Composite material for hydrometallurgy as well as preparation method and application of composite material

Abstract

The invention discloses a composite material for hydrometallurgy and a preparation method and application thereof, and belongs to the technical field of battery recovery. The composite material for hydrometallurgy contains Li element; the mass percent of Li in the composite material for hydrometallurgy is w1, the mass percent of Li in the composite material for hydrometallurgy in the form of lithium carbonate and lithium oxide is recorded as w2, and (w2 / w1) * 100% is greater than or equal to 30%; moreover, in an XRD spectrogram of the composite material for hydrometallurgy, a group of coincidence peaks 1 exist at the position of 2theta = 37.4-39 degrees, and the bottom width of the coincidence peaks 1 is smaller than or equal to 1.13 degrees. The composite material for hydrometallurgy has a good metal element recovery rate in the hydrometallurgy process, and is beneficial to reducing the cost. The preparation method comprises the following steps: carrying out ball milling on the battery waste and a co-grinding agent, and drying to obtain the degraded waste; and the degraded waste is subjected to pyrolysis incineration.

Description

Technical Field

[0001] The present invention relates to the technical field of battery recycling, and more particularly, to a composite material for hydrometallurgy, a preparation method thereof, and an application thereof. Background Art

[0002] With the rapid development of technology, the market demand in the new energy field, especially for new energy vehicles, has been continuously expanding. As the core component, lithium batteries have been widely used. However, the subsequent problem of retired battery disposal has become a bottleneck in the industry's development. The black mass recycling technology has emerged as the times require. This technology is to recycle valuable metals and materials from waste batteries and realize the green transformation of turning waste into treasure.

[0003] Currently, waste battery powder mainly comes from processes such as the disassembly, crushing, and screening of waste lithium batteries. The components of waste battery powder include metals such as lithium, cobalt, nickel, manganese, aluminum, iron, copper, etc., 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 the soil and water sources.

[0004] The mainstream method for recycling and reusing waste battery powder is hydrometallurgy. This method mainly ionizes metal elements and then separates and enriches the metals through technologies such as precipitation, electrowinning, extraction, and ion exchange. Finally, the target metal is recovered in the form of a certain chemical compound. This method can obtain relatively pure metal compounds for direct use in preparing electrode materials.

[0005] The process of hydrometallurgy includes acid leaching treatment, that is, putting black mass into concentrated acid (usually sulfuric acid) containing a reducing agent (usually hydrogen peroxide), and heating (and pressurizing). Through multiple steps of low-acid leaching and high-acid leaching, valuable metal ions are ionized and retained in the liquid phase, thereby achieving the purpose of extracting valuable metals. Among them, the reason for adding hydrogen peroxide and using concentrated acid and a relatively high temperature (usually 70°C - 90°C) for acid leaching is that this method can reduce nickel, cobalt, manganese, etc. to divalent, making them more easily dissolved into the aqueous phase. However, this method has a high cost, and the recovery rate of metal elements needs to be further improved.

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

[0007] The purpose of the present invention is to provide a composite material for hydrometallurgy, a preparation method thereof, and an application thereof to solve or improve the above technical problems.

[0008] The present invention can be implemented as follows:

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

[0010] The mass percentage of Li element in the composite material for hydrometallurgy is denoted as w1, and the total mass percentage of Li element in the composite material for hydrometallurgy in the form of lithium carbonate and lithium oxide is denoted as w2, where (w2 / w1)×100%≥30%; and, in the XRD pattern 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 ≤ 1.13°.

[0011] In an optional embodiment, the base width of the overlapping peaks 1 ≤ 1°;

[0012] And / or, in the XRD pattern 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 ≤ 1.5°.

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

[0014] Characteristic 1: The base width of the overlapping peaks 2 ≤ 1.25°;

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

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

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

[0018] In the second aspect, the present invention provides a preparation method of the composite material for hydrometallurgy according to any one of the foregoing embodiments, including the following steps: ball-milling battery waste with a co-grinding agent, drying to obtain degraded waste; 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 co-grinding agent includes water, persulfate, and an alkali agent; the mass ratio of the battery waste to water, persulfate, and the alkali agent is 1:(0.2 - 0.4):(0.5 - 1):(0.3 - 0.5);

[0021] The alkali agent includes at least one of sodium hydroxide, potassium hydroxide, and ammonia.

[0022] And / or, the persulfate includes at least one of ammonium persulfate, sodium persulfate, sodium bisulfate persulfate, potassium persulfate, and potassium bisulfate persulfate.

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

[0024] Feature 4: By mass, the ball-to-material ratio of the ball milling is 10:1 to 20:1;

[0025] Feature 5: The rotation speed of the ball milling is 400 rpm - 1000 rpm;

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

[0027] Feature 7: During the ball milling process, the temperature of the ball milling material is not lower than 60 °C, where the ball milling material is a mixture of battery waste and the co-grinding agent.

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

[0029] Feature 8: The temperature of the pyrolysis incineration is 400 °C - 600 °C;

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

[0031] Feature 10: Sulfur and coke are added during the pyrolysis incineration, and the addition amounts of sulfur and coke satisfy:

[0032] Wherein, are the elemental masses of C, Al, Ni, Co, and Mn in the battery waste, with the unit of g for each; is the mass of sulfur added during the pyrolysis incineration process, with the unit of g; is the mass of coke added during the pyrolysis incineration process, with the unit of g;

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

[0034] Wherein, are the concentrations of oxygen and sulfur dioxide in the atmosphere during the pyrolysis incineration process, with the unit of g / L for each.

[0035] In a third aspect, the present invention provides an electrode material, and the raw materials for preparing the electrode material include the composite material for hydrometallurgy according to any one of the foregoing embodiments.

[0036] In a fourth aspect, the present invention provides a battery, and the battery includes the electrode material according to the foregoing embodiments.

[0037] The beneficial effects of the present invention include:

[0038] For the composite material for hydrometallurgy provided by the present invention, the base width of the overlapping peak 1 appearing at 2θ = 37.4° to 39° is ≤ 1.13°, indicating that the crystal defect degree of the layered transition metal oxide contained in the battery waste is relatively large, and metal ions are easily released under the conditions of acids and / or reducing agents with relatively low concentrations. Since the existence forms of Li elements in the composite material for hydrometallurgy are diverse and the acid dissolution efficiencies of different Li compounds are inconsistent, among which, the acid dissolution efficiencies of Li2CO3 and Li2O are the highest. The composite material for hydrometallurgy that satisfies the base width of the overlapping peak 1 appearing at 2θ = 37.4° to 39° ≤ 1.13° and (w2 / w1) × 100% ≥ 30% in the present invention can at least have a relatively high acid dissolution efficiency of Li elements.

[0039] That is to say, for the composite material for hydrometallurgy provided by the present invention, at least the leaching efficiency of metallic Li is relatively high during the acid leaching process, the amounts of acid and reducing agent consumed during the acid leaching process are relatively small, the time consumption is short, which is beneficial to reducing costs. Description of the Drawings

[0040] In order to more clearly illustrate the technical solutions of the embodiments of the present invention, the drawings required to be 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 thus should not be regarded as limiting the scope. For those of ordinary skill in the art, other related drawings can also be obtained based on these drawings without creative efforts.

[0041] Figure 1 It is the XRD pattern of the composite material for hydrometallurgy prepared in Example 1 of the present invention;

[0042] Figure 2 It is Figure 1 the enlarged view of the first dashed box (overlapping peak 1) and the fitting peak result therein;

[0043] Figure 3 It is Figure 1 the enlarged view of the second dashed box (overlapping peak 2) and the fitting peak result therein. Detailed Embodiments

[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. Those not specified in the embodiments are carried out under conventional conditions or conditions recommended by the manufacturer. The reagents or instruments whose manufacturers are not specified are all conventional products that can be obtained through commercial purchase.

[0045] The following specifically describes the composite material for hydrometallurgy provided by the present invention, its preparation method, and its application.

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

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

[0048] Moreover, 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 ≤ 1.13°.

[0049] The composite material for hydrometallurgy that meets the above conditions has a high metal leaching efficiency during the acid leaching process, consumes less acid and reducing agent during the acid leaching process, takes less time, and is beneficial to cost reduction.

[0050] In the present invention, the battery waste used to prepare the composite material for hydrometallurgy includes layered transition metal oxides containing lithium. The above transition metals include at least one of Ni, Co, and Mn. In addition to the above transition metals, other metal elements such as Al, Ti, Zr, Sr, Mo, Ba, W, La, Ce, Bi, In, Nb, and Y may also be included. Generally, the battery waste includes lithium nickel cobalt manganate.

[0051] It should be noted that the metal ions in the layered transition metal oxides are tightly fixed in the crystal "oxygen cage", and the metal leaching process can essentially be understood as a process of destroying the "oxygen cage" structure. Due to the good layered structure of pure layered transition metal oxides, it is difficult to extract the M n+ -O 2-The key (M represents metal ions) destroys it to release metal ions. Therefore, in the hydrometallurgical process, acids and reducing agents (such as sodium sulfite, hydrogen peroxide, sodium thiosulfate, etc.) need to be added, and heating is adopted to destroy the "oxygen cage" structure of the layered transition metal oxide, so that all metal elements in it can be leached. That is to say, the leaching activation energy of the layered transition metal oxide is relatively large. Therefore, when recycling battery waste, if the regular layered structure of the layered transition metal oxide in it can be destroyed, defects are introduced, and its crystallinity is decreased, it is beneficial to improve the leaching effect of metal elements.

[0052] Under normal circumstances, in the XRD pattern of the hydrometallurgical composite material, the characteristic diffraction peaks belonging to the (006) crystal plane and (102) crystal plane of the layered transition metal oxide are included at 2θ = 37.4° - 39°. The splitting degree 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 splitting degree of the two peaks; the higher the overlapping degree of the two peaks, the greater the defects in the layered structure, and finally it is manifested as a combined peak, and the bottom width of the combined peak is narrower and the overlapping degree is higher. The combined peak 1 that appears in the hydrometallurgical composite material provided by the present invention at 2θ = 37.4° - 39° has a bottom width ≤ 1.13°, indicating that the crystal defect degree of the layered transition metal oxide is relatively large, and it is easy to release metal ions under the conditions of lower concentration of acid and / or reducing agent. Since there are still many impurity elements such as P, Al, and F in the hydrometallurgical composite material, the existing forms of Li element are diverse, including LiF, Li3PO4, LiAlO2, Li2CO3, Li2O, and Li(Ni x Co y Mn 1-x-y )O2, etc. The acid dissolution efficiencies of different Li compounds are inconsistent. Among them, the acid dissolution efficiencies of Li2CO3 and Li2O are the highest. Therefore, the hydrometallurgical composite material that satisfies the bottom width of the combined peak 1 that appears at 2θ = 37.4° - 39° in the present invention ≤ 1.13° and (w2 / w1)×100% ≥ 30% can at least have a relatively high acid dissolution efficiency of Li element.

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

[0054] Exemplarily, 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°, etc., 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° (such as 0.65°, 0.79°, 0.82°, 0.83°, 0.85°, 0.86°, 0.91°, or 0.99°, etc.). The layered structure defect of the layered transition metal oxide in the composite material for hydrometallurgy that satisfies this condition is relatively large, and it is more likely to release metal ions during the acid leaching process.

[0055] In some alternative embodiments, 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%, etc., or other values within the range of 1% to 10%, such as 5.54% to 6.82%, such as 5.54%, 5.58%, 5.62%, 5.61%, 5.65%, 5.68%, 6.78%, or 6.82%, etc.

[0056] Exemplarily, the value of (w2 / w1)×100% can be 30%, 35%, 40%, 45%, 50%, 55%, 60%, 65%, 70%, 75%, 80%, 85%, or 90%, etc., or 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] Exemplarily, the above-mentioned w2 can be obtained by measuring the mass of lithium element in the leaching solution obtained after leaching the composite material for hydrometallurgy in dilute acid (1 mol / L sulfuric acid) at 20°C to 30°C for 24 hours, and calculating the ratio of the mass of the lithium element to the mass of the composite material for hydrometallurgy.

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

[0059] The overlapping peak 2 belongs to the characteristic diffraction peaks of the (018) crystal plane and the (110) crystal plane of the layered transition metal oxide. Similarly, the splitting degree 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 splitting degree of the two peaks; the higher the overlapping degree of the two peaks, the greater the defects in the layered structure, and finally it is manifested as a combined peak, and the narrower the bottom width of the combined peak, the higher the overlapping degree. The composite material for hydrometallurgy provided by the present invention has a bottom width of the overlapping peak 2 appearing at 2θ = 63.6° - 65.2° ≤ 1.5°, indicating that the crystal defect degree of the layered transition metal oxide is relatively large, and metal ions are easily released under the conditions of low-concentration acid and / or reducing agent. In some preferred embodiments, the bottom width of the overlapping peak 2 ≤ 1.25°, such as 0.92° - 1.25°.

[0060] In some alternative embodiments, the above-mentioned composite material for hydrometallurgy further contains Ni element; the forms of existence of Ni element in the composite material for hydrometallurgy may include nickel oxides (such as NiO and Ni2O3), nickel metal, layered transition metal oxides, etc. The mass percentage of Ni element in the composite material for hydrometallurgy is denoted as w3, and the mass percentage of Ni element in the form of nickel oxide in the composite material for hydrometallurgy is denoted as w4, where 10% ≤ (w4 / w3) × 100% ≤ 80%. The composite material for hydrometallurgy satisfying the above conditions has a high acid dissolution efficiency of Ni element during the acid leaching process.

[0061] In some alternative embodiments, 0 < w3 ≤ 50%. Exemplarily, the value of w3 can be 10%, 15%, 20%, 25%, 30%, 35%, 40%, 45% or 50%, etc., or other values within the range of > 0 and ≤ 50%, such as 26.10% - 45.20%, such as 26.10%, 26.17%, 26.32%, 26.34%, 26.57%, 45.18% or 45.20%, etc.

[0062] Exemplarily, 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 within the range of 10% - 80%, such as 20.3% - 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 further contains Co element; the Co element in the hydrometallurgical composite material may exist in the form of cobalt oxide, cobalt element, layered transition metal oxide, etc. The mass percentage of Co element in the hydrometallurgical composite material is recorded as w5, and the mass percentage of Co element in the hydrometallurgical composite material in the form of cobaltous oxide is recorded as w6, wherein 10%≤(w6 / w5)×100%≤70%. The hydrometallurgical composite material that meets the above conditions has a high acid dissolution efficiency of Co element during acid leaching.

[0064] In some optional embodiments, 0<w5≤20%. Exemplarily, 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] Exemplarily, the value of (w6 / w5)×100% can be 10%, 15%, 20%, 25%, 30%, 35%, 40%, 45%, 50%, 55%, 60%, 65% or 70%, etc., or it can be other values within 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 recorded as w7, 0<w7≤20%, illustratively, 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] Exemplarily, the mass ratios of all Li elements, all Ni elements, all Co elements, and all Mn elements in the sample to be measured to the mass of the hydrometallurgical composite material, namely w1, w3, w5, and w7, can be determined by inductively coupled plasma atomic emission spectrometry (refer to Appendix A in GB / T 45203-2024). The mass percentage w3 of all Ni elements can also be determined by dimethylglyoxime gravimetry (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 Li mass percentage w1 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] Exemplarily, the measurement methods of (w2 / w1)×100%, (w4 / w3)×100%, and (w6 / w5)×100% can be as follows: Mix W g of the hydrometallurgical composite material to be measured with dilute acid (1 mol / L sulfuric acid) at a solid-liquid ratio of 1 g:50 mL and react with shaking at 20°C to 30°C for 24 h. Filter the reaction solution obtained from the reaction, and measure the contents of Ni, Co, and Li elements in the filtrate to obtain the masses of Ni, Co, and Li elements respectively. The units of all are g. The measurement methods for the contents of Ni, Co, and Li elements in the filtrate can be inductively coupled plasma atomic emission spectrometry (refer to Appendix A in GB / T 45203-2024), or the Ni content can be determined by dimethylglyoxime gravimetry or flame atomic absorption spectrometry (refer to YS / T 1342.1-2019), the Co content can be determined by potentiometric titration or flame atomic absorption spectrometry (refer to YS / T 1342.2-2019), and the Li content can be determined by flame atomic absorption spectrometry (refer to YS / T 1342.4-2019). Then:

[0069] When determined by inductively coupled plasma atomic emission spectrometry (refer to Appendix A in GB / T 45203-2024), measure the concentrations (g / L) of Ni, Co, and Li elements in the filtrate to obtain respectively V H is the volume of dilute acid added, and the unit is L.

[0070] Continuing from the above, the Ni, Co, Mn, and Li elements in the composite material for hydrometallurgy proposed by the present invention can have a relatively high leaching efficiency during the hydrometallurgy process, thus having a good recovery rate of metal elements, which is beneficial to cost reduction and efficiency improvement.

[0071] Correspondingly, the present invention also provides a method for preparing the above composite material for hydrometallurgy, which may include the following steps: ball-milling the battery waste with a co-grinding agent, drying to obtain degraded waste; pyrolyzing and incinerating the degraded waste. Further, the remaining incineration product is crushed (such as by air-flow crushing) and sieved.

[0072] In some optional embodiments, the battery waste may include at least one of waste battery monomers and electrode sheet materials. Among them, the waste battery monomers may further include at least one of various monomer batteries such as square batteries, cylindrical batteries, and soft-pack batteries.

[0073] In some optional embodiments, the battery waste may be first shredded, and then the shredded battery waste is ball-milled with a co-grinding agent. Exemplarily, the discharged waste battery monomers or / and electrode sheet materials can be crushed and sorted to obtain shredded battery waste. Among them, the crushing may include at least one of jaw crushing, hammer crushing, cone crushing, impact crushing, ball-mill crushing, rod-mill crushing, roll crushing, and high-pressure roll grinding. The sorting can adopt methods such as screening, density separation, electrostatic separation, optical separation, and vibration separation to remove or partially remove plastics, aluminum foils, copper foils, aluminum casings, and steel casings, etc., to obtain shredded 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 the battery waste to water and persulfate can be 1:(0.2 - 0.4):(0.5 - 1). Among them, the mass ratio of the battery waste to water can be 1:0.2, 1:0.25, 1:0.3, 1:0.35, or 1:0.4, etc., or other values within the range of 1:(0.2 - 0.4). The mass ratio of the battery waste to persulfate can be 1:0.5, 1:0.6, 1:0.7, 1:0.8, 1:0.9, or 1:1, etc., or other values within the range of 1:(0.5 - 1).

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

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

[0077] By using persulfate and alkali agent in the co-grinding agent simultaneously, on the one hand, the alkali agent can generate a large amount of heat when it meets water and under mechanical force; on the other hand, it can provide an alkaline environment, and the alkaline environment can corrode the current collector (such as aluminum foil), promoting the detachment of the layered transition metal oxide from the current collector; persulfate releases sulfate radicals under thermomechanical and alkaline conditions, promoting the degradation of the binder (PVDF) contained in the battery waste, attacking the transition metal in the layered transition metal oxide, and reducing it to destroy the lattice structure.

[0078] As an example, the above-mentioned alkali agent can exemplarily include at least one of sodium hydroxide, potassium hydroxide and ammonia. The persulfate used in the above co-grinding agent can exemplarily but not restrictively include at least one of ammonium persulfate, sodium persulfate, sodium bisulfate persulfate, potassium persulfate, potassium bisulfate persulfate.

[0079] In some alternative embodiments, by mass, the ball-to-material ratio of ball milling can be from 10:1 to 20:1, such as 10:1, 12:1, 15:1, 18:1 or 20:1, etc., 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 sufficient grinding; if the ball-to-material ratio is too high, it will significantly increase the equipment load and energy consumption, and may cause thermal damage to the material (especially unfavorable to heat-sensitive materials).

[0080] The rotation speed of the ball milling can be 400 rpm - 1000 rpm, such as 400 rpm, 500 rpm, 600 rpm, 700 rpm, 800 rpm, 900 rpm or 1000 rpm, etc., or other values within the range of 400 rpm - 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, etc., or other values within the range of 60 min to 120 min.

[0082] During the ball milling process, adjust the ball milling speed so that the temperature of the ball milled material is not lower than 60 °C, such as it can be 60 °C, 65 °C, 70 °C, 75 °C, 80 °C, 85 °C or 90 °C, etc. Among them, the ball milled material is a mixture of battery waste and a co-milling agent. If the temperature of the ball milled material is lower than 60 °C during the ball milling process, it is not conducive to the release of free radicals by persulfate.

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

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

[0085] In some alternative embodiments, sulfur and coke are added during the pyrolytic incineration. The addition amounts of sulfur and coke are controlled according to the elemental contents of C, Ni, Co, Mn and optionally Al (Al comes from the case where the current collector is aluminum foil) in the battery waste. By controlling the addition amounts of sulfur and coke, the addition amounts of sulfur and coke satisfy:

[0086]

[0087] Among them, are the elemental masses of C, Al, Ni, Co, Mn in the battery waste respectively, and the unit is g; is the mass of sulfur added during the pyrolytic incineration process, and the unit is g; is the mass of coke added during the pyrolytic incineration process, and the unit is g.

[0088] In some alternative embodiments, by also controlling the content ratio of oxygen and sulfur dioxide in the pyrolytic incineration atmosphere, the atmosphere during the pyrolytic incineration process satisfies:

[0089]

[0090] Among them, are the concentrations of oxygen and sulfur dioxide in the atmosphere during the pyrolytic incineration process respectively, and the unit is g / L.

[0091] In some optional embodiments, when the battery waste is provided only by used battery cells, The value is 0.

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

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

[0094] In some embodiments, the degraded waste may be mixed with sulfur and coke, and then the mixture is put into an incinerator for pyrolysis incineration.

[0095] By adding sulfur in the pyrolysis and incineration stage, sulfur roasting can produce heat. Sulfur can also burn when the oxygen concentration is low. Sulfur is more active and burns faster. It has a higher calorific value than ordinary coal and can instantly create high temperature and reducing atmosphere. It can be used for layered transition metal oxides (such as Li(Ni x Co y Mn 1-x-y )O2) to reduce the Ni, Co, and Mn elements in the sulfur dioxide, which promotes the dissociation of the crystal structure. In addition, sulfur dioxide can be generated during the combustion process. The generated sulfur dioxide can be collected and made into sulfuric acid for use in hydrometallurgy, which is conducive to shortening the sulfur melting and incineration stages in the traditional sulfuric acid production process and making the best use of resources.

[0096] By controlling the layered transition metal oxides (such as Li(Ni x Co y Mn 1-x-y The mass ratio of Ni, Co, Mn elements with oxidizing valence states and C, S with reducing properties and optional single Al (derived from the current collector aluminum foil) contained in the )O2) is adjusted to promote the reduction reaction of more transition metal elements. In addition, the flow rate of oxygen can be regulated according to the amount of SO2 generated, so that the entire redox reaction remains stable, avoiding violent reactions that make the reaction uneven and produce metal single substances. The reaction activity of single substances with acids is not as good as that of metal oxides or metal carbonates, so it is not conducive to acid leaching.

[0097] Continuing from the above, the present invention uses a two-step method to promote the crystal structure dissociation of the layered transition metal oxide in the composite material for hydrometallurgy. First, a mechanochemical method is adopted. By using persulfate and an alkaline agent as co-grinding agents to wet-grind the battery waste, persulfate generates sulfate radicals under alkaline and thermomechanical conditions. On the one hand, the radicals can promote the degradation of PVDF, which is beneficial to the separation between the layered transition metal oxide particles. On the other hand, they can attack the transition metal in the layered transition metal oxide, reduce it, and destroy the lattice structure. Then, a weak reduction method is used to heat and reduce the degraded waste, promoting the conversion of metal ions into metal compounds that are easily leached, further promoting the crystal structure dissociation of, for example, the layered transition metal oxide, increasing its lattice defects and decreasing its crystallinity, thereby facilitating the improvement of the leaching of the metal compound powder.

[0098] In addition, the present invention also provides an electrode material (such as a positive electrode material, a pole piece, etc.), and the preparation raw materials of the electrode material include the above-mentioned composite material for hydrometallurgy.

[0099] The above raw materials refer to the composite material for hydrometallurgy used in the prepared electrode material that can be traced back. If the composite material for hydrometallurgy meets the requirements defined in the present invention, the electrode material prepared with it falls within the protection scope of the present invention.

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

[0101] As an example, the above battery cell can be used in, but is not limited to, electrical devices such as vehicles, ships, or aircraft.

[0102] The present invention also provides a battery including the above battery cell.

[0103] The present invention also provides an electrical device, and the electrical device includes the above battery cell and / or battery. As an example, the electrical device can be, but is not limited to, mobile phones, tablets, laptop computers, electric toys, electric tools, battery cars, electric vehicles, ships, spacecraft, etc. Among them, electric toys can include fixed or mobile electric toys. For example, game consoles, electric vehicle toys, electric ship toys, and electric plane toys, etc. Spacecraft can include airplanes, rockets, space shuttles, and spaceships, etc.

[0104] The following further describes the features and properties of the present invention in detail with reference to embodiments.

[0105] Example 1

[0106] This example provides a composite material for hydrometallurgy, and its preparation method includes:

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

[0108] The discharged waste ternary lithium-ion aluminum shell battery monomers are successively subjected to biaxial shearing and uniaxial crushing under nitrogen protection. The obtained crushed materials are dried for 2 h in a nitrogen atmosphere at 140 °C to 150 °C, then dispersed by a disperser, and then screened to obtain large-sized materials (protective shells) and small-sized materials. The small-sized materials are screened by a circular vibrating screen, and the undersize is the primary shredded battery waste. The large-sized materials are successively subjected to cross-flow air separation and linear screen air separation to separate the separator and the aluminum shell. The remaining materials are subjected to uniaxial crushing again and then screened by a circular vibrating screen, and the undersize is the secondary shredded battery waste. The primary shredded battery waste and the secondary shredded battery waste are combined to obtain the shredded battery waste.

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

[0110] The shredded battery waste, ammonium persulfate, and water are mixed at a mass ratio of 1:0.5:0.2 and put into a ball mill. By mass, the ball-to-material ratio is 10:1 (the grinding balls are zirconium balls). The rotation speed is adjusted in the range of 400 rpm to 1000 rpm to maintain the material temperature at 60 to 80 °C, and ball milling is carried out for 60 min. Subsequently, it is dried at 120 °C 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 degraded waste are measured by inductively coupled plasma atomic emission spectrometry, and then according to = 1.2, sulfur is added and mixed evenly, and then it is transferred to an incinerator and pyrolytically incinerated at 400 °C for 1 h. During the process, the air flow rate is controlled to make the Among them, are respectively the elemental masses of C, Al, Ni, Co, and Mn in the battery waste, and the units are all g; is the mass of sulfur, and the unit is g; are respectively the concentrations of oxygen and sulfur dioxide in the atmosphere, and the units are all g / L;

[0113] Step (4): The incineration residue is subjected to air crushing and then sieved to obtain the composite material for hydrometallurgy.

[0114] Example 2

[0115] This example provides a composite material for hydrometallurgy, and its preparation method includes:

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

[0117] The discharged waste ternary lithium-ion aluminum shell battery is finely disassembled to obtain the positive electrode sheet, which is crushed, classified, and then sieved to obtain the fragmented battery waste.

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

[0119] The fragmented battery waste is 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; by mass, the ball-to-material ratio is 10:1 (the grinding balls are zirconium balls), and the rotation speed is adjusted within the range of 400 rpm to 1000 rpm to maintain the material temperature at 60 - 80 °C, and ball mill for 60 min; then dry at 120 °C for 1 h to obtain the degraded waste.

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

[0121] The element contents of C, Al, Ni, Co, and Mn in the degraded waste are measured by inductively coupled plasma atomic emission spectrometry, and then according to = 1, sulfur is added and mixed evenly, and then transferred to an incinerator for pyrolysis incineration at 400 °C for 1 h. During the process, the air flow is controlled to make the Among them, are the element masses of C, Al, Ni, Co, and Mn in the battery waste respectively, with the unit of g; is the sulfur mass, with the unit of g; are the concentrations of oxygen and sulfur dioxide in the atmosphere respectively, with the unit of g / L;

[0122] Step (4): The incineration residue is airflow crushed and then sieved to obtain the composite material for hydrometallurgy.

[0123] Example 3

[0124] This example provides a composite material for hydrometallurgy, and its preparation method includes:

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

[0126] The discharged waste ternary lithium-ion soft-pack battery monomer is successively subjected to double-shaft crushing and reamer crushing under nitrogen protection. The obtained crushed material is dried in a nitrogen atmosphere at 140 °C to 150 °C for 2 h, and then cyclone transported to a vibrating screen for screening. The material under the screen is the primary fragmented battery waste; further, the material on the screen is subjected to magnetic separation to obtain the secondary fragmented battery waste, and the primary fragmented battery waste and the secondary fragmented battery waste are combined to obtain the fragmented battery waste.

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

[0128] The crushed battery waste is 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 is 20:1 by mass (the grinding balls are zirconium balls), the rotation speed is adjusted within the range of 400 rpm to 1000 rpm to maintain the material temperature at 60 to 80° C., and the ball milling is performed for 100 minutes; then the material is dried at 120° C. for 1 hour to obtain the degraded waste.

[0129] Step (3): Obtaining incineration residues.

[0130] Inductively coupled plasma atomic emission spectrometry was used to measure the element contents of C, Al, Ni, Co, and Mn in the degraded waste. = 1.8, add sulfur and mix evenly, then transfer to the incinerator and pyrolyze at 500℃ for 1h. During the process, control the air flow so that the furnace in, are the element masses of C, Al, Ni, Co, and Mn in battery waste, respectively, all in g; is the mass of sulfur, in g; are the concentrations of oxygen and sulfur dioxide in the atmosphere, both in g / L;

[0131] Step (4): crushing the incineration residue with air flow and then sieving it to obtain a composite material for hydrometallurgy.

[0132] Example 4

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

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

[0135] The discharged waste ternary lithium-ion aluminum shell batteries are finely disassembled to obtain positive electrode sheets, the positive electrode sheets are crushed, graded, and then sieved to obtain crushed battery waste.

[0136] Step (2): Obtaining degraded waste.

[0137] The crushed battery waste is 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 is 20:1 by mass (the grinding balls are zirconium balls), the rotation speed is adjusted within the range of 400 rpm to 1000 rpm to maintain the material temperature at 60 to 80° C., and the ball milling is performed for 60 minutes; then the material is dried at 120° C. for 1 hour to obtain the degraded waste.

[0138] Step (3): Obtaining incineration residues.

[0139] Inductively coupled plasma atomic emission spectrometry was used to measure the element contents of C, Al, Ni, Co, and Mn in the degraded waste. Add sulfur and coke and mix well, then transfer to the incinerator and pyrolyze at 600℃ for 0.5h. During the process, control the air flow so that the furnace Among them, the mass ratio of sulfur to coke is 0.6:0.4. are the element masses of C, Al, Ni, Co, and Mn in battery waste, respectively, all in g; is the mass of sulfur, in g; is the mass of coke, in g; are the concentrations of oxygen and sulfur dioxide in the atmosphere, both in g / L;

[0140] Step (4): crushing the incineration residue with air flow and then sieving it to obtain a composite material for hydrometallurgy.

[0141] Example 5

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

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

[0144] The discharged waste ternary lithium-ion aluminum shell batteries are finely disassembled to obtain positive electrode sheets, the positive electrode sheets are crushed and graded, and then sieved to obtain crushed battery waste.

[0145] Step (2): Obtaining degraded waste.

[0146] The crushed battery waste is 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 is 20:1 by mass (the grinding balls are zirconium balls), the rotation speed is adjusted within the range of 400 rpm to 1000 rpm to maintain the material temperature at 60 to 80° C., and the ball milling is performed for 120 minutes; then the material is dried at 120° C. for 1 hour to obtain the degraded waste.

[0147] Step (3): Obtaining incineration residues.

[0148] Inductively coupled plasma atomic emission spectrometry was used to measure the element contents of C, Al, Ni, Co, and Mn in the degraded waste. Add sulfur and coke and mix well, then transfer to the incinerator and pyrolyze at 600℃ for 2h. During the process, control the air flow so that the furnace Among them, the mass ratio of sulfur to coke is 0.6:0.4. are the element masses of C, Al, Ni, Co, and Mn in battery waste, respectively, all in g; is the mass of sulfur, in g; is the mass of coke, in g; are the concentrations of oxygen and sulfur dioxide in the atmosphere, both in g / L;

[0149] Step (4): crushing the incineration residue with air flow and then sieving it to obtain a composite material for hydrometallurgy.

[0150] Example 6

[0151] The difference between this embodiment and embodiment 3 is that in step (2), the crushed battery waste, sodium persulfate, sodium hydroxide and water are 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 mass ratio of the crushed battery waste to sodium persulfate, sodium hydroxide and water is 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 battery waste material crushed in Example 1 was mixed with water, put into a ball mill, and ball milled for 60 minutes at a rotation speed of 700 rpm and a ball-to-material ratio of 10:1, and then dried at 120°C for 1 hour to obtain a composite material for hydrometallurgy. The mass ratio of the battery waste material 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 is not used, and the crushed battery waste is 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 carried out.

[0166] Test Example

[0167] (1) The wet metallurgy composite materials obtained in Examples 1-10 and Comparative Examples 1-3 were characterized by X-ray diffraction (XRD). The test conditions were as follows: an 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: The Jade software was used to perform baseline calibration (to obtain Baseline 1) and smoothing processing on the XRD scan data, and then the data was exported. The Origin software was used to perform fitting and peak separation on the diffraction peaks within the target range (2θ = 37.4° - 39° and 2θ = 63.6° - 65.2°). The Gaussian model was selected. The baseline of the fitted peak differed from Baseline 1 by no more than 200 a.u. (intensity). The full width at half maximum of the two fitted peaks in the target overlapping peak (Overlapping Peak 1 or Overlapping Peak 2) must fall within the target range. The total length of the full width at half maximum of the two fitted peaks in the target overlapping peak (Overlapping Peak 1 or Overlapping Peak 2) after overlapping on the abscissa was taken as the full width at half maximum of this overlapping peak.

[0168] The results of the corresponding Overlapping Peak 1 and Overlapping Peak 2 of each wet metallurgy composite material in the XRD pattern are shown in Table 1. Among them, the XRD pattern of the wet metallurgy composite material obtained in Example 1 is as Figure 1 shown, Figure 2 for Figure 1 the enlarged view of the first dashed box from left to right therein (i.e., Overlapping Peak 1) and the results of its fitted peaks, Figure 3 for Figure 1 the enlarged view of the second dashed box from left to right therein (i.e., Overlapping Peak 2) and the results of its fitted peaks.

[0169] (2) The element contents of the wet metallurgy composite materials obtained in Examples 1-10 and Comparative Examples 1-3 were tested, and the results are shown in Table 1.

[0170] In Table 1, w1, w3, w5, and w7 respectively refer to the mass ratios of all Li elements, all Ni elements, all Co elements, and all Mn elements to the mass of the wet metallurgy composite material. Specifically, the inductively coupled plasma atomic emission spectrometry (refer to Appendix A in GB / T 45203-2024) was used to determine the mass ratios of all Li elements, all Ni elements, all Co elements, and all Mn elements to the mass of the wet metallurgy composite material to be tested (referred to as the sample to be tested).

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

[0172] The measuring methods for the above (w2 / w1)×100%, (w4 / w3)×100%, and (w6 / w5)×100% are as follows: Mix Wg of the composite material for hydrometallurgy to be measured with dilute acid (1 mol / L sulfuric acid) at a solid-liquid ratio of 1 g:50 mL and a temperature of 20°C to 30°C, shake and react for 24 h, filter the reaction solution obtained from the reaction, and measure the concentrations (g / L) of Ni, Co, and Li elements in the filtrate to obtain The measuring method for the contents of Ni, Co, and Li elements in the filtrate adopts inductively coupled plasma atomic emission spectrometry (refer to Appendix A in GB / T 45203-2024); calculate according to the following formula:

[0173]

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

[0175] (3) Put the composite materials for hydrometallurgy obtained in Examples 1 to 10 and Comparative Examples 1 to 3 into the acid leaching solution (sulfuric acid solution with a pH of 0.5 to 1 and a H2O2 volume concentration of 10%) at a solid-liquid ratio of 1 g:4 g respectively, stir at 80°C for 6 h, filter to obtain the post-acid leaching solution, measure the metal concentration in the post-acid leaching solution by ICP-OES, and calculate the single-element metal leaching rates and total metal leaching rate of Li, Ni, and Co respectively. The results are shown in Table 2.

[0176] In addition, put the composite materials for hydrometallurgy obtained in Examples 1 to 3, Example 5, and Comparative Examples 1 to 3 into the acid leaching solution (sulfuric acid solutions with H2O2 volume concentrations of 5%, 10%, 15%, and 20% and a pH of 0.5 to 1) at a solid-liquid ratio of 1 g:4 g respectively, stir at 80°C for 6 h, filter to obtain the post-acid leaching solution, measure the metal concentration in the post-acid leaching solution by ICP-OES, and calculate the total metal leaching rate. The results are shown in Table 3.

[0177] Among them,

[0178]

[0179] In the formula, the leaching rate of the single-element metal M is the ratio of the total mass of the M element (M = Ni, Co, Mn or Li) in the post-leaching solution to the total mass of the M element in the composite material for hydrometallurgy; c Ni 、c Co 、c Mn 、c Li are respectively the concentrations of Ni, Co, Mn, and Li in the post-acid leaching solution, with the unit of g / L; V is the volume of the post-acid leaching solution, with the unit of L; W is the feeding amount of the composite material for hydrometallurgy, with the unit of g; w M is the mass percentage of the M element (M = Ni, Co, Mn or Li) in the composite material for hydrometallurgy. When M is Ni, w M is w3; when M is Co, w M is w5; when M is Mn, w M is w7; when M is Li, w M is w1.

[0180] Table 1

[0181]

[0182] Table 2

[0183]

[0184] Table 3

[0185]

[0186]

[0187] Combining Table 1 and Table 2, it can be seen that under the condition that the volume concentration of H2O2 is 10% in both cases, the composite material for hydrometallurgy provided by the embodiment of the present invention has higher leaching rates of single-element metals Li, Ni, and Co and the total metal leaching rate compared with the composite material for hydrometallurgy provided by the comparative example. This shows that the composite material for hydrometallurgy that satisfies the bottom width of the overlapping peak 1 ≤ 1.13° and (w2 / w1)×100% ≥ 30% can have better metal leaching effects.

[0188] In Comparative Example 1, only the fragmented battery waste was ground without pyrolysis incineration, and persulfate and alkali agent were not added during grinding. Therefore, the bottom widths of the two overlapping peaks of the composite material for hydrometallurgy obtained are larger, and (w2 / w1)×100%, (w4 / w3)×100%, and (w6 / w5)×100% are also smaller. Therefore, the metal leaching rate is the worst among all specific embodiments, and the growth rate of the metal leaching rate with the increase in the concentration of hydrogen peroxide is the highest.

[0189] Comparative Example 2 is further incinerated compared to Comparative Example 1, so the bottom widths of the overlapping peaks 1 and 2 become narrower, and (w2 / w1)×100%, (w4 / w3)×100% and (w6 / w5)×100% also increase.

[0190] Compared with Example 1, Comparative Example 3 only performed co-grinding with persulfate without incineration. The performance of the obtained hydrometallurgical composite material was similar to that of Comparative Example 2.

[0191] In Example 1, persulfate co-grinding and pyrolysis incineration were combined to obtain a hydrometallurgical composite material with greatly improved performance compared to Comparative Examples 1 to 3. However, no alkali agent was added to the co-grinding agent in Example 1, and Lower than 1.4, therefore, the overlap peak 1 of the prepared composite material for hydrometallurgy is not in the preferred range (0.65°~1°), and (w2 / w1)×100% is also not in the preferred range (above 50%), and (w4 / w3)×100% and (w6 / w5)×100% are also small, so the metal leaching rate is poor, and as the concentration of hydrogen peroxide increases during metal leaching, the metal leaching rate growth rate is large.

[0192] In Example 2, compared with Example 1, an alkali agent was added to the co-grinding agent, so (w2 / w1)×100% increased and the bottom width of the two overlapping peaks narrowed. The reason is that the addition of the alkali agent promoted the dissociation of the "oxygen cage", thereby releasing Li + and promote the collapse of the layered structure, but due to the small amount of addition, Below 1.4, The ratio of W4 / W3 to W5 is higher than 1.5, so the reduction degree of metals such as nickel, cobalt, and manganese during pyrolysis and incineration is low, so (w4 / w3)×100% and (w6 / w5)×100% are still small. The metal leaching rate of Li is significantly improved, but the metal leaching rates of Ni and Co are not significantly improved, and as the concentration of hydrogen peroxide increases during metal leaching, the metal leaching rate growth rate is relatively large.

[0193] Example 3: Further increase the amount of alkali added during grinding to improve ratio to 1.8, reducing To 1.5, therefore, the overlapping peaks 1 and 2 of the obtained hydrometallurgical composite material are further reduced, and (w2 / w1)×100%, (w4 / w3)×100% and (w6 / w5)×100% are also increased. Therefore, the metal leaching rate of the hydrometallurgical composite material is high, and the metal leaching rate does not change much with the concentration of double oxide.

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

[0195] The positive electrode plate obtained by finely disassembling the battery monomer in Example 5 was crushed to obtain fragmented battery waste as a raw material to prepare a hydrometallurgy composite material, and the grinding time was extended to 120 min. The bottom width of the overlapping peak 1 of the hydrometallurgy composite material prepared under this process was as low as 0.65°, and (w2 / w1)×100%, (w4 / w3)×100%, and (w6 / w5)×100% were as high as 89.87%, 68.2%, and 63.8%, respectively. The total metal leaching rate (hydrogen peroxide concentration was 10%) was as high as 97.6%, and the total metal leaching rate remained basically unchanged with the change of the hydrogen peroxide concentration. Although the performance of the material is excellent, it is also more labor-consuming and energy-consuming.

[0196] In Example 6, compared with Example 3, the addition amount of the alkali agent was increased, and the performance of the obtained material changed little. In Example 7, compared with Example 3, the addition amount of persulfate was reduced, and the performance of the obtained material decreased, and the metal leaching rate also decreased. In Example 8, compared with Example 3 decreased, and the total metal leaching rate of the obtained material decreased. Examples 3 and 9-10 have different As increases, the performance of the obtained material first increases and then decreases. The reason is that when the oxygen concentration during incineration is too high, the reduction reaction rate of transition metals is slower, but when the oxygen concentration during incineration is too low, transition metals are easily over-reduced, resulting in the generation of metal elements, thereby reducing the acid dissolution efficiency.

[0197] In summary, the hydrometallurgy composite material provided by the present invention has a high metal leaching efficiency during the acid leaching process, consumes less acid and reducing agent during the acid leaching process, has a short time-consuming, and is beneficial to cost reduction.

[0198] The above are only the preferred embodiments of the present invention and are not used to limit the present invention. For those skilled in the art, the present invention can have various changes and modifications. Any modification, equivalent replacement, improvement, etc. made within the spirit and principle of the present invention shall be included in the protection scope of the present invention.

Claims

1. A composite material for hydrometallurgy, characterized in that The composite material for hydrometallurgy contains Li element; The mass percentage of Li element in the composite material for hydrometallurgy is denoted as w1, and the total mass percentage of Li element in the composite material for hydrometallurgy in the form of lithium carbonate and lithium oxide is denoted as w2, where (w2 / w1)×100% ≥ 30%; and, in the XRD pattern 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 ≤ 1.13°.

2. The composite material for hydrometallurgy according to claim 1, wherein The base width of the overlapping peaks 1 ≤ 1°; And / or, in the XRD pattern 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 ≤ 1.5°.

3. The composite material for hydrometallurgy according to claim 1 or 2, characterized in that, The composite material for hydrometallurgy also has at least one of the following characteristics: Characteristic 1: The base width of the overlapping peaks 2 ≤ 1.25°; Characteristic 2: The composite material for hydrometallurgy also contains Ni element; the mass percentage of Ni element in the composite material for hydrometallurgy is denoted as w3, and the mass percentage of Ni element in the composite material for hydrometallurgy in the form of nickel oxide is denoted as w4, where 10% ≤ (w4 / w3)×100% ≤ 80%; Characteristic 3: The composite material for hydrometallurgy also contains Co element; the mass percentage of Co element in the composite material for hydrometallurgy is denoted as w5, and the mass percentage of Co element in the composite material for hydrometallurgy in the form of cobaltous oxide is denoted as w6, where 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 according to any one of claims 1 to 4, characterized in that, Including the following steps: Ball-mill the battery waste with a co-grinding agent, and dry it to obtain degraded waste; Pyrolyze and incinerate the degraded waste.

6. The preparation method according to claim 5, characterized in that, The co-grinding agent includes water and persulfate; the mass ratio of the battery waste, water, and the persulfate is 1:(0.2 - 0.4):(0.5 - 1); Or, the co-grinding agent includes water, persulfate, and an alkali agent; the mass ratio of the battery waste, water, the persulfate, and the alkali agent is 1:(0.2 - 0.4):(0.5 - 1):(0.3 - 0.5); The alkali 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-milling includes at least one of the following characteristics: Characteristic 4: By mass, the ball-to-material ratio of ball-milling is 10:1 to 20:1; Characteristic 5: The rotation speed of ball-milling is 400 rpm - 1000 rpm; Characteristic 6: The time of ball-milling is 60 min - 120 min; Characteristic 7: During ball-milling, the temperature of the ball-milled material is not lower than 60°C, where the ball-milled material is a mixture of battery waste and the co-grinding agent.

8. The preparation method according to claim 5, wherein The pyrolytic incineration includes at least one of the following characteristics: Characteristic 8: The temperature of pyrolytic incineration is 400°C - 600°C; Characteristic 9: The time of pyrolytic incineration is 0.5 h - 2 h; Characteristic 10: Sulfur and coke are added during pyrolytic incineration, and the addition amounts of the sulfur and coke satisfy: Wherein, are the elemental masses of C, Al, Ni, Co, and Mn in the battery waste, and the unit is g for all; is the mass of sulfur added during the pyrolysis and incineration process, and the unit is g; is the mass of coke added during the pyrolysis and incineration process, and the unit is g; Feature 11: The atmosphere during the pyrolysis incineration process satisfies: wherein, are respectively the concentrations of oxygen and sulfur dioxide in the atmosphere during the pyrolysis incineration process, and the unit of both is g / L.

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

10. A battery, characterized in that, The battery includes the electrode material according to claim 9.

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