CN117509687A - A method for recycling and refining lithium carbonate using waste lithium-thionyl chloride batteries - Google Patents
A method for recycling and refining lithium carbonate using waste lithium-thionyl chloride batteries Download PDFInfo
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Abstract
The invention provides a method for recycling refined lithium carbonate by using waste lithium-thionyl chloride batteries, which comprises the following steps: s1, placing a positive electrode and a negative electrode obtained by disassembling and separating a battery in 950-1050 ℃ for roasting for 2-6 hours to obtain a sintered material; s2, adding the sintering material into sulfuric acid solution, and carrying out solid-liquid separation to obtain a first solution and filter residues; s3, after the first solution is subjected to primary impurity removal and secondary impurity removal, sodium carbonate is added into the first solution to prepare lithium carbonate, and iron is recovered by utilizing filter residues. The method can effectively extract lithium in the lithium-thionyl chloride battery, can improve the extraction rate of the lithium, and the finally prepared lithium carbonate has better purity.
Description
Technical Field
The invention belongs to the technical field of lithium batteries, and particularly relates to a method for recycling and refining lithium carbonate by using waste lithium-thionyl chloride batteries.
Background
Lithium batteries are used as a hot material for research and development of new energy sources at present, and play an important role in the field of new energy sources in China. In recent years, with the emphasis on the environment, many countries have developed active policies on the application and recovery of lithium batteries, so that the development of lithium batteries is increasingly emphasized in the current society. Therefore, the lithium battery industry is upgraded, and meanwhile, higher industry standards and requirements are also provided for the field of lithium battery production and recovery.
Currently, the impressions of the public on lithium batteries are mostly ternary lithium batteries, ferric lithium phosphate batteries, ferric manganese lithium phosphate batteries and the like, and the batteries mainly have the characteristic of rechargeable circulation and occupy a larger market in the current lithium batteries. Therefore, most research is still being conducted into these rechargeable lithium batteries for recycling and utilization of lithium batteries.
The lithium-thionyl chloride battery is a battery with highest specific energy in the battery series of practical application, is not chargeable, and has specific energy of 590 W.h/kg and 1100 W.h/L, and consists of a lithium cathode, a carbon anode and a non-aqueous SOCl 2 ：LiAlCl 4 Electrolyte composition. The application of lithium-thionyl chloride batteries is the use of the series of advantages of high specific energy and long shelf life, such as cylindrical batteries discharged with small currents as power sources for CMOS memories, metering devices for water, electricity, etc., and Radio Frequency Identification (RFID) devices such as highway transit automatic electronic toll collection systems (ETC systems), program logic controllers, and wireless safety alarm systems. Because of the high cost and special handling requirements of these lithium batteries, the use in the general consumer market is still limited. Although lithium-thionyl chloride batteries are rarely used in the general consumer market, lithium-thionyl chloride batteries have a large application market because there are always some special conditions such as non-charging.
The general solid waste treatment company adopts a method of soaking batteries and then directly landfilling the batteries. This method causes a great deal of waste of lithium resources and is not recycled. Therefore, the recovery treatment method for the lithium-thionyl chloride battery has great environmental protection significance.
Disclosure of Invention
In order to solve the problems and the defects in the prior art, the invention provides a method for recycling and refining lithium carbonate by using waste lithium-thionyl chloride batteries, which can effectively extract lithium in the lithium-thionyl chloride batteries, can improve the extraction rate of the lithium, and the finally prepared lithium carbonate has better purity.
The invention provides a method for recycling refined lithium carbonate by using waste lithium-thionyl chloride batteries, which comprises the following steps: s1, placing a positive electrode and a negative electrode obtained by disassembling and separating a battery in 950-1050 ℃ for roasting for 2-6 hours to obtain a sintered material; s2, adding the sintering material into sulfuric acid solution, and carrying out solid-liquid separation to obtain a first solution and filter residues; s3, adding sodium carbonate into the first solution to prepare lithium carbonate after the first solution is subjected to primary impurity removal and secondary impurity removal, and recycling iron by utilizing filter residues; the specific operation of the first impurity removal is as follows: adjusting the pH value of the first solution to 7-8, carrying out solid-liquid separation to obtain a second solution and a first precipitate, and recovering the second solution; the specific operation of removing impurities again is as follows: adjusting the pH value of the second solution to 12-14, carrying out solid-liquid separation to obtain a third solution and a second precipitate, and recovering the third solution; and then adding sodium carbonate into the third solution to prepare the lithium carbonate.
In the above S1, the temperature may be 950 ℃, 970 ℃, 990 ℃, 1000 ℃, 1050 ℃, and the reaction time may be 2 hours, 3 hours, 4 hours, 5 hours, 6 hours, for example; in S3, the pH for the first impurity removal may be, for example, 7, 7.3, 7.6, 7.8, 8, and the pH for the second impurity removal may be, for example, 12, 12.5, 13, 13.5, 14; the above-mentioned reaction conditions are not limited to the values recited, and other values not recited in the numerical range are equally applicable.
The components of the lithium-thionyl chloride battery include: metallic lithium (negative electrode), graphite (positive electrode), polymer diaphragm, thionyl chloride (SOCl) 2 ) Electrolyte, stainless steel shell and cap. The discharging principle of the battery is as follows: 2Li+2SOCl 2 →2LiCl+SO 2 +S; therefore, lithium chloride is generated to be attached to the positive graphite after the metal lithium is discharged; elemental sulfur generated by the discharge of the electrolyte is also attached to the positive graphite. The following technical difficulties exist in the disposal and recovery of lithium-thionyl chloride batteries: (1) The activity of the residual lithium metal in the waste battery is high, and the phenomena of combustion and explosion are easy to occur; (2) The graphite is of a porous structure, and the attached lithium chloride and elemental sulfur cannot be thoroughly separated; (3) The electrolyte is easy to absorb water and decompose in the air to generate HCl and SO 2 The chemical equation is: SOCl 2 +H 2 O→2HCl+SO 2 The HCl generated in the method is not friendly to stainless steel equipment and is extremely easy to cause serious corrosion to the equipment.
At present, most manufacturers or enterprises treat used lithium-thionyl chloride by the following steps: firstly, brine bubbles are used for discharging for more than 1 month, the soaked slag is buried, and the soaked liquid enters a sewage treatment plant for treatment. The manner of this treatment brings about the following drawbacks: (1) The soaking slag contains a large amount of lithium elements, and lithium resources are wasted due to direct landfill; (2) Upon soaking, the electrolyte in the cell undergoes hydrolysis (SOCl 2 +H 2 O→2HCl+SO 2 ) Acid gas is generated, and the acid gas is dissolved in water to cause serious corrosion to equipment, especially Cl - The corrosion to the equipment is very serious, so that the soaking lithium-ion battery has very high requirements on the equipment and has higher cost.
By utilizing the method provided by the invention to treat the waste lithium-thionyl chloride battery, lithium in the waste lithium-thionyl chloride battery can be effectively extracted, the extraction efficiency of the lithium is higher, and serious corrosion to treated equipment is avoided. Specifically, in the invention, the battery is firstly subjected to positive and negative electrode separation, so that the airtight structure of the battery can be effectively destroyed, the danger that the airtight structure is easy to cause explosion and the like in the subsequent treatment process is avoided, and the positive and negative electrode separation process is safer and more reliable. Then the separated battery is roasted at high temperature, the electrolyte can be directly decomposed and dissipated in the form of gas, and the gas can be absorbed by alkali liquor absorption, so that the corrosion of the electrolyte to equipment is greatly reduced; meanwhile, in the high-temperature roasting process, other substances in the battery can be oxidized (such as metallic lithium and positive graphite) and carbonized (such as a diaphragm), wherein the graphite is oxidized to form CO 2 Is discharged atIn this process, there may be graphite that is fully oxidized and a separator that is not fully carbonized. The residual materials after high-temperature roasting are only lithium oxide (obtained by oxidizing metal lithium), stainless steel shell, diaphragm decomposition residues and a small amount of graphite attached with lithium chloride, a large amount of lithium elements exist in the residual materials, and then the lithium elements in the residual materials can be leached and extracted into solution by utilizing sulfuric acid solution treatment.
And further, the solution obtained after sulfuric acid treatment is subjected to primary impurity removal and secondary impurity removal so as to ensure that elements affecting the extraction of lithium in the solution are effectively removed, the purity of the finally prepared lithium carbonate is improved, and the prepared lithium carbonate can be directly applied to the fields of battery materials and the like. Specifically, in the above-described first impurity removal operation, aluminum ions, chromium ions, and the like in the solution are precipitated by adjusting the pH to 7 to 8 to remove the aluminum ions, the chromium ions, and the like. After removing aluminum ions and chromium ions in the solution, the pH value in the solution is continuously adjusted to 12-14, so that iron ions, magnesium ions, nickel ions and the like in the solution can be precipitated, and the purpose of removing the ions in the solution is achieved. Through first edulcoration and edulcoration once more, can effectively detach the impurity metal ion that influences the preparation of follow-up lithium carbonate, can improve the purity of lithium carbonate, guarantee that lithium carbonate has better product quality. Chromium ions in the treatment process are derived from stainless steel which is leached after sulfuric acid treatment, and a small amount of stainless steel is dissolved after the stainless steel is leached by sulfuric acid, so that chromium elements are dissolved.
In addition, after the sulfuric acid treatment, a certain amount of filter residues are left, and the filter residues are stainless steel shells, so that the filter residues can be used for recycling iron or can be sold as scrap iron to generate value, and recycling of resources is realized.
It should be noted that in the above acid treatment process, sulfuric acid is required as the acid, because if hydrochloric acid is added, the corrosion to the stainless steel shell is serious, resulting in the stainless steel shell not having a value of changing sales; if nitric acid is added, nitrate ions are introduced, and the risk of exceeding ammonia nitrogen exists, so that the cost for treating wastewater is increased.
Preferably, in S1, the firing time is 3 to 4 hours. For example, the time period may be 3 hours, 3.5 hours, or 4 hours, but the present invention is not limited to the values listed, and other values not listed in the numerical range are equally applicable. The control of the roasting time in the range is more beneficial to ensuring that the disassembled battery can be fully oxidized and decomposed, and meanwhile, more harmful gas is not generated in the roasting process due to the overlong roasting time, so that the harm to the environment and the treatment cost of the subsequent harmful gas are reduced.
Preferably, in S2, the mass fraction of the sulfuric acid solution is 5% -10%. For example, the values may be 5%, 6%, 7%, 8%, 9%, 10%, but are not limited to the values recited, and other values not recited in the numerical range are equally applicable. The sulfuric acid with the concentration range is favorable for fully extracting lithium elements in residual substances, and can ensure that fewer impurities are dissolved in acid as much as possible, so that the lithium carbonate prepared later has higher purity.
Preferably, in the first impurity removal of S3, the pH of the first solution is adjusted to 7 to 8 using sodium hydroxide.
Preferably, in the re-impurity removal of S3, the pH of the second solution is adjusted to 12 to 14 using sodium hydroxide.
Preferably, in S3, before removing impurities from the first solution, the method further includes the operations of sequentially performing pH adjustment and heat concentration on the first solution; wherein, in the operation of pH adjustment, the pH of the first solution is adjusted to 6 to 7. For example, the values may be 6, 6.2, 6.5, 6.7, and 7, but are not limited to the values recited, and other values not recited in the numerical range are equally applicable.
Preferably, the pH of the first solution is adjusted to 6 to 7 using sodium hydroxide. The first solution is adjusted to near neutral to reduce corrosion of the equipment by the solution at this stage and to be ready for subsequent decontamination operations.
Preferably, the first solution is heated and concentrated to a lithium ion concentration of 7 to 13% in the solution. For example, the values may be 7%, 8%, 9%, 10%, 11%, 12%, 13%, but are not limited to the values recited, and other values not recited in the numerical range are equally applicable.
Preferably, in the first impurity removal, the concentration of aluminum ions and chromium ions in the second solution is not higher than 100ppm, for example, 50ppm, 60ppm, 70ppm, 80ppm, 90ppm and 100ppm, but the method is not limited to the recited values, and other non-recited values in the numerical range are equally applicable; in the second impurity removal, the concentration of iron ions, magnesium ions and nickel ions in the third solution is not more than 50ppm, and may be, for example, 20ppm, 25ppm, 30ppm, 35ppm, 40ppm and 50ppm, but not limited to the values recited, and other values not recited in the numerical range are equally applicable. When the concentration of the metal ions is in the above range, it means that most of the impurity metal ions are effectively removed, and the purity of the finally prepared lithium carbonate is improved.
Preferably, sodium carbonate is added into the third solution, the solution is heated to 60-90 ℃ to react for 1.5-3 hours, solid-liquid separation is carried out, a fourth solution and a third precipitate are obtained, the third precipitate is recovered, and lithium carbonate is prepared by using the third precipitate. The heating temperature may be 60 ℃, 70 ℃, 80 ℃, 90 ℃ and the reaction time may be 1.5 hours, 2 hours, 2.5 hours, 3 hours; the above-mentioned reaction conditions are not limited to the values recited, and other values not recited in the numerical range are equally applicable.
Preferably, the third precipitate is treated as follows: mixing the third precipitate with water to obtain mixed slurry, introducing carbon dioxide into the mixed slurry, carrying out solid-liquid separation to obtain a fifth solution and a fourth precipitate, recovering the fifth solution, and carrying out heating decomposition on the fifth solution at 80-120 ℃ to obtain lithium carbonate. The above-mentioned heating temperature may be, for example, 80 ℃, 90 ℃, 100 ℃, 110 ℃, 120 ℃, but is not limited to the values listed, and other values not listed in the numerical range are equally applicable.
Preferably, the concentration of calcium ions in the fifth solution is not higher than 500ppm, and may be, for example, 100ppm, 150ppm, 200ppm, 300ppm, 400ppm, 500ppm, but is not limited to the recited values, and other values not recited in the numerical range are equally applicable. When the concentration of calcium ions is within the above range, the calcium ions in the solution are effectively removed, and the purpose of refining lithium carbonate is achieved.
Preferably, the molar ratio of lithium ions to carbonate in the mixed system after adding sodium carbonate into the third solution is 2:1.05-1.25. For example, the values may be 2:1.05, 2:1.10, 2:1.15, 2:1.20, 2:1.25, but are not limited to the recited values, and other non-recited values within the range of values are equally applicable.
Drawings
FIG. 1 is a flow chart of the process for recovering and refining lithium carbonate by using waste lithium-thionyl chloride batteries in examples 1 to 3 of the present invention.
Detailed Description
In order that those skilled in the art will better understand the present invention, a technical solution of the embodiments of the present invention will be clearly and completely described below, and it is apparent that the described embodiments are only some embodiments of the present invention, not all embodiments.
Example 1
The method for recycling refined lithium carbonate from waste lithium-thionyl chloride batteries in the embodiment is carried out according to the following steps:
s1, placing a positive electrode and a negative electrode obtained by disassembling and separating a battery in a muffle furnace, setting the temperature to 1000 ℃, and roasting for 3 hours to obtain a sintered material; in the step, the electrolyte, the diaphragm and the positive graphite powder can be all baked until gas is released;
s2, adding the sintering material into a sulfuric acid solution with the mass fraction of 10%, fully stirring and reacting, and then carrying out solid-liquid separation to obtain a first solution and filter residues; the lithium ion concentration in the first solution obtained in the step is 7.78% (mass fraction) through detection;
s3, adding sodium carbonate into the first solution to prepare lithium carbonate after the first solution is subjected to primary impurity removal and secondary impurity removal, and recycling iron by utilizing filter residues;
wherein, in S3, preparing lithium carbonate using the first solution, sodium carbonate comprises the following operations:
s3.1. (first impurity removal) adding a sodium hydroxide solution with a mass fraction of 5% into the first solution, adjusting the pH to 6, then heating the evaporated solution to enrich lithium ions, and stopping evaporation when the concentration of the lithium ions in the detected solution is 12+/-2%; continuously adding 5% sodium hydroxide solution, adjusting pH to 8, stirring for 1 hr, filtering to obtain second solution and first precipitate, recovering the second solution, and discarding the first precipitate;
the pH of the solution is adjusted to 8 to remove aluminum ions and chromium ions in the solution; washing with pure water for 4 times before discarding the first precipitate, and pouring the washing solution into the second solution for recovery; in the second solution, detecting to obtain the concentration of aluminum ions and chromium ions which are not higher than 100ppm;
s3.2. (removing impurities again) adding 5% sodium hydroxide solution to the obtained second solution, regulating pH to 12, stirring for 1 hr, filtering to obtain a third solution and a second precipitate, recovering the third solution, and discarding the second precipitate;
the pH of the solution is adjusted to 12 to remove iron ions, magnesium ions and nickel ions in the solution; washing with pure water for 4 times before discarding the second precipitate, and pouring the washing solution into the third solution for recovery; in the third solution, the concentration of iron ions, magnesium ions and nickel ions obtained by detection is not higher than 50ppm;
s3.3, detecting the concentration of lithium ions in the obtained third solution, adding sodium carbonate into the third solution according to the reaction ratio of the lithium ions and carbonate ions, heating and stirring for 2 hours at 60 ℃, filtering while the solution is hot to obtain a fourth solution and a third precipitate, washing the third precipitate with pure water at 60 ℃ for 4 times, recovering the third precipitate, and discarding the fourth solution; in the step, after adding sodium carbonate, the molar ratio of lithium ions to carbonate ions in the mixed system is 2:1.05;
s3.4, adding the obtained third precipitate into pure water, fully stirring and uniformly mixing to obtain mixed slurry, introducing carbon dioxide gas into the mixed slurry, filtering to obtain a fifth solution and a fourth precipitate, and discarding the fourth precipitate; the carbon dioxide is introduced in the step to remove calcium ions in the mixed system; detecting to obtain the calcium ion concentration in the fifth solution not higher than 500ppm;
s3.5, placing the obtained fifth solution into a crucible, and heating at 80 ℃ to decompose the fifth solution by heating to obtain lithium carbonate.
The purity of lithium carbonate prepared in this example was 99.1%, and the recovery rate was 94.2%.
Purity = 1-impurity content. The impurity elements are given by the national standard of lithium carbonate. And detecting the impurity content according to national standard requirements, and then calculating the purity.
Recovery = lithium content in lithium carbonate/lithium content in spent cells x 100%.
The following examples and comparative examples refer to example 1 in terms of purity and recovery of lithium carbonate.
Example 2
The method for recycling refined lithium carbonate from waste lithium-thionyl chloride batteries in the embodiment is carried out according to the following steps:
s1, placing a positive plate and a negative plate obtained after battery disassembly in a muffle furnace, setting the temperature to 1000 ℃, and roasting for 3.5 hours to obtain a sintered material; in the step, the electrolyte, the diaphragm and the positive graphite powder can be all baked until gas is released;
s2, adding the sintering material into a sulfuric acid solution with the mass fraction of 8%, and after fully stirring and reacting, carrying out solid-liquid separation to obtain a first solution and filter residues; the lithium ion concentration in the first solution obtained in the step is 3.78% (mass fraction) through detection;
s3, adding sodium carbonate into the first solution to prepare sodium carbonate after the first solution is subjected to primary impurity removal and secondary impurity removal, and recycling iron by utilizing filter residues;
wherein, in S3, preparing lithium carbonate using the first solution, sodium carbonate comprises the following operations:
s3.1. (first impurity removal) adding a sodium hydroxide solution with a mass fraction of 5% into the first solution, adjusting the pH to 6.5, then heating the evaporated solution to enrich lithium ions, and stopping evaporation when the concentration of lithium ions in the detected solution is 10+/-2%; continuously adding 5% sodium hydroxide solution, adjusting the pH to 7.5, stirring for 1 hour, filtering to obtain a second solution and a first precipitate, recovering the second solution, and discarding the first precipitate;
the pH of the solution is adjusted to 7.5 to remove aluminum ions and chromium ions in the solution; washing with pure water for 4 times before discarding the first precipitate, and pouring the washing solution into the second solution for recovery; in the second solution, detecting to obtain the concentration of aluminum ions and chromium ions which are not higher than 50ppm;
s3.2. (removing impurities again) adding 5% sodium hydroxide solution to the obtained second solution, regulating pH to 12, stirring for 1 hr, filtering to obtain a third solution and a second precipitate, recovering the third solution, and discarding the second precipitate;
the pH of the solution is adjusted to 13 to remove iron ions, magnesium ions and nickel ions in the solution; washing with pure water for 4 times before discarding the second precipitate, and pouring the washing solution into the third solution for recovery; in the third solution, the concentration of iron ions, magnesium ions and nickel ions obtained by detection is not higher than 30ppm;
s3.3, detecting the concentration of lithium ions in the obtained third solution, adding sodium carbonate into the third solution according to the reaction ratio of the lithium ions and carbonate ions, heating and stirring for 2 hours at 70 ℃, filtering while the solution is hot to obtain a fourth solution and a third precipitate, washing the third precipitate with pure water at 60 ℃ for 4 times, recovering the third precipitate, and discarding the fourth solution; in the step, after adding sodium carbonate, the molar ratio of lithium ions to carbonate ions in the mixed system is 2:1.15;
s3.4, adding the obtained third precipitate into pure water, fully stirring and uniformly mixing to obtain mixed slurry, introducing carbon dioxide gas into the mixed slurry, filtering to obtain a fifth solution and a fourth precipitate, and discarding the fourth precipitate; the carbon dioxide is introduced in the step to remove calcium ions in the mixed system; detecting to obtain the calcium ion concentration in the fifth solution not higher than 300ppm;
s3.5, placing the obtained fifth solution into a crucible, and heating at 100 ℃ to decompose the fifth solution by heating to obtain lithium carbonate.
The purity of lithium carbonate prepared in this example was 99.0% and the recovery rate was 93.8%.
Example 3
The method for recycling refined lithium carbonate from waste lithium-thionyl chloride batteries in the embodiment is carried out according to the following steps:
s1, placing a positive plate and a negative plate obtained after battery disassembly in a muffle furnace, setting the temperature to 1000 ℃, and roasting for 4 hours to obtain a sintered material; in the step, the electrolyte, the diaphragm and the positive graphite powder can be all baked until gas is released;
s2, adding the sintering material into a sulfuric acid solution with the mass fraction of 5%, fully stirring and reacting, and then carrying out solid-liquid separation to obtain a first solution and filter residues; the lithium ion concentration in the first solution obtained in the step is 2.54 percent (mass fraction) through detection;
s3, adding sodium carbonate into the first solution to prepare sodium carbonate after the first solution is subjected to primary impurity removal and secondary impurity removal, and recycling iron by utilizing filter residues;
wherein, in S3, preparing lithium carbonate using the first solution, sodium carbonate comprises the following operations:
s3.1. (first impurity removal) adding a sodium hydroxide solution with a mass fraction of 5% into the first solution, adjusting the pH to 6.8, then heating the evaporated solution to enrich lithium ions, and stopping evaporation when the concentration of the lithium ions in the detected solution is 8+/-2%; continuously adding 5% sodium hydroxide solution, adjusting pH to 7, stirring for 1 hr, filtering to obtain second solution and first precipitate, recovering the second solution, and discarding the first precipitate;
the pH of the solution is adjusted to 7 to remove aluminum ions and chromium ions in the solution; washing with pure water for 4 times before discarding the first precipitate, and pouring the washing solution into the second solution for recovery; in the second solution, detecting to obtain the concentration of aluminum ions and chromium ions which are not higher than 20ppm;
s3.2. (removing impurities again) adding 5% sodium hydroxide solution to the obtained second solution, regulating pH to 14, stirring for 1 hr, filtering to obtain a third solution and a second precipitate, recovering the third solution, and discarding the second precipitate;
the pH of the solution is adjusted to 13 to remove iron ions, magnesium ions and nickel ions in the solution; washing with pure water for 4 times before discarding the second precipitate, and pouring the washing solution into the third solution for recovery; in the third solution, the concentration of iron ions, magnesium ions and nickel ions obtained by detection is not higher than 50ppm;
s3.3, detecting the concentration of lithium ions in the obtained third solution, adding sodium carbonate into the third solution according to the reaction ratio of the lithium ions and carbonate ions, heating and stirring for 2 hours at 90 ℃, filtering while the solution is hot to obtain a fourth solution and a third precipitate, washing the third precipitate with pure water at 60 ℃ for 4 times, recovering the third precipitate, and discarding the fourth solution; in the step, after adding sodium carbonate, the molar ratio of lithium ions to carbonate ions in the mixed system is 2:125;
s3.4, adding the obtained third precipitate into pure water, fully stirring and uniformly mixing to obtain mixed slurry, introducing carbon dioxide gas into the mixed slurry, filtering to obtain a fifth solution and a fourth precipitate, and discarding the fourth precipitate; the carbon dioxide is introduced in the step to remove calcium ions in the mixed system; detecting to obtain the calcium ion concentration in the fifth solution not higher than 300ppm;
s3.5, placing the obtained fifth solution into a crucible, and heating at 120 ℃ to decompose the fifth solution by heating to obtain lithium carbonate.
The purity of lithium carbonate prepared in this example was 99.4% and the recovery rate was 93.5%.
Comparative example 1
This comparative example differs from example 1 in that the first impurity removal process and the second impurity removal process of S3.1 and S3.2 are omitted, that is, "continuing to add 5% by mass of sodium hydroxide solution thereto, adjusting pH to 7, stirring for 1 hour, filtering to obtain a second solution and a first precipitate, recovering the second solution, and discarding the first precipitate; adding 5% sodium hydroxide solution to the second solution, adjusting the pH to 14, stirring for 1 hour, filtering to obtain a third solution and a second precipitate, recovering the third solution, and discarding the second precipitate; in the subsequent step of adding sodium carbonate, the input amount of sodium carbonate is calculated according to the lithium ion concentration actually measured in the mixed system; the remainder was identical to example 1.
The purity of the lithium carbonate prepared in this comparative example was 72.4%. Thus, the purity of the lithium carbonate obtained in this comparative example was too low, and the lithium carbonate was not used for a large amount of application, and the recovery rate was not calculated.
Comparative example 2
This comparative example differs from example 1 in that the first impurity removal process of S3.1, namely the step of "continuing to add 5% by mass of sodium hydroxide solution thereto, adjusting pH to 7, stirring for 1 hour, filtering to obtain a second solution and a first precipitate, recovering the second solution, and discarding the first precipitate" was omitted; in the subsequent step of adding sodium carbonate, the input amount of sodium carbonate is calculated according to the lithium ion concentration actually measured in the mixed system; the remainder was identical to example 1.
The purity of the lithium carbonate prepared in this comparative example was 90.3%, and the main sources of impurities were aluminum element and chromium element, the contents of which were 2.5% and 6.3%, respectively. Thus, the purity of the lithium carbonate obtained in this comparative example was too low, and the lithium carbonate was not used for a large amount of application, and the recovery rate was not calculated.
Comparative example 3
This comparative example is different from example 1 in that the re-impurity removal process of S3.2, that is, the step of "adding 5% by mass of sodium hydroxide solution to the second solution obtained above, adjusting the pH to 12, stirring for 1 hour, then filtering to obtain a third solution and a second precipitate, recovering the third solution, and discarding the second precipitate" is omitted; in the subsequent step of adding sodium carbonate, the input amount of sodium carbonate is calculated according to the lithium ion concentration actually measured in the mixed system; the remainder was identical to example 1.
The purity of the lithium carbonate prepared in this comparative example was 82.4%, and the main sources of impurities were iron element, magnesium element and nickel element, the contents of which were 8.7%, 1.4% and 6.6%, respectively. Thus, the purity of the lithium carbonate obtained in this comparative example was too low, and the lithium carbonate was not used for a large amount of application, and the recovery rate was not calculated.
Comparative example 4
This comparative example differs from example 1 in that in S1, the firing temperature is 900 ℃; the remainder was identical to example 1.
In the comparative example, the concentration of lithium ions in the first solution in S2 was 7.82% (mass fraction); and the purity of the lithium carbonate prepared in this comparative example was 90.1%. Thus, the purity of the lithium carbonate obtained in this comparative example was also relatively low, and the lithium carbonate was not used for a large amount of application, and the recovery rate was not calculated.
Analysis of experimental results
The data in examples 1 to 3 and comparative examples 1 to 4 are summarized as shown in Table 1.
Table 1 summary of data in examples 1 to 3 and comparative examples 1 to 4
As can be seen from examples 1 to 3 of Table 1, the treatment method provided by the invention can be used for effectively extracting lithium elements from waste lithium-thionyl chloride batteries, and has higher lithium extraction rate. And the extracted lithium ions can be utilized to carry out refining recovery of lithium carbonate, and the prepared lithium carbonate has better purity and recovery rate.
Further analysis, it can be seen from comparative examples 1 to 4 that in the method for recovering and refining lithium carbonate using waste lithium-thionyl chloride batteries provided in the present invention, the impurity removal process and the roasting temperature have an important influence on the extraction rate of lithium ions or the purity and recovery rate of lithium carbonate finally prepared. The impurity removing step in the invention can effectively improve the purity and recovery rate of the finally prepared lithium carbonate, has great practical significance, and is important for both the first impurity removing step and the second impurity removing step, and the two impurity removing steps can sufficiently remove various impurity metal ions in the first solution, thereby being beneficial to improving the purity and recovery rate of the lithium carbonate. For example, omitting the two-time impurity removal treatment or one of the two-time impurity removal treatment in comparative examples 1, 2, and 3 resulted in a decrease in purity of lithium carbonate, mainly because some of the impurity metal ions were not effectively removed. And the purity and recovery rate of lithium carbonate can be effectively improved by controlling the proper roasting temperature, because the proper roasting temperature is more favorable for the decomposition of electrolyte and the oxidation and carbonization of other substances, thereby being favorable for the subsequent extraction of lithium. For example, in comparative example 4, too low a firing temperature may result in insufficient decomposition of the electrolyte, insufficient oxidation and carbonization of other substances, low content of lithium element in the solution and high impurity content, insufficient removal of impurities, and a decrease in purity of lithium carbonate.
The above embodiments are only for illustrating the technical solution of the present invention and not for limiting the scope of the present invention, and although the present invention has been described in detail with reference to the above embodiments, it should be understood by those skilled in the art that modifications or equivalent substitutions can be made to the technical solution of the present invention, but these modifications or substitutions are all within the scope of the present invention.
Claims (10)
1. The method for recycling refined lithium carbonate by using waste lithium-thionyl chloride batteries is characterized by comprising the following steps of:
s1, placing a positive electrode and a negative electrode obtained by disassembling and separating a battery in 950-1050 ℃ for roasting for 2-6 hours to obtain a sintered material;
s2, adding the sintering material into sulfuric acid solution, and carrying out solid-liquid separation to obtain a first solution and filter residues;
s3, adding sodium carbonate into the first solution to prepare lithium carbonate after the first solution is subjected to primary impurity removal and secondary impurity removal, and recycling iron by utilizing the filter residues;
the specific operation of the first impurity removal is as follows: adjusting the pH value of the first solution to 7-8, carrying out solid-liquid separation to obtain a second solution and a first precipitate, and recovering the second solution;
the specific operation of removing impurities again is as follows: adjusting the pH value of the second solution to 12-14, carrying out solid-liquid separation to obtain a third solution and a second precipitate, and recovering the third solution; and then adding the sodium carbonate into the third solution to prepare the lithium carbonate.
2. The method for recovering and refining lithium carbonate from waste lithium-thionyl chloride batteries according to claim 1, wherein the method comprises the following steps: in the step S1, the roasting time is 3 to 4 hours.
3. The method for recovering and refining lithium carbonate from waste lithium-thionyl chloride batteries according to claim 1, wherein the method comprises the following steps:
in the step S2, the mass fraction of the sulfuric acid solution is 5% -10%.
4. The method for recovering and refining lithium carbonate from waste lithium-thionyl chloride batteries according to claim 1, wherein in the step S3, before the first solution is subjected to impurity removal, the method further comprises the operations of sequentially performing pH adjustment and heating concentration on the first solution;
wherein, in the operation of pH adjustment, the pH of the first solution is adjusted to 6 to 7.
5. The method for recovering and refining lithium carbonate from a waste lithium-thionyl chloride battery according to claim 4, wherein the first solution is heated and concentrated to a lithium ion concentration of 7-13% in the solution.
6. The method for recovering and refining lithium carbonate from waste lithium-thionyl chloride batteries according to claims 1-5, which is characterized in that:
in the first impurity removal, the concentration of aluminum ions and chromium ions in the second solution is not higher than 100ppm;
in the secondary impurity removal, the concentration of iron ions, magnesium ions and nickel ions in the third solution is not higher than 50ppm.
7. The method for recovering and refining lithium carbonate from waste lithium-thionyl chloride battery according to claim 1, wherein the third solution is subjected to the following treatment:
adding sodium carbonate into the third solution, heating to 60-90 ℃ for reaction for 1.5-3 hours, carrying out solid-liquid separation to obtain a fourth solution and a third precipitate, recovering the third precipitate, and preparing the lithium carbonate by using the third precipitate.
8. The method for recovering and refining lithium carbonate from waste lithium-thionyl chloride battery according to claim 7, wherein the third precipitate is treated as follows:
mixing the third precipitate with water to obtain mixed slurry, introducing carbon dioxide into the mixed slurry, carrying out solid-liquid separation to obtain a fifth solution and a fourth precipitate, recovering the fifth solution, and carrying out heating decomposition on the fifth solution at 80-120 ℃ to obtain the lithium carbonate.
9. The method for recovering and refining lithium carbonate from waste lithium-thionyl chloride batteries according to claim 8, wherein the method comprises the steps of: the concentration of calcium ions in the fifth solution is not higher than 500ppm.
10. The method for recovering and refining lithium carbonate from waste lithium-thionyl chloride batteries according to claim 8, wherein the method comprises the steps of:
and adding the sodium carbonate into the third solution, wherein the molar ratio of lithium ions to carbonate is 2:1.05-1.25.
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