CN113026035B - Method for recovering lithium in lithium iron phosphate cathode material by utilizing waste incineration fly ash - Google Patents
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Abstract
The invention discloses a method for recovering lithium in a lithium iron phosphate cathode material by utilizing waste incineration fly ash, which fully utilizes the characteristic of high chlorine content of the waste incineration fly ash, utilizes the reaction of an electrolysis product of chlorine in the waste incineration fly ash and lithium iron phosphate cathode material powder to promote the dissolution of lithium ions in the lithium iron phosphate cathode material powder, and realizes the high-efficiency separation of lithium from chlorine, phosphorus and iron through a second electrolytic tank. The method has the advantages of simple process and strong operability, and can recover more than 96 percent of lithium in the lithium iron phosphate cathode material powder to the maximum extent.
Description
Technical Field
The field relates to a lithium ion battery recovery technology, in particular to a method for recovering lithium in a lithium iron phosphate cathode material by utilizing waste incineration fly ash.
Background
Lithium ion batteries play an indispensable role in energy regeneration. However, due to the service life of lithium batteries, scrapped lithium batteries endanger the sustainable resources and cause sustainable pollution to the environment. Recycling spent lithium ion batteries has become an essential step in the overall battery supply chain. Lithium iron phosphate batteries have been widely installed in electric vehicles due to their excellent safety.
Considering that lithium is a strategic element, the resource is limited, and the regional distribution is uneven, it is necessary to develop a new technology for recovering lithium in the lithium iron phosphate battery. Typical lithium battery recycling methods include pyrometallurgical, hydrometallurgical, biological, chemical, etc. methods. Because the chemical structure of the lithium iron phosphate battery is very stable, lithium in the lithium iron phosphate battery is difficult to effectively refine through a pyrolysis method (pyrometallurgy) and a microbial leaching technology.
Currently, most researchers are working on developing hydrometallurgical techniques, typically by mixing acid-oxygen water with various inorganic acids to dissolve lithium iron phosphate. However, the use of mixed acids during disposal is often prone to secondary contamination. Meanwhile, potential safety hazards exist in the storage and use processes of the hydrogen peroxide. Therefore, it is very important to solve the technical defects of the current lithium battery recycling technology if a lithium iron phosphate battery recycling method free from hydrogen peroxide and mixed acid can be developed.
Disclosure of Invention
The purpose of the invention is as follows: the invention aims to provide a method for recovering lithium in a lithium iron phosphate cathode material by utilizing waste incineration fly ash.
The technical scheme is as follows: the invention relates to a method for recovering lithium in a lithium iron phosphate cathode material by utilizing waste incineration fly ash, which is based on an electrolytic cell device to recover lithium ions in the lithium iron phosphate cathode material, wherein the electrolytic cell device comprises a first electrolytic cell and a second electrolytic cell, the first electrolytic cell and the second electrolytic cell respectively comprise an anode chamber, a cathode chamber, a sample area, an anode electrode and a cathode electrode, the anode chamber and the sample area of the first electrolytic cell are separated by an anion exchange membrane, and the anode electrode and the cathode electrode of the first electrolytic cell and the second electrolytic cell are respectively connected with a direct current power supply through leads, and the method comprises the following steps:
(1) putting the waste incineration fly ash in a sample area of a first electrolytic tank, and putting lithium iron phosphate cathode material powder in an anode chamber of the first electrolytic tank;
(2) adding water into the first electrolytic cell, and turning on a direct current power supply for disposal to obtain slurry;
(3) discharging slurry of an anode chamber of the first electrolytic cell to obtain acid-soluble lithium iron phosphate slurry;
(4) stirring and filtering the acid-soluble lithium iron phosphate slurry to obtain a liquid part which is a lithium iron phosphate chloride liquid;
(5) placing the lithium iron chloride phosphoric acid solution in a sample area of a second electrolytic tank, switching on a direct-current power supply for disposal, and discharging slurry in a cathode chamber of the second electrolytic tank to obtain lithium iron slurry;
(6) stirring the lithium iron slurry, and filtering to obtain a clear solution which is a lithium-containing solution.
Further, in the step (1), the mass ratio of the lithium iron phosphate cathode material powder to the waste incineration fly ash is 1-4: 10.
Further, in the step (2), the solid-to-solid ratio of the water in the first electrolytic tank to the waste incineration fly ash liquid is 0.5-2.5: 1mL: g,
further, in the step (2), the current of the DC power supply is 100-2000A, the voltage of the DC power supply is 20-400V, and the treatment time is 2-12 h.
Further, in the step (4), the stirring time is 1-6 h.
Further, in the step (5), the current of the DC power supply is 200-2000A, the voltage of the DC power supply is 20-200V, and the treatment time is 0.5-4.5 h.
Further, in the step (6), the stirring time is 10-30 min.
The reaction mechanism is as follows: after water is added into the first electrolytic tank, sodium chloride and potassium chloride salt in the waste incineration fly ash in the sample area of the first electrolytic tank are quickly dissolved into the water body. After the anode and the cathode of the first electrolytic tank are connected and electrified with direct current, chloride ions in the water body of the sample area of the first electrolytic tank rapidly migrate towards the anode electrode of the first electrolytic tank under the action of electromigration and are oxidized into chlorine after reaching the surface of the anode of the first electrolytic tank. The chlorine dissolves into the water in the anode chamber of the first electrolytic cell to generate hypochlorous acid and hydrochloric acid. And reacting the lithium iron phosphate cathode material powder placed in the anode chamber of the first electrolytic tank with hypochlorous acid and hydrochloric acid to generate acid-soluble lithium iron phosphate slurry containing lithium chloride, ferric phosphate and phosphoric acid. The acid-soluble lithium iron phosphate slurry is stirred to enable the reaction to be more sufficient, and the dissolution of the lithium iron phosphate cathode material powder is further promoted. And filtering the stirred acid-soluble lithium iron phosphate slurry to obtain a lithium iron chloride phosphoric acid solution containing lithium chloride, ferric chloride and phosphoric acid. And after the anode electrode and the cathode electrode of the second electrolytic tank are connected to a direct-current power supply through leads, iron ions and lithium ions in the lithium iron phosphate chloride solution migrate to the cathode of the second electrolytic tank. And water molecules on the surface of the cathode of the second electrolytic cell are hydrolyzed to generate hydrogen and hydroxyl. The hydroxyl radicals react with the iron ions and lithium ions that migrate to the cathode compartment of the second electrolytic cell to produce iron hydroxide and lithium hydroxide. The lithium iron slurry is stirred and then filtered to filter out ferric hydroxide, so as to obtain the lithium-containing solution.
Has the advantages that: compared with the prior art, the invention has the following remarkable advantages: the method fully utilizes the characteristic of high chlorine content of the waste incineration fly ash, utilizes the reaction of the electrolysis product of chlorine in the waste incineration fly ash and the lithium iron phosphate cathode material powder to promote the dissolution of lithium ions in the lithium iron phosphate cathode material powder, and realizes the high-efficiency separation of lithium from chlorine, phosphorus and iron through the second electrolytic tank. The method has the advantages of simple process and strong operability, and can recover more than 96 percent of lithium in the lithium iron phosphate cathode material powder to the maximum extent.
Drawings
FIG. 1 is a flow chart of the preparation process of the present invention.
Detailed Description
The technical scheme of the invention is further explained by combining the attached drawings.
The waste incineration fly ash comprises the following components: the household garbage incineration fly ash is taken from a certain normally-cooked garbage incineration power plant and collected by a bag-type dust collector. The waste incineration fly ash sample mainly contains 30-45% of CaO, 10-20% of Cl and 6-12% of Na2O、6％～12％K2O、3％～8％SO2、3％～8％SiO2、2％～6％MgO、2％～6％Fe2O3、2％～6％Al2O3、0.5％～1.5％CrO30.1 to 0.5 percent of CdO, 0.1 to 0.5 percent of NiO, 0.1 to 0.5 percent of PbO and the like.
The anion exchange membrane is purchased from national original science and technology and has the model of GCAM-S
Preparing lithium iron phosphate cathode material powder: the waste lithium iron phosphate battery is soaked in a saturated sodium chloride solution to be discharged for 24 hours so as to avoid spontaneous combustion of the battery in the later-period disassembly process. And drying the discharged waste lithium iron phosphate battery at 60 ℃ for 12 h. And (3) disassembling the dried waste lithium iron phosphate battery, and dividing the dried waste lithium iron phosphate battery into a cathode material, an anode material, an organic separator, other components and the like. The cathode material is pyrolyzed for 2h under vacuum at 450 ℃, and then the cathode material powder on the aluminum foil substrate is scraped for standby.
Example 1 influence of quality ratio of lithium iron phosphate cathode material powder and waste incineration fly ash on lithium recovery rate
As shown in fig. 1, lithium iron phosphate cathode material powder and waste incineration fly ash are respectively weighed according to a mass ratio of the lithium iron phosphate cathode material powder to the waste incineration fly ash of 0.5:10, 0.7:10, 0.9:10, 1:10, 2.5:10, 4:10, 4.5:10, 5:10 and 5.5:10, then the waste incineration fly ash is placed in a sample area of a first electrolytic cell, and the lithium iron phosphate cathode material powder is placed in an anode chamber of the first electrolytic cell. The anode chamber of the first electrolytic cell and the sample area of the first electrolytic cell are separated by an anion exchange membrane. Adding water into the first electrolytic tank according to the solid-to-liquid ratio of 0.5:1 mL/g of the waste incineration fly ash. Connecting an anode electrode and a cathode electrode of the first electrolytic tank to a direct current power supply through leads, turning on the power supply for treatment for 2h, and then discharging slurry in an anode chamber of the first electrolytic tank to obtain nine groups of acid-soluble lithium iron phosphate slurry, wherein the current of the direct current power supply is set to be 100A, and the voltage of the direct current power supply is set to be 20V. Stirring the acid-soluble lithium iron phosphate slurry for 1 hour, and filtering to obtain a liquid part which is a lithium iron chloride phosphoric acid solution, wherein the total amount is nine groups. And placing the lithium iron phosphate chloride solution in a sample area of a second electrolytic tank. Connecting an anode electrode and a cathode electrode of the second electrolytic cell to a direct current power supply through leads, turning on the power supply for disposal for 0.5h, and then discharging slurry in a cathode chamber of the second electrolytic cell to obtain nine groups of lithium iron slurry, wherein the current of the direct current power supply is 200A, and the voltage of the direct current power supply is 20V. Stirring the lithium iron slurry for 10 minutes, and filtering to obtain a clear solution which is a lithium-containing solution, wherein the clear solution comprises nine groups.
And (3) detecting the lithium concentration: the concentration of lithium ions in the lithium-containing solution was measured using an inductively coupled plasma emission spectrometer (model: 5900ICP-OES, Agilent). The specific test results of the lithium ion concentration in the lithium-containing solution of this example are shown in table 1.
TABLE 1 detection results of lithium ion concentration in lithium-containing solution
And (3) measuring the lithium content in the lithium iron phosphate cathode material powder: the lithium content in the lithium iron phosphate cathode material powder is measured according to the lithium iron phosphate chemical analysis method (YS/T1028). The lithium content in the lithium iron phosphate cathode material powder was determined to be 4.40%.
Lithium recoveryRate: the recovery rate of lithium in the lithium iron phosphate cathode material powder is calculated according to the formula (1), wherein RLiFor lithium recovery rate, V is the volume (L) of the lithium-containing solution, c is the concentration (mg/L) of lithium ions in the lithium-containing solution, m is the mass (mg) of the lithium iron phosphate cathode material powder, and α is the lithium content in the lithium iron phosphate cathode material powder. The test results of this example are shown in Table 2.
TABLE 2 influence of the quality ratio of lithium iron phosphate cathode material powder to waste incineration fly ash on the recovery rate of lithium
As can be seen from table 2, when the mass ratio of the lithium iron phosphate cathode material powder to the waste incineration fly ash is less than 1:10, the lithium recovery rate does not change significantly with the decrease in the mass ratio of the lithium iron phosphate cathode material powder to the waste incineration fly ash. When the mass ratio of the lithium iron phosphate cathode material powder to the waste incineration fly ash is 1-4: 10, connecting the anode and the cathode of the first electrolytic tank with direct current, rapidly transferring chloride ions in the water body of the sample area to the anode electrode of the first electrolytic tank under the action of electromigration, and oxidizing the chloride ions into chlorine after reaching the surface of the anode. The chlorine gas dissolves into the water in the anode chamber of the first electrolytic cell to generate hypochlorous acid and hydrochloric acid. And reacting the lithium iron phosphate cathode material powder placed in the anode chamber of the first electrolytic tank with hypochlorous acid and hydrochloric acid to generate acid-soluble lithium iron phosphate slurry containing lithium chloride, ferric phosphate and phosphoric acid. The acid-soluble lithium iron phosphate slurry is stirred to enable the reaction to be more sufficient, and the dissolution of the lithium iron phosphate cathode material powder is further promoted. And filtering the stirred acid-soluble lithium iron phosphate slurry to obtain a lithium iron chloride phosphoric acid solution containing lithium chloride, ferric chloride and phosphoric acid. Finally, the lithium recovery rates were all greater than 88%. When the mass ratio of the lithium iron phosphate cathode material powder to the waste incineration fly ash is more than 4:10, the lithium recovery rate is obviously reduced along with the further increase of the mass ratio of the lithium iron phosphate cathode material powder to the waste incineration fly ash. Therefore, the benefit and the cost are combined, and when the mass ratio of the lithium iron phosphate cathode material powder to the waste incineration fly ash is 1-4: 10, the lithium recovery rate of the lithium iron phosphate cathode material powder is improved.
Example 2 influence of liquid-solid ratio of fly ash from incineration of Water and garbage on lithium recovery ratio
Weighing lithium iron phosphate cathode material powder and waste incineration fly ash respectively according to the mass ratio of the lithium iron phosphate cathode material powder to the waste incineration fly ash of 2.5:10, then placing the waste incineration fly ash in a sample area of a first electrolytic tank, and placing the lithium iron phosphate cathode material powder in an anode chamber of the first electrolytic tank. The anode chamber of the first electrolytic cell and the sample area of the first electrolytic cell are separated by an anion exchange membrane. Water is added into the first electrolytic tank according to the solid-to-solid ratio of 0.25:1mL, 0.35:1mL, 0.45:1mL, 0.5:1mL, 1.5:1mL, 2.5:1mL, 2.6:1mL, 2.8:1mL and 3:1 mL. Connecting an anode electrode and a cathode electrode of the first electrolytic tank to a direct current power supply through leads, turning on the power supply for treatment for 7h, and then discharging slurry in an anode chamber of the first electrolytic tank to obtain nine groups of acid-soluble lithium iron phosphate slurry, wherein the current of the direct current power supply is set to 1050A, and the voltage of the direct current power supply is set to 210V. Stirring the acid-soluble lithium iron phosphate slurry for 3.5h, and filtering to obtain a liquid part which is a lithium iron chloride phosphoric acid solution, wherein the total amount is nine groups. And placing the lithium iron phosphate chloride solution in a sample area of a second electrolytic tank. Connecting an anode electrode and a cathode electrode of the second electrolytic cell to a direct current power supply through leads, turning on the power supply for treatment for 2.5h, and then discharging slurry in a cathode chamber of the second electrolytic cell to obtain nine groups of lithium iron slurry, wherein the current of the direct current power supply is 1100A, and the voltage of the direct current power supply is 110V. Stirring the lithium iron slurry for 20 minutes, and filtering to obtain a clear solution which is a lithium-containing solution, wherein the clear solution comprises nine groups.
The lithium ion concentration was measured in the same manner as in example 1, and the specific measurement results of the lithium ion concentration in the lithium-containing solution of this example are shown in Table 3.
TABLE 3 detection results of lithium ion concentration in lithium-containing solution
| Liquid-solid ratio of water to waste incineration fly ash | Concentration of lithium ions in lithium-containing solution | Relative error |
| 0.25:1mL:g | 314.89mg/L | ±0.1％ |
| 0.35:1mL:g | 341.07mg/L | ±0.1％ |
| 0.45:1mL:g | 360.95mg/L | ±0.1％ |
| 0.5:1mL:g | 381.54mg/L | ±0.1％ |
| 1.5:1mL:g | 391.37mg/L | ±0.1％ |
| 2.5:1mL:g | 396.50mg/L | ±0.1％ |
| 2.6:1mL:g | 369.30mg/L | ±0.1％ |
| 2.8:1mL:g | 344.21mg/L | ±0.2％ |
| 3:1mL:g | 317.05mg/L | ±0.2％ |
The lithium content in the lithium iron phosphate cathode material powder was measured in the same manner as in example 1, and the lithium content in the lithium iron phosphate cathode material powder was measured to be 4.40%.
Lithium recovery was calculated as in example 1. The test results of this example are shown in Table 4.
TABLE 4 influence of liquid-solid ratio of water and waste incineration fly ash on lithium recovery rate
As can be seen from Table 4, when the solid-to-solid ratio of water to the fly ash from incineration of refuse is less than 0.5:1mL: g, less water is added to the electrolytic cell, the migration resistance of chloride ions in the sample region of the first electrolytic cell is greater, and less hypochlorous acid is transferred to the anode chamber of the first electrolytic cell and converted, which finally results in a significant decrease in the recovery rate of phosphorus as the solid-to-solid ratio of water to fly ash from incineration of refuse decreases. When the solid-to-solid ratio of water to the waste incineration fly ash liquid is 0.5-2.5: 1mL: g, connecting the anode and the cathode of the first electrolytic cell with direct current, rapidly transferring chloride ions in the water body of the sample area of the first electrolytic cell to the anode electrode of the first electrolytic cell under the action of electromigration, and oxidizing the chloride ions into chlorine after reaching the surface of the anode of the first electrolytic cell. The chlorine dissolves into the water in the anode chamber of the first electrolytic cell to generate hypochlorous acid and hydrochloric acid. And reacting the lithium iron phosphate cathode material powder placed in the anode chamber of the first electrolytic tank with hypochlorous acid and hydrochloric acid to generate acid-soluble lithium iron phosphate slurry containing lithium chloride, ferric phosphate and phosphoric acid. Finally, the lithium recovery rates were all greater than 90%. When the liquid-solid ratio of the water to the waste incineration fly ash is more than 2.5:1mL: g, the lithium recovery rate is obviously reduced along with the further increase of the liquid-solid ratio of the water to the waste incineration fly ash. Therefore, the benefit and the cost are combined, and when the solid-to-liquid ratio of the water to the waste incineration fly ash is 0.5-2.5: 1mL: g, the lithium recovery rate of the lithium iron phosphate cathode material powder is improved.
Example 3 influence of stirring time of acid-soluble lithium iron phosphate slurry on lithium recovery rate
Weighing lithium iron phosphate cathode material powder and waste incineration fly ash respectively according to the mass ratio of the lithium iron phosphate cathode material powder to the waste incineration fly ash of 2.5:10, then placing the waste incineration fly ash in a sample area of a first electrolytic tank, and placing the lithium iron phosphate cathode material powder in an anode chamber of the first electrolytic tank. The anode chamber of the first electrolytic cell and the sample area of the first electrolytic cell are separated by an anion exchange membrane. Adding water into the first electrolytic tank according to the solid-to-liquid ratio of 2.5:1mL of the waste incineration fly ash. Connecting an anode electrode and a cathode electrode of the first electrolytic tank to a direct current power supply through leads, switching on the power supply for treatment for 12h, and then discharging slurry in an anode chamber of the first electrolytic tank to obtain acid-soluble lithium iron phosphate slurry, wherein the current of the direct current power supply is set to 2000A, and the voltage of the direct current power supply is set to 400V. Acid-soluble lithium iron phosphate slurry is respectively stirred for 0.5h, 0.7h, 0.9h, 1h, 3.5h, 6h, 6.2h, 6.5h and 7h, and filtered to obtain liquid part, namely lithium iron chloride phosphoric acid liquid, which is nine groups in total. And placing the lithium iron phosphate chloride solution in a sample area of a second electrolytic tank. Connecting an anode electrode and a cathode electrode of the second electrolytic cell to a direct current power supply through leads, turning on the power supply for treatment for 4.5h, and then discharging slurry in a cathode chamber of the second electrolytic cell to obtain nine groups of lithium iron slurry, wherein the current of the direct current power supply is 2000A, and the voltage of the direct current power supply is 200V. Stirring the lithium iron slurry for 30 minutes, and filtering to obtain a clear solution which is a lithium-containing solution, wherein the clear solution comprises nine groups.
The lithium ion concentration was measured in the same manner as in example 1, and the specific measurement results of the lithium ion concentration in the lithium-containing solution of this example are shown in Table 5.
TABLE 5 detection results of lithium ion concentration in lithium-containing solution
The lithium content in the lithium iron phosphate cathode material powder was measured in the same manner as in example 1, and the lithium content in the lithium iron phosphate cathode material powder was measured to be 4.40%.
Lithium recovery was calculated as in example 1. The test results of this example are shown in Table 6.
TABLE 6 influence of stirring time of acid-soluble lithium iron phosphate slurry on lithium recovery rate
As can be seen from table 6, when the stirring time of the acid-soluble lithium iron phosphate slurry is less than 1 hour, the stirring time is short, and the lithium iron phosphate cathode material powder is not sufficiently dissolved, the phosphorus recovery rate is significantly reduced as the stirring time of the acid-soluble lithium iron phosphate slurry is reduced. When the stirring time of the acid-soluble lithium iron phosphate slurry is equal to 1-6 h, the acid-soluble lithium iron phosphate slurry is stirred to enable the reaction to be more sufficient, and the dissolution of the lithium iron phosphate cathode material powder is further promoted. Finally, the lithium recovery rates were all greater than 91%. When the stirring time of the acid-soluble lithium iron phosphate slurry is longer than 6 hours, the lithium recovery rate does not change remarkably along with the further increase of the stirring time of the acid-soluble lithium iron phosphate slurry. Therefore, the benefits and the cost are combined, and when the stirring time of the acid-soluble lithium iron phosphate slurry is equal to 1-6 h, the lithium recovery rate of the lithium iron phosphate cathode material powder is improved.
Claims (4)
1. A method for recovering lithium in a lithium iron phosphate cathode material by utilizing waste incineration fly ash is characterized in that the method is based on an electrolytic cell device for recovering lithium ions in the lithium iron phosphate cathode material, the electrolytic cell device comprises a first electrolytic cell and a second electrolytic cell, the first electrolytic cell and the second electrolytic cell respectively comprise an anode chamber, a cathode chamber, a sample area, an anode electrode and a cathode electrode, the anode chamber and the sample area of the first electrolytic cell are separated by an anion exchange membrane, the anode electrode and the cathode electrode of the first electrolytic cell and the second electrolytic cell are respectively connected with a direct current power supply through leads, and the method comprises the following steps:
(1) placing waste incineration fly ash in a sample area of a first electrolytic tank, and placing lithium iron phosphate cathode material powder in an anode chamber of the first electrolytic tank, wherein the mass ratio of the lithium iron phosphate cathode material powder to the waste incineration fly ash is 1-4: 10;
(2) adding water into a first electrolytic tank, and turning on a direct current power supply to treat the water to obtain slurry, wherein the solid-to-solid ratio of the water to the waste incineration fly ash liquid in the first electrolytic tank is 0.5-2.5: 1mL: g;
(3) discharging slurry of an anode chamber of the first electrolytic cell to obtain acid-soluble lithium iron phosphate slurry;
(4) stirring and filtering the acid-soluble lithium iron phosphate slurry to obtain a liquid part which is a lithium iron phosphate chloride solution, wherein the stirring time is 1-6 h;
(5) placing the lithium iron chloride phosphoric acid solution in a sample area of a second electrolytic tank, switching on a direct-current power supply for disposal, and discharging slurry in a cathode chamber of the second electrolytic tank to obtain lithium iron slurry;
(6) stirring the lithium iron slurry, and filtering to obtain a clear solution which is a lithium-containing solution.
2. The method for recovering lithium in the lithium iron phosphate cathode material by using the waste incineration fly ash as claimed in claim 1, wherein in the step (2), the current of the direct current power supply is 100-2000A, the voltage of the direct current power supply is 20-400V, and the disposal time is 2-12 h.
3. The method for recovering lithium in the lithium iron phosphate cathode material by using the waste incineration fly ash as claimed in claim 1, wherein in the step (5), the current of the direct current power supply is 200-2000A, the voltage of the direct current power supply is 20-200V, and the disposal time is 0.5-4.5 h.
4. The method for recovering lithium in the lithium iron phosphate cathode material by using waste incineration fly ash as claimed in claim 1, wherein in the step (6), the stirring time is 10-30 min.
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