enters the next step; by analyzing the content of Li, Ni, Co and Mn ions in the filtrate, the leaching efficiency of lithium in the positive electrode reaches 99%, and the leaching efficiency of Ni, Co and Mn in the positive electrode is higher than 98%.
Sixthly, adding the filter residue in the last step into 1mol/L nitric acid according to the liquid-solid ratio of 60:1, treating for 1h at 60 ℃, then filtering, and returning the filtrate to the fifth step to recover valuable elements in the filtrate; washing the filter cake with deionized water to pH 6.8-7, and drying in an oven at 100 deg.C for 12 hr; the dried material is sieved by a 400-mesh sieve, the undersize is the conductive agent, and the oversize is discarded.
In the embodiment, the filtrate obtained in the sixth step is returned, so that 100% of Li, Ni, Co and Mn elements in the waste anode can be recovered; 93 percent of aluminum in the positive electrode enters the tail gas absorption liquid in the fourth step, and Al (OH)3Recovering the precipitate, and introducing the rest leachate obtained in the fifth step in the form of impurities; more than 98% of the conductive agent in the positive electrode is recovered.
Claims (15)
1. A method for recovering valuable components in a waste lithium battery anode based on a molten salt system is characterized in that waste anode materials, ammonium chloride and molten salt are mixed to prepare pellets, and then heat treatment is carried out; then separating the molten salt to obtain reaction slag enriched with positive valuable elements;
the melting point of the molten salt is 180-280 ℃;
the heat treatment temperature is greater than or equal to the melting point of the molten salt;
the waste positive electrode material comprises a positive electrode active material and an aluminum current collector;
the molten salt is a complex salt of two or more of halide, nitrate, hydroxide, sulfate and acetate of alkali metal; the alkali metal is lithium.
2. The method for recovering valuable components from the positive electrode of the waste lithium battery based on the molten salt system as claimed in claim 1, wherein the molten salt is 0.62x LiNO3-0.38xLiOH-(1-x)CH3COOLi；0.6≤x≤0.8；0.59LiNO3-0.41LiOH；0.88LiNO3-any of 0.12 LiCl.
3. The method for recovering valuable components in the positive electrode of the waste lithium battery based on the molten salt system as claimed in claim 2, wherein the molten salt is prepared by the following steps: obtaining molten salt components, adding the molten salt components into deionized water according to a liquid-solid ratio of (0.5:1) - (1:1), uniformly stirring, then placing the mixture into a reaction furnace under the protection of argon or nitrogen, firstly keeping the temperature at 80-100 ℃ for 12-24h, then heating to a temperature 20-120 ℃ higher than the theoretical melting point of a molten salt system, then keeping the temperature for 2-4 h, and then cooling along with the furnace under the protection of inert gas; and (4) finely grinding the cooling material taken out of the furnace to below 200 meshes to obtain the cooling material.
4. The method for recovering valuable components from the positive electrode of the waste lithium battery based on the molten salt system as claimed in any one of claims 1 to 3, wherein the mass ratio of the waste positive electrode material, the ammonium chloride and the molten salt heat treatment is (1-3): (2-4): (4-6).
5. The method for recovering valuable components from the positive electrode of the waste lithium battery based on the molten salt system as claimed in claim 1, wherein the waste positive electrode material is obtained by heat treatment of a waste positive plate at 400-450 ℃.
6. The method for recovering valuable components from the positive electrode of the waste lithium battery based on the molten salt system as claimed in claim 1, wherein the waste positive electrode material comprises an aluminum current collector, a conductive agent and a positive electrode active material.
7. The method for recovering valuable components from the anode of the waste lithium battery based on the molten salt system as claimed in claim 1, wherein the particle size of the waste anode material is 200-400 meshes.
8. The method for recovering valuable components from the positive electrode of the waste lithium battery based on the molten salt system as claimed in claim 1, wherein the positive active material in the waste positive material is a ternary positive active material of nickel, cobalt and manganese.
9. The method for recovering valuable components from the positive electrode of the waste lithium battery based on the molten salt system as claimed in claim 1, wherein the heat treatment is performed after the waste positive electrode material, ammonium chloride and molten salt are mixed and pressed into pellets.
10. The method for recovering valuable components from the positive electrode of the waste lithium battery based on the molten salt system as claimed in claim 9, wherein the particle size of the pellets is 20-50 mm.
11. The method for recovering valuable components from the positive electrode of the waste lithium battery based on the molten salt system as claimed in claim 9, wherein the temperature of the heat treatment is 1-2 times of the melting point temperature of the molten salt.
12. The method for recovering valuable components from the positive electrode of the waste lithium battery based on the molten salt system as claimed in claim 1, wherein the time for the heat treatment is 60min to 120 min;
in the heat treatment process, alkali liquor is adopted to recycle tail gas discharged in the heat treatment process; and recovering the aluminum hydroxide from the tail gas absorption liquid.
13. The method for recovering valuable components from the positive electrode of waste lithium batteries based on the molten salt system as claimed in claim 12, wherein the alkali solution is a lithium hydroxide solution.
14. The method for recovering valuable components from the positive electrode of the waste lithium battery based on the molten salt system as claimed in claim 1, wherein reaction slag is subjected to water leaching and solid-liquid separation to obtain carbon slag and leachate enriched with valuable elements of the positive electrode.
15. The method for recovering valuable components from the positive electrode of the waste lithium battery based on the molten salt system as claimed in claim 14, wherein the carbon slag is subjected to impurity removal treatment, and the steps are as follows: and (3) placing the carbon residue in a mixed acid solution of hydrochloric acid and nitric acid, treating, then carrying out solid-liquid separation, washing the separated solid with water, drying, sieving, and recovering to obtain the conductive agent.
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