A synergistic pickling method for full-chain integrated recovery of waste battery copper-aluminum materials, a pickling device and application thereof

Abstract

This application belongs to the field of waste lithium battery recycling technology, specifically relating to a synergistic acid washing method, acid washing equipment, and its application for the integrated recycling of copper and aluminum materials from waste batteries. The acid washing method includes: a synergistic acid washing step: mixing dried copper and aluminum materials with high Cu... 2+ The pickling solution is used for synergistic pickling, wherein the high Cu 2+ Pickling solution is obtained by enriching Cu in pyrolytic copper and aluminum materials through pickling. 2+ A solution with a concentration of ≥15 g / L, wherein the high Cu 2+ Before the pickling solution is used to co-pickle the dried copper and aluminum material, the high Cu content is first... 2+ H in pickling solution + The concentration was adjusted to 1-2 mol / L. The method of this application uses high Cu... 2+ The pickling solution synergistically pickles the dried copper and aluminum materials, thereby achieving the desired Cu concentration in the pickling solution. 2+ The removal of hydrogen has solved the problems of hydrogen production and heat accumulation in the acid washing process. It has the advantages of energy saving and cost reduction, stability and safety, and high efficiency of recycling. The reaction efficiency and leaching efficiency of ternary materials are higher than those of conventional acid washing.

Description

Technical Field

[0001] This application relates to the field of waste lithium battery recycling technology, specifically to a synergistic acid washing method, acid washing equipment, and its application for the integrated recycling of copper and aluminum materials from waste batteries across the entire chain. Background Technology

[0002] Lithium-ion battery production lines are widely used in digital 3C products, energy storage, and new energy vehicles. However, the average lifespan of lithium batteries is only about 5 to 8 years, and the metals such as Ni, Co, Mn, Li, Cu, and Al in retired and scrapped lithium batteries still have high value. Currently, the lithium-ion battery industry is promoting the integration of the entire lithium battery chain, and battery recycling is a crucial link in the integration of the entire new energy vehicle industry chain, and an important part of the circular economy. Therefore, recycling and processing waste lithium batteries can not only reduce heavy metal pollution to the environment, but also recover high-value metals for reuse, generating certain economic benefits, avoiding resource waste, forming a closed-loop system, and reducing dependence on external mineral resources. Furthermore, the implementation of the entire chain integration has set higher standards for lithium battery recycling, and a reasonable recycling plan is conducive to promoting the integrated development of the new energy battery industry chain.

[0003] Currently, the most common pretreatment methods for handling waste lithium batteries are high-temperature pyrolysis and low-temperature drying. Both methods produce battery powder and copper-aluminum materials. The total content of Ni, Co, Mn, and Li in the battery powder is usually above 60%, and it can be directly leached. The copper-aluminum materials will still contain about 10% Ni, Co, Mn, and Li, and must be acid-washed before they can be sold. The pyrolyzed copper-aluminum materials contain CuO and Cu2O, and acid washing alone will cause Cu... 2+ Large amounts of these materials enter the pickling solution, increasing the cost of impurity removal. The dried copper and aluminum materials contain aluminum fragments, diaphragms, and organic matter, which will rapidly accumulate heat and produce hydrogen during the pickling process, causing problems such as solution temperature rise, severe bubbling, and even overflow.

[0004] It is evident that the current pickling processes for pyrolytic copper and aluminum materials and dried copper and aluminum materials still have significant shortcomings.

[0005] Therefore, this application is hereby submitted. Summary of the Invention

[0006] The purpose of this application is to provide a synergistic acid washing method for the integrated recycling of copper and aluminum materials from waste batteries, which can improve the problems of heat accumulation and hydrogen production during the acid washing process.

[0007] The purpose of this application also includes providing a co-processing acid washing device for copper and aluminum materials from waste batteries. This device, through its specific connection method, can optimize the acid washing process and effectively improve the problems of heat accumulation and hydrogen production during the acid washing process.

[0008] The purpose of this application also includes providing a synergistic acid washing method for the integrated recycling of copper and aluminum materials from waste batteries across the entire supply chain, and its application in the recycling of waste lithium batteries.

[0009] The purpose of this application also includes providing a method for recycling waste lithium batteries, wherein the recycling process is optimized.

[0010] To achieve at least one of the above-mentioned objectives of this application, the following technical solutions may be adopted:

[0011] Firstly, this application provides a synergistic acid washing method for the integrated recycling of copper and aluminum materials from waste batteries across the entire supply chain, comprising the following steps:

[0012] Collaborative pickling step: Dry copper and aluminum materials are pickled together with high Cu... 2+ The pickling solution is used for synergistic pickling, wherein the high Cu 2+ Pickling solution is obtained by enriching Cu in pyrolytic copper and aluminum materials through pickling. 2+ A solution with a concentration of ≥15 g / L, wherein the high Cu 2+ Before the pickling solution is used to co-pickle the dried copper and aluminum material, the high Cu content is first... 2+ H in pickling solution + The concentration was adjusted to 1-2 mol / L.

[0013] In some embodiments of this application, an enrichment pickling step is included before the synergistic pickling step: pyrolytic copper-aluminum material and acid solution are mixed for enrichment pickling to obtain Cu 2+ Solutions with a concentration of ≥15 g / L.

[0014] In some embodiments of this application, the dried copper-aluminum material and the high Cu 2+ The solid-liquid ratio of the pickling solution is 1g:(8-12)mL;

[0015] Preferably, the pickling time for the synergistic pickling is 10 min to 15 min.

[0016] In some embodiments of this application, the synergistic pickling is carried out under stirring conditions, preferably at a stirring speed of 200 rpm to 300 rpm.

[0017] In some embodiments of this application, after the synergistic pickling, the process further includes solid-liquid separation to obtain a post-synergistic pickling solution and dried copper-aluminum slag, and detecting Ni in the post-synergistic pickling solution. 2+ and Co 2+ Concentration, when Ni 2+ +Co 2+ When the concentration of Ni in the synergistic pickling solution is ≥30 g / L, the solution is collected as the copper removal solution; when the Ni concentration in the synergistic pickling solution is ≥30 g / L, the solution is collected as the copper removal solution. 2+ +Co 2+When the concentration is <30g / L, the synergistic pickling solution is recycled.

[0018] In some embodiments of this application, recycling the synergistic pickling solution includes: removing the H from the synergistic pickling solution. + The concentration is adjusted to 2.5 mol / L to 4 mol / L and reused in the enrichment acid washing process as the acid solution.

[0019] In some embodiments of this application, the Cu in the copper-removed solution 2+ <200mg / L, pH 1~1.5.

[0020] In some embodiments of this application, the nickel and cobalt content in the dried copper-aluminum slag is <2%.

[0021] In some embodiments of this application, the Cu is obtained 2+ The solution with a concentration of ≥15 g / L comprises: a post-enriched acid-wash solution and pyrolytic copper-aluminum slag obtained by solid-liquid separation after the enriched acid washing, and the detection of Cu in the post-enriched acid-wash solution. 2+ Concentration, when Cu 2+ When the concentration is ≥15 g / L, the enriched pickling solution will be used as the high Cu concentration. 2+ Pickling solution, when Cu in the enriched pickling solution is... 2+ When the concentration is <15g / L, the enriched pickling solution is recycled.

[0022] In some embodiments of this application, recycling the enriched pickling solution includes: removing the H from the enriched pickling solution. + The concentration is adjusted to 2.5 mol / L to 4 mol / L and reused in the enrichment acid washing process as the acid solution.

[0023] In some embodiments of this application, the high Cu 2+ The initial pH of the pickling solution is 1 to 1.5, and the nickel and cobalt content in the pyrolytic copper-aluminum slag is <3%.

[0024] In some embodiments of this application, in the enrichment pickling, the solid-liquid ratio of the pyrolytic copper-aluminum material and the acid solution is 1g:(8-12)mL;

[0025] Preferably, the pickling time for enrichment pickling is 20 min to 25 min.

[0026] In some embodiments of this application, the enrichment rinsing is carried out under stirring conditions, preferably at a stirring speed of 200 rpm to 300 rpm.

[0027] In some embodiments of this application, the H+ of the acid solution +The concentration is 2.5 mol / L to 4 mol / L;

[0028] Preferably, the acid solution is dilute sulfuric acid.

[0029] In some embodiments of this application, obtaining the pyrolytic copper-aluminum material includes: pyrolyzing waste polymer batteries at 700℃-800℃ for 25min-35min to obtain pyrolytic material, crushing, sieving and magnetically separating the pyrolytic material, and the low magnetic material on the 60-80 mesh sieve is the pyrolytic copper-aluminum material.

[0030] In some embodiments of this application, obtaining the dried copper-aluminum material includes: drying waste aluminum-cased lithium batteries at 130°C-180°C for 25 min to 30 min to obtain dried material, and then sieving and gravity sorting the dried material to obtain the dried copper-aluminum material.

[0031] In some embodiments of this application, before drying the waste aluminum-cased lithium batteries, the waste aluminum-cased lithium batteries are further crushed, and the oxygen concentration in the furnace during crushing and drying is <1%.

[0032] Secondly, this application provides a co-acid washing device for waste battery copper and aluminum materials for realizing the above-mentioned integrated recycling method of waste battery copper and aluminum materials, which includes an enrichment acid washing device and a co-acid washing device.

[0033] The enrichment acid washing device includes a first reaction vessel, a first centrifuge, an enrichment acid washing liquid collector, a first concentration detection mechanism, and a high Cu... 2+ The system includes a pickling solution discharge pipe and a first reflux pipe; the outlet of the first reaction vessel is connected to the first centrifuge, and the first centrifuge is connected to the enriched pickling solution collector to collect the liquid separated by the first centrifuge; a first concentration detection mechanism is installed inside the enriched pickling solution collector to detect the Cu concentration within the collector. 2+ Concentration, the high Cu 2+ The pickling solution discharge pipe is connected to the second reaction vessel, and the first reflux pipe is connected to the first reaction vessel;

[0034] The synergistic pickling device includes a second reaction vessel, a second centrifuge, a synergistic pickling post-liquid collector, a second concentration detection mechanism, a copper removal post-liquid discharge pipe, and a second reflux pipe. The outlet of the second reaction vessel is connected to the second centrifuge, and the second centrifuge is connected to the synergistic pickling post-liquid collector to collect the liquid separated by the second centrifuge. The second concentration detection mechanism is located inside the synergistic pickling post-liquid collector to detect the Ni concentration within the synergistic pickling post-liquid collector. 2+ and Co 2+The concentration is specified, the copper removal liquid discharge pipe is connected to the subsequent copper removal equipment, and the second reflux pipe is connected to the first reaction vessel.

[0035] Thirdly, this application provides a synergistic acid washing method for the integrated recycling of copper and aluminum materials from waste batteries, applied to the recycling of waste lithium batteries.

[0036] Fourthly, this application provides a method for recycling waste lithium batteries, which includes the aforementioned integrated acid washing method for recycling copper and aluminum materials from waste batteries across the entire chain.

[0037] Compared with the prior art, the beneficial effects of this application include:

[0038] Based on the inherent compositional characteristics of pyrolytic and dried copper-aluminum materials, the main principle of this application is as follows: enrichment acid washing dissolves CuO and Cu2O from the pyrolytic copper-aluminum materials, yielding high Cu content. 2+ Pickling solution; because Cu in the synergistic pickling process 2+ Replace H + The active site undergoes a substitution reaction with Al to precipitate elemental copper, while simultaneously inhibiting hydrogen production and heat accumulation. The aluminum scrap and the elemental copper precipitated on its surface form (-)Al|Al 3+ (aq)|Cu 2+ (aq)|Cu micro galvanic cells accelerate the reaction and improve copper removal efficiency.

[0039] Compared to traditional copper-aluminum pickling processes, the method described in this application has significant advantages. First, the process route designed in this application features a semi-closed loop, eliminating the need for additional auxiliary materials for copper removal, inhibiting hydrogen production during pickling, and preventing heat buildup. Second, the pickling solution is recycled between enrichment pickling and co-pickling, reducing the consumption of sulfuric acid and water. Third, the leaching efficiency of Ni, Co, Mn, and their oxides depends on the pH and temperature of the reaction system, and the Cu content from the co-pickling of the dried copper-aluminum material is significantly improved. 2+ Can replace H + The heat generated by the reaction with Al can increase the reaction temperature and reduce sulfuric acid consumption, resulting in a more stable pH in the solution system, higher leaching efficiency, and a smoother reaction process. Fourth, the Cu in the solution after copper removal... 2+ The concentration has reached the requirements of the first-stage copper removal process in the leaching process, effectively reducing the auxiliary materials, labor and time costs of downstream copper removal. Attached Figure Description

[0040] To more clearly illustrate the technical solutions of the embodiments of this application, the accompanying drawings used in the embodiments will be briefly introduced below. It should be understood that the following drawings only show some embodiments of this application and should not be regarded as a limitation of the scope. For those skilled in the art, other related drawings can be obtained based on these drawings without creative effort.

[0041] Figure 1 This is a process flow diagram of Embodiment 1 of this application;

[0042] Figure 2 The XRD diffraction pattern of the pyrolytic copper-aluminum material in Example 1 of this application is shown below.

[0043] Figure 3 This is the XRD diffraction pattern of the dried copper-aluminum material in Example 1 of this application. Detailed Implementation

[0044] To make the objectives, technical solutions, and advantages of the embodiments of this application clearer, the technical solutions in the embodiments of this application will be clearly and completely described below. Where specific conditions are not specified in the embodiments, conventional conditions or conditions recommended by the manufacturer shall apply. Reagents or instruments whose manufacturers are not specified are all conventional products that can be purchased commercially.

[0045] The embodiments of this application will be described in detail below with reference to examples. However, those skilled in the art will understand that the following examples are for illustrative purposes only and should not be considered as limiting the scope of this application. Unless otherwise specified in the examples, conventional conditions or conditions recommended by the manufacturer shall apply. Reagents or instruments whose manufacturers are not specified are all commercially available conventional products.

[0046] The endpoints and any values ​​of the ranges disclosed in this application are not limited to the precise ranges or values, and such ranges or values ​​should be understood to include values ​​close to such ranges or values. For numerical ranges, the endpoint values ​​of the various ranges, the endpoint values ​​of the various ranges and individual point values, and individual point values ​​can be combined with each other to obtain one or more new numerical ranges, which should be considered as specifically disclosed herein.

[0047] This application provides a synergistic acid washing method for the integrated recycling of copper and aluminum materials from waste batteries, comprising the following steps:

[0048] S1. Obtain pyrolytic copper-aluminum material.

[0049] Waste polymer batteries are pyrolyzed at high temperatures and then sorted to obtain pyrolytic copper-aluminum materials. Specifically, waste polymer batteries are pyrolyzed at 700-800℃ for 25-35 minutes to obtain pyrolytic material. The pyrolytic material is then crushed, sieved, and magnetically separated. The low-magnetic material on a 60-80 mesh sieve is the pyrolytic copper-aluminum material. The pyrolysis temperature can be, for example, any one or a range of any two of 700℃, 720℃, 730℃, 750℃, 760℃, 780℃, 790℃, and 800℃. The pyrolysis time can be, for example, any one or a range of any two of 25 minutes, 28 minutes, 30 minutes, 32 minutes, 33 minutes, and 35 minutes.

[0050] S2. Obtain dried copper and aluminum materials.

[0051] Waste aluminum-cased lithium batteries are dried at low temperatures and then sorted to obtain dried copper-aluminum materials. Specifically, the waste aluminum-cased lithium batteries are crushed, and the crushed waste aluminum-cased lithium batteries are dried at 130-180℃ for 25-30 minutes to obtain dried materials. The oxygen concentration in the furnace during crushing and drying is <1%. The dried materials are then sieved and gravity-separated to obtain dried copper-aluminum materials. The drying temperature can be, for example, any one or a range of any two of 130℃, 135℃, 140℃, 150℃, 160℃, 165℃, 170℃, and 180℃. The drying time can be, for example, any one or a range of any two of 25min, 26min, 27min, 28min, 29min, and 30min.

[0052] S3, enrichment pickling.

[0053] Pyrolytic copper-aluminum material is mixed with an acid solution for enrichment and acid washing. The acid solution contains H₂... + The concentration is 2.5–4 mol / L (for example, the concentration of an acid solution can be any one of 2.5, 2.8, 3, 3.5, 3.8, or 4 mol / L, or any value in between). Acid solutions include dilute sulfuric acid. The solid-liquid ratio of pyrolytic copper-aluminum material to dilute sulfuric acid solution is 1 g:(8-12) mL (e.g., any one or a range between 1:8, 1:9, 1:10, 1:11, 1:12, preferably 1:10). The pickling time is 20-25 min (e.g., any one or a range between 20, 21, 22, 23, 24, 25 min). The initial temperature is room temperature, and the stirring speed is 200-300 rpm (e.g., any one or a range between 200, 220, 240, 250, 280, 300 rpm). Subsequently, solid-liquid separation is performed to obtain enriched pickling solution and pyrolytic copper-aluminum slag. The Cu content in the enriched pickling solution is then detected. 2+ Concentration, when Cu 2+When the concentration is ≥15 g / L, the concentrated pickling solution is used as a high Cu solution. 2+ Pickling solution; high Cu 2+ The initial pH of the pickling solution is 1 to 1.5 (for example, the pH can be any one of 1, 1.1, 1.2, 1.3, 1.4, 1.5 or any range between two of them), and the nickel and cobalt content in the pyrolytic copper-aluminum slag is <3%.

[0054] When Cu in the pickling solution is enriched 2+ When <15g / L, enrich the H in the pickling solution. + The concentration is adjusted to 2.5–4 mol / L (for example, adjusted to any one of 2.5, 28, 3, 3.5, 3.8, or 4 mol / L, or any value between two of them), and reused as an acid solution in the enrichment and acid washing process.

[0055] S4, Cooperative pickling.

[0056] High Cu 2+ H in pickling solution + The concentration was adjusted back to 1 mol / L-2 mol / L (e.g., adjusted to any one or any two of 1, 1.2, 1.4, 1.6, 1.8, 2 mol / L) and co-washed with dried copper and aluminum materials. The dried copper and aluminum materials and high Cu... 2+ The solid-liquid ratio of the pickling solution is 1 g:(8-12) mL (e.g., any one or a range between 1:8, 1:9, 1:10, 1:11, 1:12, preferably 1:10), the pickling time is 10-15 min (e.g., any one or a range between 10, 11, 12, 13, 14, 15 min), the initial temperature is room temperature, and the stirring speed is 200-300 rpm (e.g., any one or a range between 200, 220, 240, 250, 280, 300 rpm). Subsequently, solid-liquid separation is performed to obtain the co-pickled solution and dried copper-aluminum slag. The Ni content in the co-pickled solution is then measured. 2+ and Co 2 + Concentration, when Ni 2+ +Co 2+ When the concentration is ≥30 g / L, the acid pickling solution is collected as the copper removal solution. The Cu in the copper removal solution... 2+ <200 mg / L, pH 1–1.5 (e.g., pH can be any one of 1, 1.1, 1.2, 1.3, 1.4, 1.5 or any range between two), and nickel and cobalt content in dried copper-aluminum slag <2%. When the Ni content in the synergistic pickling solution is <200 mg / L... 2+ +Co 2+ When <30g / L, the H in the synergistic pickling solution will be used to... +The concentration is adjusted to 2.5–4 mol / L (for example, adjusted to any one of 2.5, 28, 3, 3.5, 3.8, or 4 mol / L, or any value between two of them), and reused as an acid solution in the enrichment and acid washing process.

[0057] It should be understood that the core of this application lies in the use of high Cu 2+ The pickling solution performs synergistic pickling on dried copper and aluminum materials, utilizing the low hydrogen ion concentration (H+) + High Cu (1-2 mol / L) 2+ Pickling solutions can improve hydrogen production and heat accumulation during the pickling process, while high Cu... 2+ Pickling solution can be obtained directly using the method provided in this application (enrichment pickling by mixing pyrolytic copper-aluminum material and acid solution), or it can be obtained by purchasing commercially available high-Cu byproducts from pickling pyrolytic copper-aluminum material and acid solution from other manufacturers. 2+ Pickling solution.

[0058] Secondly, this application also provides a co-acid washing device for copper and aluminum materials from waste batteries, which includes an enrichment acid washing device and a co-acid washing device.

[0059] The enrichment acid washing apparatus includes a first reaction vessel, a first centrifuge, an enrichment acid washing liquid collector, a first concentration detection mechanism, and a high Cu... 2+ The pickling solution discharge pipe and the first reflux pipe are included; the outlet of the first reaction vessel is connected to the first centrifuge, and the first centrifuge is connected to the enriched pickling solution collector to collect the liquid separated by the first centrifuge; a first concentration detection mechanism is installed inside the enriched pickling solution collector to detect the Cu concentration within the enriched pickling solution collector. 2+ Concentration, high Cu 2+ The pickling solution discharge pipe is connected to the second reactor, and the first reflux pipe is connected to the first reactor.

[0060] The co-pickled liquid apparatus includes a second reaction vessel, a second centrifuge, a co-pickled liquid collector, a second concentration detection mechanism, a copper-removed liquid discharge pipe, and a second reflux pipe. The outlet of the second reaction vessel is connected to the second centrifuge, and the second centrifuge is connected to the co-pickled liquid collector to collect the liquid separated by the second centrifuge. The second concentration detection mechanism is located inside the co-pickled liquid collector to detect the Ni concentration within the co-pickled liquid collector. 2+ and Co 2+ The concentration is such that the copper-removed liquid discharge pipe is connected to the subsequent copper removal equipment, and the second reflux pipe is connected to the first reaction vessel.

[0061] It should be understood that the reaction vessel, centrifuge, collector, and concentration detection mechanism disclosed in this application are all conventional mechanisms. This application achieves the process flow involved in the synergistic acid washing method for recycling copper and aluminum materials from waste batteries by using specific connection methods and connection positions of the above-mentioned mechanisms.

[0062] Furthermore, this application provides the application of the integrated, end-to-end acid washing method for recycling copper and aluminum materials from waste batteries, as described in any of the foregoing embodiments, in the treatment of copper and aluminum materials from waste batteries. Specifically, this application provides a method for recycling waste lithium batteries, which includes the aforementioned integrated, end-to-end acid washing method for recycling copper and aluminum materials from waste batteries. This integrated, end-to-end acid washing method for recycling copper and aluminum materials from waste batteries allows for better recycling of waste lithium batteries, is simple to operate, and significantly improves the leaching rate of ternary materials.

[0063] The features and performance of this application will be further described in detail below with reference to the embodiments.

[0064] Example 1

[0065] A collaborative acid washing method for the integrated recycling of copper and aluminum materials from waste batteries across the entire supply chain; please refer to [link / reference]. Figure 1 This includes the following steps:

[0066] (1) Waste polymer batteries are pyrolyzed at high temperature in a rotary kiln at 750℃ for 30 minutes. The pyrolyzed material is then crushed, sieved, and magnetically separated. The low-magnetic material on the 60-mesh sieve is the pyrolyzed copper-aluminum material (see [reference]). Figure 2 ).

[0067] (2) After crushing the waste aluminum-cased lithium batteries, dry them at a low temperature in a drying oven at 150℃ for 30 minutes. The oxygen concentration in the crushing chamber and the oven is <1%. The dried material is then sieved and sorted by gravity to obtain dried copper-aluminum material (see [reference]). Figure 3 ).

[0068] (3) The pyrolytic copper-aluminum material is added to a dilute sulfuric acid reactor for enrichment and acid washing. The solid-liquid ratio is 1g:10mL, and the dilute sulfuric acid contains H2. + The concentration was 3 mol / L, the acid washing time was 20 min, the initial temperature was room temperature, and the stirring speed was 250 rpm.

[0069] (4) After enrichment and acid washing, the slurry is centrifuged and dewatered to obtain pyrolytic copper-aluminum slag and enriched acid-washed liquid. The Cu in the enriched acid-washed liquid is... 2+ <15g / L then H + The concentration was adjusted back to 3 mol / L and then reused in the enrichment acid washing process.

[0070] (5) Enriching Cu in the pickling solution 2+≥15g / L is defined as high Cu 2+ Pickling solution, H + The concentration was adjusted back to 1 mol / L for synergistic pickling of dried copper and aluminum materials.

[0071] (6) Add the dried copper and aluminum material to the high Cu 2+ The pickling solution was used for synergistic pickling in a reaction vessel with a solid-liquid ratio of 1g:10mL, a pickling time of 10min, an initial temperature of room temperature, and a stirring rate of 250rpm.

[0072] (7) After co-acid washing, the slurry is centrifuged and dewatered to obtain dried copper-aluminum slag and co-acid washing liquid. The co-acid washing liquid contains Ni 2+ +Co 2+ <30g / L then H + The concentration was adjusted back to 3 mol / L and then reused in the enrichment acid washing process.

[0073] (8) Ni in the synergistic pickling solution 2+ +Co 2+ A concentration of ≥30g / L is defined as copper-removed liquid, which can be directly transported to the downstream leaching stage for secondary copper removal.

[0074] Example 2

[0075] A synergistic acid washing method for the integrated recycling of copper and aluminum materials from waste batteries, comprising the following steps:

[0076] (1) The waste polymer battery is pyrolyzed in a rotary kiln at a high temperature of 750°C for 30 minutes. The pyrolyzed material is crushed, sieved and magnetically separated in sequence. The low magnetic material on the 60-mesh sieve is the pyrolyzed copper-aluminum material.

[0077] (2) After crushing the waste aluminum-shell lithium battery, dry it at low temperature in a drying oven at 150°C for 30 minutes. The oxygen concentration in the crushing chamber and the oven is <1%. The dried material is then sieved and sorted by gravity to obtain dried copper-aluminum material.

[0078] (3) The pyrolytic copper-aluminum material is added to a dilute sulfuric acid reactor for enrichment and acid washing. The solid-liquid ratio is 1g:10mL, and the dilute sulfuric acid contains H2. + The concentration was 3 mol / L, the acid washing time was 20 min, the initial temperature was room temperature, and the stirring speed was 250 rpm.

[0079] (4) After enrichment and acid washing, the slurry is centrifuged and dewatered to obtain pyrolytic copper-aluminum slag and enriched acid-washed liquid. The Cu in the enriched acid-washed liquid is... 2+ <15g / L then H + The concentration was adjusted back to 3 mol / L and then reused in the enrichment acid washing process.

[0080] (5) Enriching Cu in the pickling solution2+ ≥15g / L is defined as high Cu 2+ Pickling solution, H + The concentration was adjusted back to 2 mol / L for synergistic pickling of dried copper and aluminum materials.

[0081] (6) Add the dried copper and aluminum material to the high Cu 2+ The pickling solution was used for synergistic pickling in a reaction vessel with a solid-liquid ratio of 1g:10mL, a pickling time of 10min, an initial temperature of room temperature, and a stirring rate of 250rpm.

[0082] (7) After co-acid washing, the slurry is centrifuged and dewatered to obtain dried copper-aluminum slag and co-acid washing liquid. The co-acid washing liquid contains Ni 2+ +Co 2+ <30g / L then H + The concentration was adjusted back to 3 mol / L and then reused in the enrichment acid washing process.

[0083] (8) Ni in the synergistic pickling solution 2+ +Co 2+ A concentration of ≥30g / L is defined as copper-removed liquid, which can be directly transported to the downstream leaching stage for secondary copper removal.

[0084] Example 3

[0085] A synergistic acid washing method for the integrated recycling of copper and aluminum materials from waste batteries, comprising the following steps:

[0086] (1) The waste polymer battery is pyrolyzed in a rotary kiln at a high temperature of 750°C for 30 minutes. The pyrolyzed material is crushed, sieved and magnetically separated in sequence. The low magnetic material on the 60-mesh sieve is the pyrolyzed copper-aluminum material.

[0087] (2) After crushing the waste aluminum-shell lithium battery, dry it at low temperature in a drying oven at 150°C for 30 minutes. The oxygen concentration in the crushing chamber and the oven is <1%. The dried material is then sieved and sorted by gravity to obtain dried copper-aluminum material.

[0088] (3) The pyrolytic copper-aluminum material is added to a dilute sulfuric acid reactor for enrichment and acid washing. The solid-liquid ratio is 1g:10mL, and the dilute sulfuric acid contains H2. + The concentration was 3 mol / L, the acid washing time was 25 min, the initial temperature was room temperature, and the stirring speed was 250 rpm.

[0089] (4) After enrichment and acid washing, the slurry is centrifuged and dewatered to obtain pyrolytic copper-aluminum slag and enriched acid-washed liquid. The Cu in the enriched acid-washed liquid is... 2+ <15g / L then H + The concentration was adjusted back to 3 mol / L and then reused in the enrichment acid washing process.

[0090] (5) Enriching Cu in the pickling solution 2+ ≥15g / L is defined as high Cu 2+ Pickling solution, H + The concentration was adjusted back to 2 mol / L for synergistic pickling of dried copper and aluminum materials.

[0091] (6) Add the dried copper and aluminum material to the high Cu 2+ The pickling solution was used for synergistic pickling in a reaction vessel with a solid-liquid ratio of 1g:10mL, a pickling time of 15min, an initial temperature of room temperature, and a stirring rate of 250rpm.

[0092] (7) After co-acid washing, the slurry is centrifuged and dewatered to obtain dried copper-aluminum slag and co-acid washing liquid. The co-acid washing liquid contains Ni 2+ +Co 2+ <30g / L then H + The concentration was adjusted back to 3 mol / L and then reused in the enrichment acid washing process.

[0093] (8) Ni in the synergistic pickling solution 2+ +Co 2+ A concentration of ≥30g / L is defined as copper-removed liquid, which can be directly transported to the downstream leaching stage for secondary copper removal.

[0094] Example 4

[0095] A synergistic acid washing method for the integrated recycling of copper and aluminum materials from waste batteries, comprising the following steps:

[0096] (1) The waste polymer battery is pyrolyzed in a rotary kiln at a high temperature of 700℃ for 35 minutes. The pyrolyzed material is crushed, sieved and magnetically separated in sequence. The low magnetic material on the 60-mesh sieve is the pyrolyzed copper-aluminum material.

[0097] (2) After crushing the waste aluminum-shell lithium battery, dry it at low temperature in a drying oven at 130°C for 30 minutes. The oxygen concentration in the crushing chamber and the oven is <1%. The dried material is then sieved and sorted by gravity to obtain dried copper-aluminum material.

[0098] (3) The pyrolytic copper-aluminum material was added to a dilute sulfuric acid reactor for enrichment and acid washing, with a solid-liquid ratio of 1g:8mL. The dilute sulfuric acid contained H... + The concentration was 3.5 mol / L, the acid washing time was 22 min, the initial temperature was room temperature, and the stirring speed was 200 rpm.

[0099] (4) After enrichment and acid washing, the slurry is centrifuged and dewatered to obtain pyrolytic copper-aluminum slag and enriched acid-washed liquid. The Cu in the enriched acid-washed liquid is... 2+ <15g / L then H + The concentration was adjusted back to 3.5 mol / L and then reused in the enrichment acid washing process.

[0100] (5) Enriching Cu in the pickling solution 2+ ≥15g / L is defined as high Cu 2+ Pickling solution, H + The concentration was adjusted back to 1.6 mol / L for synergistic pickling of dried copper and aluminum materials.

[0101] (6) Add the dried copper and aluminum material to the high Cu 2+ The pickling solution was used for synergistic pickling in a reaction vessel with a solid-liquid ratio of 1g:8mL, a pickling time of 12min, an initial temperature of room temperature, and a stirring rate of 200rpm.

[0102] (7) After co-acid washing, the slurry is centrifuged and dewatered to obtain dried copper-aluminum slag and co-acid washing liquid. The co-acid washing liquid contains Ni 2+ +Co 2+ <30g / L then H + The concentration was adjusted back to 3.5 mol / L and then reused in the enrichment acid washing process.

[0103] (8) Ni in the synergistic pickling solution 2+ +Co 2+ A concentration of ≥30g / L is defined as copper-removed liquid, which can be directly transported to the downstream leaching stage for secondary copper removal.

[0104] Example 5

[0105] A synergistic acid washing method for the integrated recycling of copper and aluminum materials from waste batteries, comprising the following steps:

[0106] (1) The waste polymer battery is pyrolyzed in a rotary kiln at a high temperature of 800℃ for 25 minutes. The pyrolyzed material is crushed, sieved and magnetically separated in sequence. The low magnetic material on the 80-mesh sieve is the pyrolyzed copper-aluminum material.

[0107] (2) After crushing the waste aluminum-shell lithium battery, dry it at low temperature in a drying oven at 180°C for 25 minutes. The oxygen concentration in the crushing chamber and the oven is <1%. The dried material is then sieved and sorted by gravity to obtain dried copper-aluminum material.

[0108] (3) The pyrolytic copper-aluminum material was added to a dilute sulfuric acid reactor for enrichment and acid washing, with a solid-liquid ratio of 1g:12mL. The dilute sulfuric acid contained H2O. + The concentration was 4 mol / L, the acid washing time was 20 min, the initial temperature was room temperature, and the stirring speed was 300 rpm.

[0109] (4) After enrichment and acid washing, the slurry is centrifuged and dewatered to obtain pyrolytic copper-aluminum slag and enriched acid-washed liquid. The Cu in the enriched acid-washed liquid is... 2+ <15g / L then H + The concentration was adjusted back to 4 mol / L and then reused in the enrichment acid washing process.

[0110] (5) Enriching Cu in the pickling solution 2+ ≥15g / L is defined as high Cu 2+ Pickling solution, H + The concentration was adjusted back to 1.4 mol / L for synergistic pickling of dried copper and aluminum materials.

[0111] (6) Add the dried copper and aluminum material to the high Cu 2+ The pickling solution was used for synergistic pickling in a reaction vessel with a solid-liquid ratio of 1g:12mL, a pickling time of 10min, an initial temperature of room temperature, and a stirring rate of 300rpm.

[0112] (7) After co-acid washing, the slurry is centrifuged and dewatered to obtain dried copper-aluminum slag and co-acid washing liquid. The co-acid washing liquid contains Ni 2+ +Co 2+ <30g / L then H + The concentration was adjusted back to 4 mol / L and then reused in the enrichment acid washing process.

[0113] (8) Ni in the synergistic pickling solution 2+ +Co 2+ A concentration of ≥30g / L is defined as copper-removed liquid, which can be directly transported to the downstream leaching stage for secondary copper removal.

[0114] Comparative Example 1

[0115] This comparative example provides a method for conventional acid washing of waste aluminum-cased lithium batteries, which includes the following steps:

[0116] (1) The same batch of dried copper-aluminum material obtained in Example 1 was put into a dilute sulfuric acid reactor for enrichment and acid washing. The solid-liquid ratio was 1g:10mL, and the dilute sulfuric acid contained H2. + The concentration was 3 mol / L, the acid washing time was 20 min, the initial temperature was room temperature, and the stirring speed was 250 rpm.

[0117] (2) Subsequently, solid-liquid separation was performed to obtain conventional pickling solution and dried copper-aluminum slag.

[0118] Comparative Example 2

[0119] This comparative example is basically the same as Example 3, except that: in this comparative example, steps (4) and (5) of Example 3 are omitted, and Cu in the enriched acid washing solution is directly added. 2+ <15g / L, H + The concentration was adjusted back to 2 mol / L for synergistic pickling of dried copper and aluminum materials.

[0120] The specific operating method is as follows:

[0121] A synergistic acid washing method for the integrated recycling of copper and aluminum materials from waste batteries, comprising the following steps:

[0122] (1) The same batch of pyrolytic copper-aluminum material obtained in Example 3 was added to a dilute sulfuric acid reactor for enrichment and acid washing. The solid-liquid ratio was 1g:10mL, and the dilute sulfuric acid contained H2. + The concentration was 3 mol / L, the acid washing time was 25 min, the initial temperature was room temperature, and the stirring speed was 250 rpm.

[0123] (2) After enrichment and acid washing, the slurry is centrifuged and dewatered to obtain pyrolytic copper-aluminum slag and enriched acid-washed liquid. The Cu in the enriched acid-washed liquid is... 2+ <15g / L, H + The concentration was adjusted back to 2 mol / L for synergistic pickling of dried copper and aluminum materials.

[0124] (3) The same batch of dried copper-aluminum material obtained in Example 3 was added to Cu 2+ Co-acid washing was carried out in a reactor with enriched acid washing solution of <15g / L, with a solid-liquid ratio of 1g:10mL, an acid washing time of 15min, an initial temperature of room temperature, and a stirring rate of 250rpm.

[0125] (4) After co-acid washing, the slurry is centrifuged and dewatered to obtain dried copper-aluminum slag and co-acid washing liquid. The co-acid washing liquid contains Ni 2+ +Co 2+ <30g / L then H + The concentration was adjusted back to 3 mol / L and then reused in the enrichment acid washing process.

[0126] (5) Ni in the synergistic pickling solution 2+ +Co 2+ A concentration of ≥30g / L is defined as copper-removed liquid, which can be directly transported to the downstream leaching stage for secondary copper removal.

[0127] Experimental Example

[0128] The ICP test results of the raw materials used in Examples 1-5 and Comparative Example 2 are shown in Table 1. The ICP test results of the pickling solution and pickling residue obtained by enrichment pickling and synergistic pickling are shown in Tables 2 and 3.

[0129] Table 1. Statistical table of test data for raw materials under different examples

[0130]

[0131]

[0132] Table 2. Statistical table of detection data of pickling solution under different examples

[0133]

[0134] Table 3. Statistical table of detection data of pickling residue under different examples

[0135]

[0136]

[0137] As can be seen from Tables 1, 2, and 3, this application employs enrichment pickling, and the main process in enrichment pickling is Cu enrichment. 2+ ,because Cu in the synergistic pickling process 2+ Replace H + The active sites undergo a displacement reaction with Al to precipitate elemental copper. Throughout the enrichment and acid washing process, the pH and reaction rate of the system remain relatively stable. Subsequent use of high-Cu... 2+ The pickling solution is used to synergistically pickle dried copper and aluminum materials, which can not only remove high Cu content. 2+ Cu in pickling solution 2+ It can also effectively improve the problems of hydrogen production and heat accumulation that are easily generated during pickling of dried copper and aluminum materials in the existing technology. It has the advantages of energy saving, cost reduction, stability and safety, and high efficiency of recycling, and provides a new method for pickling copper and aluminum materials from waste lithium batteries.

[0138] Comparing Example 3 and Comparative Example 2, it can be seen that in Comparative Example 2, Cu was directly enriched in the pickling solution. 2+ <15g / L, H + The concentration was adjusted back to 2 mol / L for synergistic pickling of the copper-aluminum material for drying. At this point, due to the insufficient enrichment of metal elements in Comparative Example 2, the high Cu content obtained in Comparative Example 2 resulted in... 2+ The metal element content in the pickling solution was significantly lower than that in Example 3, resulting in a significantly lower metal element content after synergistic pickling, which fully demonstrates that high Cu content... 2+ Cu in pickling solution 2+ It has a better leaching effect at ≥15g / L.

[0139] The pickling residue and pickling solution obtained in Example 1 and Comparative Example 1 were compared. Please refer to Table 4 for the comparison data.

[0140] Table 4. Statistical table of pickling residue and pickling solution obtained from co-pilot pickling and conventional pickling.

[0141]

[0142] As shown in the table above, in Comparative Example 1, when the dried copper-aluminum material is directly pickled, rapid heat accumulation and hydrogen production occur during the pickling process, causing problems such as solution temperature rise and bubbling. However, in this application, a high Cu content is used for the dried copper-aluminum material. 2+ Co-acid pickling with pickling solution, high Cu2+ H in pickling solution + The lower concentration results in significantly reduced heat accumulation and hydrogen production rates compared to conventional pickling. Solution temperature rise and bubbling are less pronounced. Furthermore, the pickling residue obtained through the synergistic pickling method of this application has a higher copper content and a lower Ni content. In addition, the Ni and Co contents in the pickling solution obtained through the synergistic pickling method of this application are significantly higher than those of conventional pickling, and the Cu and Al contents are also significantly higher. This fully demonstrates that the synergistic pickling reaction efficiency and the leaching efficiency of ternary materials in this application are higher than those of conventional pickling.

[0143] Furthermore, it should be noted that extending the pickling time does not necessarily increase the concentration of metal ions. In this application, the concentration of metal ions is increased by enriching the pickling solution and adjusting the H2O of the synergistic pickling solution. + After concentration, return to the enrichment pickling step. The purpose is to reuse the enrichment pickling solution and the co-pickled pickling solution, provided that the copper ion concentration in the enrichment pickling solution does not reach 15 g / L or the nickel-cobalt concentration does not reach 30 g / L, thereby reducing the consumption of water and acid.

[0144] Unless otherwise stated, “copper” and “Cu” are used interchangeably in this document and refer to copper ions (Cu). 2+ ); "aluminum" and "Al" are used interchangeably in this article and refer to aluminum ions (Al). 3+ ); "Ni" and "Ni" are used interchangeably in this article and refer to nickel ions (Ni 2+ ); "Co" and "Co" are used interchangeably in this article and refer to cobalt ions (Co ions). 2+ ); "Manganese" and "Mn" are used interchangeably in this article and refer to manganese ions (Mn 2+ ); "lithium" and "Li" are used interchangeably in this article and refer to lithium ions (Li ions). + ).

[0145] The preferred embodiments of this application have been described in detail above; however, this application is not limited thereto. Within the scope of the technical concept of this application, various simple modifications can be made to the technical solution of this application, including combining various technical features in any other suitable manner. These simple modifications and combinations should also be considered as the content disclosed in this application and are all within the protection scope of this application.

[0146] Industrial applicability

[0147] Based on the inherent compositional characteristics of pyrolytic and dried copper-aluminum materials, the main principle of this application is as follows: enrichment acid washing dissolves CuO and Cu2O from the pyrolytic copper-aluminum materials, yielding high Cu content. 2+ Pickling solution; because Cu in the synergistic pickling process 2+ Replace H +The active site undergoes a substitution reaction with Al to precipitate elemental copper, while simultaneously inhibiting hydrogen production and heat accumulation. The aluminum scrap and the elemental copper precipitated on its surface form (-)Al|Al 3+ (aq)|Cu 2+ (aq)|Cu micro galvanic cells accelerate the reaction and improve copper removal efficiency.

[0148] Compared to traditional copper-aluminum pickling processes, the method described in this application has significant advantages. First, the process route designed in this application features a semi-closed loop, eliminating the need for additional auxiliary materials for copper removal, inhibiting hydrogen production during pickling, and preventing heat buildup. Second, the pickling solution is recycled between enrichment pickling and co-pickling, reducing the consumption of sulfuric acid and water. Third, the leaching efficiency of Ni, Co, Mn, and their oxides depends on the pH and temperature of the reaction system, and the Cu content from the co-pickling of the dried copper-aluminum material is significantly improved. 2+ Can replace H + The reaction with Al generates heat, which can increase the reaction temperature and reduce sulfuric acid consumption, making the pH of the solution system more stable and the reaction process smoother. Fourth, the Cu in the solution after copper removal... 2+ The concentration has reached the requirements of the first-stage copper removal process in the leaching process, effectively reducing the auxiliary materials, labor and time costs of downstream copper removal.

Claims

1. A synergistic acid washing method for the integrated recycling of copper and aluminum materials from waste batteries across the entire supply chain, characterized in that, Includes the following steps: Collaborative pickling step: Dry copper and aluminum materials are pickled together with high Cu... 2+ The pickling solution is used for synergistic pickling, wherein the high Cu 2+ Pickling solution is obtained by enriching Cu in pyrolytic copper and aluminum materials through pickling. 2+ A solution with a concentration of ≥15 g / L, wherein the high Cu 2+ Before the pickling solution is used to co-pickle the dried copper and aluminum material, the high Cu content is first... 2+ H in pickling solution + Adjust the concentration to 1-2 mol / L.

2. The synergistic acid washing method for the integrated recycling of copper and aluminum materials from waste batteries according to claim 1, characterized in that, The co-pickled step is preceded by an enrichment pickling step: pyrolytic copper-aluminum material and acid solution are mixed for enrichment pickling to obtain Cu. 2+ Solutions with a concentration of ≥15 g / L.

3. The synergistic acid washing method for the integrated recycling of copper and aluminum materials from waste batteries according to any one of claims 1-2, characterized in that, In the synergistic pickling process, the dried copper-aluminum material and the high Cu content... 2+ The solid-liquid ratio of the pickling solution is 1g:(8-12)mL; The pickling time for the synergistic pickling is 10-15 minutes.

4. The synergistic acid washing method for the integrated recycling of copper and aluminum materials from waste batteries according to any one of claims 1-2, characterized in that, The synergistic pickling is carried out under stirring conditions at a stirring speed of 200-300 rpm.

5. The synergistic acid washing method for the integrated recycling of copper and aluminum materials from waste batteries according to claim 2, characterized in that, Following the synergistic pickling, the process further includes solid-liquid separation to obtain a post-synergistic pickling solution and dried copper-aluminum slag, and detection of Ni in the post-synergistic pickling solution. 2+ and Co 2+ Concentration, when Ni 2+ +Co 2+ When the concentration of Ni in the synergistic pickling solution is ≥30 g / L, the solution is collected as the copper removal solution; when the Ni concentration in the synergistic pickling solution is ≥30 g / L, the solution is collected as the copper removal solution. 2+ +Co 2+ When the concentration is <30g / L, the synergistic pickling solution is recycled.

6. The synergistic acid washing method for the integrated recycling of copper and aluminum materials from waste batteries according to claim 5, characterized in that, The recycling of the synergistic pickling solution includes: removing the H from the synergistic pickling solution. + The concentration is adjusted to 2.5~4 mol / L and reused in the enrichment acid washing process as the acid solution.

7. The synergistic acid washing method for the integrated recycling of copper and aluminum materials from waste batteries according to claim 5, characterized in that, Cu in the copper removal solution 2+ <200mg / L, pH 1~1.

5.

8. The synergistic acid washing method for the integrated recycling of copper and aluminum materials from waste batteries according to claim 5, characterized in that, The nickel and cobalt content in the dried copper-aluminum slag is less than 2%.

9. The synergistic acid washing method for the integrated recycling of copper and aluminum materials from waste batteries according to claim 2, characterized in that, Obtain the Cu 2+ The solution with a concentration of ≥15 g / L comprises: a post-enriched acid-wash solution and pyrolytic copper-aluminum slag obtained by solid-liquid separation after the enriched acid washing, and the detection of Cu in the post-enriched acid-wash solution. 2+ Concentration, when Cu 2+ When the concentration is ≥15 g / L, the enriched pickling solution will be used as the high Cu concentration. 2+ Pickling solution, when Cu in the enriched pickling solution is... 2+ When the concentration is <15g / L, the enriched pickling solution is recycled.

10. The synergistic acid washing method for the integrated recycling of copper and aluminum materials from waste batteries according to claim 9, characterized in that, The recycling of the enriched pickling solution includes: removing the H from the enriched pickling solution. + The concentration is adjusted to 2.5~4 mol / L and reused in the enrichment acid washing process as the acid solution.

11. The synergistic acid washing method for the integrated recycling of copper and aluminum materials from waste batteries according to any one of claims 9-10, characterized in that, The high Cu 2+ The initial pH of the pickling solution is 1~1.5, and the nickel and cobalt content in the pyrolytic copper-aluminum slag is <3%.

12. The synergistic acid washing method for the integrated recycling of copper and aluminum materials from waste batteries according to any one of claims 9-10, characterized in that, In the enrichment pickling process, the solid-liquid ratio of the pyrolytic copper-aluminum material to the acid solution is 1 g: (8-12) mL; the pickling time for the enrichment pickling process is 20-25 min.

13. The synergistic acid washing method for the integrated recycling of copper and aluminum materials from waste batteries according to any one of claims 9-10, characterized in that, The enrichment rinsing is carried out under stirring conditions at a stirring speed of 200-300 rpm.

14. The synergistic acid washing method for the integrated recycling of copper and aluminum materials from waste batteries according to any one of claims 9-10, characterized in that, The acid solution has H + The concentration is 2.5~4 mol / L; the acid solution is dilute sulfuric acid.

15. The synergistic acid washing method for the integrated recycling of copper and aluminum materials from waste batteries according to claim 1, characterized in that, Obtaining the pyrolytic copper-aluminum material includes: pyrolyzing waste polymer batteries at 700-800℃ for 25-35 minutes to obtain pyrolytic material, crushing, sieving and magnetically separating the pyrolytic material, and the low magnetic material on the 60-80 mesh sieve is the pyrolytic copper-aluminum material.

16. The synergistic acid washing method for the integrated recycling of copper and aluminum materials from waste batteries according to claim 1, characterized in that, Obtaining the dried copper-aluminum material includes: drying waste aluminum-cased lithium batteries at 130-180℃ for 25-30 minutes to obtain dried material, and then sieving and gravity sorting the dried material to obtain the dried copper-aluminum material.

17. The synergistic acid washing method for the integrated recycling of copper and aluminum materials from waste batteries according to claim 16, characterized in that, Before drying the waste aluminum-cased lithium batteries, the process also includes crushing the waste aluminum-cased lithium batteries, with the oxygen concentration in the furnace during crushing and drying being <1%.

18. A co-acid washing device for waste battery copper and aluminum materials used to implement the co-acid washing method for the integrated recycling of waste battery copper and aluminum materials as described in any one of claims 1-17, characterized in that, It includes an enrichment pickling device and a co-pilot pickling device; The enrichment acid washing device includes a first reaction vessel, a first centrifuge, an enrichment acid washing liquid collector, a first concentration detection mechanism, and a high Cu... 2+ The pickling solution discharge pipe and the first reflux pipe; the synergistic pickling device includes a second reaction vessel, a second centrifuge, a synergistic pickling post-liquid collector, a second concentration detection mechanism, a copper removal post-liquid discharge pipe and a second reflux pipe; The outlet of the first reaction vessel is connected to the first centrifuge, and the first centrifuge is connected to the enriched acid-washing liquid collector to collect the liquid separated by the first centrifuge. The first concentration detection mechanism is disposed in the enriched acid-washing liquid collector to detect the Cu in the enriched acid-washing liquid collection mechanism. 2+ Concentration, the high Cu 2+ The pickling solution discharge pipe is connected to the second reaction vessel, and the first reflux pipe is connected to the first reaction vessel; the outlet of the second reaction vessel is connected to the second centrifuge, and the second centrifuge is connected to the co-piloted pickling solution collector to collect the liquid separated by the second centrifuge; the second concentration detection mechanism is installed in the co-piloted pickling solution collector to detect the Ni concentration within the co-piloted pickling solution collector. 2+ and Co 2+ The concentration is specified, the copper removal liquid discharge pipe is connected to the subsequent copper removal equipment, and the second reflux pipe is connected to the first reaction vessel.

19. The application of the integrated recycling method for copper and aluminum materials from waste batteries as described in any one of claims 1-17 in the recycling of waste lithium batteries.

20. A method for recycling waste lithium batteries, characterized in that, It includes the synergistic acid washing method for the integrated recycling of copper and aluminum materials from waste batteries as described in any one of claims 1-17.

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