Substance containing non-lithium metal element and preparation method therefor

Abstract

The present application provides a substance containing a non-lithium metal element and a preparation method therefor. The substance comprises a first component and a second component. The first component comprises Me and / or MeO; and the second component comprises MeCO3. The Me element is selected from at least one of Ni, Co, and Mn. In the present application, the non-lithium metal element is the described Me element. MeCO3 in the substance containing the non-lithium metal element reacts with an acid to produce CO2, and the presence of CO2 can reduce the proportion of H2 in a gas produced when the substance containing the non-lithium metal element reacts with the acid, thereby mitigating a potential safety hazard problem caused by hydrogen gas produced by acid dissolution in the process of preparing a precursor of a battery positive electrode material.

Description

A substance containing a non-lithium metal element and its preparation method

[0001] This application claims priority to Chinese Patent No. 202510009957.0, filed on January 3, 2025, entitled "A Substance Containing a Non-Lithium Metal Element", and Chinese Patent No. 202511011247.8, filed on July 22, 2025, entitled "A Substance Containing a Non-Lithium Metal Element and a Method for Preparing the Same", the entire contents of which are incorporated herein by reference. Technical Field

[0002] This application relates to the technical field of substances containing non-lithium metal elements, and in particular to a substance containing non-lithium metal elements and a method for preparing the same. Background Technology

[0003] With the rapid development of the new energy industry, nickel compounds are being produced in large quantities and widely used in ternary batteries. However, most of the precursors for ternary battery cathode materials are currently made from raw materials with high nickel and cobalt content and low impurities, such as nickel cobalt hydroxide, high-grade nickel matte, and nickel sulfide. These materials are complex to obtain and costly. In addition, the use of nickel cobalt waste, nickel cobalt hazardous waste, and other miscellaneous materials to make precursors for ternary batteries is rarely used due to their high impurity content, low nickel and cobalt content, high production costs, and especially safety concerns.

[0004] Currently, in the process of preparing precursor materials for ternary battery cathodes, at least one of the following powders, such as nickel powder, cobalt powder, manganese powder, nickel oxide, cobalt oxide, and manganese oxide, is usually directly used and mixed in a certain proportion. After acid dissolution, nickel, cobalt, and manganese sulfates are obtained. Then, alkali (such as NaOH) and ammonia are added to carry out a precipitation reaction to obtain the cathode material precursor.

[0005] In the process of preparing precursors by directly mixing the aforementioned metal powders or corresponding oxides, elements such as nickel, cobalt, and manganese exist almost entirely in the form of oxides and / or elemental metals, which can react with hydrogen ions in acids to generate hydrogen gas. In order to ensure the high purity of the precursor, the purity of various raw materials is usually controlled. This results in the generation of little or no other gases during the preparation of precursors by acid dissolution of the aforementioned metal powders and corresponding oxides, leading to a high proportion of H2 in the generated gases, which poses a safety hazard, especially in large-scale production processes, which can bring even greater safety risks. Summary of the Invention

[0006] The purpose of this application is to provide a substance containing non-lithium metal elements and its preparation method. Reducing the proportion of element Me (Me) in the substance as a metallic element decreases the generation of H2 during acid dissolution. Simultaneously, by fixing the Me element in the form of carbonate, the carbonate generates CO2 during the acid dissolution process of the precursor preparation. This not only reduces H2 generation but also lowers the proportion of H2 in the gaseous state, thereby mitigating the safety hazard caused by the high proportion of H2 generated during acid dissolution in the preparation of battery cathode material precursors. The specific technical solution is as follows:

[0007] The first aspect of this application provides a substance containing a non-lithium metal element, wherein the substance comprises a first component and a second component; the first component comprises Me and / or MeO; the second component comprises MeCO3; wherein the Me element is selected from at least one of Ni, Co, and Mn.

[0008] In some embodiments of this application, the content of the first component in the substance is 20 wt% to 90 wt%, preferably 30 wt% to 50 wt%. In some embodiments of this application, the first component comprises water.

[0009] In some embodiments of this application, the content of the second component in the substance is 10 wt% to 80 wt%, preferably 50 wt% to 70 wt%.

[0010] In some embodiments of this application, the first component comprises water, and the mass percentage of the components other than water in the first component is 10% to 80% based on the mass of the substance.

[0011] In some embodiments of this application, the first component comprises water, and the mass percentage of the components other than water in the first component is 15% to 40% based on the mass of the substance.

[0012] Preferably, the mass ratio of the second component to the components other than water in the first component is (0.25 to 3.5):1.

[0013] In some embodiments of this application, the content of the Me element in the substance is 55wt% to 65wt%.

[0014] In some embodiments of this application, the Me element includes Ni, Co, and Mn; in the substance, the content of Ni is 40wt% to 50wt%, the content of Co is 5wt% to 7wt%, and the content of Mn is 6wt% to 10wt%.

[0015] In some embodiments of this application, the substance further includes a third component, which includes at least one of Al, Fe, Mg, Ca or Cu elements; preferably, the content of the third component in the substance is 0.5 wt% to 2 wt%.

[0016] In some embodiments of this application, the specific surface area of ​​the substance is 30 m². 2 / g~60m 2 / g. In some embodiments of this application, the specific surface area of ​​the substance is 44m². 2 / g~55m 2 / g.

[0017] In some embodiments of this application, the Dv10 of the substance is 0.5 μm to 2 μm, the Dv50 is 2.5 μm to 10 μm, and the Dv90 is 30 μm to 45 μm. 。 In some embodiments of this application, the Dv10 of the substance is 0.5 μm to 1.2 μm, the Dv50 is 3 μm to 8 μm, and the Dv90 is 37 μm to 45 μm.

[0018] In some embodiments of this application, the substance further includes Li element, and the mass percentage of Li element is less than or equal to 0.5 wt% based on the mass of the substance.

[0019] A second aspect of this application provides a method for preparing a substance containing a non-lithium metal element in any of the foregoing embodiments, comprising the following steps:

[0020] S100. Obtain a material containing Li2CO3, a first substance and MeCO3, wherein the first substance includes elemental Me and / or MeO, and the Me element is selected from at least one of Ni, Co and Mn.

[0021] S200. The material is mixed with a sulfuric acid solution a to carry out an acid dissolution reaction, and then filtered to obtain a filtrate and a filter residue, wherein the filter residue includes the substance containing non-lithium metal elements.

[0022] In some embodiments of this application, the molar number of Li element in the material is n1, and the molar number of Me element is n2, satisfying n1 < n2.

[0023] In some embodiments of this application, the molar number of Li elements in the material is n1, the molar number of Me elements is n2, and the molar number of hydrogen elements in the sulfuric acid solution a is r, satisfying n1 < r < n1 + 2n2. 。

[0024] In some embodiments of this application, the temperature of the acid dissolution reaction is 55°C to 85°C.

[0025] In some embodiments of this application, the filtrate comprises Li2SO4 and MeSO4.

[0026] In some embodiments of this application, step S100 includes the following steps:

[0027] S100-a, Obtain raw material a containing Li2CO3 and the first substance;

[0028] S100-b, Obtain raw material b containing MeSO4;

[0029] S100-c, Mix raw material a and raw material b, perform a first high-temperature reaction, filter, and obtain filter residue, wherein the filter residue contains the material; wherein, the number of moles of Li2CO3 in raw material a is S1, the number of moles of MeSO4 in raw material b is S2, and S2 < S1.

[0030] In some embodiments of this application, the temperature of the first high-temperature reaction is 40°C to 85°C.

[0031] In some embodiments of this application, the temperature of the first high-temperature reaction is 55°C to 85°C.

[0032] In some embodiments of this application, step S100 includes the following steps:

[0033] S100-I, Obtain raw material a containing Li2CO3 and the first substance;

[0034] S100-II: The raw material a and the sulfuric acid solution b are mixed, reacted, and filtered to obtain filter residue, wherein the filter residue contains the material.

[0035] In some embodiments of this application, the number of moles of Li2CO3 in raw material a is S1, and the number of moles of H2SO4 in sulfuric acid solution b is S3, where S1:S3 = 1:(0.05~0.8).

[0036] In some embodiments of this application, S1:S3 = 1:(0.2~0.8).

[0037] In some embodiments of this application, in step S200, a first electrolysis reaction is also carried out during the acid dissolution reaction.

[0038] In some embodiments of this application, MeSO4 is generated during the acid dissolution reaction, and the first electrolysis reaction includes electrolyzing the MeSO4.

[0039] In some embodiments of this application, the conditions for the first electrolysis reaction are: the electrolysis current density is 20 mA / cm². 2 ~60mA / cm 2 The electrolysis voltage is 3V to 5V; the electrolysis temperature is 55℃ to 85℃.

[0040] A third aspect of this application provides a method for preparing a substance containing a non-lithium metal element in any of the foregoing embodiments, comprising the following steps:

[0041] Sa, obtaining raw material a containing Li2CO3 and the first substance, wherein the first substance includes elemental Me and / or MeO, and the element Me is selected from at least one of Ni, Co and Mn;

[0042] Sb, obtain raw material c containing MeSO4;

[0043] Sc. Mix raw material a and raw material c, perform a second high-temperature reaction, filter, and obtain filter residue containing the aforementioned substances; wherein, the molar number of Li2CO3 in raw material a is S1, and the molar number of MeSO4 in raw material c is S4, where S1 ≤ S4 ≤ 1.5 × S1 。

[0044] In some embodiments of this application, the temperature of the second high-temperature reaction is 40°C to 85°C.

[0045] In some embodiments of this application, the temperature of the second high-temperature reaction is 55°C to 85°C.

[0046] In some embodiments of this application, a second electrolysis reaction is also carried out during the second high-temperature reaction.

[0047] In some embodiments of this application, the conditions for the second electrolysis reaction are: the current density of electrolysis is 20 mA / cm². 2 ~60mA / cm 2 The electrolysis voltage is 3V to 5V; the electrolysis temperature is 55℃ to 85℃.

[0048] The beneficial effects of this application are:

[0049] This application provides a substance containing a non-lithium metal element, comprising a first component and a second component; the first component includes Me and / or MeO; the second component includes MeCO3; wherein the Me element is selected from at least one of Ni, Co, and Mn. In this application, the non-lithium metal element is the aforementioned Me element. The MeCO3 in the substance containing the non-lithium metal element reacts with acid to produce CO2. The presence of CO2 can reduce the proportion of H2 in the gas produced when the substance containing the non-lithium metal element reacts with acid, thereby mitigating the safety hazard caused by hydrogen gas generated during the preparation of the precursor of the battery cathode material.

[0050] The methods for preparing substances containing non-lithium metal elements provided in this application can all produce the substances containing non-lithium metal elements described in this application. The contents of the first and second components obtained are also within the above-mentioned range (the content of the first component is 20wt% to 90wt%, and the content of the second component is 10wt% to 80wt%). When the content of the second component is within the above-mentioned range, not only can the ratio of H2 to CO2 be controlled during the preparation of the cathode material precursor, minimizing the proportion of H2, but the amount of raw materials used can also be reduced, such as raw material b, sulfuric acid solution b, and raw material c, thereby reasonably controlling the preparation cost.

[0051] Of course, implementing any product or method of this application does not necessarily require achieving all of the advantages described above at the same time. Attached Figure Description

[0052] The accompanying drawings, which are provided to further illustrate this application and form part of this application, illustrate exemplary embodiments of this application and are used to explain this application, but do not constitute an undue limitation of this application.

[0053] Figure 1 is a thermogravimetric analysis diagram of the substance containing non-lithium metal elements in Example 3;

[0054] Figure 2 is the XRD pattern of raw material a after reduction roasting in Example 3;

[0055] Figure 3 is a flowchart of one embodiment of the present application for preparing a substance containing non-lithium metal elements;

[0056] Figure 4 is a flowchart of another embodiment of this application for preparing a substance containing non-lithium metal elements. Detailed Implementation

[0057] To make the objectives, technical solutions, and advantages of this application clearer, the following detailed description is provided with reference to the accompanying drawings and embodiments. Obviously, the described embodiments are merely some embodiments of this application, and not all embodiments. All other embodiments obtained by those skilled in the art based on this application are within the scope of protection of this application.

[0058] The first aspect of this application provides a substance containing a non-lithium metal element, wherein the substance comprises a first component and a second component; the first component comprises Me and / or MeO; the second component comprises MeCO3; wherein the Me element is selected from at least one of Ni, Co, and Mn. In this application, the non-lithium metal element is the aforementioned Me element. The MeCO3 in the substance containing the non-lithium metal element not only reduces the production of H2, but also produces CO2 when reacting with acid. The presence of CO2 can reduce the proportion of H2 in the gas produced when the substance containing the non-lithium metal element reacts with acid, thereby improving the safety hazard caused by hydrogen gas generated by acid dissolution during the preparation of the precursor of the battery cathode material. In this application, the aforementioned acid is the acid used in the preparation of the precursor of the battery cathode material, and this application is not limited to it. The aforementioned "Me element selected from at least one of Ni, Co, and Mn" means that the Me element in Me, MeO, and MeCO3 is independently selected from at least one of Ni, Co, and Mn. It should be noted that the Me element in the first component can exist as an element, i.e., Me, or as an oxide, i.e., MeO, or both.

[0059] In some embodiments of this application, the content W1 of the first component in the substance is 20 wt% to 90 wt%, preferably 30 wt% to 50 wt%. In this application, the content of the first component in the substance refers to the mass percentage of the first component based on the mass of the substance. For example, the content of the first component is selected from any value of 20 wt%, 25 wt%, 30 wt%, 35 wt%, 40 wt%, 45 wt%, 50 wt%, 55 wt%, 60 wt%, 65 wt%, 70 wt%, 71 wt%, 72 wt%, 73 wt%, 74 wt%, 75 wt%, 76 wt%, 77 wt%, 78 wt%, 79 wt%, 80 wt%, 81 wt%, 82 wt%, 83 wt%, 84 wt%, 85 wt%, 86 wt%, 87 wt%, 88 wt%, 89 wt%, 90 wt%, or between any two of the above figures. The first component reacts with acid to produce H2 but not CO2. By controlling the content of the first component within the aforementioned range, the proportion of H2 in the gas produced when substances containing non-lithium metal elements react with acid can be reduced, thereby mitigating the safety hazard caused by hydrogen gas generated during acid dissolution in the preparation of battery cathode materials precursors. It is understood that the first component may contain a certain amount of water; therefore, the content W1 of the first component mentioned above includes the content of water. The water can exist in the form of crystal water and / or free water; this application does not limit the form in which water exists.

[0060] In some embodiments of this application, the first component comprises water, and the mass percentage W1' of the components other than water in the first component is 10% to 80% based on the mass of the substance. In some embodiments of this application, W1' is 15% to 40%. For example, W1' is selected from any value of 10%, 11%, 12%, 13%, 14%, 15%, 16%, 17%, 18%, 19%, 20%, 25%, 30%, 35%, 40%, 45%, 50%, 55%, 60%, 65%, 70%, 71%, 72%, 73%, 74%, 75%, 76%, 77%, 78%, 79%, 80%, or between any two of the above figures. The components other than water in the first component, namely Me and / or MeO, can reduce the proportion of H2 in the gas generated when substances containing non-lithium metal elements react with acid by controlling the mass percentage of the components other than water within the above range. This can improve the safety hazards caused by hydrogen gas generated by acid dissolution during the preparation of the precursor of battery cathode material.

[0061] In some embodiments of this application, the content of the second component W2 in the substance is 10 wt% to 80 wt%, preferably 50 wt% to 70 wt%. In this application, the content of the second component in the substance refers to the mass percentage of the second component based on the mass of the substance. For example, the content of the second component is selected from 10wt%, 11wt%, 12wt%, 13wt%, 14wt%, 15wt%, 16wt%, 17wt%, 18wt%, 19wt%, 20wt%, 21wt%, 22wt%, 23wt%, 24wt%, 25wt%, 26wt%, 27wt%, 28wt%, 29wt%, 30wt%, 31wt%, 32wt%, 33wt%, 34wt%, 35wt%, 36wt%, 37wt%, 38wt%, 39wt%, 40wt%, 41wt%, 42wt%, 43wt%, 44wt%, 45wt%. Any value of 46wt%, 47wt%, 48wt%, 49wt%, 50wt%, 51wt%, 52wt%, 53wt%, 54wt%, 55wt%, 56wt%, 57wt%, 58wt%, 59wt%, 60wt%, 61wt%, 62wt%, 63wt%, 64wt%, 65wt%, 66wt%, 67wt%, 68wt%, 69wt%, 70wt%, 71wt%, 72wt%, 73wt%, 74wt%, 75wt%, 76wt%, 77wt%, 78wt%, 79wt%, 80wt%, or any two of the above numbers. The second component contains MeCO3, which can produce H2 when reacting with acid. By controlling the content of the second component within the above range, the proportion of H2 in the gas produced when substances containing non-lithium metal elements react with acid can be reduced, thereby improving the safety hazards caused by hydrogen gas generated by acid dissolution during the preparation of battery cathode material precursors.

[0062] In some embodiments of this application, the mass ratio of the second component to the components of the first component other than water is (0.25 to 3.5):1. For example, the mass ratio of the second component to the components of the first component other than water is selected from any one of 0.25:1, 0.5:1, 1:1, 1.5:1, 2:1, 2.5:1, 3:1, 3.5:1, or any two of the above ratios.

[0063] In some embodiments of this application, the content m of element Me in the substance is 55wt% to 65wt%. In this application, the content of element Me in the substance refers to the mass percentage of element Me based on the mass of the substance. For example, the content of element Me is selected from any value of 55wt%, 56wt%, 57wt%, 58wt%, 59wt%, 60wt%, 61wt%, 62wt%, 63wt%, 64wt%, 65wt%, or any two of the above values. In substances containing non-lithium metal elements, an element Me content within the above range indicates a high content of nickel / cobalt / manganese. Nickel / cobalt / manganese substances can exist in the form of elements, oxides, or carbonates, are easily soluble in acid, and acid dissolution of substances containing non-lithium metal elements yields a high-purity solution containing Ni / Co / Mn elements. The content of other metal cations is relatively low, which is beneficial for preparing precursors for battery cathode materials.

[0064] In some embodiments of this application, the element Me includes Ni, Co, and Mn; in the substance, the content of Ni (m1) is 40 wt% to 50 wt%, the content of Co (m2) is 5 wt% to 7 wt%, and the content of Mn (m3) is 6 wt% to 10 wt%. In this application, the content of Ni in the substance refers to the mass percentage of Ni based on the mass of the substance; the content of Co in the substance refers to the mass percentage of Co based on the mass of the substance; and the content of Mn in the substance refers to the mass percentage of Mn based on the mass of the substance. For example, the content of Ni is selected from any value of 40 wt%, 41 wt%, 42 wt%, 43 wt%, 44 wt%, 45 wt%, 46 wt%, 47 wt%, 48 wt%, 49 wt%, and 50 wt%, or between any two of the above values. For example, the content of Co is any value of 5 wt%, 6 wt%, and 7 wt%, or between any two of the above values. For example, the Mn content can be any value among 6wt%, 7wt%, 8wt%, 9wt%, and 10wt%, or between any two of the above values. When Ni, Co, and Mn are within the above ranges, similar proportions of positive electrode active material precursors can be obtained, resulting in good performance.

[0065] In some embodiments of this application, the substance further includes a third component, which includes at least one of Al, Fe, Mg, Ca, or Cu elements. In some embodiments of this application, the content of the third component W3 in the substance is 0.5 wt% to 2 wt%. In this application, the content of the third component in the substance refers to the mass percentage of the third component based on the mass of the substance. For example, the content of the third component is any value among 0.5 wt%, 0.6 wt%, 0.7 wt%, 0.8 wt%, 0.9 wt%, 1.0 wt%, 1.1 wt%, 1.2 wt%, 1.3 wt%, 1.4 wt%, 1.5 wt%, 1.6 wt%, 1.7 wt%, 1.8 wt%, 1.9 wt%, and 2 wt%, or between any two of the above figures. The third component mainly consists of impurity elements in substances containing non-lithium metal elements. Its type and content are primarily influenced by the source of the substance. The fact that the content of the third component is within the aforementioned range indicates a very low content of impurity elements, which is beneficial for obtaining high-quality, high-performance cathode material precursors. In this application, the third component refers to impurity elements in the substance, specifically at least one of Al, Fe, Mg, Ca, or Cu elements.

[0066] In some embodiments of this application, the specific surface area (BET) of the substance is 30 m². 2 / g~60m 2 / g. In some embodiments of this application, the specific surface area (BET) of the substance is 44m². 2 / g~55m 2 / g. For example, the specific surface area of ​​a substance is 30m². 2 / g、31m 2 / g、32m 2 / g、33m 2 / g、34m 2 / g、35m 2 / g、36m 2 / g、37m 2 / g、38m 2 / g、39m 2 / g、40m 2 / g、41m 2 / g、42m 2 / g、43m 2 / g、44m 2 / g、45m 2 / g、46m 2 / g、47m 2 / g、48m 2 / g、49m 2 / g, 50m 2 / g、51m2 / g、52m 2 / g、53m 2 / g、54m 2 / g、55m 2 / g、56m 2 / g、57m 2 / g、58m 2 / g、59m 2 / g、60m 2 The specific surface area of ​​the substance is within any value in / g or between any two of the above numbers. By adjusting the specific surface area of ​​the substance within the above range, it is more conducive to reacting with acid, thereby improving the efficiency in the preparation process of battery cathode material precursors and the performance of the cathode material precursors.

[0067] In some embodiments of this application, the Dv10 of the substance is 0.5 μm to 2 μm, the Dv50 is 2.5 μm to 10 μm, and the Dv90 is 30 μm to 45 μm. 。 In some embodiments of this application, the Dv10 of the substance is 0.5 μm to 1.2 μm, the Dv50 is 3 μm to 8 μm, and the Dv90 is 37 μm to 45 μm. For example, the Dv10 of the substance is any value of 0.5 μm, 0.6 μm, 0.7 μm, 0.8 μm, 0.9 μm, 1.0 μm, 1.1 μm, 1.2 μm, 1.3 μm, 1.4 μm, 1.5 μm, 1.6 μm, 1.7 μm, 1.8 μm, 1.9 μm, or 2 μm, or between any two of the above values. For example, the Dv50 of a substance is any value among 2.5 μm, 3 μm, 3.5 μm, 4 μm, 4.5 μm, 5 μm, 5.5 μm, 6 μm, 6.5 μm, 7 μm, 7.5 μm, 8 μm, 8.5 μm, 9 μm, 9.5 μm, and 10 μm, or between any two of the above numbers. For example, the Dv90 of a substance is any value among 30 μm, 31 μm, 32 μm, 33 μm, 34 μm, 35 μm, 36 μm, 37 μm, 38 μm, 39 μm, 40 μm, 41 μm, 42 μm, 43 μm, 44 μm, 45 μm, and 45 μm, or between any two of the above numbers. By controlling the Dv10, Dv50, and Dv90 of the material within the above range, the particle size is smaller, especially the Dv50 is between 2.5 μm and 10 μm, the material has higher activity, which is beneficial to obtaining a high-performance cathode material precursor.

[0068] In this application, Dv10, Dv50 and Dv90 are all volume average particle sizes.

[0069] In some embodiments of this application, the substance also includes Li element, and the mass percentage content of Li element W5 is less than or equal to 0.5 wt% based on the mass of the substance. For example, the mass percentage content of Li element can be any value from 0.01 wt%, 0.05 wt%, 0.1 wt%, 0.15 wt%, 0.2 wt%, 0.25 wt%, 0.3 wt%, 0.35 wt%, 0.4 wt%, 0.45 wt%, 0.5 wt%, or between any two of the above values. A Li element content within the above range indicates a low Li element content, which is beneficial for obtaining a high-purity precursor for ternary battery cathode materials. It can also be seen that the Li element recovery effect is relatively good.

[0070] The second aspect of this application provides a method for preparing a substance containing a non-lithium metal element in any of the foregoing embodiments, as shown in Figures 3 and 4, which includes the following steps:

[0071] S100. Obtain a material containing Li2CO3, a first substance and MeCO3, wherein the first substance includes elemental Me and / or MeO, and the element Me is selected from at least one of the elements Ni, Co and Mn.

[0072] S200. The material is mixed with a sulfuric acid solution a to carry out an acid dissolution reaction, filtered, and filtrate and filter residue are obtained. The filter residue includes substances containing non-lithium metal elements.

[0073] In some embodiments of this application, the sulfuric acid solution 'a' is an aqueous solution of sulfuric acid. This application does not limit its concentration, as long as it achieves the purpose of this application. For example, its molar concentration is 2 mol / L to 18.4 mol / L.

[0074] In some embodiments of this application, the preparation method of the substance containing a non-lithium metal element in any of the foregoing embodiments includes the following steps:

[0075] S100. Obtain a material containing Li2CO3, a substance containing Me element, and MeCO3; wherein, the substance containing Me element includes elemental Me and / or MeO, and the Me element is a non-lithium metal element selected from at least one of Ni element, Co element, and Mn element; in this application, the substance containing Me element is also the first substance mentioned above.

[0076] S200. The material from step S100 is mixed with sulfuric acid, subjected to acid dissolution reaction, and filtered to obtain filtrate and filter residue. The filter residue includes substances containing non-lithium metal elements.

[0077] In some embodiments of this application, the molar number of Li elements in the material is n1, and the molar number of Me elements is n2, where n1 < n2. In this application, the Li elements in the material all originate from Li₂CO₃; therefore, the molar number of Li elements in the material is also the molar number of Li elements in Li₂CO₃. In this application, the Me elements in the material all originate from the first substance and MeCO₃; the first substance is the substance containing Me elements. Therefore, the molar number of Me elements in the material is the sum of the molar number of Me elements in the substance containing Me elements and in MeCO₃. The material in this application also contains some Li₂CO₃ impurities. Removing the Li₂CO₃ using sulfuric acid can yield a high-quality substance containing non-lithium metal elements.

[0078] In some embodiments of this application, the number of moles of Li in the material is n1, the number of moles of Me is n2, and the number of moles of hydrogen in the sulfuric acid solution a is r, where n1 < r < n1 + 2n2. 。 That is, the hydrogen element in the sulfuric acid solution a is used to replace the Li element in the material, where r is greater than n1. At the same time, the hydrogen element should not be too high to avoid replacing too much nickel, cobalt and manganese elements and reducing the yield.

[0079] In some embodiments of this application, the element Me includes the elements Ni, Co, and Mn, elemental Me includes elemental Ni and elemental Co, and MeO includes MnO.

[0080] In some embodiments of this application, the element Me includes the elements Ni, Co, and Mn, and the materials include Li2CO3, elemental Ni, elemental Co, MnO, NiCO3, CoCO3, and MnCO3.

[0081] In some embodiments of this application, the acid dissolution reaction temperature is 55°C to 85°C. For example, the acid dissolution reaction temperature can be any value among 55°C, 60°C, 65°C, 70°C, 80°C, and 85°C, or any two of the above values. This application does not have a particular limitation on the acid dissolution reaction time, as long as the purpose of this application can be achieved. For example, the acid dissolution reaction time is 2 hours to 10 hours.

[0082] In some embodiments of this application, step S200, the acid dissolution reaction includes the following reactions:

[0083] Li2CO3+H2SO4=Li2SO4+CO2↑+H2O;

[0084] Me + H₂SO₄ = H₂↑ + MeSO₄;

[0085] MeO + H2SO4 = H2O + MeSO4;

[0086] MeCO3+H2SO4=MeSO4+CO2↑+H2O;

[0087] MeSO4+Li2CO3=Li2SO4+MeCO3↓.

[0088] In some embodiments of this application, the filtrate contains Li2SO4 and MeSO4.

[0089] In this application, during the acid dissolution reaction, Li₂CO₃ reacts more strongly with H. Therefore, the acid dissolution reaction can be used to elute lithium carbonate from the material containing Li₂CO₃, the first substance, and MeCO₃ into the liquid phase. This not only improves the purity of the solid phase and yields a high-purity substance containing non-lithium metal elements, but also allows for the recovery of lithium carbonate from the material in the liquid phase. Of course, during the acid dissolution process, H is in slightly excess compared to Li, which may cause some nickel, cobalt, and manganese elements to be eluted into the liquid phase. To improve the yield of nickel, cobalt, and manganese elements, MeSO₄ in the liquid phase can be returned to the solid phase by electrolysis, as detailed later.

[0090] In some embodiments of this application, step S100, as shown in FIG3, includes one of the following steps to obtain a material containing Li2CO3, the first substance, and MeCO3:

[0091] S100-a, obtain raw material a containing Li2CO3 and the first substance;

[0092] S100-b, Obtain raw material b containing MeSO4;

[0093] S100-c. Mix raw material a and raw material b, carry out the first high-temperature reaction, filter, and obtain filter residue containing the following materials; wherein, the molar number of Li2CO3 in raw material a is S1, the molar number of MeSO4 in raw material b is S2, and S2 < S1. 。

[0094] In some embodiments of this application, in step S100-c, the obtained materials include Li2CO3, MeCO3, and Me and / or MeO. Step S100-c includes at least the following reaction process:

[0095] MeSO4+Li2CO3=MeCO3↓+Li2SO4.

[0096] In some embodiments of this application, in one of the above methods, the number of moles of Li2CO3 in raw material a, S1, is greater than the number of moles of MeSO4 in raw material b, S2. This allows part of the Li2CO3 in raw material a to be removed by MeSO4 and the other part by sulfuric acid, which not only yields more MeCO3 but also reduces costs.

[0097] In some embodiments of this application, in one of the above methods, raw material b can be an aqueous solution containing MeSO4. After solid raw material a and raw material b are mixed, MeSO4 reacts with Li2CO3 to generate MeCO3 precipitate and water-soluble Li2SO4, so that Me element exists in the solid phase and Li element exists in the liquid phase. The Li element existing in the liquid phase can achieve Li element recovery. The Li2CO3 remaining in the solid phase reacts further with sulfuric acid solution a to transfer the Li element in the solid phase to the liquid phase, thereby obtaining a substance containing non-lithium metal elements with high purity. In this application, the above-mentioned aqueous solution containing MeSO4 can be obtained by mixing solid MeSO4 salt with water, and the solid MeSO4 salt can be purchased.

[0098] In some embodiments of this application, in one of the above methods, raw material b is an aqueous solution containing MeSO4. MeSO4 can be at least one of NiSO4, CoSO4, and MnSO4. For example, raw material a can be reacted at high temperature with an aqueous solution of NiSO4, or with an aqueous solution of CoSO4, or with aqueous solutions of NiSO4 and CoSO4, or with aqueous solutions of NiSO4, CoSO4, and MnSO4. A more preferred method is to react raw material a at high temperature with an aqueous solution of NiSO4, CoSO4, and MnSO4. This yields raw material b with a suitable ratio of Ni, Co, and Mn elements, which helps to control the Ni, Co, and Mn element ratios in the product within a suitable range.

[0099] In one of the above methods, the solid-liquid ratio of MeSO4 to water in the aqueous solution containing MeSO4 is 10 g / L to 150 g / L, preferably 30 g / L to 80 g / L. For example, the solid-liquid ratio of MeSO4 to water can be any value from 10 g / L, 20 g / L, 30 g / L, 40 g / L, 50 g / L, 60 g / L, 70 g / L, 80 g / L, 90 g / L, 100 g / L, 110 g / L, 120 g / L, 130 g / L, 140 g / L, 150 g / L, or any two of the above values.

[0100] In some embodiments of this application, in one of the above methods, raw material b can of course be a solid salt containing MeSO4. Raw material a is mixed with the solid-phase raw material b containing MeSO4, and then water is added. MeSO4 reacts with Li2CO3 to generate MeCO3 precipitate and water-soluble Li2SO4, so that Me element exists in the solid phase and Li element exists in the liquid phase. The Li element present in the liquid phase can be recovered. The Li2CO3 remaining in the solid phase reacts further with a sulfuric acid-containing solution a to transfer the Li element from the solid phase to the liquid phase, thereby obtaining a substance containing non-lithium metal elements. In this application, the aforementioned solid salt of MeSO4 can be commercially available.

[0101] Of course, the method of obtaining raw material b can be other than one of the above methods. This application does not strictly limit the method of obtaining raw material b, as long as it can achieve the purpose of this application.

[0102] In some embodiments of this application, in one of the above methods, the temperature of the first high-temperature reaction is 40°C to 85°C. In some embodiments of this application, in one of the above methods, the temperature of the first high-temperature reaction is 55°C to 85°C. For example, the temperature of the first high-temperature reaction can be any value among 40°C, 45°C, 50°C, 55°C, 60°C, 65°C, 70°C, 80°C, and 85°C, or any two of the above values. A temperature within the above range for the first high-temperature reaction is beneficial for the complete reaction of raw material a and raw material b, and for increasing the reaction rate. In this application, exemplarily, the time of the first high-temperature reaction is 2 hours to 10 hours. For example, the time of the first high-temperature reaction can be any value among 2 hours, 3 hours, 4 hours, 5 hours, 6 hours, 7 hours, 8 hours, 9 hours, and 10 hours, or any two of the above values.

[0103] In this application, in one of the above methods, using raw material b containing MeSO4 to prepare MeCO3 can generate more MeCO3 and increase the content of MeCO3 in the solid phase.

[0104] In some embodiments of this application, step S100, as shown in FIG4, includes the following steps in another way of obtaining the material containing Li2CO3, the first substance, and MeCO3:

[0105] S100-I, obtain raw material a containing Li2CO3 and the first substance;

[0106] S100-II: Mix raw material a and sulfuric acid solution b, react, filter, and obtain filter residue containing the material.

[0107] In some embodiments of this application, in the second method described above, the molar number of Li₂CO₃ in raw material a is S₁, and the molar number of H₂SO₄ in the sulfuric acid solution b is S₃, with S₁:S₃ = 1:(0.05~0.8). In some embodiments of this application, S₁:S₃ = 1:(0.2~0.8), and step S₁₀₀-II involves the addition of insufficient acid, which can achieve efficient recovery of Li element from raw material a. For example, S₁:S₃ can be any ratio among 1:0.05, 1:0.1, 1:0.15, 1:0.2, 1:0.3, 1:0.4, 1:0.5, 1:0.6, 1:0.7, and 1:0.8, or any two of the above ratios. By adjusting the S1:S3 ratio within the aforementioned range, as much Li2CO3 as possible reacts with sulfuric acid, while a small amount of Me and / or MeO reacts with sulfuric acid. The resulting MeSO4 further reacts with Li2CO3, producing MeCO3 precipitate and water-soluble Li2SO4. In other words, Li elements exist in the liquid phase for easy recovery, while Me elements exist in the solid phase for subsequent reactions. The material obtained through this method has relatively less MeCO3 precipitate and is also less expensive.

[0108] In some embodiments of this application, in the second method described above, the materials obtained in step S100-II include Li2CO3, MeCO3, and elemental Me and / or MeO. Step S100-II includes at least one of the following reaction processes:

[0109] Li2CO3+H2SO4=Li2SO4+CO2↑+H2O;

[0110] Me + H₂SO₄ = H₂↑ + MeSO₄;

[0111] MeO + H2SO4 = H2O + MeSO4;

[0112] MeSO4+Li2CO3=MeCO3↓+Li2SO4.

[0113] In some embodiments of this application, in the second method described above, raw material a is a solid phase. After adding sulfuric acid solution b to raw material a, the sulfuric acid reacts with Li₂CO₃, and also reacts with a small amount of Me and / or MeO to generate MeSO₄. MeSO₄ continues to react with Li₂CO₃ to generate MeCO₃ precipitate and water-soluble Li₂SO₄, so that Me element exists in the solid phase and Li element exists in the liquid phase. The Li element existing in the liquid phase can be recovered, and the Me element existing in the solid phase further reacts with sulfuric acid solution a to obtain a substance containing non-lithium metal elements.

[0114] In some embodiments of this application, in the second method described above, in step S100-II, the sulfuric acid solution b is an aqueous solution of sulfuric acid. This application does not limit its concentration, as long as it achieves the purpose of this application. For example, its molar concentration is 2 mol / L to 18.4 mol / L.

[0115] In some embodiments of this application, in the second method described above, the reaction temperature in step S100-II is 55℃ to 85℃. At this reaction temperature, the precipitation reaction between MeSO4 and Li2CO3 can proceed more fully. This application does not have a particular limitation on the reaction time in step S100-II; an exemplary value is 2h to 10h. For example, the reaction temperature in step S100-II can be any value among 55℃, 60℃, 65℃, 70℃, 80℃, and 85℃, or any two of the above values. For example, the reaction time in step S100-II can be any value among 2h, 3h, 4h, 5h, 6h, 7h, 8h, 9h, and 10h, or any two of the above values.

[0116] In some embodiments of this application, the raw material a in step S100-a and step S100-I can be the same. This application does not limit the method of obtaining raw material a, as long as it achieves the purpose of this application. For example, raw material a can be obtained by purchase, or raw material a can be obtained according to the following steps: obtaining waste cathode material. Taking waste ternary cathode material as an example, the waste ternary cathode material (LiMeO2) is reduced and roasted to obtain raw material a. During the reduction and roasting process, reducing substances, such as carbon monoxide (CO) and / or carbon powder (C), can be introduced to convert the lithium element in the waste ternary cathode material into Li2CO3, and the Me element in the ternary cathode material into elemental Me and / or MeO.

[0117] In some embodiments of this application, the reducing agent is CO, and the reaction equations for the reduction roasting stage include:

[0118] 2LiMeO2+2CO=Li2CO3+Me+MeO+CO2↑.

[0119] In some embodiments of this application, the reducing agent is carbon powder, and an inert gas, such as nitrogen, is introduced to carry out the reduction roasting. The reaction equations for this reduction roasting stage include:

[0120] 2LiMeO2+C=Li2CO3+Me+MeO.

[0121] In this application, the implementation scheme corresponding to one of the above methods and the implementation scheme corresponding to the second method are two parallel implementation schemes, and no implementation scheme in the implementation scheme corresponding to one of the above methods is combined with any implementation scheme in the implementation scheme corresponding to the second method.

[0122] In some embodiments of this application, a first electrolysis reaction is also performed during step S200, in addition to the acid dissolution reaction. In some embodiments of this application, MeSO4 is generated during the acid dissolution reaction, and the first electrolysis reaction includes electrolyzing the MeSO4. The MeSO4 in the liquid phase obtained from the acid dissolution can be further converted into solid Me and / or MeO2, which not only improves the recovery rate of substances containing non-lithium metal elements but also purifies Li2SO4 in the liquid phase.

[0123] Specifically, during the first electrolysis reaction, possible reactions include, but are not limited to:

[0124] 2NiSO4+2H2O=2Ni+2H2SO4+O2↑;

[0125] 2CoSO4+2H2O=2Co+2H2SO4+O2↑;

[0126] NiSO4+MnSO4+2H2O=Ni+MnO2+2H2SO4;

[0127] CoSO4+MnSO4+2H2O=Co+MnO2+2H2SO4.

[0128] In some embodiments of this application, when Me is selected from Ni, Co, and Mn, the product obtained after electrolysis of CoSO4 includes elemental Co and sulfuric acid; the product obtained after electrolysis of NiSO4 includes elemental Ni and sulfuric acid; and the product obtained after electrolysis of MnSO4 includes MnO2 and sulfuric acid. The proportions of nickel, cobalt, and manganese in MeSO4 are not limited in this application, but are generally similar to the proportions of nickel, cobalt, and manganese in the cathode material. Exemplarily, the first electrolysis reaction includes the following reaction:

[0129] Electrolysis of MeSO4 in the system generates sulfuric acid, recycling a portion of the sulfuric acid and reducing its usage. Furthermore, it allows Li2CO3 in the solid phase to continue reacting with sulfuric acid, forming Li2SO4 that can exist in the liquid phase, thus improving lithium elution recovery. The process also purifies the solid phase containing Me and / or MeO, as well as MeCO3, yielding high-purity substances containing non-lithium metal elements. Electrolysis also produces elemental Ni, elemental Co, and MnO2, further enriching Me in the solid phase and improving its recovery rate. In addition, the reaction time can be significantly shortened.

[0130] In some embodiments of this application, the current density of the first electrolysis reaction is 20 mA / cm². 2 ~60mA / cm 2 The voltage of the first electrolysis reaction is 3V to 5V, and the temperature of the first electrolysis reaction is 55℃ to 85℃. In some embodiments of this application, the current density of the first electrolysis reaction is 40mA / cm². 2 ~50mA / cm 2 The voltage is 4.5V to 4.8V, and the temperature is 80℃ to 85℃. For example, the current density of the first electrolysis reaction is 20mA / cm². 2 25mA / cm 2 30mA / cm 2 35mA / cm 2 40mA / cm 2 45mA / cm 2 50mA / cm 2 55mA / cm 2 60mA / cm 2 The voltage of the first electrolysis reaction can be any value in the above range or between any two of the above numbers. For example, the voltage of the first electrolysis reaction can be any value in the range of 3V, 3.5V, 4V, 4.5V, and 5V or between any two of the above numbers. For example, the temperature of the first electrolysis reaction can be selected from any value in the range of 55℃, 60℃, 65℃, 70℃, 80℃, and 85℃ or between any two of the above numbers. By controlling the current density, voltage, and temperature of the first electrolysis reaction within the above ranges, it is beneficial to ensure the full progress of the MeSO4 electrolysis reaction and increase the reaction rate. The generated sulfuric acid further reacts with Li2CO3 to generate Li2SO4, thereby improving the lithium recovery rate. In addition, solid phase substances such as Ni, Co, and MnO2 are also generated, improving the purity and yield of Me element in the solid phase.

[0131] In some embodiments of this application, the current density of the first electrolysis reaction is 40 mA / cm². 2 ~50mA / cm 2 Electrolysis at a voltage of 4.5V–4.8V and a temperature of 80℃–85℃ not only improves lithium recovery but also yields high-purity nickel-cobalt metal powder and manganese oxide powder. The nickel-cobalt metal powder and manganese oxide powder obtained under high current density electrolysis can be directly used as precursors for preparing cathode materials through acid dissolution.

[0132] In some embodiments of this application, the first electrolysis reaction can be carried out under weakly acidic to neutral conditions during the acid dissolution reaction in step S200, for example, at a pH of 5 to 7, to initiate the first electrolysis reaction and avoid the H+ in the acid dissolution reaction. +Electrolysis. A third aspect of this application provides a method for preparing a substance containing a non-lithium metal element in any of the foregoing embodiments, comprising the following steps:

[0133] Sa, obtaining raw material a containing Li2CO3 and a first substance, wherein the first substance includes elemental Me and / or MeO, and the element Me is selected from at least one of the elements Ni, Co, and Mn;

[0134] Sb, obtain raw material c containing MeSO4;

[0135] Sc. Mix raw material a and raw material c, carry out a second high-temperature reaction, filter, and obtain filter residue containing the following substances: S1 moles of Li2CO3 in raw material a, and S4 moles of MeSO4 in raw material c, where S1 ≤ S4 ≤ 1.5 × S1 。 By adjusting the relationship between S1 and S4 to meet the above range, MeSO4 reacts with Li2CO3 to generate MeCO3 precipitate and water-soluble Li2SO4, and Li2CO3 is basically completely reacted. Then, after filtration, the filter residue is a substance containing non-lithium metal elements, including the first component MeCO3 and the second component Me and / or MeO.

[0136] In some embodiments of this application, step Sc includes at least the following reaction process:

[0137] MeSO4+Li2CO3=MeCO3↓+Li2SO4.

[0138] In some embodiments of this application, an excess of MeSO4 is directly added, simplifying the steps for preparing substances containing non-lithium metal elements.

[0139] In some embodiments of this application, the temperature of the second high-temperature reaction is 40°C to 85°C. In some embodiments of this application, the temperature of the second high-temperature reaction is 55°C to 85°C. For example, the temperature of the second high-temperature reaction can be any value among 40°C, 45°C, 50°C, 55°C, 60°C, 65°C, 70°C, 80°C, and 85°C, or any two of the above values. A temperature within the above range is beneficial for the complete reaction of raw material a and raw material c, and for increasing the reaction rate.

[0140] In some embodiments of this application, a second electrolysis reaction is also carried out during the second high-temperature reaction. In some embodiments of this application, the second electrolysis reaction includes electrolyzing MeSO4 to convert it into Me / MeO2, which can improve the recovery rate of substances containing non-lithium metal elements.

[0141] Specifically, during the second electrolysis reaction, possible reactions include, but are not limited to:

[0142] 2NiSO4+2H2O=2Ni+2H2SO4+O2↑;

[0143] 2CoSO4+2H2O=2Co+2H2SO4+O2↑;

[0144] NiSO4+MnSO4+2H2O=Ni+MnO2+2H2SO4;

[0145] CoSO4+MnSO4+2H2O=Co+MnO2+2H2SO4.

[0146] In some embodiments of this application, when Me is selected from Ni, Co, and Mn, the product obtained after electrolysis of CoSO4 includes elemental Co and sulfuric acid; the product obtained after electrolysis of NiSO4 includes elemental Ni and sulfuric acid; and the product obtained after electrolysis of MnSO4 includes sulfuric acid containing MnO2. The proportions of nickel, cobalt, and manganese in MeSO4 are not limited in this application, but are generally similar to the proportions of nickel, cobalt, and manganese in the positive electrode material. Exemplarily, the second electrolysis reaction includes the following reaction:

[0147] In this application, the second high-temperature reaction combined with the second electrolysis reaction can more thoroughly convert Li2CO3 into Li2SO4. That is, by electrolyzing MeSO4 in the system to generate sulfuric acid, the sulfuric acid reacts with Li2CO3 to generate Li2SO4(aq), thereby improving the lithium elution recovery rate and purifying the solid phase containing Me and / or MeO and MeCO3.

[0148] In some embodiments of this application, the current density of the second electrolysis reaction is 20 mA / cm². 2 ~60mA / cm 2 The voltage for the second electrolysis reaction is 3V to 5V, and the temperature is 55℃ to 85℃. For example, the current density for the second electrolysis reaction is 20mA / cm². 2 25mA / cm 2 30mA / cm 2 35mA / cm 2 40mA / cm 2 45mA / cm 2 50mA / cm 2 55mA / cm 2 60mA / cm 2The voltage of the second electrolysis reaction can be any value from 3V, 3.5V, 4V, 4.5V, or 5V, or any two of the above values. Similarly, the temperature of the second electrolysis reaction can be selected from any value from 55℃, 60℃, 65℃, 70℃, 80℃, or 85℃, or any two of the above values. By controlling the current density, voltage, and temperature of the second electrolysis reaction within the above ranges, it is beneficial for the MeSO4 electrolysis reaction to proceed fully and for the reaction rate to be increased.

[0149] In some embodiments of this application, the second electrolysis reaction can begin simultaneously with the second high-temperature reaction, or it can begin after the second high-temperature reaction. The second electrolysis reaction is stopped when the ratio of the molar content of lithium in the liquid phase of the system to the molar content of lithium in Li₂CO₃ in raw material a is greater than or equal to 0.95 during the second high-temperature reaction and the second electrolysis reaction.

[0150] The method for preparing the substance containing non-lithium metal elements provided in this application includes a reaction in solution in steps S100 and / or S200. Therefore, water will be present in the first component of the obtained substance containing non-lithium metal elements, and some water will inevitably remain even after drying. The drying conditions are conventional conditions in the art, such as a temperature of 100℃ to 120℃ and a drying time of 1h to 3h.

[0151] Example

[0152] The embodiments and comparative examples provided below illustrate the implementation of this application in more detail. Various tests and evaluations were conducted according to the methods described below. Furthermore, unless otherwise specified, "parts" and "%" are quality standards.

[0153] Test methods and equipment:

[0154] Thermogravimetric analysis:

[0155] Thermogravimetric analysis (TGA) was used to perform thermogravimetric tests on the products obtained in each embodiment, with a test temperature range of 30℃ to 750℃. Thermogravimetric analysis yielded the content of the second component MeCO3 (W2) and the water content (W4) in the product.

[0156] The loss at the first stage is the water content in the product, while the losses at the second and third stages are the CO2 content generated by the decomposition of MeCO3 in the product.

[0157] Let the relative molecular mass of MeCO3 be 58 + 12 + 48 = 118 g / mol.

[0158] ICP test:

[0159] The mass percentages of Ni, Co, Mn, Al, Fe, Cu, Ca, Mg, and Li in the non-lithium metal elements prepared in each embodiment were measured using inductively coupled plasma spectroscopy. The mass percentages of Al, Fe, Cu, Ca, and Mg were the mass percentages of the impurity elements (third component), W3, and the mass percentage of Li was W5.

[0160] The content of the first component, W1, is equal to 100% - W2 - W3 - W5.

[0161] The mass percentage of the components other than water in the first component is W1' = 100% - W2 - W3 - W5 - W4.

[0162] It is understandable that the prepared substance containing non-lithium metal elements is a mixture of multiple components. Among them, the content of impurity elements and lithium elements is relatively small. The mass percentage of each element is recorded as the mass percentage of the corresponding substance. Therefore, the final values ​​W1 and W1' are approximate estimates and may have some error compared with the actual content of non-lithium metal elements in the substance.

[0163] BET Test:

[0164] The specific surface area of ​​the substances containing non-lithium metal elements prepared in each example was tested using the nitrogen adsorption method.

[0165] Particle size test:

[0166] The Dv10, Dv50, and Dv90 of the substances containing non-lithium metal elements prepared in each embodiment were tested using a laser particle size analyzer.

[0167] The following explanation uses an 811 battery as an example to illustrate the solution of this patent. However, the solution of this patent is not limited to the 811 battery. Here, 811 battery refers to LiNi... 0.8 Co 0.1 Mn 0.1 Batteries with O2 as the main positive electrode active material.

[0168] Obtaining ternary electrode powder: Disassemble waste ternary 811 lithium-ion batteries, crush and sieve the positive electrode material layer obtained from the disassembly to obtain positive electrode material layer powder. Pre-treat the positive electrode material layer powder in a rotary kiln at 550℃ by introducing air to remove residual conductive agent and binder. The pre-treatment time is 2 hours. Then, pass it through a 150-mesh sieve to obtain ternary material layer powder.

[0169] Unless otherwise specified, the following examples and comparative examples all use the ternary material layer powder prepared as described above.

[0170] Example 1 (Preparation of a substance containing a non-lithium metal element using sulfuric acid)

[0171] (1) Preparation of raw material a

[0172] 100g of ternary material layer powder was mixed evenly with 10wt% carbon powder, and then subjected to reduction calcination under nitrogen atmosphere at 650℃ for 3 hours. The resulting raw material a consisted of lithium carbonate, nickel metal, cobalt metal, and manganese oxide. The carbon powder content was calculated based on the mass of the ternary material layer powder. The molar ratio of lithium, nickel, cobalt, and manganese in raw material a was approximately 1:0.8:0.1:0.1.

[0173] (2) Preparation of materials containing Li2CO3, the first substance and MeCO3

[0174] Raw material a was acid-dissolved using sulfuric acid with a molar concentration of 4.8 mol / L. The molar ratio of Li to H, S1:S3, was 1:0.5. The acid-dissolving temperature was 75℃, and the dissolving time was 3 hours. After acid dissolution, the mixture was filtered to obtain a filter residue and a filtrate. The filter residue contained Li₂CO₃, MeCO₃, and the first substance Me and MeO, thus yielding a material containing Li₂CO₃, the first substance, and MeCO₃. Specifically, the molar amount of Li (n1) in the filter residue was approximately 0.5 mol, and the molar amount of Me (n2) was approximately 1 mol.

[0175] (3) Preparation of substances containing non-lithium metal elements

[0176] The filter residue from step (2) was acid-dissolved again. The sulfuric acid molar concentration was 4.8 mol / L, the number of hydrogen moles r in the sulfuric acid was 1 mol, the acid dissolution time was 4.5 h, and the acid dissolution temperature was 75 °C. After the reaction was completed, the residue was filtered to obtain a substance containing non-lithium metal elements.

[0177] Thermogravimetric analysis (TGA) was performed on the product prepared in Example 1. The results showed that the content of the second component MeCO3, W2, was approximately 18.4 wt%; the mass percentage of the first component, excluding water, W1', was approximately 71 wt%, with a water content of approximately 9 wt%, and the content of the first component W1 was approximately 80 wt%. The above product is a substance containing non-lithium metal elements.

[0178] The product prepared in Example 1 was subjected to ICP testing. The test results showed that the Me element content was 64.2 wt%, of which the Ni element content was 48.56 wt%, the Co element content was 6.46 wt%, and the Mn element content was 9.18 wt%.

[0179] ICP testing revealed that the product also contained impurity elements (i.e., the third component) and lithium. The impurity elements were Al, Fe, Cu, Ca, and Mg, with contents of 0.55wt%, 0.51wt%, 0.001wt%, 0.15wt%, and 0.02wt%, respectively. The lithium content was 0.41wt%.

[0180] Example 2 (Preparation of a substance containing non-lithium metal elements using MeSO4)

[0181] (1) Preparation of raw material a

[0182] 100g of ternary material layer powder was mixed evenly with 12wt% carbon powder, and then subjected to reduction calcination under nitrogen atmosphere at 600℃ for 3.5h. The resulting raw material a consisted of lithium carbonate, nickel metal, cobalt metal, and manganese oxide. The carbon powder content was calculated based on the mass of the ternary material layer powder. The molar ratio of lithium, nickel, cobalt, and manganese in raw material a was approximately 1:0.8:0.1:0.1.

[0183] (2) Preparation of raw material b containing MeSO4

[0184] NiSO4, CoSO4, and MnSO4 were mixed in a molar ratio of 8:1:1, added to water, and an aqueous solution was prepared with a solid-liquid ratio of 30 g / L to obtain raw material b.

[0185] (3) Preparation of materials containing Li2CO3, the first substance and MeCO3

[0186] Raw material a and raw material b were mixed and subjected to a first high-temperature reaction. The molar ratio of lithium carbonate to MeSO4, S1:S2, was 1:0.5. The first high-temperature reaction temperature was 75℃, and the reaction time was 15 hours. After the reaction, the mixture was filtered to obtain a filter residue and a filtrate. The filter residue contained Li2CO3, MeCO3, and the first substance Me and MeO, i.e., a material containing Li2CO3, the first substance, and MeCO3 was obtained. The molar number of MeSO4 was the sum of the molar numbers of NiSO4, CoSO4, and MnSO4 in raw material b. In the filter residue, the molar number of Li, n1, was approximately 0.5 mol, and the molar number of Me, n2, was approximately 1.25 mol.

[0187] (4) Preparation of substances containing non-lithium metal elements

[0188] The above filter residue was acid-dissolved, with the molar amount of sulfuric acid being the same as the molar amount of lithium carbonate in raw material a. The acid dissolution time was 4.5 h, and the temperature was raised to 75 °C during the acid dissolution process. After the reaction was completed, the residue was filtered to obtain a solid that does not contain lithium, i.e., a substance containing non-lithium metal elements.

[0189] Thermogravimetric analysis (TGA) was performed on the product prepared in Example 2. The results showed that the content of the second component MeCO3, W2, was approximately 55.1 wt%; the mass percentage of the first component other than water, W1', was approximately 32 wt%, the water content was approximately 11 wt%, and the content of the first component, W1, was approximately 43 wt%. The above product is a substance containing non-lithium metal elements.

[0190] The product prepared in Example 2 was subjected to ICP testing. The test results showed that the Me element content was 63.7 wt%, of which the Ni element content was 47.16 wt%, the Co element content was 6.84 wt%, and the Mn element content was 9.7 wt%.

[0191] ICP testing revealed that the product also contained impurity elements (i.e., the third component) and lithium. The impurity elements were Al, Fe, Cu, Ca, and Mg, with contents of 0.54 wt%, 0.55 wt%, 0.007 wt%, 0.17 wt%, and 0.03 wt%, respectively. The lithium content was 0.44 wt%.

[0192] Example 3 (Preparation of a substance containing a non-lithium metal element using MeSO4)

[0193] (1) Preparation of raw material a

[0194] 100g of ternary material layer powder was mixed evenly with 10wt% carbon powder, and then subjected to reduction calcination under nitrogen atmosphere at 700℃ for 2 hours. The resulting raw material a contained lithium carbonate, nickel metal, cobalt metal, and manganese oxide, as shown in Figure 2. The XRD pattern of raw material a showed characteristic peaks for lithium carbonate, nickel metal, cobalt metal, and manganese oxide. The carbon powder content was calculated based on the mass of the ternary material layer powder. The molar ratio of lithium, nickel, cobalt, and manganese in raw material a was approximately 1:0.8:0.1:0.1.

[0195] (2) Preparation of raw material b containing MeSO4

[0196] NiSO4, CoSO4, and MnSO4 were mixed in a molar ratio of 8:1:1 and a solid-liquid ratio of 80 g / L to prepare an aqueous solution, thus obtaining raw material b.

[0197] (3) Preparation of materials containing Li2CO3, the first substance and MeCO3

[0198] Raw material a and raw material b were mixed and subjected to a first high-temperature reaction. The molar ratio of lithium carbonate to MeSO4, S1:S2, was 1:0.6. The first high-temperature reaction temperature was 80℃, and the reaction time was 14 hours. After the reaction, the mixture was filtered to obtain a filter residue and a filtrate. The filter residue contained Li2CO3, MeCO3, and the first substance Me and MeO, i.e., a material containing Li2CO3, the first substance, and MeCO3. The molar number of MeSO4 was simply the sum of the molar numbers of NiSO4, CoSO4, and MnSO4 in raw material b. In the filter residue, the molar number of Li, n1, was approximately 0.4 mol, and the molar number of Me, n2, was approximately 1.3 mol.

[0199] (4) Preparation of substances containing non-lithium metal elements

[0200] The filter residue from step (3) was acid-dissolved again. The sulfuric acid molar concentration was 4.8 mol / L, the molar ratio of sulfuric acid to lithium carbonate in raw material a was 0.8:1, the molar number r of hydrogen in sulfuric acid was 0.8 mol, the acid dissolution time was 4 h, the acid dissolution temperature was 80 °C, and the mixture was filtered after the reaction was completed to obtain a substance containing non-lithium metal elements.

[0201] Thermogravimetric analysis (TGA) was performed on the product prepared in Example 3. The results showed that the water content was approximately 10.7 wt%, the content of the second component MeCO3 (W2) was approximately 67 wt%, the mass percentage of the first component other than water (W1') was approximately 20.57 wt%, and the content of the first component (W1) was approximately 31.3 wt%. This product contains a non-lithium metal element, and its TGA spectrum is shown in Figure 1. Figure 1 also indicates that the product contains MeCO3.

[0202] The product prepared in Example 3 was subjected to ICP testing, and the results are shown in Table 1. The results indicate that the Me element content was 56.7 wt%, of which the Ni element content was 43.65 wt%, the Co element content was 6.73 wt%, and the Mn element content was 6.32 wt%. The ICP test also showed that the substance containing non-lithium metal elements contained impurity elements and lithium. The impurity elements were Al, Fe, Cu, Ca, and Mg, with contents of 0.65 wt%, 0.58 wt%, 0.001 wt%, 0.12 wt%, and 0.025 wt%, respectively. The lithium element content was 0.35 wt%.

[0203] The BET test was performed on the substance containing non-lithium metal elements prepared in Example 3, and the specific surface area was 44.98 m². 2 / g indicates that the material containing non-lithium metal elements has more pores, which can improve the reactivity and make the subsequent preparation of precursors easier.

[0204] The particle size of the product prepared in Example 3 was tested. The Dv10 was 0.683 μm, the Dv50 was 3.32 μm, and the Dv90 was 37 μm. This particle size range and distribution indicate that the particles are generally fine and small in size. This will accelerate the chemical reaction rate during the preparation of the precursor dissolution process. Substances containing non-lithium metal elements have higher activity.

[0205] Example 4

[0206] Similar to Example 1, the only difference is that in step (2), the amount of sulfuric acid used is different, and the molar ratio of Li to H elements S1:S3 is 1:0.8; a substance containing non-lithium metal elements is obtained, including Me / MeO and MeCO3.

[0207] Example 5

[0208] Similar to Example 1, the only difference is that in step (2), the amount of sulfuric acid used is different, and the molar ratio of Li to H elements S1:S3 is 1:0.2; a substance containing non-lithium metal elements is obtained, including Me / MeO and MeCO3.

[0209] Example 6 (Acid Dissolution + Electrolysis)

[0210] Except for step (4), which is performed according to the following steps, the rest is the same as in Example 3, as follows:

[0211] The filter residue from step (3) is subjected to acid dissolution again. The molar ratio of sulfuric acid to lithium carbonate in raw material a is 0.5:1, the molar number r of hydrogen in sulfuric acid is 0.5 mol, the acid dissolution time is 2 h, and the acid dissolution temperature is 80℃. When the pH of the system reaches 6 during the acid dissolution process, the first electrolysis reaction is carried out on the system. The anode is graphite, the cathode is graphite, the voltage of the first electrolysis reaction is 3.5V, the temperature is 80℃, and the current density is 42mA / cm. 2 After the 10Ah condition is met, the first electrolysis reaction ends. After filtration, the residue is obtained, which is a substance containing non-lithium metal elements.

[0212] During acid dissolution, elements such as Ni, Co, and Mn are dissolved. H2SO4 generated by electrolysis of MeSO4 can be used to further dissolve Li2CO3, yielding a first and second component that are almost free of lithium. This method can reduce the amount of acid used, improve the purity of the product, and further enrich Ni, Co, and Mn elements in the solid phase, thereby increasing the recovery rate of Ni, Co, and Mn elements.

[0213] Thermogravimetric analysis (TGA) was performed on the product prepared in Example 6. The results showed that the content of the second component MeCO3 was approximately 59.3 wt%; the mass percentage of the first component excluding water, W1', was approximately 28 wt%, the water content was approximately 11 wt%, and the content of the first component W1 was approximately 39 wt%. The above product is a substance containing non-lithium metal elements.

[0214] ICP testing was performed on the product prepared in Example 6. The Me element content was 60.5 wt%, of which the Ni element content was 45.25 wt%, the Co element content was 7.57 wt%, and the Mn element content was 7.68 wt%. The ICP test showed that the substance containing non-lithium metal elements also contained impurity elements and lithium. The impurity elements were Al, Fe, Cu, Ca, and Mg, with contents of 0.74 wt%, 0.41 wt%, 0.01 wt%, 0.27 wt%, and 0.041 wt%, respectively. The lithium element content was 0.21 wt%.

[0215] The BET test was performed on the substance containing non-lithium metal elements prepared in Example 6, and the specific surface area was 52.92 m². 2 / g; Particle size analysis of the product prepared in Example 6 showed that Dv10 was 0.824 μm, Dv50 was 3.97 μm, and Dv90 was 40.5 μm.

[0216] Compared with Example 3, this embodiment shows that combining the electrolysis and acid dissolution processes can reduce the amount of acid used and shorten the reaction time.

[0217] Example 7

[0218] (1) Preparation of raw material a

[0219] Except for the reduction roasting temperature of 700℃ and the reduction roasting time of 2.5h, the rest is the same as step (1) in Example 1.

[0220] (2) Preparation of raw material c containing MeSO4

[0221] NiSO4, CoSO4, and MnSO4 were mixed in a molar ratio of 8:1:1, added to water, and an aqueous solution was prepared with a solid-liquid ratio of 30 g / L to obtain raw material c.

[0222] (3) Preparation of substances containing non-lithium metal elements

[0223] Raw material a and raw material c were mixed and subjected to a second high-temperature reaction. The molar ratio of lithium carbonate to MeSO4, S1:S4, was 1:1.2. The temperature of the second high-temperature reaction was 70°C and the reaction time was 16 hours. After the reaction was completed, the mixture was filtered to obtain filter residue and filtrate. The filter residue contained non-lithium metal elements.

[0224] Thermogravimetric analysis was performed on the product prepared in Example 7. The results showed that the content of MeCO3 in the second component was 68 wt%; the mass percentage of the components other than water in the first component was 20 wt%, and the water content was 9.5 wt%.

[0225] Example 8

[0226] Similar to Example 3, the only difference is that the first high-temperature reaction temperature in step (3) is 55°C.

[0227] Thermogravimetric analysis (TGA) was performed on the product prepared in Example 8. The results showed that the water content was approximately 11.3 wt%, the content of the second component MeCO3 (W2) was approximately 63 wt%, the mass percentage of the first component other than water (W1') was approximately 24 wt%, and the content of the first component (W1) was approximately 35.3 wt%. This product contains a substance with non-lithium metal elements.

[0228] ICP testing of the product prepared in Example 8 showed that the Me element content was 58.1 wt%, of which the Ni element content was 44.21 wt%, the Co element content was 6.55 wt%, and the Mn element content was 7.34 wt%. ICP testing also indicated that the substance containing non-lithium metal elements contained impurity elements and lithium. The impurity elements were Al, Fe, Cu, Ca, and Mg, with contents of 0.54 wt%, 0.47 wt%, 0.001 wt%, 0.17 wt%, and 0.018 wt%, respectively, and the lithium element content was 0.3 wt%.

[0229] Table 1

[0230] Application examples of substances containing non-lithium metal elements

[0231] Example a

[0232] 100g of the substance containing non-lithium metal elements obtained in Example 3 was mixed with excess sulfuric acid and completely dissolved. The generated gas was collected.

[0233] Gas chromatography analysis of the gas components revealed that the gas contained 36.2 wt% H2 and 63.8 wt% CO2. The presence of CO2 reduced the risk of H2 explosion. This demonstrates that using the precursor containing non-lithium metal elements provided in this application to prepare battery cathode materials can reduce the safety hazards caused by hydrogen gas generated during acid dissolution. This embodiment also suggests that the product contains MeCO3 and elemental Me.

[0234] It should be noted that, in this document, relational terms such as "first" and "second" are used only to distinguish one entity or operation from another, and do not necessarily require or imply any such actual relationship or order between these entities or operations. Furthermore, the terms "comprising," "including," or any other variations thereof are intended to cover non-exclusive inclusion, such that a process, method, or article that comprises a list of elements includes not only those elements but also other elements not expressly listed, or elements inherent to such a process, method, or article.

[0235] The element connected by the terms "one of," "among," "a kind of," or other similar terms refers to any one of the listed elements. For example, "one of A or B" means only A or only B; similarly, "one of A, B, and C" means only A, only B, or only C. The element connected by the terms "at least one of," "at least one of," "at least one of," or other similar terms refers to any combination of the listed elements. For example, "at least one of A or B" means only A, only B, A and B; similarly, "at least one of A, B, or C" means only A, only B, only C, only A and B, only A and C, only B and C, A and B and C.

[0236] The above description is only a preferred embodiment of this application and is not intended to limit this application. Any modifications, equivalent substitutions, improvements, etc., made within the spirit and principles of this application should be included within the scope of protection of this application.

Claims

1. A substance containing a non-lithium metal element, wherein, The substance comprises a first component and a second component; The first component includes Me and / or MeO; The second component includes MeCO3; The Me element is selected from at least one of Ni, Co, and Mn.

2. The substance according to claim 1, wherein, In the substance, the content of the first component is 20 wt% to 90 wt%, preferably 30 wt% to 50 wt%; and / or, In the substance, the content of the second component is 10 wt% to 80 wt%, preferably 50 wt% to 70 wt%.

3. The substance according to claim 1, wherein, The first component contains water, and based on the mass of the substance, the mass percentage of the components other than water in the first component is 10% to 80%, preferably 15% to 40%. Preferably, the mass ratio of the second component to the components other than water in the first component is (0.25 to 3.5):

1.

4. The substance according to claim 1, wherein, In the substance, the content of the Me element is 55wt% to 65wt%; Preferably, the Me element includes Ni, Co, and Mn elements; In the substance, the content of Ni is 40wt% to 50wt%, the content of Co is 5wt% to 7wt%, and the content of Mn is 6wt% to 10wt%.

5. The substance according to claim 1, wherein it satisfies at least one of the following conditions: Condition a: The substance further includes a third component, which includes at least one of Al, Fe, Mg, Ca or Cu elements; preferably, the content of the third component in the substance is 0.5 wt% to 2 wt%. Condition b: The specific surface area of ​​the substance is 30 m². 2 / g~60m 2 / g, preferably, the specific surface area of ​​the substance is 44m². 2 / g~55m 2 / g; Condition c: The Dv10 of the substance is 0.5μm to 2μm, Dv50 is 2.5μm to 10μm, and Dv90 is 30μm to 45μm. Preferably, Dv10 is 0.5μm to 1.2μm, Dv50 is 3μm to 8μm, and Dv90 is 37μm to 45μm. Condition d: The substance also includes Li element, and the mass percentage of Li element is less than or equal to 0.5 wt% based on the mass of the substance.

6. A method for preparing a substance containing a non-lithium metal element as described in any one of claims 1 to 5, comprising the following steps: S100. Obtain a material containing Li2CO3, a first substance and MeCO3, wherein the first substance includes elemental Me and / or MeO, and the Me element is selected from at least one of Ni, Co and Mn. S200. The material is mixed with a sulfuric acid solution a to carry out an acid dissolution reaction, and then filtered to obtain a filtrate and a filter residue, wherein the filter residue includes the substance containing non-lithium metal elements.

7. The preparation method according to claim 6, wherein at least one of the following conditions is met: Condition a: In the material, the number of moles of Li element is n1, and the number of moles of Me element is n2, satisfying n1 < n2; Condition b: The number of moles of Li in the material is n1, the number of moles of Me is n2, and the number of moles of hydrogen in the sulfuric acid solution a is r, satisfying n1 < r < n1 + 2n2; Condition c: The temperature of the acid dissolution reaction is 55℃~85℃; Condition d: The filtrate contains Li2SO4 and MeSO4.

8. The preparation method according to claim 6, wherein, Step S100 includes the following steps: S100-a, Obtain raw material a containing Li2CO3 and the first substance; S100-b, Obtain raw material b containing MeSO4; S100-c: Mix the raw material a and the raw material b, perform a first high-temperature reaction, filter, and obtain filter residue, wherein the filter residue contains the material; Wherein, the number of moles of Li2CO3 in raw material a is S1, and the number of moles of MeSO4 in raw material b is S2, where S2 < S1; Preferably, the temperature of the first high-temperature reaction is 40°C to 85°C; Preferably, the temperature of the first high-temperature reaction is 55°C to 85°C.

9. The preparation method according to claim 6, wherein, Step S100 includes the following steps: S100-I, Obtain raw material a containing Li2CO3 and the first substance; S100-II: Mix the raw material a and the sulfuric acid-containing solution b, react, filter, and obtain filter residue, wherein the filter residue contains the material; Preferably, the number of moles of Li2CO3 in raw material a is S1, and the number of moles of H2SO4 in sulfuric acid solution b is S3, where S1:S3 = 1:(0.05~0.8). More preferably, S1:S3 = 1:(0.2~0.8).

10. The preparation method according to any one of claims 6 to 9, wherein, In step S200, a first electrolysis reaction is also carried out during the acid dissolution reaction; Preferably, MeSO4 is generated during the acid dissolution reaction, and the first electrolysis reaction includes electrolyzing the MeSO4; More preferably, the conditions for the first electrolysis reaction are: The current density of the electrolysis is 20 mA / cm². 2 ~60mA / cm 2 ; The electrolysis voltage is 3V to 5V; The electrolysis temperature is 55℃~85℃.

11. A method for preparing a substance containing a non-lithium metal element as described in any one of claims 1 to 5, comprising the following steps: Sa, obtaining raw material a containing Li2CO3 and a first substance, wherein the first substance includes elemental Me and / or MeO, and the element Me is selected from at least one of Ni, Co, and Mn; Sb, obtain raw material c containing MeSO4; Sc. Mix the raw material a and the raw material c, carry out a second high-temperature reaction, filter, and obtain filter residue, wherein the filter residue contains the substance; Wherein, the number of moles of Li2CO3 in raw material a is S1, and the number of moles of MeSO4 in raw material c is S4, where S1≤S4≤1.5×S1; Preferably, the temperature of the second high-temperature reaction is 40°C to 85°C; Preferably, the temperature of the second high-temperature reaction is 55°C to 85°C; More preferably, a second electrolysis reaction is also carried out during the second high-temperature reaction; More preferably, the conditions for the second electrolysis reaction are: The current density of the electrolysis is 20 mA / cm². 2 ~60mA / cm 2 ; The electrolysis voltage is 3V to 5V; The electrolysis temperature is 55℃~85℃.

Images