Method for anaerobically cracking power battery

Abstract

Disclosed is a method for anaerobically cracking a power battery, which includes the following steps: disassembling a waste power battery to obtain a battery cell; taking out a diaphragm from the battery cell for later use, and pyrolyzing the battery cell to obtain electrode powder; extracting nickel, cobalt and manganese elements from the electrode powder with an extraction buffer, filtering, taking the filtrate, then adjusting the filtrate with a nickel solution, a cobalt solution and a manganese solution to obtain a solution A, adding the solution A dropwise into ammonium hydroxide under stirring, and then adding an alkali solution under stirring to obtain a solution B; subjecting the solution B to a hydrothermal reaction, filtering, and roasting to obtain a catalyst, such that a chemical formula of the catalyst is Ni.sup.2+.sub.1-x-yCo.sup.2+.sub.xMn.sup.2+.sub.yO, where 0.25≤x<0.45, 0.25≤y<0.45.

Claims

1. A method for anaerobically cracking a power battery, comprising: (1) disassembling a waste power battery in sequence to obtain a battery cell and a metal shell, respectively; (2) taking out a diaphragm from the battery cell, cleaning the diaphragm for later use, and pyrolyzing the battery cell to obtain electrode powder; (3) extracting nickel, cobalt and manganese elements from the electrode powder with an extraction buffer, filtering, taking the filtrate, then adjusting the filtrate with a nickel solution, a cobalt solution and a manganese solution to obtain a solution A, adding the solution A dropwise into ammonium hydroxide under stirring, and then adding an alkali solution under stirring to obtain a solution B; (4) subjecting the solution B to a hydrothermal reaction, filtering, baking and roasting to obtain a catalyst; (5) soaking the diaphragm in the step (2) with a solvent, subjecting to vacuum treatment, crushing and grinding to obtain powder; and (6) mixing and reacting the powder with the catalyst in the step (4) to obtain C1-C4 and C5-C10 micromolecular organic substances; wherein a chemical formula of the catalyst of step (4) is Ni.sup.2+.sub.1-x-yCo.sup.2+.sub.xMn.sup.2+.sub.yO, where 0.25≤x<0.45, 0.25≤y<0.45.

2. The method of claim 1, wherein the pyrolyzing in the step (2) is conducted at a temperature of 400° C.-600° C. for 2-8 h in a vacuum environment.

3. The method of claim 1, wherein the extraction buffer in the step (3) is one of a mixed solution of nitric acid and an oxidant, or hydrochloric acid; and the oxidant is at least one of hydrogen peroxide, potassium peroxide, sodium hypochlorite or potassium hypochlorite.

4. The method of claim 1, wherein the nickel solution, the cobalt solution and the manganese solution in the step (3) are at least one of nitrate, hydrochloride or sulfate of nickel, cobalt and manganese.

5. The method of claim 1, wherein the molar ratio of nickel, cobalt and manganese in the solution A in the step (3) is 1:(0.5-3):(0.5-3).

6. The method of claim 1, wherein the hydrothermal reaction in the step (4) is conducted at a temperature of 100° C.-150° C. for 2-6 hours.

7. The method of claim 1, wherein the roasting in the step (4) is conducted at a temperature of 450° C.-500° C. under an atmosphere of nitrogen for 1-2 hours.

8. The method of claim 1, wherein the solvent in the step (5) is amyl acetate.

9. The method of claim 1, wherein the vacuum treatment in the step (5) is conducted at a temperature of 80° C.-120° C. for 30-120 min.

10. The method of claim 1, wherein the reaction in the step (6) is conducted at a temperature of 400° C.-700° C. for 4-8 h.

Description

BRIEF DESCRIPTION OF THE DRAWINGS

(1) FIG. 1 is an SEM image of a catalyst prepared in Example 2;

(2) FIG. 2 is a graph comparing the yields of micromolecular organic substances prepared in Example 2 and Comparative Example 1; and

(3) FIG. 3 is a gas chromatography detection diagram of the micromolecular organic substance prepared in Example 2.

DETAILED DESCRIPTION

(4) In order to enable those skilled in the art to understand the technical solution of the present disclosure more clearly, the following examples are listed for illustration. It should be pointed out that, the following examples do not limit the claimed scope of the present disclosure.

(5) Unless otherwise specified, the raw materials, reagents or devices used in the following examples can be obtained through conventional commercial approaches or by existing known methods.

Example 1

(6) The method for anaerobically cracking a power battery of this example includes the following specific steps:

(7) (1) a waste power battery was discharged and disassembled in sequence to obtain a battery cell and a metal shell, respectively;

(8) (2) a diaphragm was taken out from the battery cell, washed with deionized water until no attachment visible to the naked eyes was found, and the remaining battery cell was pyrolyzed under an atmosphere of vacuum and at a temperature of 500° C. for 4 h to obtain electrode powder;

(9) (3) nickel, cobalt and manganese elements were extracted from the electrode powder with an extraction buffer (with the molar ratio of water, hydrochloric acid and hydrogen peroxide of 1:1:1) according to a solid-to-liquid ratio of 1:3, a current collector was directly recovered, the solution was filtered, the filter residue was removed, the filtrate was measured for the contents of nickel, cobalt and manganese respectively by a dimethylglyoxime gravimetric method, a potentiometric titration method and an EDTA titration method, 10 mL of the filtrate was adjusted with a nickel solution, a cobalt solution and a manganese solution (each with a concentration of 4 mol/L) respectively until the molar ratio of nickel, cobalt and manganese in the filtrate was 1:0.5:0.5, so as to obtain a solution A (the total concentration of the three elements of nickel, cobalt and manganese was 2 mol/L), the solution A was added dropwise into aqueous ammonia of a concentration of 0.2 mol/L at a volume ratio of 1:3, and stirred for 5 min at the same time at a rotation speed of 50 r/min, then added with a 2 mol/L NaOH solution at a proportion of 0.1 mL, and stirred at the original rotation speed for 5 min to obtain a solution B;

(10) (4) the solution B was put into a polytetrafluoroethylene reaction kettle for a hydrothermal reaction at 100° C. for 2 hours, the precipitate was filtered, and the filter residue was washed with deionized water for 3 times, baked at 60° C. for 4 hours, and then roasted at 450° C. under a nitrogen atmosphere for 1 hour to obtain a catalyst of Ni.sup.2+.sub.0.5Co.sup.2+.sub.0.25Mn.sup.2+.sub.0.25O;

(11) (5) the diaphragm in the step (2) was soaked with amyl acetate (soaked according to a solid-to-liquid ratio of 1:0.4 at 70° C. for 12 hours), then subjected to vacuum treatment under a vacuum condition at 80° C. for 30 min, crushed, and ground into powder; and

(12) (6) the powder was mixed with the catalyst Ni.sup.2+.sub.0.5Co.sup.2+.sub.0.25Mn.sup.2+.sub.0.25O obtained in the step (4) uniformly at a mass ratio of 200:1, and placed into a high-pressure reactor, the reactor was vacuumized, nitrogen was introduced into the reactor, and a reaction was carried out at 400° C. under a nitrogen atmosphere for 4 h to obtain micromolecular organic substances, and then the reacted catalyst was pyrolyzed, extracted with the extraction buffer and recycled.

Example 2

(13) The method for anaerobically cracking a power battery of this example includes the following specific steps:

(14) (1) a waste power battery was discharged and disassembled in sequence to obtain a battery cell and a metal shell, respectively, wherein the metal shell was directly recycled;

(15) (2) a diaphragm was taken out from the battery cell, washed with deionized water until no attachment visible to the naked eyes was found, and the remaining battery cell was pyrolyzed under vacuum and at a temperature of 500° C. for 4 h to obtain electrode powder;

(16) (3) nickel, cobalt and manganese elements were extracted from the electrode powder with an extraction buffer (with the molar ratio of water, hydrochloric acid and hydrogen peroxide of 1:2:2) according to a solid-to-liquid ratio of 1:3, a current collector was directly recovered, the solution was filtered, the filter residue was removed, the filtrate was measured for the contents of nickel, cobalt and manganese respectively by a dimethylglyoxime gravimetric method, a potentiometric titration method and an EDTA titration method, 250 mL of the filtrate was adjusted with a nickel solution, a cobalt solution and a manganese solution (each with a concentration of 6 mol/L) respectively until the molar ratio of nickel, cobalt and manganese in the filtrate was 1:2:2, so as to obtain a solution A (the total concentration of the three elements of nickel, cobalt and manganese was 4 mol/L), the solution A was added dropwise into aqueous ammonia of a concentration of 0.5 mol/L at a volume ratio of 1:5, and stirred at a rotation speed of 500 r/min for 30 min, then added with a 4 mol/L NaOH solution at a proportion of 20 mL, and stirred at a rotation speed of 500 r/min for 5 min to obtain a solution B;

(17) (4) the solution B was put into a polytetrafluoroethylene reaction kettle for a hydrothermal reaction at 120° C. for 4 hours, the precipitate was filtered, and the filter residue was washed with deionized water for 5 times, baked at 70° C. for 14 hours, and then roasted at 480° C. under a nitrogen atmosphere for 1.5 hour to obtain a catalyst of Ni.sup.2+.sub.0.2Co.sup.2+.sub.0.4Mn.sup.2+.sub.0.4O;

(18) (5) the diaphragm was soaked with amyl acetate according to a solid-to-liquid ratio of 1:0.6 at 75° C. for 18 hours, then subjected to treatment under a vacuum condition at 100° C. for 80 min, crushed, and ground into powder; and

(19) (6) the powder was mixed with the catalyst Ni.sup.2+.sub.0.2Co.sup.2+.sub.0.4Mn.sup.2+.sub.0.4O obtained in the step (4) uniformly at a mass ratio of 200:1, and placed into a high-pressure reactor, the reactor was vacuumized, nitrogen was introduced into the reactor, and a reaction was carried out at 550° C. under a nitrogen atmosphere for 6 h to obtain micromolecular organic substances, and then the reacted catalyst was pyrolyzed, extracted with the extraction buffer and recycled.

Example 3

(20) The method for anaerobically cracking a power battery of this example includes the following specific steps:

(21) (1) a waste power battery was discharged and disassembled in sequence to obtain a battery cell and a metal shell, respectively, wherein the metal shell was directly recycled;

(22) (2) a diaphragm was taken out from the battery cell, washed with deionized water until no attachment visible to the naked eyes was found, and the remaining battery cell was pyrolyzed under vacuum and at a temperature of 500° C. for 4 h to obtain electrode powder;

(23) (3) nickel, cobalt and manganese elements were extracted from the electrode powder with an extraction buffer (with the molar ratio of water, hydrochloric acid and hydrogen peroxide of 1:3:3) according to a solid-to-liquid ratio of 1:3, a current collector was directly recovered, the solution was filtered, the filter residue was removed, the filtrate was measured for the contents of nickel, cobalt and manganese respectively by a dimethylglyoxime gravimetric method, a potentiometric titration method and an EDTA titration method, 500 mL of the filtrate was adjusted with a nickel solution, a cobalt solution and a manganese solution (each with a concentration of 6 mol/L) respectively until the molar ratio of nickel, cobalt and manganese in the filtrate was 1:3:3, so as to obtain a solution A (the total concentration of the three elements of nickel, cobalt and manganese was 6 mol/L), the solution A was added dropwise into aqueous ammonia of a concentration of 0.8 mol/L at a volume ratio of 1:7, and stirred at a rotation speed of 1000 r/min for 60 min, then added with a 6 mol/L NaOH solution at a proportion of 45 mL, and stirred at a rotation speed of 1000 r/min for 30 min to obtain a solution B;

(24) (4) the solution B was put into a polytetrafluoroethylene reaction kettle for a hydrothermal reaction at 150° C. for 6 hours, the precipitate was filtered, and the filter residue was washed with deionized water for 7 times, baked at 80° C. for 24 hours, and then roasted at 500° C. under a nitrogen atmosphere for 2 hour to obtain a catalyst of Ni.sup.2+.sub.0.142Co.sup.2+.sub.0.429Mn.sup.2+.sub.0.429O;

(25) (5) the diaphragm was soaked with amyl acetate according to a solid-to-liquid ratio of 1:0.8 at 80° C. for 24 hours, then subjected to treatment under a vacuum condition at 120° C. for 120 min, crushed, and ground into powder; and

(26) (6) the powder was mixed with the catalyst Ni.sup.2+.sub.0.142Co.sup.2+.sub.0.429Mn.sup.2+.sub.0.429O obtained in the step (4) uniformly at a mass ratio of 200:1, and placed into a high-pressure reactor, the reactor was vacuumized, nitrogen was introduced into the reactor, and a reaction was carried out at 700° C. under a nitrogen atmosphere for 8 h to obtain micromolecular organic substances, and then the reacted catalyst was pyrolyzed, extracted with the extraction buffer and recycled.

Comparative Example 1 (CN108941162A)

(27) A process of anaerobically cracking, recycling and sorting a lithium battery includes the following steps:

(28) Step 1: the lithium battery was fed into a crusher for crushing;

(29) Step 2: the lithium battery was crushed by the crusher, and conveyed to an air separator through a conveying device;

(30) Step 3: metal blocks and plastic shells with larger specific gravity were sorted out by the air separator, and a mixed material of positive and negative plates, diaphragms and plastics with smaller specific gravity was conveyed into a high-temperature anaerobic cracking furnace through the conveying device after vacuumizing, wherein the temperature of the high-temperature anaerobic cracking furnace was higher than 300° C., the high-temperature anaerobic cracking furnace was vacuumized and kept closed before the mixed material was added into it, the conveying device kept a vacuum state during the conveying process, the plastics and diaphragms doped in the mixed material were cracked to generate a combustible gas, and the combustible gas was discharged and collected, and only positive and negative plates and a small amount of metals were left in the cracked mixed material;

(31) Step 4: the positive and negative plates were fed into a high-speed decomposition machine, the positive and negative plates were crushed into powder again by the high-speed decomposition machine for decomposition and separation, and the materials were decomposed into metal particles with larger particle sizes and positive and negative electrode powder with smaller particle sizes by the decomposition machine;

(32) Step 5: the decomposed and separated materials entered a cyclone collector through negative pressure, and the collected positive and negative electrode powder was subjected to aggregation by the cyclone collector through a dust collecting system equipped with a fan, such that the positive and negative electrode powder was collected by the dust collecting system;

(33) Step 6: after the collection through the cyclone collector, the remaining material of coarse particles was screened by a screening device, so as to screen out positive and negative electrode power, copper-aluminum mixtures and large metal particles with increasing particle sizes respectively;

(34) Step 7: the metal mixture as screened out was subjected to screening and grading and multiple times of sorting according to specific gravity, so as to separate copper and aluminum with different specific gravities; and

(35) Step 8: the obtained positive and negative electrode powder, metals and plastics were classified.

(36) Comparison of Degradation Effects:

(37) Anaerobic cracking was carried out according to the aforementioned Example 2 and Comparative Example 1, respectively, and the obtained products were detected by gas chromatography. The yield results are shown in FIG. 2. As could be seen from FIG. 2, for the product in the Comparative Example 1, the yield of the micromolecular products of C1-C10 is relatively low, while the yield of the macromolecular products of C11 and above is relatively high. On the contrary, in the Example 2, the yield of micromolecular products of C1-C4 and C5-C10 is relatively high, while the yield of macromolecular products is relatively low. The gas chromatography detection results are shown in FIG. 3. Therefore, it shows that the anaerobic cracking effect of the Example 2 is better than that of the Comparative Example 1, and the products are micromolecular organic substances of industrial utilization values. The simply recycled diaphragm of the Comparative Example 1 is a mixture of multiple macromolecular polymers and might be damaged, and thus its recovery value is not high. However, in the present disclosure, the diaphragm after degradation on one hand can be used as combustible gas to serve as an energy source, and on the other hand can be used as an industrial raw material.

(38) The method for anaerobically cracking the power battery as provided by the present disclosure has been described in detail above. The principle and implementation of the present disclosure have been described by applying specific embodiments herein. The description of the above embodiments is only used for facilitating understanding of the method of the present disclosure and the core idea thereof, including the best mode, and also enables any person skilled in the art to practice the present disclosure, including manufacturing and using any device or system, and implementing any combined method. It should be noted that, several improvements and modifications may be made by persons of ordinary skill in the art without departing from the principle of the present disclosure, and these improvements and modifications should also be considered within the protection scope of the present disclosure. The claimed scope of the present disclosure is defined by the claims, and may include other embodiments that can come into the minds of those skilled in the art. If these other embodiments have structural elements that are not different from those recited by the literal language of the claims, or if they include equivalent structural elements that are not materially different from those recited by the literal language of the claims, then these other embodiments should also be included within the scope of the claims.