A recycling process for waste battery positive electrode materials

Abstract

The present invention relates to a recycling process for positive electrode materials of waste batteries, and belongs to the technical field of battery recycling. The specific recycling process includes the treatment of positive electrode materials of waste batteries, the adsorption of metal ions and the recovery of products. The present invention uses styrene-divinylbenzene copolymer as a carrier, and adopts four resins to cooperate with 1-ethyl-3-methylimidazole chloride solution to treat the positive electrode material. Through the series use of the four resins, the gradual separation and enrichment of metal ions are achieved, the interference of impurities is reduced, and the efficient and selective recovery of lithium, nickel, cobalt and manganese ions in the positive electrode materials of waste batteries is achieved, and the recovery rate of metal ions is effectively improved.

Description

Technical Field

[0001] The invention belongs to the technical field of battery recycling and relates to a recycling process for positive electrode materials of waste batteries. Background Art

[0002] The battery market has a wide range of applications, especially in mobile devices, electric vehicles, and energy storage systems. As these technologies become more popular, the amount of waste batteries generated is also increasing rapidly. The heavy metals and chemicals contained in these waste batteries, if not properly handled, will cause serious pollution to the environment. In addition, if the valuable materials in the battery, such as lithium, cobalt, and nickel, are not effectively recycled, it will lead to a waste of resources and increase the production costs of enterprises. The existing waste battery positive electrode material recycling scheme has some shortcomings, such as low recycling efficiency, possible secondary pollution, and high recycling costs, which limit its use in practical applications. In order to overcome these limitations, the research and improvement of waste battery positive electrode material recycling technology has become a top priority to promote the sustainable development of enterprises. Summary of the invention

[0003] The purpose of the present invention is to provide a recycling process for positive electrode materials of waste batteries. The present invention uses styrene-divinylbenzene copolymer as a carrier, adopts four resins to cooperate with 1-ethyl-3-methylimidazole chloride solution to treat the positive electrode material, and realizes the gradual separation and enrichment of metal ions through the series use of the four resins, reduces the interference of impurities, realizes the efficient and selective recovery of lithium, nickel, cobalt and manganese ions in the positive electrode materials of waste batteries, and effectively improves the recovery rate of metal ions.

[0004] The purpose of the present invention can be achieved by the following technical solutions:

[0005] A recycling process for waste battery positive electrode materials, the recycling process comprising the following steps:

[0006] (1) crushing the positive electrode material of the waste battery and passing it through a 100-200 mesh sieve to obtain a crushed material;

[0007] (2) mixing the crushed material with a 1-ethyl-3-methylimidazolium chloride solution, stirring at 55-65° C. for 3-5 hours to obtain a mixed material;

[0008] (3) mixing the mixture with resin 1, stirring, centrifuging, and filtering to obtain a lithium-containing adsorption resin and a filtrate 1; washing the lithium-containing adsorption resin, desorbing, and centrifuging; adjusting the pH of the aqueous phase, stirring, centrifuging, and filtering to obtain a lithium-containing precipitate; washing with deionized water, and drying in an oven at 80° C. for 24 h; and then calcining in a muffle furnace to obtain Li2O;

[0009] (4) mixing the filtrate 1 with the resin 2, stirring, centrifuging, and filtering to obtain a nickel-containing adsorption resin and the filtrate 2, washing the nickel-containing adsorption resin, desorbing, and centrifuging, adjusting the pH of the aqueous phase, stirring, centrifuging, and filtering to obtain a nickel-containing precipitate, washing with deionized water, and drying in an oven at 80° C. for 24 h, and then calcining in a muffle furnace to obtain NiO;

[0010] (5) mixing the filtrate 2 with the resin 3, stirring, centrifuging, filtering to obtain a cobalt-containing adsorption resin and the filtrate 3, washing the cobalt-containing adsorption resin, desorbing, centrifuging, adjusting the pH of the aqueous phase, stirring, centrifuging, filtering to obtain a cobalt-containing precipitate, washing with deionized water, drying in an oven at 80° C. for 24 h, and then calcining in a muffle furnace to obtain Co3O4;

[0011] (6) The filtrate 3 and the resin 4 are mixed and stirred, centrifuged, and filtered to obtain a manganese-containing adsorption resin and a filtrate 4; the manganese-containing adsorption resin is washed, desorbed, and centrifuged; the pH of the aqueous phase is adjusted, stirred, centrifuged, and filtered to obtain a manganese-containing precipitate; the precipitate is washed with deionized water, dried in an oven at 80° C. for 24 h, and then calcined in a muffle furnace to obtain Mn2O3.

[0012] Furthermore, the crushed material in step (2) is mixed with a 1-ethyl-3-methylimidazolium chloride solution at a mass ratio of 1:8-12; the concentration of the 1-ethyl-3-methylimidazolium chloride solution is 0.8-1.2 mol / L.

[0013] Furthermore, the preparation method of the resin 1 in the step (3) is: after mixing styrene-divinylbenzene copolymer, 3-aminopropyltriethoxysilane, tetrabutyl titanate and potassium persulfate, adding citric acid to adjust the pH to 2-4, introducing nitrogen, and stirring at room temperature for 0.5-1.5 days to obtain resin 1;

[0014] The mass ratio of the styrene-divinylbenzene copolymer, 3-aminopropyltriethoxysilane and tetrabutyl titanate is 10-12:1.3-1.5:0.8-1.2; the mass of the potassium persulfate accounts for 0.8-1.2% of the styrene-divinylbenzene copolymer.

[0015] Furthermore, the preparation method of the resin 2 in step (4) is: after mixing styrene-divinylbenzene copolymer, 4-vinylaniline, methacrylic acid and potassium persulfate, nitrogen is introduced, and stirred at 60-70° C. for 0.5-1.5 days to obtain resin 2;

[0016] The mass ratio of the styrene-divinylbenzene copolymer, 4-vinylaniline and methacrylic acid is 9-11:1-3:0.8-2.2; the mass of the potassium persulfate accounts for 1.1-1.5% of the styrene-divinylbenzene copolymer.

[0017] Furthermore, the preparation method of the resin 3 in step (5) is as follows: styrene-divinylbenzene copolymer, 4-vinylpyridine, diethylenetriamine and potassium persulfate are mixed, nitrogen is introduced, and the mixture is stirred at 65-75° C. for 0.5-1.5 d to obtain the resin 3;

[0018] The mass ratio of the styrene-divinylbenzene copolymer, 4-vinylpyridine and diethylenetriamine is 8-12:1.3-1.6:0.7-1.1; and the amount of potassium persulfate used accounts for 1.3-1.7% of the styrene-divinylbenzene copolymer.

[0019] Furthermore, the preparation method of the resin 4 in step (6) is: after mixing styrene-divinylbenzene copolymer, (3-acrylamidopropyl)trimethylammonium chloride, sodium styrene sulfonate and potassium persulfate, nitrogen is introduced, and the mixture is stirred at 80-90° C. for 0.5-1.5 d to obtain resin 4;

[0020] The mass ratio of the styrene-divinylbenzene copolymer, (3-acrylamidopropyl)trimethylammonium chloride and sodium styrene sulfonate is 9-13:1.4-2.2:0.9-1.7; the mass of the potassium persulfate accounts for 1.2-1.4% of the styrene-divinylbenzene copolymer.

[0021] Furthermore, the washing liquid used in the washing step is composed of dimethyl sulfoxide and deionized water in a mass ratio of 1.5-3.5:6.3-7.9; the parameters of the desorption step are: the mass of the desorption liquid is 8-12 times that of the corresponding desorbed resin, and the desorption time is 1-2h; the desorption liquid is composed of dilute hydrochloric acid solution and EDTA solution in a mass ratio of 1:0.38-0.72, the concentration of the dilute hydrochloric acid solution is 0.04-0.1mol / L, and the concentration of the EDTA solution is 0.1-0.3mol / L.

[0022] Furthermore, the pH in step (3) is adjusted to 9.5-11.5; the pH in step (4) is adjusted to 10-12; the pH in step (5) is adjusted to 7-9; the pH in step (6) is adjusted to 8-10; the reagents used for adjusting the pH are all NaOH solutions with a concentration of 0.5-1.5 mol / L; the dripping speed of the NaOH solution is controlled to 4-6 mL / min.

[0023] Furthermore, the parameters of the centrifugation step are: at room temperature, the centrifugal speed is 2000-6000 rpm, and the centrifugal time is 10-20 min; the pore size of the filter membrane used in the filtration step is 0.45 μm; and the speed of the stirring step is 40-120 rpm.

[0024] Beneficial effects of the present invention:

[0025] The present invention utilizes 1-ethyl-3-methylimidazolium chloride solution to promote the dissolution and release of metal ions from positive electrode materials. The imidazole ring in the 1-ethyl-3-methylimidazolium chloride solution can form a stable complex with the metal ions, protect the metal ions from being precipitated or polymerized, form a stable and uniform dissolving solution, improve the interface effect between the positive electrode material and the resin, and help the metal ions to achieve transfer from the solid surface to the resin.

[0026] The silanol groups in the 3-aminopropyltriethoxysilane in the resin 1 of the present invention can covalently bond with the benzene rings on the surface of the styrene-divinylbenzene copolymer, and at the same time introduce amino groups; tetrabutyl titanate is hydrolyzed under acidic conditions, and during the hydrolysis process, the butoxy groups of the tetrabutyl titanate are replaced by water molecules to form Ti-OH groups, and these Ti-OH groups can undergo condensation reactions with the amino groups introduced after the surface modification of the styrene-divinylbenzene copolymer to form stable Ti-O-Si bonds, thereby fixing TiO2 nanoparticles on the surface of the styrene-divinylbenzene copolymer to generate TiO2, and the high specific surface area of ​​TiO2 provides more physical adsorption sites for lithium ions, and then ion exchange occurs with lithium ions through the negative charge sites on the TiO2 surface, and the oxygen atoms on the TiO2 surface can interact with lithium ions to form surface complexes, thereby achieving adsorption of lithium ions.

[0027] The 4-vinylaniline and methacrylic acid in the resin 2 of the present invention introduce an amine group and a carboxylic acid group on the surface of the copolymer. The nitrogen atom of the amine group and the oxygen atom of the carboxylic acid group both contain lone pairs of electrons and can serve as electron donors. The nickel ion, as a Lewis acid, can accept lone pairs of electrons from oxygen and nitrogen atoms in its empty d orbital to form a coordination bond when the nickel ion approaches the carboxylic acid group and the amine group. In general, the nickel ion tends to form an octahedral coordination geometry in which six coordination sites are evenly distributed around the nickel ion. In this case, the two carboxylic acid groups and the four amine groups can serve as ligands, providing their oxygen and nitrogen atoms as coordination sites, thereby achieving adsorption of the nickel ion.

[0028] 4-vinylpyridine in the resin 3 of the present invention is used as a nitrogen-containing monomer to introduce basic nitrogen atoms through polymerization to form an amine functional group containing a lone pair of electrons, which is helpful to form a stable aminated graft chain and form a stable complex with the cobalt ion through a coordination bond; diethylenetriamine is used as a polyamine monomer, which increases the density of the amine functional group in the polymer, helps to form a multi-dentate coordination environment and thus enhances the adsorption capacity for cobalt ions. The presence of the polyamine group may also enhance the adsorption of hydrated water molecules of cobalt ions through hydrogen bonding, thereby improving the affinity of the adsorbent for cobalt ions; cobalt ions exist in the form of hydrated ions in the solution. When they come into contact with the amine functional group, a stable coordination bond is formed due to the interaction between the lone pair of electrons on the nitrogen atom and the empty d orbital of the cobalt ion. The formation of the coordination bond causes the cobalt ion to be desolvated from the solution and fixed on the surface of the polymer, thereby achieving adsorption of the cobalt ion.

[0029] The (3-acrylamidopropyl)trimethylammonium chloride and sodium styrene sulfonate in the resin 4 of the present invention introduce quaternary ammonium salt and sulfonic acid group on the surface of the copolymer, wherein the strong adsorption capacity of the quaternary ammonium salt and sulfonic acid group helps the metal ions to diffuse quickly into the interior of the resin, the quaternary ammonium salt functional group combines with the manganese ion through ion exchange, and the sulfonic acid functional group combines with the manganese ion by forming a stable ion-dipole interaction or coordination bond, thereby enhancing the adsorption of manganese ions.

[0030] The styrene-divinylbenzene copolymer in the present invention has a three-dimensional cross-linked network structure as a polymer carrier. The network structure not only provides a large number of physical adsorption sites, but also gives the material excellent pore characteristics and mechanical properties, so that the material can maintain structural stability in multiple adsorption-desorption cycles. The styrene-divinylbenzene copolymer is used as a carrier to treat the positive electrode material with four resins in coordination with a 1-ethyl-3-methylimidazole chloride solution. Through the series use of the four resins, the gradual separation and enrichment of metal ions are achieved, the interference of impurities is reduced, and the efficient and selective recovery of lithium, nickel, cobalt and manganese ions in the positive electrode material of waste batteries is achieved, and the recovery rate of metal ions is effectively improved. DETAILED DESCRIPTION

[0031] In order to further illustrate the technical means and effects adopted by the present invention to achieve the predetermined invention purpose, the specific implementation methods, structures, features and effects of the present invention are described in detail below in combination with the embodiments.

[0032] Example 1

[0033] A recycling process for waste battery positive electrode materials, the recycling process of this embodiment comprises the following steps:

[0034] (1) crushing the positive electrode material of the waste battery and passing it through a 100-mesh sieve to obtain a crushed material;

[0035] (2) mixing the crushed material with a 1-ethyl-3-methylimidazolium chloride solution, and stirring at 55° C. for 3 h to obtain a mixture;

[0036] (3) The mixed material and resin 1 are mixed and stirred at a mass ratio of 1:0.02, centrifuged, and filtered to obtain a lithium-containing adsorption resin and a filtrate 1, the lithium-containing adsorption resin is washed, desorbed, and centrifuged, the pH of the aqueous phase is adjusted, stirred, centrifuged, and filtered to obtain a lithium-containing precipitate, which is washed with deionized water and dried in an oven at 80° C. for 24 hours, and then calcined in a muffle furnace to obtain Li2O;

[0037] (4) mixing the filtrate 1 and the resin 2 in a mass ratio of 1:0.02, centrifuging, filtering to obtain a nickel-containing adsorption resin and a filtrate 2, washing the nickel-containing adsorption resin, desorbing, centrifuging, adjusting the pH of the aqueous phase, stirring, centrifuging, filtering to obtain a nickel-containing precipitate, washing with deionized water, drying in an oven at 80° C. for 24 h, and then calcining in a muffle furnace to obtain NiO;

[0038] (5) mixing the filtrate 2 and the resin 3 in a mass ratio of 1:0.02, centrifuging, filtering to obtain a cobalt-containing adsorption resin and a filtrate 3, washing the cobalt-containing adsorption resin, desorbing, centrifuging, adjusting the pH of the aqueous phase, stirring, centrifuging, filtering to obtain a cobalt-containing precipitate, washing with deionized water, drying in an oven at 80° C. for 24 h, and then calcining in a muffle furnace to obtain Co3O4;

[0039] (6) The filtrate 3 and the resin 4 are mixed and stirred in a mass ratio of 1:0.02, centrifuged, and filtered to obtain a manganese-containing adsorption resin and a filtrate 4. The manganese-containing adsorption resin is washed, desorbed, and centrifuged. The pH of the aqueous phase is adjusted, stirred, centrifuged, and filtered to obtain a manganese-containing precipitate. After washing with deionized water, the precipitate is dried in an oven at 80° C. for 24 hours, and then calcined in a muffle furnace to obtain Mn2O3.

[0040] The crushed material in step (2) of this embodiment is mixed with 1-ethyl-3-methylimidazolium chloride solution in a mass ratio of 1:8; the concentration of the 1-ethyl-3-methylimidazolium chloride solution in this embodiment is 0.8 mol / L.

[0041] The preparation method of resin 1 in step (3) of this embodiment is as follows: styrene-divinylbenzene copolymer, 3-aminopropyltriethoxysilane, tetrabutyl titanate and potassium persulfate are mixed, citric acid is added dropwise to adjust the pH to 2, nitrogen is introduced, and the mixture is stirred at room temperature for 0.5 d to obtain resin 1;

[0042] The mass ratio of the styrene-divinylbenzene copolymer, 3-aminopropyltriethoxysilane and tetrabutyl titanate in this embodiment is 10:1.3:0.8; the mass of the potassium persulfate in this embodiment accounts for 0.8% of the styrene-divinylbenzene copolymer.

[0043] The preparation method of resin 2 in step (4) of this embodiment is as follows: styrene-divinylbenzene copolymer, 4-vinylaniline, methacrylic acid and potassium persulfate are mixed, nitrogen is introduced, and the mixture is stirred at 60° C. for 0.5 to obtain resin 2;

[0044] The mass ratio of the styrene-divinylbenzene copolymer, 4-vinylaniline and methacrylic acid in this embodiment is 9:1:0.8; the mass of the potassium persulfate in this embodiment accounts for 1.1% of the styrene-divinylbenzene copolymer.

[0045] The preparation method of resin 3 in step (5) of this embodiment is as follows: styrene-divinylbenzene copolymer, 4-vinylpyridine, diethylenetriamine and potassium persulfate are mixed, nitrogen is introduced, and the mixture is stirred at 65° C. for 0.5 d to obtain resin 3;

[0046] The mass ratio of the styrene-divinylbenzene copolymer, 4-vinylpyridine and diethylenetriamine in this embodiment is 8:1.3:0.7; the amount of potassium persulfate in this embodiment accounts for 1.3% of the styrene-divinylbenzene copolymer.

[0047] The preparation method of resin 4 in step (6) of this embodiment is as follows: styrene-divinylbenzene copolymer, (3-acrylamidopropyl)trimethylammonium chloride, sodium styrene sulfonate and potassium persulfate are mixed, nitrogen is introduced, and the mixture is stirred at 80° C. for 0.5 d to obtain resin 4;

[0048] The mass ratio of the styrene-divinylbenzene copolymer, (3-acrylamidopropyl)trimethylammonium chloride and sodium styrene sulfonate in this embodiment is 9:1.4:0.9; the mass of the potassium persulfate in this embodiment accounts for 1.2% of the styrene-divinylbenzene copolymer.

[0049] The washing liquid used in the washing step of this embodiment is composed of dimethyl sulfoxide and deionized water in a mass ratio of 1.5:6.3; the parameters of the desorption step of this embodiment are: the mass of the desorption liquid is 8 times that of the corresponding desorbed resin, and the desorption time is 1h; the desorption liquid of this embodiment is composed of dilute hydrochloric acid solution and EDTA solution in a mass ratio of 1:0.38, the concentration of the dilute hydrochloric acid solution of this embodiment is 0.04mol / L, and the concentration of the EDTA solution of this embodiment is 0.1mol / L.

[0050] The pH in step (3) of this embodiment is adjusted to 9.5; the pH in step (4) of this embodiment is adjusted to 10; the pH in step (5) of this embodiment is adjusted to 7; the pH in step (6) of this embodiment is adjusted to 8; the reagents used for adjusting the pH in this embodiment are all NaOH solutions with a concentration of 0.5 mol / L; the dropping speed of the NaOH solution in this embodiment is controlled to 4 mL / min.

[0051] The parameters of the centrifugation step of this embodiment are: at room temperature, the centrifugal speed is 2000 rpm, and the centrifugation time is 10 min; the pore size of the filter membrane used in the filtration step of this embodiment is 0.45 μm; the speed of the stirring step of this embodiment is 40 rpm.

[0052] Example 2

[0053] A recycling process for waste battery positive electrode materials, the recycling process of this embodiment comprises the following steps:

[0054] (1) crushing the positive electrode material of the waste battery and passing it through a 200-mesh sieve to obtain a crushed material;

[0055] (2) mixing the crushed material with a 1-ethyl-3-methylimidazolium chloride solution, and stirring at 65° C. for 5 h to obtain a mixture;

[0056] (3) The mixed material and resin 1 are mixed and stirred at a mass ratio of 1:0.08, centrifuged, and filtered to obtain a lithium-containing adsorption resin and a filtrate 1, the lithium-containing adsorption resin is washed, desorbed, and centrifuged, the pH of the aqueous phase is adjusted, stirred, centrifuged, and filtered to obtain a lithium-containing precipitate, which is washed with deionized water and dried in an oven at 80° C. for 24 h, and then calcined in a muffle furnace to obtain Li2O;

[0057] (4) mixing the filtrate 1 and the resin 2 in a mass ratio of 1:0.08, centrifuging, filtering to obtain a nickel-containing adsorption resin and a filtrate 2, washing the nickel-containing adsorption resin, desorbing, centrifuging, adjusting the pH of the aqueous phase, stirring, centrifuging, filtering to obtain a nickel-containing precipitate, washing with deionized water, drying in an oven at 80° C. for 24 h, and then calcining in a muffle furnace to obtain NiO;

[0058] (5) mixing the filtrate 2 and the resin 3 in a mass ratio of 1:0.08, centrifuging, filtering to obtain a cobalt-containing adsorption resin and a filtrate 3, washing the cobalt-containing adsorption resin, desorbing, centrifuging, adjusting the pH of the aqueous phase, stirring, centrifuging, filtering to obtain a cobalt-containing precipitate, washing with deionized water, drying in an oven at 80° C. for 24 h, and then calcining in a muffle furnace to obtain Co3O4;

[0059] (6) The filtrate 3 and the resin 4 are mixed and stirred at a mass ratio of 1:0.08, centrifuged, and filtered to obtain a manganese-containing adsorption resin and a filtrate 4. The manganese-containing adsorption resin is washed, desorbed, and centrifuged. The pH of the aqueous phase is adjusted, stirred, centrifuged, and filtered to obtain a manganese-containing precipitate. After washing with deionized water, the precipitate is dried in an oven at 80° C. for 24 hours, and then calcined in a muffle furnace to obtain Mn2O3.

[0060] The crushed material in step (2) of this embodiment is mixed with 1-ethyl-3-methylimidazolium chloride solution in a mass ratio of 1:12; the concentration of the 1-ethyl-3-methylimidazolium chloride solution in this embodiment is 1.2 mol / L.

[0061] The preparation method of resin 1 in step (3) of this embodiment is as follows: styrene-divinylbenzene copolymer, 3-aminopropyltriethoxysilane, tetrabutyl titanate and potassium persulfate are mixed, citric acid is added dropwise to adjust the pH to 4, nitrogen is introduced, and the mixture is stirred at room temperature for 1.5 days to obtain resin 1;

[0062] The mass ratio of the styrene-divinylbenzene copolymer, 3-aminopropyltriethoxysilane and tetrabutyl titanate in this embodiment is 12:1.5:1.2; the mass of the potassium persulfate in this embodiment accounts for 1.2% of the styrene-divinylbenzene copolymer.

[0063] The preparation method of resin 2 in step (4) of this embodiment is as follows: styrene-divinylbenzene copolymer, 4-vinylaniline, methacrylic acid and potassium persulfate are mixed, nitrogen is introduced, and the mixture is stirred at 70° C. for 1.5 days to obtain resin 2;

[0064] The mass ratio of the styrene-divinylbenzene copolymer, 4-vinylaniline and methacrylic acid in this embodiment is 11:3:2.2; the mass of the potassium persulfate in this embodiment accounts for 1.5% of the styrene-divinylbenzene copolymer.

[0065] The preparation method of resin 3 in step (5) of this embodiment is as follows: styrene-divinylbenzene copolymer, 4-vinylpyridine, diethylenetriamine and potassium persulfate are mixed, nitrogen is introduced, and the mixture is stirred at 75° C. for 1.5 days to obtain resin 3;

[0066] The mass ratio of the styrene-divinylbenzene copolymer, 4-vinylpyridine and diethylenetriamine in this embodiment is 12:1.6:1.1; the amount of potassium persulfate in this embodiment accounts for 1.7% of the styrene-divinylbenzene copolymer.

[0067] The preparation method of resin 4 in step (6) of this embodiment is as follows: styrene-divinylbenzene copolymer, (3-acrylamidopropyl)trimethylammonium chloride, sodium styrene sulfonate and potassium persulfate are mixed, nitrogen is introduced, and the mixture is stirred at 90° C. for 1.5 days to obtain resin 4;

[0068] The mass ratio of the styrene-divinylbenzene copolymer, (3-acrylamidopropyl)trimethylammonium chloride and sodium styrene sulfonate in this embodiment is 13:2.2:1.7; the mass of the potassium persulfate in this embodiment accounts for 1.4% of the styrene-divinylbenzene copolymer.

[0069] The washing liquid used in the washing step of this embodiment is composed of dimethyl sulfoxide and deionized water in a mass ratio of 3.5:7.9; the parameters of the desorption step of this embodiment are: the mass of the desorption liquid is 12 times that of the corresponding desorbed resin, and the desorption time is 2h; the desorption liquid of this embodiment is composed of dilute hydrochloric acid solution and EDTA solution in a mass ratio of 1:0.72, the concentration of the dilute hydrochloric acid solution of this embodiment is 0.1mol / L, and the concentration of the EDTA solution of this embodiment is 0.3mol / L.

[0070] The pH in step (3) of this embodiment is adjusted to 11.5; the pH in step (4) of this embodiment is adjusted to 12; the pH in step (5) of this embodiment is adjusted to 9; the pH in step (6) of this embodiment is adjusted to 10; the reagents used for adjusting the pH in this embodiment are all NaOH solutions with a concentration of 1.5 mol / L; the dropping speed of the NaOH solution in this embodiment is controlled to 6 mL / min.

[0071] The parameters of the centrifugation step of this embodiment are: at room temperature, the centrifugal speed is 6000 rpm, and the centrifugation time is 20 min; the pore size of the filter membrane used in the filtration step of this embodiment is 0.45 μm; the speed of the stirring step of this embodiment is 120 rpm.

[0072] Example 3

[0073] A recycling process for waste battery positive electrode materials, the recycling process of this embodiment comprises the following steps:

[0074] (1) crushing the positive electrode material of the waste battery and passing it through a 150-mesh sieve to obtain a crushed material;

[0075] (2) mixing the crushed material with a 1-ethyl-3-methylimidazolium chloride solution, and stirring at 60° C. for 4 hours to obtain a mixture;

[0076] (3) The mixed material and resin 1 are mixed and stirred at a mass ratio of 1:0.05, centrifuged, and filtered to obtain a lithium-containing adsorption resin and a filtrate 1, the lithium-containing adsorption resin is washed, desorbed, and centrifuged, the pH of the aqueous phase is adjusted, stirred, centrifuged, and filtered to obtain a lithium-containing precipitate, which is washed with deionized water and dried in an oven at 80° C. for 24 hours, and then calcined in a muffle furnace to obtain Li2O;

[0077] (4) mixing the filtrate 1 and the resin 2 in a mass ratio of 1:0.05, centrifuging, filtering to obtain a nickel-containing adsorption resin and the filtrate 2, washing the nickel-containing adsorption resin, desorbing, centrifuging, adjusting the pH of the aqueous phase, stirring, centrifuging, filtering to obtain a nickel-containing precipitate, washing with deionized water, drying in an oven at 80° C. for 24 h, and then calcining in a muffle furnace to obtain NiO;

[0078] (5) mixing the filtrate 2 and the resin 3 in a mass ratio of 1:0.05, centrifuging, filtering to obtain a cobalt-containing adsorption resin and a filtrate 3, washing the cobalt-containing adsorption resin, desorbing, centrifuging, adjusting the pH of the aqueous phase, stirring, centrifuging, filtering to obtain a cobalt-containing precipitate, washing with deionized water, drying in an oven at 80° C. for 24 h, and then calcining in a muffle furnace to obtain Co3O4;

[0079] (6) The filtrate 3 and the resin 4 are mixed and stirred at a mass ratio of 1:0.05, centrifuged, and filtered to obtain a manganese-containing adsorption resin and a filtrate 4. The manganese-containing adsorption resin is washed, desorbed, and centrifuged. The pH of the aqueous phase is adjusted, stirred, centrifuged, and filtered to obtain a manganese-containing precipitate. After washing with deionized water, the precipitate is dried in an oven at 80° C. for 24 hours, and then calcined in a muffle furnace to obtain Mn2O3.

[0080] The crushed material in step (2) of this embodiment is mixed with 1-ethyl-3-methylimidazolium chloride solution in a mass ratio of 1:10; the concentration of the 1-ethyl-3-methylimidazolium chloride solution in this embodiment is 1 mol / L.

[0081] The preparation method of resin 1 in step (3) of this embodiment is as follows: styrene-divinylbenzene copolymer, 3-aminopropyltriethoxysilane, tetrabutyl titanate and potassium persulfate are mixed, citric acid is added dropwise to adjust the pH to 3, nitrogen is introduced, and the mixture is stirred at room temperature for 1 day to obtain resin 1;

[0082] The mass ratio of the styrene-divinylbenzene copolymer, 3-aminopropyltriethoxysilane and tetrabutyl titanate in this embodiment is 11:1.4:1; the mass of the potassium persulfate in this embodiment accounts for 1% of the styrene-divinylbenzene copolymer.

[0083] The preparation method of resin 2 in step (4) of this embodiment is as follows: styrene-divinylbenzene copolymer, 4-vinylaniline, methacrylic acid and potassium persulfate are mixed, nitrogen is introduced, and the mixture is stirred at 65° C. for 1 day to obtain resin 2;

[0084] The mass ratio of the styrene-divinylbenzene copolymer, 4-vinylaniline and methacrylic acid in this embodiment is 10:2:1.5; the mass of the potassium persulfate in this embodiment accounts for 1.3% of the styrene-divinylbenzene copolymer.

[0085] The preparation method of resin 3 in step (5) of this embodiment is as follows: styrene-divinylbenzene copolymer, 4-vinylpyridine, diethylenetriamine and potassium persulfate are mixed, nitrogen is introduced, and the mixture is stirred at 70° C. for 1 day to obtain resin 3;

[0086] The mass ratio of the styrene-divinylbenzene copolymer, 4-vinylpyridine and diethylenetriamine in this embodiment is 10:1.45:0.9; the amount of potassium persulfate in this embodiment accounts for 1.5% of the styrene-divinylbenzene copolymer.

[0087] The preparation method of resin 4 in step (6) of this embodiment is as follows: styrene-divinylbenzene copolymer, (3-acrylamidopropyl)trimethylammonium chloride, sodium styrene sulfonate and potassium persulfate are mixed, nitrogen is introduced, and the mixture is stirred at 85° C. for 1 day to obtain resin 4;

[0088] The mass ratio of the styrene-divinylbenzene copolymer, (3-acrylamidopropyl)trimethylammonium chloride and sodium styrene sulfonate in this embodiment is 11:1.8:1.3; the mass of the potassium persulfate in this embodiment accounts for 1.3% of the styrene-divinylbenzene copolymer.

[0089] The washing liquid used in the washing step of this embodiment is composed of dimethyl sulfoxide and deionized water in a mass ratio of 2.5:7.1; the parameters of the desorption step of this embodiment are: the mass of the desorption liquid is 10 times that of the corresponding desorbed resin, and the desorption time is 1.5h; the desorption liquid of this embodiment is composed of dilute hydrochloric acid solution and EDTA solution in a mass ratio of 1:0.55, the concentration of the dilute hydrochloric acid solution of this embodiment is 0.07mol / L, and the concentration of the EDTA solution of this embodiment is 0.2mol / L.

[0090] The pH in step (3) of this embodiment is adjusted to 10.5; the pH in step (4) of this embodiment is adjusted to 11; the pH in step (5) of this embodiment is adjusted to 8; the pH in step (6) of this embodiment is adjusted to 9; the reagents used for adjusting the pH in this embodiment are all NaOH solutions with a concentration of 1 mol / L; the dropping speed of the NaOH solution in this embodiment is controlled to 5 mL / min.

[0091] The parameters of the centrifugation step of this embodiment are: at room temperature, the centrifugal speed is 4000 rpm, and the centrifugation time is 15 min; the pore size of the filter membrane used in the filtration step of this embodiment is 0.45 μm; the speed of the stirring step of this embodiment is 80 rpm.

[0092] Comparative Example 1

[0093] On the basis of Example 3, step (2) was removed and gradient resin treatment was directly performed, and other conditions were consistent with Example 3.

[0094] Comparative Example 2

[0095] On the basis of Example 3, the styrene-divinylbenzene copolymer was removed and replaced with an equal weight of polyethylene, and the other conditions were consistent with Example 3.

[0096] Comparative Example 3

[0097] On the basis of Example 3, the desorption liquid in step (4) was changed to deionized water, and the other conditions were consistent with Example 3.

[0098] Comparative Example 4

[0099] On the basis of Example 3, tetrabutyl titanate in Resin 1 was removed and replaced with methacrylic acid of equal weight, and other conditions were consistent with Example 3.

[0100] Comparative Example 5

[0101] On the basis of Example 3, methacrylic acid in Resin 2 was removed and replaced with an equal weight of 4-vinylaniline. Other conditions were consistent with those in Example 3.

[0102] Comparative Example 6

[0103] On the basis of Example 3, the diethylenetriamine in Resin 3 was removed and replaced with an equal weight of 4-vinylpyridine. Other conditions were the same as those in Example 3.

[0104] Comparative Example 7

[0105] On the basis of Example 3, (3-acrylamidopropyl)trimethylammonium chloride in Resin 4 was removed and replaced with an equal weight of sodium styrene sulfonate. Other conditions were consistent with those in Example 3.

[0106] The Li2O, NiO, Co3O4 and Mn2O3 recovered in Examples 1-3 and Comparative Examples 1-3 were weighed respectively, and the comprehensive recovery rates of lithium, nickel, cobalt and manganese were calculated. The results are recorded as shown in Table 1.

[0107] Table 1

[0108]

[0109] As shown in Table 1, the comprehensive recovery rates of lithium, nickel, cobalt and manganese obtained by the recovery schemes of Examples 1-3 are significantly higher than those of Comparative Examples 1-3, indicating that the recovery process of the present invention can well recover lithium, nickel, cobalt and manganese, and improve the overall recovery rate of waste battery positive electrode materials. Comparative Example 1 removes the auxiliary leaching of waste battery positive electrode materials by 1-ethyl-3-methylimidazolium chloride solution, which may lead to a decrease in the release rate of metal ions, or cause the metal ions to spontaneously precipitate and aggregate in the subsequent recovery process; Comparative Example 2 replaces styrene-divinylbenzene copolymer with polyethylene, which lacks the network structure, pore characteristics and mechanical properties of styrene-divinylbenzene copolymer, and cannot maintain structural stability in multiple adsorption-desorption cycles, affecting the introduction of subsequent functional groups; Comparative Example 3 replaces dimethyl sulfoxide with deionized water and uses deionized water as a washing liquid, dimethyl sulfoxide can penetrate the polymer network and dissolve various types of residues, while deionized water is only used to rinse water-soluble impurities, and cannot effectively remove unreacted monomers and initiator residues on the adsorption resin, which affects the subsequent desorption recovery process.

[0110] In Comparative Examples 4-7, the monomers introduced into the resins were changed. The comprehensive recovery rates of lithium obtained from Resin 1 in Comparative Example 4 and nickel obtained from Resin 2 in Comparative Example 5 were significantly increased, while the comprehensive recovery rates of other metal ions were decreased, indicating that the recovery products of the changed resins were mixed with other metal products and the required metals could not be effectively recovered; the comprehensive recovery rates of cobalt obtained from Resin 3 in Comparative Example 6 and manganese obtained from Resin 4 in Comparative Example 7 were significantly decreased, indicating that the single monomer could not achieve the adsorption effect of the composite monomer used in the present invention on cobalt and manganese metal ions.

[0111] The above description is only a preferred embodiment of the present invention and does not limit the present invention in any form. Although the present invention has been disclosed as a preferred embodiment as above, it is not used to limit the present invention. Any technical personnel in this field can make some changes or modify the technical contents disclosed above into equivalent embodiments without departing from the scope of the technical solution of the present invention. However, any brief modifications, equivalent changes and modifications made to the above embodiments based on the technical essence of the present invention without departing from the content of the technical solution of the present invention are still within the scope of the technical solution of the present invention.

Claims

1. A process for recycling positive electrode materials of waste batteries, characterized in that: The recovery process comprises the following steps: (1) The positive electrode material of the waste battery is crushed and passed through a 100-200 mesh sieve to obtain a crushed material; (2) Mixing the crushed material with 1-ethyl-3-methylimidazolium chloride solution, stirring at 55-65° C. for 3-5 hours to obtain a mixture; (3) The mixed material and resin 1 are mixed and stirred, centrifuged, and filtered to obtain a lithium-containing adsorption resin and a filtrate 1; the lithium-containing adsorption resin is washed, desorbed, and centrifuged; the pH of the aqueous phase is adjusted, stirred, centrifuged, and filtered to obtain a lithium-containing precipitate; the precipitate is washed with deionized water, dried in an oven at 80° C. for 24 h, and then calcined in a muffle furnace to obtain Li2O; (4) Mixing the filtrate 1 and the resin 2, stirring, centrifuging, and filtering to obtain a nickel-containing adsorption resin and a filtrate 2, washing the nickel-containing adsorption resin, desorbing, and centrifuging, adjusting the pH of the aqueous phase, stirring, centrifuging, and filtering to obtain a nickel-containing precipitate, washing with deionized water, and drying in an oven at 80° C. for 24 hours, and then calcining in a muffle furnace to obtain NiO; (5) Mixing the filtrate 2 and the resin 3, stirring, centrifuging, and filtering to obtain the cobalt-containing adsorption resin and the filtrate 3, washing the cobalt-containing adsorption resin, desorbing, and centrifuging, adjusting the pH of the aqueous phase, stirring, centrifuging, and filtering to obtain a cobalt-containing precipitate, washing with deionized water, and drying in an oven at 80°C for 24 hours, and then calcining in a muffle furnace to obtain Co3O4; (6) Mixing the filtrate 3 and the resin 4, stirring, centrifuging, and filtering to obtain a manganese-containing adsorption resin and a filtrate 4, washing the manganese-containing adsorption resin, desorbing, and centrifuging, adjusting the pH of the aqueous phase, stirring, centrifuging, and filtering to obtain a manganese-containing precipitate, washing with deionized water, and drying in an oven at 80° C. for 24 hours, and then calcining in a muffle furnace to obtain Mn2O3; The preparation method of the resin 1 in step (3) is as follows: after mixing styrene-divinylbenzene copolymer, 3-aminopropyltriethoxysilane, tetrabutyl titanate and potassium persulfate, adding citric acid dropwise to adjust the pH to 2-4, introducing nitrogen, and stirring at room temperature for 0.5-1.5 days to obtain the resin 1; Wherein, the mass ratio of the styrene-divinylbenzene copolymer, 3-aminopropyltriethoxysilane and tetrabutyl titanate is 10-12:1.3-1.5:0.8-1.2; the mass of the potassium persulfate accounts for 0.8-1.2% of the styrene-divinylbenzene copolymer; The preparation method of the resin 2 in step (4) is as follows: styrene-divinylbenzene copolymer, 4-vinylaniline, methacrylic acid and potassium persulfate are mixed, nitrogen is introduced, and the mixture is stirred at 60-70° C. for 0.5-1.5 days to obtain the resin 2; Wherein, the mass ratio of the styrene-divinylbenzene copolymer, 4-vinylaniline and methacrylic acid is 9-11:1-3:0.8-2.2; the mass of the potassium persulfate accounts for 1.1-1.5% of the styrene-divinylbenzene copolymer; The preparation method of the resin 3 in step (5) is as follows: styrene-divinylbenzene copolymer, 4-vinylpyridine, diethylenetriamine and potassium persulfate are mixed, nitrogen is introduced, and the mixture is stirred at 65-75° C. for 0.5-1.5 days to obtain the resin 3; Wherein, the mass ratio of the styrene-divinylbenzene copolymer, 4-vinylpyridine and diethylenetriamine is 8-12:1.3-1.6:0.7-1.1; the amount of potassium persulfate accounts for 1.3-1.7% of the styrene-divinylbenzene copolymer; The preparation method of the resin 4 in step (6) is as follows: styrene-divinylbenzene copolymer, (3-acrylamidopropyl)trimethylammonium chloride, sodium styrene sulfonate and potassium persulfate are mixed, nitrogen is introduced, and the mixture is stirred at 80-90° C. for 0.5-1.5 days to obtain the resin 4; The mass ratio of the styrene-divinylbenzene copolymer, (3-acrylamidopropyl)trimethylammonium chloride and sodium styrene sulfonate is 9-13:1.4-2.2:0.9-1.7; the mass of the potassium persulfate accounts for 1.2-1.4% of the styrene-divinylbenzene copolymer.

2. A recycling process for waste battery positive electrode materials according to claim 1, characterized in that: The crushed material in step (2) is mixed with a 1-ethyl-3-methylimidazolium chloride solution at a mass ratio of 1:8-12; the concentration of the 1-ethyl-3-methylimidazolium chloride solution is 0.8-1.2 mol / L.

3. According to the recycling process of the positive electrode material of waste batteries according to claim 1, it is characterized in that: The washing liquid used in the washing step is composed of dimethyl sulfoxide and deionized water in a mass ratio of 1.5-3.5:6.3-7.9; the parameters of the desorption step are: the mass of the desorption liquid is 8-12 times that of the corresponding desorbed resin, and the desorption time is 1-2h; the desorption liquid is composed of dilute hydrochloric acid solution and EDTA solution in a mass ratio of 1:0.38-0.72, the concentration of the dilute hydrochloric acid solution is 0.04-0.1mol / L, and the concentration of the EDTA solution is 0.1-0.3mol / L.

4. The process for recycling positive electrode materials of waste batteries according to claim 1, characterized in that: The pH in step (3) is adjusted to 9.5-11.5; the pH in step (4) is adjusted to 10-12; the pH in step (5) is adjusted to 7-9; the pH in step (6) is adjusted to 8-10; the reagents used for adjusting the pH are all NaOH solutions with a concentration of 0.5-1.5 mol / L; the dripping speed of the NaOH solution is controlled to be 4-6 mL / min.

5. The process for recycling positive electrode materials of waste batteries according to claim 1, characterized in that: The calcination temperature in step (3) is 700-900°C; the calcination temperature in step (4) is 400-600°C; the calcination temperature in step (5) is 200-400; the calcination temperature in step (6) is 450-500; and the calcination time is 3-5h.

6. The process for recycling positive electrode materials of waste batteries according to claim 1, characterized in that: The parameters of the centrifugation step are: at room temperature, the centrifugal speed is 2000-6000 rpm, and the centrifugal time is 10-20 min; the pore size of the filter membrane used in the filtration step is 0.45 μm; and the speed of the stirring step is 40-120 rpm.

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