CN113511664A - Method for preparing battery-grade lithium carbonate by selectively extracting lithium from battery waste - Google Patents
Method for preparing battery-grade lithium carbonate by selectively extracting lithium from battery waste Download PDFInfo
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Abstract
The invention relates to the technical field, in particular to a method for preparing battery-grade lithium carbonate by selectively extracting lithium from battery waste, which comprises the following steps of firstly, adding the powdery battery waste and a certain proportion of additives into a grinding machine, and grinding and mixing to obtain mixed powder; and step two, calcining the mixed powder in the step one in a resistance furnace at high temperature to obtain calcined mixed powder. And step three, carrying out three-stage cross-flow water leaching on the calcined mixed powder to obtain a lithium solution. And step four, precipitating the water-leached lithium solution by using lithium hydroxide, removing impurities by using lithium type ion exchange resin and precipitating by using sodium carbonate to obtain the battery-grade lithium carbonate. According to the invention, through the methods of mechanical activation and calcination, lithium oxygen bonds in the nickel cobalt lithium manganate serving as the cathode material component in the battery waste are destroyed, and then lithium is selectively extracted from the battery waste in a water leaching manner, so that the lithium recovery process flow is shortened, and the loss of lithium caused by long-flow treatment is avoided.
Description
Technical Field
The invention relates to the technical field of recovery of old lithium ion batteries, in particular to a method for preparing battery-grade lithium carbonate by selectively extracting lithium from battery waste.
Background
From 2015, the new energy automobile sales volume continuously accounts for the top of the world for five years in China, the new energy automobile sales volume is 124.2 thousands of automobiles and 120.6 thousands of automobiles respectively, the new energy automobile sales volume is 136.6 thousands of automobiles and 136.7 thousands of automobiles respectively in 2020, the year-on-year increase is 7.5%, the increase rate is changed from negative to positive in the last year, and the market share of the new energy automobile sales volume reaches 5.4%. By the end of 2020, the new energy automobile holding amount in China reaches 564 thousands.
The power battery is used as the core of a new energy automobile, and the accumulated matching amount of the power battery in China exceeds 200GWH by 2019. The power battery loading capacity is 17.5GWH, which is reduced by 40% on the same scale. Wherein the accumulated loading amount of the ternary batteries is 12615MWh, which accounts for 72.2% of the total loading amount; the total loading capacity of the lithium iron phosphate battery is 4743.2MWh, which accounts for 27.1% of the total loading capacity.
The power battery is used as the core of a new energy automobile, and as long as 2020, the accumulative capacity of the power battery in China is about 270GWH, and the scale is the first in the world. Wherein, the ratio of the lithium iron phosphate and the ternary battery is about 54 percent and 40 percent respectively. The proportion of the ternary batteries in the pure electric passenger vehicle and the commercial vehicle is about 71 percent and 17 percent respectively, and the proportion of the lithium iron phosphate batteries is about 23 percent and 78 percent respectively; the matching proportion of the ternary lithium iron phosphate battery and the lithium iron phosphate battery in the plug-in hybrid electric vehicle is about 53 percent and 33 percent respectively.
With the rapid development of new energy automobiles, large-scale retired power batteries will be brought in the future. The scrappage of the power lithium battery reaches 25Gwh in 2020, which is about 20 ten thousand tons. The scrappage in 2023 years will reach 101Gwh, about 80 ten thousand tons. It is predicted that by 2030, the scrap amount will reach 375Gwh, about 300 million tons. The size of the whole battery recycling market reaches 450 million yuan, wherein the echelon utilization is 310 million yuan, and the recycling is 140 million yuan.
At present, the recovery of lithium ion batteries in industry mainly focuses on the recovery and reuse of cobalt, nickel and other valuable metals, the extraction of lithium is not considered yet, lithium is treated as waste residues in a pyrogenic recovery process, and is recovered in a form of crude lithium carbonate at the flow end in a wet recovery process.
At present, most methods for extracting lithium from waste lithium ion battery active materials utilize various organic acids, inorganic acids, mixed acids and a reducing agent for reduction and acid leaching, various valuable metals are transferred into a solution and then separated by methods such as chemical precipitation, extraction, ion exchange and the like, and compounds of Ni, Co, Mn and Li with certain purity are obtained respectively. However, these methods have the disadvantage that lithium metal is recovered at the end of the process as crude lithium carbonate. Long recovery process, low lithium metal yield and low added value of lithium products.
CN201810231801.7 proposes a method for selectively extracting lithium from lithium-containing battery waste. Mixing and leaching the pretreated battery waste and an oxide aqueous solution in a closed container, adjusting the pH value of the lithium solution by using two combinations of sodium hydroxide, potassium hydroxide, ammonia water and ammonium salt to purify the lithium solution, and adding sodium carbonate into the purified solution to precipitate lithium to obtain a lithium carbonate product. The oxidizing aqueous solution used in the method uses ozone or perchloric acid solution and the like, equipment is required to be sealed or chlorine corrosion is required to be prevented, the requirements on equipment materials, tightness and the like are high during industrial application, the equipment cost is increased, and meanwhile, unnecessary impurities such as chloride ions and the like are introduced into the lithium solution, so that the quality of a subsequent lithium carbonate product is not improved. In addition, sodium hydroxide, potassium hydroxide, ammonia water, ammonium salts and other neutralizing agents used in the purification process can also bring impurities of sodium, potassium or ammonium, so that the quality of the lithium carbonate product is influenced, and the treatment cost of subsequent wastewater is increased due to the existence of the ammonium.
CN201910716016.5 provides a method for efficiently and selectively extracting lithium from waste lithium batteries by flash reduction, wherein a positive electrode material of a lithium battery and a reducing gas are added into a flash furnace in a spraying mode, the positive electrode material of the lithium battery falls from the flash furnace in a suspension state and is completely reduced within 2-10 seconds, the differential transformation of lithium, nickel, manganese and cobalt is realized, the high-efficiency separation of lithium is realized after the transformation calcine is dissolved in water, and a lithium-rich solution is obtained. The method adopts a flash furnace to treat the lithium battery anode material, has high equipment requirement and large industrial application difficulty, and lithium is recovered in a solution form in the process, so that the added value of the product is low.
CN202010166805.9 provides a method for selectively extracting lithium and electrolytically separating and recovering manganese dioxide from waste lithium ion battery powder, which is to mix the waste lithium ion battery powder with concentrated sulfuric acid, perform acid roasting, mechanically stir and leach with pure water, remove impurities step by step through sulfide precipitation and oxidation neutralization precipitation of lithium-containing leachate, remove manganese through electrolysis, add saturated sodium carbonate solution to precipitate lithium, and produce lithium carbonate. The method adopts concentrated sulfuric acid for acid roasting, has large operation difficulty and many potential safety hazards during industrial application, and uses sulfide for precipitation and impurity removal, so that the obtained nickel cobalt manganese sulfide can generate a large amount of hydrogen sulfide gas during acid leaching in the subsequent recycling process, thereby causing environmental pollution and being not beneficial to recycling of metals such as nickel, cobalt, manganese and the like in the residue after selective recycling of lithium.
CN202010651899.9 provides a method for selectively extracting lithium by a roasting method of anode and cathode powder materials of waste lithium ion batteries, which is to subject the anode and cathode powder materials of the waste lithium batteries to fluidized bed sulfuration roasting, multistage weak acid leaching, sodium carbonate lithium precipitation and MVR evaporation crystallization to enable lithium element to be selectively leached with high efficiency and to be recovered in the form of lithium carbonate, and the recovery rate reaches more than 95%. The fluidized bed fluidized roasting and multistage weak acid leaching are carried out in the method, compared with water leaching, the dosage of sulfuric acid in weak acid leaching is larger, nickel, cobalt and manganese can be leached to different degrees, and the leaching selectivity of lithium is reduced. In addition, the difficulty of practical operation is increased by repeatedly adjusting the pH value of the leaching solution, and the industrial application is not facilitated.
CN202010105226.3 proposes a method and apparatus for selectively extracting lithium. And acid leaching the lithium ion battery electrode powder in a reaction kettle at high temperature and high pressure to obtain a lithium-containing solution. The method adopts high-temperature and high-pressure equipment to selectively leach lithium, has high equipment safety requirement, small processing capacity and difficult industrial application, only obtains a lithium solution product, and has low added value of the product.
CN202010995471.6 proposes a method for preferentially extracting lithium and cooperatively recovering manganese from waste lithium ion batteries, which comprises the steps of finely grinding a positive electrode active material obtained by the pretreatment of the waste lithium ion batteries and a carbonaceous reducing agent, adding a chlorinating agent into the ground material to perform anaerobic roasting, then performing water leaching and H2SO4Removing calcium, NaOH, manganese and Na by precipitation2CO3And precipitating to obtain the battery-grade lithium carbonate. The method adopts reduction roasting, one or more of calcium chloride, zinc chloride, copper chloride, barium chloride, sodium chloride and potassium chloride are added in the process, so that new impurity chloride ions or other cations are introduced into a lithium solution, manganese is removed by NaOH precipitation and impurity sodium ions are introduced, and meanwhile, the impurity removal depth of calcium removal by calcium sulfate precipitation is limited, so that the subsequent lithium carbonate product can hardly reach the level of battery-grade lithium carbonate.
Therefore, in order to solve the above problems, it is urgently needed to develop a method for preparing battery-grade lithium carbonate by selectively extracting lithium from battery waste, so as to shorten the recovery process flow of lithium in the battery waste, avoid the introduction of other impurities due to the addition of auxiliaries and reagents in the process, solve the problems of long lithium recovery flow, low lithium recovery rate and low added value of lithium products in the recovery process of the battery waste, and simultaneously give consideration to comprehensive recycling residues of other metals, thereby facilitating the recycling of other valuable metals, namely nickel, cobalt and manganese.
Disclosure of Invention
The invention aims to provide a method for preparing battery-grade lithium carbonate by selectively extracting lithium from battery waste, which aims to solve the problems that the recovery of an industrial lithium ion battery mainly focuses on the recovery and reutilization of cobalt, nickel and other valuable metals, the extraction of lithium is not considered yet, the lithium is treated as waste residues in a pyrogenic recovery process, and the lithium is recovered at the tail end of a flow in a wet recovery process, which are proposed in the background art.
In order to achieve the purpose, the invention provides the following technical scheme: a method for preparing battery-grade lithium carbonate by selectively extracting lithium from battery waste, comprising the following steps:
step one, adding powdery battery waste and a certain proportion of additives into a grinding machine, and grinding and mixing to obtain mixed powder;
and step two, calcining the mixed powder in the step one in a resistance furnace at high temperature to obtain calcined mixed powder.
Step three, adding a certain amount of leaching agent into the mixed powder in the step two to carry out three-stage cross-flow leaching, selectively transferring lithium in the battery powder into a leaching solution to obtain a lithium-containing solution, and leaving nickel, cobalt, manganese and the like in leaching residues;
step four, adding a lithium hydroxide solution with a certain concentration into the lithium-containing solution obtained in the step three, precipitating and removing impurities, and removing a small amount of impurities such as nickel, cobalt, manganese, copper, iron, aluminum and the like in the lithium-containing solution;
step five, carrying out ion exchange impurity removal on the precipitation impurity-removed liquid obtained in the step four, and removing trace impurities such as calcium, magnesium and the like in the lithium-containing solution;
and step six, adding a certain amount of saturated sodium carbonate solution into the ion exchange impurity-removed solution obtained in the step five, and precipitating to obtain the battery-grade lithium carbonate.
Preferably, in the first step, the battery waste is a waste nickel cobalt manganese ternary lithium battery, and is subjected to mechanical crushing, winnowing, screening and other pretreatment to obtain a positive-negative electrode mixture, wherein the main components of the positive-negative electrode mixture are a nickel cobalt lithium manganate positive electrode material and a graphite negative electrode material.
Preferably, the temperature of the step other than medium-high temperature calcination is 550-650 ℃, the heat preservation time is 30-180 min, the ratio of the battery powder to the additive is 1: 0.75-1.5, and the additive is sodium bisulfate.
Preferably, the leaching agent used for leaching in the third step is deionized water.
Preferably, in the third step, three sections of cross-flow leaching are performed, the first-section leaching solution, namely the lithium-containing solution, enters a subsequent impurity removal process, and the second-section and third-section leaching solutions are used as the first-section and second-section slurry solutions of the next cycle and are circularly entered into the leaching process.
Preferably, three-stage cross-flow leaching is adopted in the leaching in the third step, the liquid-solid ratio of the three-stage leaching is 3:1, the leaching temperature is 30-60 ℃, and the time is 30-90 min.
Preferably, the concentration of the precipitator in the fourth step is 100-150 g/L, the precipitation reaction temperature is 60-95 ℃, and the end point pH is 10-11.
Preferably, the ion exchange resin used in the fifth step is chelating ion exchange resin D402, and the ion exchange resin in the fifth step is a lithium type resin treated by a lithium hydroxide solution.
Preferably, lithium is selectively extracted from the battery waste by a calcining and cross-flow leaching method, and battery-grade lithium carbonate is prepared by lithium hydroxide precipitation impurity removal, lithium type resin ion exchange deep impurity removal and lithium carbonate precipitation, so that the lithium leaching selectivity, the lithium solution concentration and the lithium product purity are improved, and certain economic benefit and social benefit are achieved.
Compared with the prior art, the invention has the beneficial effects that:
1. through the method of mechanical activation and calcination, the lithium oxygen bond in the nickel cobalt lithium manganate serving as the positive material component in the battery waste is destroyed, and then lithium is selectively extracted from the battery waste in a water leaching mode, so that the lithium recovery process flow is shortened, and the loss of lithium caused by long-flow treatment is avoided.
2. Through the three-stage cross-flow water leaching process, the lithium leaching rate is improved, the lithium concentration in the leaching solution is increased, the subsequent lithium recovery is facilitated, the working procedures of evaporation concentration, crystallization and the like in the traditional lithium recovery are avoided, and the loss of lithium metal in the crystallization process is avoided.
3. The concentration and the purity of the lithium solution are further improved by the processes of lithium hydroxide precipitation and lithium type chelating resin impurity removal, and the battery-grade lithium carbonate is prepared by a method of direct sodium carbonate precipitation, so that the additional value of a lithium product is improved.
Drawings
FIG. 1 is a schematic view of the manufacturing process of the present invention.
Detailed Description
The technical solutions in the embodiments of the present invention will be clearly and completely described below with reference to the drawings in the embodiments of the present invention, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all of the embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
Referring to fig. 1, an embodiment of the present invention:
a method for preparing battery-grade lithium carbonate by selectively extracting lithium from battery waste comprises
The method comprises the following steps:
step one, adding powdery battery waste and a certain proportion of additives into a grinding machine, and grinding and mixing to obtain mixed powder;
and step two, calcining the mixed powder in the step one in a resistance furnace at high temperature to obtain calcined mixed powder.
Step three, adding a certain amount of leaching agent into the mixed powder in the step two to carry out three-stage cross-flow leaching, selectively transferring lithium in the battery powder into a leaching solution to obtain a lithium-containing solution, and leaving nickel, cobalt, manganese and the like in leaching residues;
step four, adding a lithium hydroxide solution with a certain concentration into the lithium-containing solution obtained in the step three, precipitating and removing impurities, and removing a small amount of impurities such as nickel, cobalt, manganese, copper, iron, aluminum and the like in the lithium-containing solution;
step five, carrying out ion exchange impurity removal on the precipitate impurity-removed liquid obtained in the step four to remove trace calcium, magnesium and other impurities in the lithium-containing solution;
and step six, adding a certain amount of saturated sodium carbonate solution into the ion exchange impurity-removed solution obtained in the step five, and precipitating to obtain the battery-grade lithium carbonate.
Further, in the step one, the waste battery materials are waste nickel cobalt manganese ternary lithium batteries, and are subjected to mechanical crushing, winnowing, screening and other pretreatment to obtain a positive-negative electrode mixed material, wherein the main components of the positive-negative electrode mixed material are a nickel cobalt lithium manganate positive electrode material and a graphite negative electrode material.
Furthermore, in the second step, the high-temperature calcination temperature is 550-650 ℃, the heat preservation time is 30-180 min, the ratio of the battery powder to the additive is 1: 0.75-1.5, and the additive is sodium bisulfate.
Further, the leaching agent used in the leaching in the third step is deionized water.
Further, in the third step, three sections of cross-flow leaching are carried out, the first section of leaching solution, namely the lithium-containing solution enters the subsequent impurity removal process, and the second section of leaching solution and the third section of leaching solution are used as the next circulation first section of slurrying solution and the second section of slurrying solution to circularly enter the leaching process.
Further, three-section cross-flow leaching is adopted in the leaching in the third step, the liquid-solid ratio of the three-section leaching is 3:1, the leaching temperature is 30-60 ℃, and the time is 30-90 min.
Further, in the fourth step, the concentration of the precipitator is 100-150 g/L, the precipitation reaction temperature is 60-90 ℃, and the end point pH is 10-11.
Further, the ion exchange resin used in the fifth step is chelating ion exchange resin D402, and the ion exchange resin used in the fifth step is lithium type resin treated by lithium hydroxide solution.
Furthermore, lithium is selectively extracted from the battery waste by a method of calcination and cross-flow leaching, and battery-grade lithium carbonate is prepared by lithium hydroxide precipitation impurity removal, lithium type resin ion exchange deep impurity removal and lithium carbonate precipitation, so that the selectivity of lithium leaching, the concentration of a lithium solution and the purity of a lithium product are improved, and certain economic benefits and social benefits are achieved.
The first embodiment is as follows:
and (3) material mixing and calcining: taking 150g of battery waste, adding 150g of sodium bisulfate, mixing and grinding until the granularity of the mixture is less than 100 meshes, placing the mixture into a crucible, placing the crucible into a box-type resistance furnace for high-temperature calcination at the calcination temperature of 550 ℃ for 30min, naturally cooling to room temperature after calcination, and grinding the calcined material until the granularity is less than 100 meshes for later use.
Three sections of cross-flow leaching steps: pulping 100g of calcined material with 300mL of deionized water, heating the first-stage leaching slurry in a water bath to 60 ℃, leaching with stirring water for 1h, carrying out solid-liquid separation, keeping the first-stage leaching solution for later use, leaching the first-stage leaching residue in a second stage, pulping the first-stage leaching residue with 300mL of deionized water, heating the second-stage leaching slurry in a water bath to 30 ℃, leaching with stirring water for 60min, finishing the solid-liquid separation, leaching the second-stage leaching solution in the next cycle to obtain a first-stage leaching solution, and leaching the second-stage leaching residue in a third stage. Pulping three-stage leaching residues by using 300mL of deionized water, heating the three-stage leaching slurry in a water bath to 30 ℃, stirring and leaching for 60min, performing solid-liquid separation after leaching, allowing three-stage leaching solution to enter the next cycle, leaching at the second stage to serve as pulping solution, and drying the three-stage leaching residues for later use. After three-stage leaching, the total leaching rate of lithium is 95.5%, and the total leaching rates of nickel, cobalt and manganese are 2.4%, 2.7% and 42.4% respectively.
Impurity removal: and (3) taking 200mL of first-stage leaching solution, adding 100g/L of lithium hydroxide solution, adjusting the pH value of the system to 10.5, stirring for reaction for 1h, carrying out solid-liquid separation, keeping the filtrate for later use, drying the filter residue, mixing the filter residue with the third-stage leaching residue, and keeping. The concentration of the lithium solution after precipitation and impurity removal is 8.4g/L, and the impurities of nickel, cobalt, manganese, copper, aluminum and iron are all less than 0.002 g/L.
Taking 50mL of D401 resin, washing the resin with 3% dilute sulfuric acid and deionized water respectively after being filled into a column until the effluent is neutral and has pH =4-5, regenerating the resin into lithium type resin by using 4% lithium hydroxide solution, washing the resin with deionized water until the effluent has pH =8-9, taking 200mL of the solution after precipitation and impurity removal to carry out ion exchange impurity removal at the flow rate of 100mL/h, wherein main impurities of calcium and magnesium in the solution after impurity removal are both less than 0.001 g/L.
And (3) lithium precipitation: taking 200mL of the solution after impurity removal, stirring and heating to above 90 ℃, adding 80mL of saturated sodium carbonate solution, carrying out precipitation reaction for 1h, filtering while the solution is hot, and washing the filter residue for 2 times by using pure water at 80 ℃ according to a liquid-solid ratio of 2: 1. After the filter residue is dried, the index requirement of battery-grade lithium carbonate (YS/T582-2013) is met;
example two:
and (3) material mixing and calcining: taking 3.0kg of battery waste, adding 3.5kg of sodium bisulfate, mixing and grinding until the granularity of the mixture is less than 100 meshes, placing the mixture into a crucible, placing the crucible into a box-type resistance furnace for high-temperature calcination at 600 ℃, keeping the temperature for 120min, naturally cooling to room temperature after calcination, and grinding the calcined material until the granularity is less than 100 meshes for later use.
Three sections of cross-flow leaching steps: 0.5kg of calcined material is slurried with 1.5L of first-stage leaching solution, the first-stage leaching slurry is placed in a water bath and heated to 60 ℃, stirred and soaked for 90min, solid-liquid separation is carried out, the first-stage leaching solution is reserved, and the first-stage leaching residue is subjected to second-stage leaching. Pulping the first-stage leaching residue by using 1.5L of second-stage leaching solution, heating the second-stage leaching slurry in a water bath to 60 ℃, leaching for 90min by stirring water, finishing solid-liquid separation after leaching, leaching the second-stage leaching solution in the next cycle for the first-stage leaching solution to be used as pulping solution, leaching the second-stage leaching residue in the third-stage leaching solution, pulping the third-stage leaching residue by using 1.5L of deionized water, heating the third-stage leaching slurry in the water bath to 60 ℃, leaching for 90min by stirring water, finishing solid-liquid separation after leaching, leaching the third-stage leaching solution in the next cycle for the second-stage leaching solution to be used as pulping solution, and drying the third-stage leaching residue for later use. After three-stage leaching, the total leaching rate of lithium is 94.7%, and the total leaching rates of nickel, cobalt and manganese are 1.9%, 2.3% and 45.9% respectively.
Impurity removal: taking 1.5L of first-stage leaching solution, adding 150g/L of lithium hydroxide solution, adjusting the pH of the system to 10.5, stirring and reacting for 90min, carrying out solid-liquid separation, keeping the filtrate for later use, drying the filter residue, mixing the filter residue with the third-stage leaching residue, and keeping. The concentration of the lithium solution after precipitation and impurity removal is 9.1g/L, and the impurities of nickel, cobalt, manganese, copper, aluminum and iron are all less than 0.002 g/L.
And (3) taking 1L of the D401 resin, loading the D401 resin into a column, washing the D401 resin with 3% dilute sulfuric acid and deionized water respectively until the effluent water is neutral and has the pH =4-5, regenerating the D401 resin into a lithium type resin by using a 4% lithium hydroxide solution, and washing the D401 resin with the deionized water until the effluent water has the pH = 8-9. And (3) taking 2L of the solution after precipitation and impurity removal to carry out ion exchange impurity removal at the flow rate of 1L/h, wherein main impurities of calcium and magnesium in the solution after impurity removal are both less than 0.001 g/L.
And (3) lithium precipitation: taking 2L of the solution after impurity removal, stirring and heating to above 90 ℃, adding 0.8L of saturated sodium carbonate solution for precipitation reaction for 1h, filtering while hot, and washing the filter residue for 2 times by using pure water at 80 ℃ according to a liquid-solid ratio of 2: 1. And after the filter residue is dried, the index requirement of the battery-grade lithium carbonate is met.
It will be evident to those skilled in the art that the invention is not limited to the details of the foregoing illustrative embodiments, and that the present invention may be embodied in other specific forms without departing from the spirit or essential attributes thereof. The present embodiments are therefore to be considered in all respects as illustrative and not restrictive, the scope of the invention being indicated by the appended claims rather than by the foregoing description, and all changes which come within the meaning and range of equivalency of the claims are therefore intended to be embraced therein. Any reference sign in a claim should not be construed as limiting the claim concerned.
Claims (9)
1. A method for preparing battery-grade lithium carbonate by selectively extracting lithium from battery waste is characterized by comprising the following specific steps:
step one, adding powdery battery waste and a certain proportion of additives into a grinding machine, and grinding and mixing to obtain mixed powder;
step two, calcining the mixed powder in the step one in a resistance furnace at high temperature to obtain calcined mixed powder;
step three, adding a certain amount of leaching agent into the mixed powder in the step two to carry out three-stage cross-flow leaching, selectively transferring lithium in the battery powder into a leaching solution to obtain a lithium-containing solution, and leaving nickel, cobalt, manganese and the like in leaching residues;
step four, adding a lithium hydroxide solution with a certain concentration into the lithium-containing solution obtained in the step three, precipitating and removing impurities, and removing a small amount of impurities such as nickel, cobalt, manganese, copper, iron, aluminum and the like in the lithium-containing solution;
step five, carrying out ion exchange impurity removal on the precipitate impurity-removed liquid obtained in the step four to remove trace calcium, magnesium and other impurities in the lithium-containing solution;
and step six, adding a certain amount of saturated sodium carbonate solution into the ion exchange impurity-removed solution obtained in the step five, and precipitating to obtain the battery-grade lithium carbonate.
2. The method of claim 1 for preparing battery grade lithium carbonate by selectively extracting lithium from battery waste, wherein the method comprises the following steps: in the first step, the battery waste is a positive and negative electrode mixed material obtained by performing mechanical crushing, winnowing, screening and other pretreatment on a waste nickel-cobalt-manganese ternary lithium battery, and the main components of the positive electrode material and the negative electrode material are nickel-cobalt lithium manganate positive electrode material and graphite negative electrode material.
3. The method of claim 1 for preparing battery grade lithium carbonate by selectively extracting lithium from battery waste, wherein the method comprises the following steps: in the second step, the high-temperature calcination temperature is 550-650 ℃, the heat preservation time is 30-180 min, the ratio of the battery powder to the additive is 1: 0.75-1.5, and the additive is sodium bisulfate.
4. The method of claim 1 for preparing battery grade lithium carbonate by selectively extracting lithium from battery waste, wherein the method comprises the following steps: and the leaching agent used in the leaching in the third step is deionized water.
5. The method of claim 1 for preparing battery grade lithium carbonate by selectively extracting lithium from battery waste, wherein the method comprises the following steps: in the third step, three sections of cross-flow leaching are carried out, the first section of leaching solution, namely the lithium-containing solution enters the subsequent impurity removal process, and the second section of leaching solution and the third section of leaching solution are used as the first section of next circulation and the second section of slurry solution to circularly enter the leaching process.
6. The method of claim 1 for preparing battery grade lithium carbonate by selectively extracting lithium from battery waste, wherein the method comprises the following steps: three-section cross-flow leaching is adopted in the leaching in the third step, the liquid-solid ratio of the three-section leaching is 3:1, the leaching temperature is 30-60 ℃, and the time is 30-90 min.
7. The method of claim 1 for preparing battery grade lithium carbonate by selectively extracting lithium from battery waste, wherein the method comprises the following steps: in the fourth step, the concentration of the precipitator is 100-150 g/L, the precipitation reaction temperature is 60-95 ℃, and the end point pH is 10-11.
8. The method of claim 1 for preparing battery grade lithium carbonate by selectively extracting lithium from battery waste, wherein the method comprises the following steps: the ion exchange resin used in the fifth step is chelating ion exchange resin D402, and the ion exchange resin used in the fifth step is lithium type resin treated by lithium hydroxide solution.
9. The method of claim 1 for preparing battery grade lithium carbonate by selectively extracting lithium from battery waste, wherein the method comprises the following steps: selectively extracting lithium from the battery waste by a calcining and cross-flow leaching method, and preparing battery-grade lithium carbonate by lithium hydroxide precipitation impurity removal, lithium type resin ion exchange deep impurity removal and lithium carbonate precipitation, so that the lithium leaching selectivity, the lithium solution concentration and the lithium product purity are improved, and certain economic benefits and social benefits are achieved.
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN115849415A (en) * | 2023-03-02 | 2023-03-28 | 矿冶科技集团有限公司 | Method for preparing battery-grade lithium carbonate |
| CN116119690A (en) * | 2022-12-16 | 2023-05-16 | 安徽格派锂电循环科技有限公司 | Method for selectively recycling lithium from waste lithium battery |
| CN117317428A (en) * | 2023-10-24 | 2023-12-29 | 金驰能源材料有限公司 | Full-process recovery process of waste power battery |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| AR019418A1 (en) * | 1998-07-16 | 2002-02-20 | Chemetall Foote Corp | PROCESS FOR RECOVERING LITHIUM CARBONATE FROM A SALMUERA CONTAINING LITHIUM AND MAGNESIUM. |
| CN104538696A (en) * | 2015-01-08 | 2015-04-22 | 兰州理工大学 | Method for recycling metal from waste lithium ion battery with Ni-Co lithium manganite positive electrode materials |
| CN108832215A (en) * | 2018-06-14 | 2018-11-16 | 中国科学院过程工程研究所 | A kind of method of selective recovery anode material for lithium-ion batteries |
| CN110117020A (en) * | 2018-02-07 | 2019-08-13 | 中国科学院过程工程研究所 | A method of it is handled using mineral element phase transfer containing lithium minerals |
| CN110615453A (en) * | 2019-09-26 | 2019-12-27 | 黄冈师范学院 | Method for directly preparing battery-grade lithium carbonate |
-
2021
- 2021-08-25 CN CN202110980418.3A patent/CN113511664A/en active Pending
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| AR019418A1 (en) * | 1998-07-16 | 2002-02-20 | Chemetall Foote Corp | PROCESS FOR RECOVERING LITHIUM CARBONATE FROM A SALMUERA CONTAINING LITHIUM AND MAGNESIUM. |
| CN104538696A (en) * | 2015-01-08 | 2015-04-22 | 兰州理工大学 | Method for recycling metal from waste lithium ion battery with Ni-Co lithium manganite positive electrode materials |
| CN110117020A (en) * | 2018-02-07 | 2019-08-13 | 中国科学院过程工程研究所 | A method of it is handled using mineral element phase transfer containing lithium minerals |
| CN108832215A (en) * | 2018-06-14 | 2018-11-16 | 中国科学院过程工程研究所 | A kind of method of selective recovery anode material for lithium-ion batteries |
| CN110615453A (en) * | 2019-09-26 | 2019-12-27 | 黄冈师范学院 | Method for directly preparing battery-grade lithium carbonate |
Non-Patent Citations (4)
| Title |
|---|
| CHAOPENG等: "Selective extraction of lithium (Li) and preparation of battery grade lithium carbonate (Li2CO3) from spent Li-ion batteries in nitrate system", 《JOURNAL OF POWER SOURCES》 * |
| 吴芳: "从废旧锂离子二次电池中回收钴和锂", 《中国有色金属学报》 * |
| 王大辉等: "机械力作用对钴酸锂硫酸化焙烧产物的影响", 《无机盐工业》 * |
| 甘先豪: "LiNi0.6Co0.2Mn0.2O2-NaHSO4·H2O体系焙烧过程物相变化及金属回收的研究", 《中国优秀硕士学位论文全文数据库（电子期刊） 工程科技Ⅰ辑》 * |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN116119690A (en) * | 2022-12-16 | 2023-05-16 | 安徽格派锂电循环科技有限公司 | Method for selectively recycling lithium from waste lithium battery |
| CN115849415A (en) * | 2023-03-02 | 2023-03-28 | 矿冶科技集团有限公司 | Method for preparing battery-grade lithium carbonate |
| CN117317428A (en) * | 2023-10-24 | 2023-12-29 | 金驰能源材料有限公司 | Full-process recovery process of waste power battery |
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