A composite material for hydrometallurgy and a preparation method and application thereof

Abstract

This invention discloses a composite material for hydrometallurgy, its preparation method, and its application, belonging to the field of battery recycling technology. The composite material for hydrometallurgy contains Li; the mass percentage of Li in the composite material is w1, and the mass percentage of Li in the form of lithium carbonate and lithium oxide is w2, where (w2 / w1)×100%≥30%; furthermore, in the XRD pattern of the composite material, there is a set of overlapping peaks 1 at 2θ=37.4°~39°, with a base width ≤1.13°. This composite material for hydrometallurgy exhibits good metal element recovery rate during hydrometallurgical processes, which is beneficial for cost reduction. The preparation method includes: ball milling battery waste with a co-grinding agent, drying to obtain degraded waste; and pyrolyzing and incinerating the degraded waste.

Description

Technical Field

[0001] This invention relates to the field of battery recycling technology, and more specifically, to a composite material for hydrometallurgy, its preparation method, and its application. Background Technology

[0002] With the rapid development of technology, the market demand in the new energy field, especially new energy vehicles, is constantly expanding, and lithium batteries, as their core component, have been widely used. However, the disposal of retired batteries has become a bottleneck for the industry's development. Black Mass recycling technology has emerged to address this need. This technology recycles and reuses valuable metals and materials from waste batteries, achieving a green transformation from waste to valuable resources.

[0003] Currently, waste battery powder mainly originates from the dismantling, crushing, and screening processes of waste lithium batteries. The components of waste battery powder include metals such as lithium, cobalt, nickel, manganese, aluminum, iron, and copper, as well as non-metallic materials such as carbon powder and plastics. If waste battery powder is not properly treated, the loss of valuable metals will lead to resource waste, while non-metallic materials such as carbon powder and plastics may pollute soil and water sources.

[0004] The mainstream method for recycling and reusing waste battery powder is hydrometallurgy. This method mainly involves ionizing metal elements, then separating and enriching the metals through techniques such as precipitation, electrowinning, extraction, and ion exchange, and finally recovering the target metal in a certain chemical state. This method can obtain relatively pure metal compounds that can be directly used to prepare electrode materials.

[0005] Hydrometallurgical processes include acid leaching, where black powder is immersed in concentrated acid (usually sulfuric acid) containing a reducing agent (usually hydrogen peroxide), and heated (and pressurized). This process combines low-acid leaching and high-acid leaching in multiple steps to ionize the valuable metals, which are then retained in the liquid phase, thus achieving the extraction of valuable metals. The reason for adding hydrogen peroxide and using concentrated acid and relatively high temperatures (usually 70℃~90℃) for acid leaching is that this method can reduce elements such as nickel, cobalt, and manganese to divalent states, making them easier to dissolve into the aqueous phase. However, this method is costly, and the metal recovery rate needs further improvement.

[0006] In view of this, the present invention is proposed. Summary of the Invention

[0007] The purpose of this invention is to provide a composite material for hydrometallurgy, its preparation method and application, in order to solve or improve the above-mentioned technical problems.

[0008] This invention can be implemented as follows:

[0009] In a first aspect, the present invention provides a composite material for hydrometallurgy, wherein the composite material for hydrometallurgy contains Li element;

[0010] The mass percentage of Li in the composite material for hydrometallurgy is denoted as w1, and the total mass percentage of Li in the form of lithium carbonate and lithium oxide in the composite material for hydrometallurgy is denoted as w2, wherein (w2 / w1)×100%≥30%; and, in the XRD spectrum of the composite material for hydrometallurgy, there is a set of overlapping peaks 1 at 2θ=37.4°~39°, and the bottom width of the overlapping peaks 1 is ≤1.13°.

[0011] In an optional implementation, the base width of the coincident peak 1 is ≤1°;

[0012] And / or, in the XRD spectrum of the composite material used in hydrometallurgy, there is a set of overlapping peaks 2 at 2θ = 63.6° to 65.2°, and the bottom width of the overlapping peaks 2 is ≤1.5°.

[0013] In an optional embodiment, the composite material for hydrometallurgy also has at least one of the following characteristics:

[0014] Feature 1: The base width of the coincidence peak 2 is ≤1.25°;

[0015] Feature 2: The composite material for hydrometallurgy also contains Ni element; the mass percentage of Ni element in the composite material for hydrometallurgy is recorded as w3, and the mass percentage of Ni element in the composite material for hydrometallurgy in the form of nickel oxide is recorded as w4, wherein 10%≤(w4 / w3)×100%≤80%;

[0016] Feature 3: The composite material for hydrometallurgy also contains Co; the mass percentage of Co in the composite material for hydrometallurgy is denoted as w5, and the mass percentage of Co in the form of cobalt oxide in the composite material for hydrometallurgy is denoted as w6, wherein 10% ≤ (w6 / w5) × 100% ≤ 70%.

[0017] In optional implementations, 1% ≤ w1 ≤ 10%; and / or, 0 < w3 ≤ 50%; and / or, 0 < w5 ≤ 20%.

[0018] In a second aspect, the present invention provides a method for preparing a composite material for hydrometallurgy as described in any of the foregoing embodiments, comprising the following steps: ball milling battery waste with a co-grinding agent, drying to obtain degraded waste; and pyrolyzing and incinerating the degraded waste.

[0019] In an optional embodiment, the co-grinding agent includes water and persulfate; the mass ratio of battery waste to water and persulfate is 1:(0.2-0.4):(0.5-1);

[0020] Alternatively, the grinding agent includes water, persulfate, and alkali; the mass ratio of battery waste to water, persulfate, and alkali is 1:(0.2~0.4):(0.5~1):(0.3~0.5);

[0021] Alkali agents include at least one of sodium hydroxide, potassium hydroxide, and ammonia.

[0022] And / or, persulfates include at least one of ammonium persulfate, sodium persulfate, sodium persulfate, potassium persulfate, and potassium persulfate.

[0023] In an optional embodiment, the ball mill includes at least one of the following features:

[0024] Feature 4: The ball-to-material ratio of the ball mill is 10:1 to 20:1 by mass;

[0025] Feature 5: The ball mill's rotation speed is 400 rpm to 1000 rpm;

[0026] Feature 6: The ball milling time is 60 min to 120 min;

[0027] Feature 7: The temperature of the ball milling material during the ball milling process is not lower than 60℃, wherein the ball milling material is a mixture of battery waste and co-grinding agent.

[0028] In an optional implementation, pyrolysis incineration includes at least one of the following features:

[0029] Feature 8: The pyrolysis incineration temperature is 400℃~600℃;

[0030] Feature 9: The pyrolysis incineration time is 0.5h to 2h;

[0031] Feature 10: Sulfur and coke are added during pyrolysis incineration, and the amounts of sulfur and coke added meet the following requirements:

[0032] in, These represent the elemental masses of C, Al, Ni, Co, and Mn in battery waste, all in grams. The mass of sulfur added during the pyrolysis incineration process is expressed in grams. The mass of coke added during the pyrolysis incineration process is expressed in grams.

[0033] Feature 11: The atmosphere during the pyrolysis incineration process satisfies:

[0034] in, These represent the concentrations of oxygen and sulfur dioxide in the atmosphere during the pyrolysis incineration process, respectively, both in g / L.

[0035] Thirdly, the present invention provides an electrode material, the raw materials for which the preparation of the electrode material includes the composite material for hydrometallurgy of any of the foregoing embodiments.

[0036] Fourthly, the present invention provides a battery comprising the electrode material of the foregoing embodiments.

[0037] The beneficial effects of this invention include:

[0038] The composite material for hydrometallurgy provided by this invention exhibits a peak width ≤1.13° at 2θ = 37.4°–39°, indicating that the layered transition metal oxides contained in battery waste have significant crystal defects, making them prone to releasing metal ions under low-concentration acid and / or reducing agent conditions. Since Li exists in various forms in the composite material for hydrometallurgy, the acid solubility efficiencies of different Li compounds vary, with Li₂CO₃ and Li₂O exhibiting the highest acid solubility efficiencies. The composite material for hydrometallurgy that satisfies the requirements of a peak width ≤1.13° at 2θ = 37.4°–39° and (w₂ / w₁) × 100% ≥ 30% can possess at least a high acid solubility efficiency for Li.

[0039] In other words, the composite material for hydrometallurgy provided by this invention has a high leaching efficiency of at least metallic Li during the acid leaching process, consumes less acid and reducing agent, and takes less time, which helps to reduce costs. Attached Figure Description

[0040] To more clearly illustrate the technical solutions of the embodiments of the present invention, 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 the present invention and should not be regarded as a limitation on the scope. For those skilled in the art, other related drawings can be obtained based on these drawings without creative effort.

[0041] Figure 1 The image shows the XRD pattern of the hydrometallurgical composite material prepared in Example 1 of this invention.

[0042] Figure 2 for Figure 1 Enlarged view of the first dashed box (overlapping peak 1) and its fitting peak results;

[0043] Figure 3 for Figure 1 Enlarged view of the second dashed box (overlapping peak 2) and its fitted peak results. Detailed Implementation

[0044] To make the objectives, technical solutions, and advantages of the embodiments of the present invention clearer, the technical solutions in the embodiments of the present invention 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 following is a detailed description of the composite material for hydrometallurgy provided by the present invention, its preparation method, and its application.

[0046] This invention provides a composite material for hydrometallurgy, which contains Li element;

[0047] The mass percentage of Li in the composite material for hydrometallurgy is denoted as w1, and the total mass percentage of Li in the composite material for hydrometallurgy, in the form of lithium carbonate and lithium oxide, is denoted as w2, wherein (w2 / w1)×100%≥30%.

[0048] Furthermore, in the XRD spectrum of the composite material used in hydrometallurgy, there is a set of overlapping peaks 1 at 2θ = 37.4° to 39°, and the bottom width of overlapping peak 1 is ≤ 1.13°.

[0049] Composite materials for hydrometallurgy that meet the above conditions have high metal leaching efficiency during acid leaching, consume less acid and reducing agent, and have a shorter leaching time, which helps to reduce costs.

[0050] In this invention, the battery waste used to prepare the composite material for hydrometallurgical processes includes lithium-containing layered transition metal oxides. The transition metals include at least one of Ni, Co, and Mn, and may also include metal elements such as Al, Ti, Zr, Sr, Mo, Ba, W, La, Ce, Bi, In, Nb, and Y. Typically, the battery waste includes lithium nickel cobalt manganese oxide.

[0051] It should be noted that in layered transition metal oxides, metal ions are tightly bound within a crystalline "oxygen cage," and the metal leaching process can essentially be understood as a process of disrupting the "oxygen cage" structure. Pure layered transition metal oxides, due to their well-defined layered structure, make it difficult to remove M ions without the addition of a reducing agent. n+ -O 2-The leaching of metal elements occurs when the bonds (M represents metal ions) are broken, releasing the metal ions. Therefore, in hydrometallurgical processes, acids and reducing agents (such as sodium sulfite, hydrogen peroxide, sodium thiosulfate, etc.) are added, and heating is employed to disrupt the "oxygen cage" structure of layered transition metal oxides, allowing all metal elements to leach out. In other words, layered transition metal oxides have a relatively high leaching activation energy. Therefore, in the recycling of battery waste, disrupting the regular layered structure of the layered transition metal oxides, introducing defects, and reducing their crystallinity will improve the leaching effect of metal elements.

[0052] Under normal circumstances, in the XRD spectrum of the composite material for hydrometallurgy, the 2θ = 37.4° to 39° contains characteristic diffraction peaks belonging to the (006) and (102) crystal planes of layered transition metal oxides. The degree of splitting of the two peaks reflects the integrity of the layered structure of the layered transition metal oxide. The better the layered structure, the higher the degree of splitting of the two peaks. The higher the degree of overlap of the two peaks, the greater the defects in the layered structure, which eventually manifests as a single peak. The narrower the bottom width of this single peak, the higher the degree of overlap. The composite material for hydrometallurgy provided by this invention has a bottom width of ≤1.13° at 2θ = 37.4° to 39°, indicating that the crystal defects of the layered transition metal oxide are relatively large, and it is easy to release metal ions under low concentrations of acid and / or reducing agent conditions. Since the composite material for hydrometallurgy also contains many impurity elements such as P, Al and F, the existence of Li element is diverse, including LiF, Li3PO4, LiAlO2, Li2CO3, Li2O and Li(Ni x Co y Mn 1-x-y O2, etc. The acid solubility efficiencies of different Li compounds vary, with Li2CO3 and Li2O exhibiting the highest efficiencies. Therefore, the hydrometallurgical composite material that satisfies the requirements of a bottom width ≤1.13° for the overlapping peak 1 appearing at 2θ = 37.4°–39° and (w2 / w1) × 100% ≥ 30% can possess at least a high Li element acid solubility efficiency.

[0053] It should be noted that in this article, "acid dissolution efficiency" refers to the rate and extent to which the metal components in battery waste are dissolved into the solution by acid during the acid leaching process. The higher the degree of acid dissolution, the higher the acid dissolution efficiency, and the more valuable metals are successfully extracted, which is beneficial for subsequent separation and recycling.

[0054] For example, in the XRD pattern of the composite material for hydrometallurgy, the base width of the overlapping peak 1 can be 0.1°, 0.2°, 0.3°, 0.4°, 0.5°, 0.6°, 0.7°, 0.8°, 0.9°, 0.99°, 1.0°, 1.1°, or 1.13°, or other values ​​within the range of ≤1.13°. In some preferred embodiments, the base width of the overlapping peak 1 is ≤1°, such as 0.65° to 1° (e.g., 0.65°, 0.79°, 0.82°, 0.83°, 0.85°, 0.86°, 0.91°, or 0.99°). Composite materials for hydrometallurgy that meet this condition have larger layered structure defects in the layered transition metal oxides, making it easier to release metal ions during acid leaching.

[0055] In some alternative implementations, 1% ≤ w1 ≤ 10%. Exemplarily, the value of w1 can be 1%, 1.5%, 2%, 2.5%, 3%, 3.5%, 4%, 4.5%, 5%, 5.5%, 6%, 6.5%, 7%, 7.5%, 8%, 8.5%, 9%, 9.5%, or 10%, or other values ​​within the range of 1% to 10%, such as 5.54% to 6.82%, or 5.54%, 5.58%, 5.62%, 5.61%, 5.65%, 5.68%, 6.78%, or 6.82%.

[0056] For example, the value of (w2 / w1)×100% can be 30%, 35%, 40%, 45%, 50%, 55%, 60%, 65%, 70%, 75%, 80%, 85%, or 90%, etc., or it can be other values ​​within the range of ≥30%, such as 42.09% to 89.87%, such as 42.09%, 55.61%, 56.22%, 56.52%, 56.72%, 57.52%, 70.46%, or 89.87%, etc.

[0057] For example, w2 can be obtained by measuring the mass of lithium in the leachate obtained after the composite material for hydrometallurgy is leached in dilute acid (1 mol / L sulfuric acid) at 20℃~30℃ for 24h, and calculating the proportion of the mass of the lithium to the mass of the composite material for hydrometallurgy.

[0058] In some alternative embodiments, the XRD pattern of the composite material for hydrometallurgy has a set of overlapping peaks 2 at 2θ = 63.6° to 65.2°, with the base width of the overlapping peaks 2 ≤ 1.5°.

[0059] The overlapping peak 2 is attributed to the characteristic diffraction peaks of the (018) and (110) crystal planes of the layered transition metal oxide. Similarly, the degree of splitting of the two peaks reflects the integrity of the layered structure of the layered transition metal oxide. The better the layered structure, the higher the degree of splitting of the two peaks. The higher the degree of overlap of the two peaks, the greater the defects in the layered structure, which ultimately manifests as a single peak. The narrower the base width of this single peak, the higher the degree of overlap. The composite material for hydrometallurgy provided by this invention has an overlapping peak 2 with a base width ≤ 1.5° at 2θ = 63.6° to 65.2°, indicating that the crystal defects of the layered transition metal oxide are relatively large, and it is easy to release metal ions under low concentrations of acid and / or reducing agent conditions. In some preferred embodiments, the base width of the overlapping peak 2 is ≤ 1.25°, such as 0.92° to 1.25°.

[0060] In some optional embodiments, the above-mentioned hydrometallurgical composite material also contains Ni element; the Ni element in the hydrometallurgical composite material may exist in the form of nickel oxides (such as NiO and Ni2O3), elemental nickel, layered transition metal oxides, etc. The mass percentage of Ni element in the hydrometallurgical composite material is denoted as w3, and the mass percentage of Ni element in the form of nickel oxide in the hydrometallurgical composite material is denoted as w4, wherein 10% ≤ (w4 / w3) × 100% ≤ 80%. The hydrometallurgical composite material that meets the above conditions has a high Ni element acid dissolution efficiency during acid leaching.

[0061] In some alternative implementations, 0 < w3 ≤ 50%. For example, the value of w3 can be 10%, 15%, 20%, 25%, 30%, 35%, 40%, 45%, or 50%, etc., or it can be other values ​​in the range of >0 and ≤50%, such as 26.10% to 45.20%, such as 26.10%, 26.17%, 26.32%, 26.34%, 26.57%, 45.18%, or 45.20%, etc.

[0062] For example, the value of (w4 / w3)×100% can be 10%, 15%, 20%, 25%, 30%, 35%, 40%, 45%, 50%, 55%, 60%, 65%, 70%, 75%, or 80%, etc., or other values ​​in the range of 10% to 80%, such as 20.3% to 68.2%, such as 20.3%, 20.9%, 22.6%, 24.0%, 24.5%, 27.9%, 46.6%, or 68.2%, etc.

[0063] In some optional embodiments, the above-mentioned hydrometallurgical composite material also contains Co. The Co in the hydrometallurgical composite material may exist in forms such as cobalt oxide, elemental cobalt, or layered transition metal oxides. The mass percentage of Co in the hydrometallurgical composite material is denoted as w5, and the mass percentage of Co in the form of cobalt(II) oxide is denoted as w6, wherein 10% ≤ (w6 / w5) × 100% ≤ 70%. The hydrometallurgical composite material meeting the above conditions exhibits high Co dissolution efficiency during acid leaching.

[0064] In some alternative implementations, 0 < w5 ≤ 20%. For example, the value of w5 can be 20%, 18%, 15%, 12%, 10%, 8%, 6%, 4%, 2%, or 1%, etc., or it can be other values ​​in the range of >0 and ≤20%, such as 4.76% to 6.23%, such as 4.76%, 4.89%, 4.93%, 5.00%, 5.05%, 5.11%, 6.16%, or 6.23%, etc.

[0065] For example, the value of (w6 / w5)×100% can be 10%, 15%, 20%, 25%, 30%, 35%, 40%, 45%, 50%, 55%, 60%, 65%, or 70%, etc., or other values ​​in the range of 10% to 70%, such as 16.8% to 63.8%, such as 16.8%, 18.4%, 20.5%, 22.2%, 23.7%, 27.6%, 47.4%, or 63.8%, etc.

[0066] In some optional embodiments, the above-mentioned composite material for hydrometallurgy also contains Mn element; the mass percentage of Mn element in the composite material for hydrometallurgy is denoted as w7, where 0 < w7 ≤ 20%. For example, the value of w7 can be 20%, 18%, 15%, 12%, 10%, 8%, 6%, 4%, 2%, or 1%, etc., or it can be other values ​​in the range of >0 and ≤20%, such as 4.86% to 7.15%, such as 4.86%, 4.93%, 6.87%, 6.86%, 6.92%, 7.05%, 7.11%, or 7.15%, etc.

[0067] For example, inductively coupled plasma atomic emission spectrometry (ICP-AES) can be used to determine the mass ratios of all Li, Ni, Co, and Mn elements in the sample to the mass of the composite material used in hydrometallurgy, i.e., w1, w3, w5, and w7. Alternatively, the mass percentage w3 of all Ni elements can be determined by the dimethylglyoxime gravimetric method (refer to YS / T 1342.1-2019), the mass percentage w5 of all Co elements can be determined by potentiometric titration or flame atomic absorption spectrometry (refer to YS / T 1342.2-2019), the mass percentage w1 of Li elements can be determined by flame atomic absorption spectrometry (refer to YS / T 1342.4-2019), and the mass percentage w7 of all Mn elements can be determined by potentiometric titration or flame atomic absorption spectrometry (refer to YS / T 1342.3-2019). Preferably, inductively coupled plasma atomic emission spectrometry is used to test w1, w3, w5, and w7.

[0068] For example, the determination methods for (w2 / w1)×100%, (w4 / w3)×100%, and (w6 / w5)×100% can be as follows: Wg of the composite material to be tested for hydrometallurgical processing is mixed with dilute acid (1mol / L sulfuric acid) at a solid-liquid ratio of 1g:50mL and shaken for 24h at 20℃~30℃. The reaction solution is filtered, and the content of Ni, Co, and Li elements in the filtrate is measured to obtain the mass of Ni, Co, and Li elements respectively. All units are in grams. The methods for determining the content of Ni, Co, and Li elements in the filtrate can be inductively coupled plasma atomic emission spectrometry (refer to Appendix A of GB / T45203-2024), or the Ni content can be determined by the dimethylglyoxime gravimetric method or flame atomic absorption spectrometry (refer to YS / T 1342.1-2019), the Co content by potentiometric titration or flame atomic absorption spectrometry (refer to YS / T 1342.2-2019), and the Li content by flame atomic absorption spectrometry (refer to YS / T 1342.4-2019). Therefore:

[0069] When inductively coupled plasma atomic emission spectrometry (ICP-AES) is used for determination (refer to Appendix A of GB / T 45203-2024), the concentrations (g / L) of Ni, Co, and Li elements in the filtrate are measured, and the results are obtained respectively. V H The volume of dilute acid added is expressed in liters (L).

[0070] As mentioned above, the Ni, Co, Mn and Li elements in the composite material for hydrometallurgy proposed in this invention can have high leaching efficiency in the hydrometallurgical process, thus achieving good metal element recovery rate, which is beneficial for cost reduction and efficiency improvement.

[0071] Accordingly, the present invention also provides a method for preparing the above-mentioned composite material for hydrometallurgy, which may include the following steps: ball milling battery waste with a co-grinding agent, drying to obtain degraded waste; and pyrolyzing and incinerating the degraded waste. Further, the incineration residue is crushed (e.g., by air jet milling) and sieved.

[0072] In some alternative embodiments, battery waste may include at least one of waste battery cells and electrode materials. The waste battery cells may further include at least one of various single-cell batteries such as prismatic batteries, cylindrical batteries, and pouch batteries.

[0073] In some optional embodiments, the battery waste can be first crushed, and then the crushed battery waste can be ball-milled with a co-grinding agent. For example, discharged waste battery cells and / or electrode materials can be crushed and sorted to obtain crushed battery waste. Crushing can include at least one of jaw crushers, hammer crushers, cone crushers, impact crushers, ball milling, rod milling, roller crushing, and high-pressure roller milling. Sorting can be performed using methods such as sieving, density sorting, electrostatic separation, optical separation, and vibration sorting to remove or partially remove plastics, aluminum foil, copper foil, aluminum shells, and steel shells, resulting in crushed battery waste enriched with positive electrode active materials (and negative electrode active materials).

[0074] In some optional embodiments, the co-grinding agent may include water and persulfate; the mass ratio of battery waste to water and persulfate may be 1:(0.2-0.4):(0.5-1). Specifically, the mass ratio of battery waste to water may be 1:0.2, 1:0.25, 1:0.3, 1:0.35, or 1:0.4, or other values ​​within the range of 1:(0.2-0.4). The mass ratio of battery waste to persulfate may be 1:0.5, 1:0.6, 1:0.7, 1:0.8, 1:0.9, or 1:1, or other values ​​within the range of 1:(0.5-1).

[0075] By using persulfate in the co-grinding agent, persulfate can release sulfate radicals during ball milling, promote the degradation of the binder (PVDF) contained in battery waste, attack the transition metals in layered transition metal oxides, reduce them, and thus destroy the crystal lattice structure.

[0076] In some alternative embodiments, the co-grinding agent includes water, persulfate, and an alkali; the mass ratio of battery waste to water, persulfate, and alkali is 1:(0.2-0.4):(0.5-1):(0.3-0.5). The mass ratio of battery waste to water can be 1:0.2, 1:0.25, 1:0.3, 1:0.35, or 1:0.4, or other values ​​within the range of 1:(0.2-0.4). The mass ratio of battery waste to persulfate can be 1:0.5, 1:0.6, 1:0.7, 1:0.8, 1:0.9, or 1:1, or other values ​​within the range of 1:(0.5-1). The mass ratio of battery waste to alkaline agent can be 1:0.3, 1:0.35, 1:0.4, 1:0.45 or 1:0.5, or other values ​​within the range of 1:(0.3 to 0.5).

[0077] By using persulfate and alkali in the co-grinding agent, on the one hand, the alkali can generate a large amount of heat when it comes into contact with water and under mechanical force; on the other hand, it can provide an alkaline environment, which can corrode the current collector (such as aluminum foil) and promote the detachment of layered transition metal oxides from the current collector; under thermomechanical and alkaline conditions, persulfate releases sulfate free radicals, which promotes the degradation of the binder (PVDF) contained in battery waste, attacks the transition metal in the layered transition metal oxide, reduces it and thus destroys the crystal structure.

[0078] By way of example, the alkaline agent described above may include at least one of sodium hydroxide, potassium hydroxide, and ammonia. The persulfate used in the co-grinding agent described above may, by example but not in a limited sense, include at least one of ammonium persulfate, sodium persulfate, sodium persulfate, potassium persulfate, and potassium persulfate.

[0079] In some alternative implementations, the ball-to-material ratio in the ball mill can be from 10:1 to 20:1 by mass, such as 10:1, 12:1, 15:1, 18:1, or 20:1, or other values ​​within the range of 10:1 to 20:1. The grinding balls used in the ball milling process can be zirconium balls. If the ball-to-material ratio is too low, it is not conducive to thorough grinding; if the ball-to-material ratio is too high, it will significantly increase the equipment load and energy consumption, and may lead to thermal damage to the material (especially detrimental to heat-sensitive materials).

[0080] The rotational speed of the ball mill can be from 400 rpm to 1000 rpm, such as 400 rpm, 500 rpm, 600 rpm, 700 rpm, 800 rpm, 900 rpm or 1000 rpm, or other values ​​within the range of 400 rpm to 1000 rpm.

[0081] The ball milling time can be 60 min to 120 min, such as 60 min, 70 min, 80 min, 90 min, 100 min, 110 min or 120 min, or other values ​​within the range of 60 min to 120 min.

[0082] During ball milling, the mill speed should be adjusted to ensure the temperature of the milled material is not lower than 60℃, such as 60℃, 65℃, 70℃, 75℃, 80℃, 85℃, or 90℃. The milled material is a mixture of battery waste and a co-grinding agent. If the temperature of the milled material is lower than 60℃ during ball milling, it is detrimental to the release of free radicals from persulfate.

[0083] In some alternative implementations, pyrolysis incineration can be carried out in an incinerator. The temperature of pyrolysis incineration can be 400°C to 600°C, such as 400°C, 450°C, 500°C, 550°C, or 600°C, or other values ​​within the range of 400°C to 600°C.

[0084] The pyrolysis incineration time can be 0.5h to 2h, such as 0.5h, 0.6h, 0.7h, 0.8h, 0.9h, 1h or 2h, or other values ​​within the range of 0.5h to 2h.

[0085] In some optional embodiments, sulfur and coke are added during pyrolysis incineration. The amount of sulfur and coke added is controlled based on the elemental content of C, Ni, Co, Mn, and optionally Al (Al derived from aluminum foil as the current collector) in the battery waste. By controlling the amount of sulfur and coke added, the following conditions are met:

[0086]

[0087] in, These represent the elemental masses of C, Al, Ni, Co, and Mn in battery waste, all in grams. The mass of sulfur added during the pyrolysis incineration process is expressed in grams. The mass of coke added during the pyrolysis incineration process is expressed in grams.

[0088] In some alternative implementations, the atmosphere during pyrolysis combustion is further optimized by controlling the ratio of oxygen to sulfur dioxide in the pyrolysis combustion atmosphere to ensure that the following conditions are met:

[0089]

[0090] in, These represent the concentrations of oxygen and sulfur dioxide in the atmosphere during the pyrolysis incineration process, respectively, both in g / L.

[0091] In some alternative implementations, when battery waste is supplied solely by spent battery cells, The value is 0.

[0092] For example, The value can be 1.4, 1.5, 1.6, 1.7, 1.8, 1.9 or 2, or other values ​​in the range of 1.4 to 2.

[0093] For example, The value can be 1.1, 1.2, 1.3, 1.4 or 1.5, or other values ​​in the range of 1.1 to 1.5.

[0094] In some implementations, the degradation waste may be mixed with sulfur and coke, and then the mixture may be fed into an incinerator for pyrolysis and incineration.

[0095] By adding sulfur during the pyrolysis and incineration stage, sulfur roasting can generate heat. Sulfur can also burn even at low oxygen concentrations. Sulfur is relatively reactive, burns quickly, and has a higher calorific value than ordinary coal. It can instantly create high temperatures and a reducing atmosphere, and can be used for layered transition metal oxides (such as Li(Ni)). x Co y Mn 1-x-y The reduction of Ni, Co, and Mn elements in O2 promotes the dissociation of the crystal structure. In addition, sulfur can generate sulfur dioxide flue gas during combustion. The sulfur dioxide generated can be collected and used to produce sulfuric acid in hydrometallurgy, which helps to shorten the sulfur melting and incineration stages in the traditional sulfuric acid production process, making full use of resources.

[0096] By controlling the layered transition metal oxides (such as Li(Ni)) in battery waste x Co y Mn 1-x-y The mass ratio of oxidizing elements Ni, Co, and Mn in the SO2 (O2) to reducing elements C and S, and optionally elemental Al (derived from the current collector aluminum foil), promotes the reduction reaction of more transition metal elements. Furthermore, the oxygen flow rate can be adjusted according to the amount of SO2 produced, thus stabilizing the entire redox reaction and preventing vigorous reactions that could lead to uneven reaction and the production of elemental metals. Elemental metals are less reactive with acids than metal oxides or metal carbonates, thus hindering acid leaching.

[0097] Continuing from the above, this invention employs a two-step method to promote the dissociation of the crystal structure of layered transition metal oxides in composite materials for hydrometallurgical applications. First, a mechanochemical method is used, employing persulfate and an alkali as co-grinding agents to wet-mill battery waste. Under alkaline and thermomechanical conditions, persulfate generates sulfate free radicals. These free radicals can promote PVDF degradation, thus facilitating the separation between layered transition metal oxide particles. Furthermore, they can attack and reduce the transition metals within the layered transition metal oxides, disrupting their crystal structure. Then, a weak reduction method is used to heat and reduce the degraded waste, promoting the conversion of metal ions into easily leached metal compounds. This further promotes the dissociation of the crystal structure of layered transition metal oxides, increasing lattice defects and decreasing crystallinity, thereby improving the leaching of the metal compound powder.

[0098] In addition, the present invention also provides an electrode material (such as a positive electrode material, an electrode sheet, etc.), the raw materials for which the electrode material is prepared include the above-mentioned composite material for hydrometallurgy.

[0099] The aforementioned raw materials refer to hydrometallurgical composite materials used in the preparation of electrode materials that can be traced back to their source. If the hydrometallurgical composite material meets the requirements of this invention, the electrode material prepared using it as a raw material falls within the protection scope of this invention.

[0100] The present invention also provides a battery cell comprising the above-mentioned electrode material.

[0101] For example, the aforementioned battery cells can be used, but are not limited to, in electrical devices such as vehicles, ships, or aircraft.

[0102] The present invention also provides a battery comprising the above-described battery cells.

[0103] The present invention also provides an electrical device comprising the aforementioned battery cell and / or battery. As examples, the electrical device may include, but is not limited to, mobile phones, tablets, laptops, electric toys, power tools, electric vehicles, electric cars, ships, spacecraft, etc. Electric toys may include stationary or mobile electric toys, such as game consoles, electric car toys, electric ship toys, and electric airplane toys, etc., while spacecraft may include airplanes, rockets, space shuttles, and spacecraft, etc.

[0104] The features and performance of the present invention will be further described in detail below with reference to embodiments.

[0105] Example 1

[0106] This embodiment provides a composite material for hydrometallurgy, the preparation method of which includes:

[0107] Step (1): Obtain the fragmented battery waste.

[0108] Discharged waste ternary lithium-ion aluminum-cased battery cells are subjected to biaxial shearing and uniaxial crushing under nitrogen protection. The resulting crushed material is dried at 140℃~150℃ in a nitrogen atmosphere for 2 hours, then dispersed by a dispersant and screened to obtain large pieces (protective shells) and small pieces. The small pieces are screened using a circular vibrating screen, and the undersize is the primary crushed battery waste. The large pieces are subjected to baffled air separation and linear air separation to separate the separator and aluminum shell. The remaining material is crushed again by uniaxial crushing and then screened by a circular vibrating screen to obtain the undersize is the secondary crushed battery waste. The primary and secondary crushed battery waste are combined to obtain the crushed battery waste.

[0109] Step (2): Obtain the degraded waste.

[0110] The crushed battery waste was mixed with ammonium persulfate and water at a mass ratio of 1:0.5:0.2 and put into a ball mill. The ball-to-material ratio was 10:1 by mass (the grinding balls were zirconium balls). The rotation speed was adjusted within the range of 400 rpm to 1000 rpm to maintain the material temperature at 60 to 80 ℃ for 60 min. Then it was dried at 120 ℃ for 1 h to obtain the degraded waste.

[0111] Step (3): Obtain the incineration residue.

[0112] The elemental contents of C, Al, Ni, Co, and Mn in the degradation waste were measured using inductively coupled plasma atomic emission spectrometry (ICP-AES), and then based on... =1.2 Add sulfur and mix thoroughly, then transfer to an incinerator for pyrolysis and incineration at 400℃ for 1 hour. During the process, control the air flow rate to ensure proper ventilation inside the furnace. in, These represent the elemental masses of C, Al, Ni, Co, and Mn in battery waste, all in grams. The mass of sulfur is expressed in grams. These represent the concentrations of oxygen and sulfur dioxide in the atmosphere, respectively, both in g / L.

[0113] Step (4): After the incineration residue gas stream is broken up and sieved, a composite material for hydrometallurgy is obtained.

[0114] Example 2

[0115] This embodiment provides a composite material for hydrometallurgy, the preparation method of which includes:

[0116] Step (1): Obtain the fragmented battery waste.

[0117] The discharged waste ternary lithium-ion aluminum-cased batteries are carefully disassembled to obtain the positive electrode sheet. The positive electrode sheet is then crushed, graded, and sieved to obtain the crushed battery waste.

[0118] Step (2): Obtain the degraded waste.

[0119] The crushed battery waste was mixed with ammonium persulfate, sodium hydroxide and water in a mass ratio of 1:0.5:0.2:0.2 and put into a ball mill. The ball-to-material ratio was 10:1 by mass (zirconia balls were used for grinding). The rotation speed was adjusted within the range of 400 rpm to 1000 rpm to maintain the material temperature at 60 to 80 ℃ for 60 min. Then it was dried at 120 ℃ for 1 h to obtain the degraded waste.

[0120] Step (3): Obtain the incineration residue.

[0121] The elemental contents of C, Al, Ni, Co, and Mn in the degradation waste were measured using inductively coupled plasma atomic emission spectrometry (ICP-AES), and then based on... =1. Add sulfur and mix thoroughly, then transfer to an incinerator for pyrolysis and incineration at 400℃ for 1 hour. During the process, control the air flow rate to ensure proper ventilation inside the furnace. in, The values ​​are: C, Al, Ni, Co, and Mn mass in battery waste (g); sulfur mass (g); and oxygen and sulfur dioxide concentrations in the atmosphere (g / L).

[0122] Step (4): After the incineration residue gas stream is broken up and sieved, a composite material for hydrometallurgy is obtained.

[0123] Example 3

[0124] This embodiment provides a composite material for hydrometallurgy, the preparation method of which includes:

[0125] Step (1): Obtain the fragmented battery waste.

[0126] Discharged waste ternary lithium-ion soft-pack battery cells are subjected to biaxial crushing and reamer crushing under nitrogen protection. The resulting crushed material is dried at 140℃~150℃ in a nitrogen atmosphere for 2 hours, and then conveyed by cyclone to a vibrating screen for screening. The undersize material is the primary crushed battery waste. The oversize material is further subjected to magnetic separation to obtain secondary crushed battery waste. The primary and secondary crushed battery wastes are combined to obtain the crushed battery waste.

[0127] Step (2): Obtain the degraded waste.

[0128] The crushed battery waste was mixed with sodium persulfate, sodium hydroxide and water in a mass ratio of 1:1:0.3:0.2 and put into a ball mill. The ball-to-material ratio was 20:1 by mass (zirconia balls were used for grinding). The rotation speed was adjusted within the range of 400 rpm to 1000 rpm to maintain the material temperature at 60 to 80 ℃ for 100 min. Then it was dried at 120 ℃ for 1 h to obtain the degraded waste.

[0129] Step (3): Obtain the incineration residue.

[0130] The elemental contents of C, Al, Ni, Co, and Mn in the degradation waste were measured using inductively coupled plasma atomic emission spectrometry (ICP-AES), and then based on... =1.8 Add sulfur and mix thoroughly, then transfer to an incinerator for pyrolysis incineration at 500℃ for 1 hour. During the process, control the air flow rate to ensure proper ventilation inside the furnace. in, These represent the elemental masses of C, Al, Ni, Co, and Mn in battery waste, all in grams. The mass of sulfur is expressed in grams. These represent the concentrations of oxygen and sulfur dioxide in the atmosphere, respectively, both in g / L.

[0131] Step (4): After the incineration residue gas stream is broken up and sieved, a composite material for hydrometallurgy is obtained.

[0132] Example 4

[0133] This embodiment provides a composite material for hydrometallurgy, the preparation method of which includes:

[0134] Step (1): Obtain the fragmented battery waste.

[0135] The discharged waste ternary lithium-ion aluminum-cased batteries are carefully disassembled to obtain the positive electrode sheet. The positive electrode sheet is then crushed, graded, and sieved to obtain the crushed battery waste.

[0136] Step (2): Obtain the degraded waste.

[0137] The crushed battery waste was mixed with sodium persulfate, sodium hydroxide and water in a mass ratio of 1:0.5:0.5:0.4 and put into a ball mill. The ball-to-material ratio was 20:1 by mass (zirconia balls were used for grinding). The rotation speed was adjusted within the range of 400 rpm to 1000 rpm to maintain the material temperature at 60 to 80 ℃ for 60 min. Then it was dried at 120 ℃ for 1 h to obtain the degraded waste.

[0138] Step (3): Obtain the incineration residue.

[0139] The elemental contents of C, Al, Ni, Co, and Mn in the degradation waste were measured using inductively coupled plasma atomic emission spectrometry (ICP-AES), and then based on... Sulfur and coke are added and mixed evenly, then transferred to an incinerator for pyrolysis and combustion at 600℃ for 0.5 hours. During the process, the air flow rate is controlled to ensure proper ventilation within the furnace. The mass ratio of sulfur to coke is 0.6:0.4. These represent the elemental masses of C, Al, Ni, Co, and Mn in battery waste, all in grams. The mass of sulfur is expressed in grams. The mass of coke is expressed in grams. These represent the concentrations of oxygen and sulfur dioxide in the atmosphere, respectively, both in g / L.

[0140] Step (4): After the incineration residue gas stream is broken up and sieved, a composite material for hydrometallurgy is obtained.

[0141] Example 5

[0142] This embodiment provides a composite material for hydrometallurgy, the preparation method of which includes:

[0143] Step (1): Obtain the fragmented battery waste.

[0144] The discharged waste ternary lithium-ion aluminum-cased batteries are carefully disassembled to obtain the positive electrode sheet. The positive electrode sheet is then crushed, graded, and sieved to obtain shredded battery waste.

[0145] Step (2): Obtain the degraded waste.

[0146] The crushed battery waste was mixed with ammonium persulfate, sodium hydroxide and water in a mass ratio of 1:1:0.4:0.4 and put into a ball mill. The ball-to-material ratio was 20:1 by mass (zirconia balls were used for grinding). The rotation speed was adjusted within the range of 400 rpm to 1000 rpm to maintain the material temperature at 60 to 80 ℃ for 120 min. Then it was dried at 120 ℃ for 1 h to obtain the degraded waste.

[0147] Step (3): Obtain the incineration residue.

[0148] The elemental contents of C, Al, Ni, Co, and Mn in the degradation waste were measured using inductively coupled plasma atomic emission spectrometry (ICP-AES), and then based on... Sulfur and coke are added and mixed evenly, then transferred to an incinerator for pyrolysis and combustion at 600℃ for 2 hours. During the process, the air flow rate is controlled to ensure proper ventilation within the furnace. The mass ratio of sulfur to coke is 0.6:0.4. These represent the elemental masses of C, Al, Ni, Co, and Mn in battery waste, all in grams. The mass of sulfur is expressed in grams. The mass of coke is expressed in grams. These represent the concentrations of oxygen and sulfur dioxide in the atmosphere, respectively, both in g / L.

[0149] Step (4): After the incineration residue gas stream is broken up and sieved, a composite material for hydrometallurgy is obtained.

[0150] Example 6

[0151] The difference between this embodiment and embodiment 3 is that in step (2), the crushed battery waste is mixed with sodium persulfate, sodium hydroxide and water in a mass ratio of 1:1:0.5:0.2.

[0152] Example 7

[0153] The difference between this embodiment and embodiment 3 is that in step (2), the crushed battery waste is mixed with sodium persulfate, sodium hydroxide and water in a mass ratio of 1:0.5:0.3:0.2.

[0154] Example 8

[0155] The difference between this embodiment and embodiment 3 is that in step (3),

[0156] Example 9

[0157] The difference between this embodiment and embodiment 3 is that in step (3),

[0158] Example 10

[0159] The difference between this embodiment and embodiment 3 is that in step (3),

[0160] Comparative Example 1

[0161] In this comparative example, the shredded battery waste from Example 1 was mixed with water and placed in a ball mill. The mixture was ball-milled for 60 minutes at 700 rpm and a ball-to-material ratio of 10:1, followed by drying at 120°C for 1 hour to obtain a composite material for hydrometallurgical applications. The mass ratio of battery waste to water was 1:0.2.

[0162] Comparative Example 2

[0163] The difference between this comparative example and Example 1 is that in step (2), ammonium persulfate was not used, and the crushed battery waste was directly mixed with water and ball-milled.

[0164] Comparative Example 3

[0165] The difference between this comparative example and Example 1 is that steps (3) and (4) are not performed.

[0166] Test case

[0167] (1) X-ray diffraction (XRD) characterization was performed on the composite materials for hydrometallurgy obtained in Examples 1-10 and Comparative Examples 1-3. The test conditions were as follows: Ultima IV X-ray powder diffractometer was used, and the test conditions were continuous scanning with a scanning speed of 2° / min. The data analysis method was as follows: Jade software was used to perform baseline calibration (to obtain baseline 1) and smoothing on the XRD scan data. Then, the exported data was used to fit and separate the diffraction peaks in the target range (2θ = 37.4° to 39° and 2θ = 63.6° to 65.2°) using Origin software. The Gaussian model was selected, and the baseline of the fitted peak was no more than 200 a.u. (intensity) different from baseline 1. The bottom width of the fitted peaks of the two peaks in the target coincident peak (coinciding peak 1 or coinciding peak 2) must fall within the target range. The total length of the fitted peaks of the two peaks in the target coincident peak (coinciding peak 1 or coinciding peak 2) on the abscissa was taken as the bottom width of the coincident peak.

[0168] The results of the coincidence peaks 1 and 2 in the XRD patterns of the various hydrometallurgical composite materials are shown in Table 1. The XRD pattern of the hydrometallurgical composite material obtained in Example 1 is shown below. Figure 1 As shown, Figure 2 for Figure 1 The magnified view of the first dashed box from left to right (i.e., coincident peak 1) and its fitted peak results. Figure 3 for Figure 1 Enlarged view of the second dashed box from left to right (i.e., coincident peak 2) and its fitted peak results.

[0169] (2) The elemental content of the hydrometallurgical composite materials obtained in Examples 1-10 and Comparative Examples 1-3 was tested, and the results are shown in Table 1.

[0170] In Table 1, w1, w3, w5, and w7 refer to the mass ratios of all Li, Ni, Co, and Mn elements to the mass of the composite material used in hydrometallurgy, respectively. Specifically, inductively coupled plasma atomic emission spectrometry (ICP-A) was used to determine the mass ratios of all Li, Ni, Co, and Mn elements in the composite material to be tested (hereinafter referred to as the test sample) to the mass of the test sample.

[0171] In Table 1, w2 refers to the total mass percentage of Li in the form of lithium carbonate and lithium oxide in the composite material for hydrometallurgy; w4 refers to the mass percentage of Ni in the form of nickel oxide in the composite material for hydrometallurgy; and w6 refers to the mass percentage of Co in the form of cobalt oxide in the composite material for hydrometallurgy.

[0172] The determination methods for (w2 / w1)×100%, (w4 / w3)×100%, and (w6 / w5)×100% are as follows: Wg of the composite material to be tested for hydrometallurgical processing is mixed with dilute acid (1mol / L sulfuric acid) at a solid-liquid ratio of 1g:50mL and shaken for 24h at 20℃~30℃. The resulting reaction solution is filtered, and the concentrations (g / L) of Ni, Co, and Li elements in the filtrate are measured to obtain the results. The content of Ni, Co, and Li elements in the filtrate was determined by inductively coupled plasma atomic emission spectrometry (refer to Appendix A of GB / T 45203-2024); calculated according to the following formula:

[0173]

[0174] V H The volume (L) of dilute acid added.

[0175] (3) The hydrometallurgical composite materials obtained in Examples 1-10 and Comparative Examples 1-3 were respectively added to the acid leaching solution (a sulfuric acid solution with a pH of 0.5-1 and a H2O2 volume concentration of 10%) at a solid-liquid ratio of 1g:4g. The solution was stirred at 80°C for 6 hours, filtered to obtain the acid leaching solution, and the metal concentration in the acid leaching solution was determined by ICP-OES. The leaching rates of Li, Ni and Co as individual elements and the total metal leaching rate were calculated. The results are shown in Table 2.

[0176] In addition, the hydrometallurgical composite materials obtained in Examples 1-3, Example 5, and Comparative Examples 1-3 were respectively added to acid leaching solutions (sulfuric acid solutions with pH = 0.5-1 and H2O2 volume concentrations of 5%, 10%, 15%, and 20%) at a solid-liquid ratio of 1g:4g. The solutions were stirred at 80°C for 6 hours, filtered to obtain the acid leaching solution, and the metal concentration in the acid leaching solution was determined by ICP-OES. The total metal leaching rate was calculated, and the results are shown in Table 3.

[0177] in,

[0178]

[0179] In the formula, the leaching rate of a single-element metal M is the ratio of the total mass of element M (M = Ni, Co, Mn, or Li) in the leaching solution to the total mass of element M in the composite material used in hydrometallurgy; c Ni c Co c Mn c Li V represents the concentrations of Ni, Co, Mn, and Li in the acid leaching solution, in g / L; V represents the volume of the acid leaching solution, in L; W represents the amount of composite material fed into the hydrometallurgical process, in g; w M w represents the mass percentage of element M (M = Ni, Co, Mn, or Li) in the composite material used in hydrometallurgy. When M is Ni, w M For w3, when M is Co, w M For w5, when M is Mn, w M For w7, when M is Li, w M For w1.

[0180] Table 1

[0181]

[0182] Table 2

[0183]

[0184] Table 3

[0185]

[0186]

[0187] As can be seen from Tables 1 and 2, under the condition that the volume concentration of H2O2 is 10%, the hydrometallurgical composite material provided in the embodiments of the present invention has a higher single-element metal leaching rate of Li, Ni and Co and a higher total metal leaching rate than the hydrometallurgical composite material provided in the comparative example. This indicates that the hydrometallurgical composite material that meets the requirements of the bottom width of the coincidence peak 1 ≤ 1.13° and (w2 / w1)×100% ≥ 30% can have a better metal leaching effect.

[0188] Comparative Example 1 involved grinding the fragmented battery waste without pyrolysis and incineration, and no persulfate or alkali was added during grinding. As a result, the two overlapping peaks of the resulting hydrometallurgical composite material had larger base widths, and the (w2 / w1)×100%, (w4 / w3)×100%, and (w6 / w5)×100% values ​​were also smaller. Therefore, the metal leaching rate was the worst among all specific embodiments, and the metal leaching rate showed the highest growth rate with increasing hydrogen peroxide concentration.

[0189] Compared to Comparative Example 1, Comparative Example 2 was further incinerated, so the base widths of the coincidence peaks 1 and 2 became narrower, and the percentages of (w2 / w1)×100%, (w4 / w3)×100%, and (w6 / w5)×100% also increased.

[0190] Compared to Example 1, Comparative Example 3 only underwent co-grinding with persulfate without incineration, and the resulting hydrometallurgical composite material had similar properties to Comparative Example 2.

[0191] Example 1 combined persulfate co-grinding and pyrolysis combustion, resulting in a composite material for hydrometallurgy with significantly improved properties compared to Comparative Examples 1-3. However, no alkali was added to the co-grinding agent in Example 1, and... The concentration is below 1.4, so the overlap peak 1 of the prepared hydrometallurgical composite material is not in its preferred range (0.65°~1°), and (w2 / w1)×100% is also not in its preferred range (above 50%). Furthermore, (w4 / w3)×100% and (w6 / w5)×100% are also relatively small. Therefore, the metal leaching rate is poor, and the metal leaching rate increases significantly with the increase of hydrogen peroxide concentration during metal leaching.

[0192] Compared to Example 1, Example 2 added an alkali to the co-grinding agent, resulting in an increase in (w2 / w1)×100% and a narrower lower width of the two overlapping peaks. This is because the addition of the alkali promoted the dissociation of the "oxygen cage," thereby releasing Li. + And it promotes the disintegration of layered structures, but due to insufficient addition, and Below 1.4, The concentration is above 1.5, therefore the reduction degree of metals such as nickel, cobalt, and manganese during pyrolysis incineration is relatively low, resulting in relatively low (w4 / w3)×100% and (w6 / w5)×100%. The metal leaching rate of Li is significantly improved, but the metal leaching rates of Ni and Co are not significantly improved. Moreover, the metal leaching rate increases rapidly with the increase of hydrogen peroxide concentration during metal leaching.

[0193] Example 3 further increases the amount of alkali added during grinding to improve... The proportion was reduced to 1.8. The overlap peaks 1 and 2 of the composite material for hydrometallurgy are further reduced to 1.5, while the (w2 / w1)×100%, (w4 / w3)×100% and (w6 / w5)×100% are also increased. Therefore, the metal leaching rate of the composite material for hydrometallurgy is high, and the metal leaching rate does not change much with the concentration of oxidizing agent.

[0194] The coincidence peaks 1 and 2 of the hydrometallurgical composite material prepared in Example 4 are further reduced compared to Example 3, while (w2 / w1)×100%, (w4 / w3)×100% and (w6 / w5)×100% are further increased. Therefore, the metal leaching rate of the hydrometallurgical composite material is higher than that of Example 3.

[0195] Example 5 uses the fragmented battery waste obtained from the fine dismantling of battery cells and the crushing of the positive electrode sheets as raw materials to prepare a composite material for hydrometallurgy. The grinding time was extended to 120 minutes. The composite material prepared under this process exhibits a low base width of peak 1 (0.65°), and high (w2 / w1)×100%, (w4 / w3)×100%, and (w6 / w5)×100% values ​​of 89.87%, 68.2%, and 63.8%, respectively. The total metal leaching rate (with a hydrogen peroxide concentration of 10%) reaches 97.6%, and the total metal leaching rate remains essentially unchanged with variations in hydrogen peroxide concentration. Although the material exhibits excellent performance, the process is labor-intensive and energy-intensive.

[0196] Compared to Example 3, Example 6 increased the amount of alkali agent added, but the performance of the resulting material did not change significantly. Compared to Example 3, Example 7 decreased the amount of persulfate added, resulting in a decrease in the performance of the resulting material and a lower metal leaching rate. Compared to Example 3, Example 8… The reduction in leaching rate resulted in a decrease in the total metal leaching rate of the obtained material. Examples 3 and 9-10 exhibited different characteristics. along with The performance of the resulting material initially increases and then decreases as the oxygen concentration increases. This is because when the oxygen concentration is too high during incineration, the reduction reaction of the transition metals is slower. However, when the oxygen concentration is too low during incineration, the transition metals are easily over-reduced, leading to the production of elemental metals, which reduces the acid dissolution efficiency.

[0197] In summary, the composite material for hydrometallurgy provided by this invention has a high metal leaching efficiency during the acid leaching process, consumes less acid and reducing agent, and has a shorter processing time, which helps to reduce costs.

[0198] The above description is merely a preferred embodiment of the present invention and is not intended to limit the invention. Various modifications and variations can be made to the present invention by those skilled in the art. Any modifications, equivalent substitutions, improvements, etc., made within the spirit and principles of the present invention should be included within the scope of protection of the present invention.

Claims

1. A composite material for hydrometallurgy, characterized by, The composite material used in hydrometallurgy contains Li. The mass percentage of Li in the composite material for hydrometallurgy is denoted as w1, and the total mass percentage of Li in the composite material for hydrometallurgy, in the form of lithium carbonate and lithium oxide, is denoted as w2, wherein (w2 / w1)×100%≥30%; and, in the XRD spectrum of the composite material for hydrometallurgy, there is a set of overlapping peaks 1 at 2θ=37.4°~39°, and the base width of the overlapping peaks 1 is ≤1.13°; in the XRD spectrum of the composite material for hydrometallurgy, there is a set of overlapping peaks 2 at 2θ=63.6°~65.2°, and the base width of the overlapping peaks 2 is ≤1.5°.

2. The composite material for hydrometallurgy according to claim 1, characterized by, The bottom width of the overlapping peak 1 is ≤1°.

3. The composite material for hydrometallurgy according to claim 1 or 2, characterized by, The composite material for hydrometallurgy also has at least one of the following characteristics: Feature 1: The base width of the overlapping peak 2 is ≤1.25°; Feature 2: The composite material for hydrometallurgy also contains Ni; the mass percentage of Ni in the composite material for hydrometallurgy is denoted as w3, and the mass percentage of Ni in the composite material for hydrometallurgy, expressed as nickel oxide, is denoted as w4, wherein 10% ≤ (w4 / w3) × 100% ≤ 80%; Feature 3: The composite material for hydrometallurgy also contains Co; the mass percentage of Co in the composite material for hydrometallurgy is denoted as w5, and the mass percentage of Co in the form of cobalt oxide in the composite material for hydrometallurgy is denoted as w6, wherein 10%≤(w6 / w5)×100%≤70%.

4. The composite material for hydrometallurgy according to claim 3, characterized in that, 1% ≤ w1 ≤ 10%; and / or, 0 < w3 ≤ 50%; and / or, 0 < w5 ≤ 20%.

5. A method for preparing a composite material for hydrometallurgy as described in any one of claims 1 to 4, characterized in that, Includes the following steps: Battery waste is ball-milled with a co-grinding agent and then dried to obtain degraded waste. The degraded waste is then subjected to pyrolysis and incineration.

6. The preparation method according to claim 5, characterized in that, The co-grinding agent comprises water and persulfate; the mass ratio of the battery waste to water and the persulfate is 1:(0.2~0.4):(0.5~1); Alternatively, the co-grinding agent comprises water, persulfate, and an alkali; the mass ratio of the battery waste to water, the persulfate, and the alkali is 1:(0.2~0.4):(0.5~1):(0.3~0.5); The alkaline agent includes at least one of sodium hydroxide, potassium hydroxide, and ammonia.

7. The preparation method according to claim 5, characterized in that, The ball mill includes at least one of the following features: Feature 4: The ball-to-material ratio of the ball mill is 10:1 to 20:1 by mass; Feature 5: The ball mill's rotation speed is 400 rpm to 1000 rpm; Feature 6: The ball milling time is 60 min to 120 min; Feature 7: The temperature of the ball milling material during the ball milling process is not lower than 60°C, wherein the ball milling material is a mixture of battery waste and a co-grinding agent.

8. The preparation method according to claim 5, characterized in that, The pyrolysis incineration includes at least one of the following characteristics: Feature 8: The pyrolysis incineration temperature is 400℃~600℃; Feature 9: The pyrolysis incineration time is 0.5h~2h; feature 10: Sulfur and coke are added during pyrolysis incineration, and the amounts of sulfur and coke added satisfy the following: ; in, These represent the elemental masses of C, Al, Ni, Co, and Mn in battery waste, all in grams. The mass of sulfur added during the pyrolysis incineration process is expressed in grams. ; Feature 11: The atmosphere during the pyrolysis incineration process satisfies: =1.1~1.5; in, These represent the concentrations of oxygen and sulfur dioxide in the atmosphere during the pyrolysis incineration process, respectively, both in g / L.

9. An electrode material, characterized in that, The raw materials for preparing the electrode material include the composite material for hydrometallurgy as described in any one of claims 1 to 4.

10. A battery, characterized in that, The battery comprises the electrode material as described in claim 9.

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