A prelithiation multi-element precursor, a preparation method thereof, and a multi-element positive electrode material and a manufacturing method thereof

Abstract

The application provides a pre-lithiated multi-element precursor, a preparation method thereof, a multi-element positive electrode material and a manufacturing method thereof. The pre-lithiated multi-element precursor comprises a multi-element main component with pores and lithium source nanoparticles arranged in the pores. The pre-lithiated multi-element precursor provided by the application uses the pore characteristics of the main component to uniformly pre-arrange lithium sources in the interior of the main component, generate nanoparticles and stably fix the nanoparticles, so that the pre-lithiated multi-element precursor can be directly used for sintering to obtain a multi-element positive electrode material without additional addition of lithium salt. In this way, the problems of uneven lithium distribution, poor consistency and difficult compensation of lithium volatilization can be solved, so that the consistency and electrochemical performance of the obtained multi-element positive electrode material are improved, and the process is simplified, and energy consumption and cost are controlled.

Description

Technical Field

[0001] This invention belongs to the field of battery technology and relates to a pre-lithiated multi-element precursor and its preparation method, and a multi-element cathode material and its manufacturing method. Background Technology

[0002] Lithium-ion batteries have become the core power source for portable electronic devices, electric vehicles, and large-scale energy storage systems due to their advantages such as high energy density, long cycle life, and environmental friendliness. With the continuous increase in the driving range requirements of electric vehicles, higher demands are being placed on the energy density of lithium-ion batteries. High-nickel ternary cathode materials (such as NCM and NCA) are currently the core materials for power batteries due to their high energy density.

[0003] Currently, ternary cathode materials are typically prepared in industry by high-temperature solid-state sintering of hydroxide precursors with lithium sources. However, this method has some inherent drawbacks: since both the precursor and lithium salt are micron-sized particles, and mechanical solid-solid mixing makes it difficult to achieve uniform distribution of the lithium source at the microscale, especially to penetrate into the pores inside the precursor, the lithium distribution in the sintered material is uneven, affecting consistency; during high-temperature sintering, especially in high-nickel systems, the lithium source after solid-solid mixing is prone to volatilization and loss. To suppress cation mixing, an excess of lithium source is usually added, but precise control of the excess lithium is difficult, and it is easy to leave high residual alkali on the surface, deteriorating processing performance; moreover, the mechanical solid-solid mixing process easily destroys the spherical structure of the precursor and the stacking structure of the primary particles, affecting the performance of the final product. Summary of the Invention

[0004] In view of the problems existing in the prior art, the purpose of this invention is to provide a pre-lithiated multi-element precursor and its preparation method, and a multi-element cathode material and its manufacturing method. The pre-lithiated multi-element precursor includes a porous multi-element main component and lithium source nanoparticles disposed in the pores. This invention utilizes the porosity characteristics of the main component to uniformly pre-place a lithium source inside the main component, generating and stably fixing nanoscale particles. This allows the pre-lithiated multi-element precursor to be directly used for sintering to obtain a multi-element cathode material without the need for additional lithium salt mixing. This solves the problems of uneven lithium distribution, poor consistency, and difficulty in compensating for lithium volatilization, thereby improving the consistency and electrochemical performance of the obtained multi-element cathode material. It also simplifies the process and controls energy consumption and cost.

[0005] To achieve this objective, the present invention adopts the following technical solution: In a first aspect, the present invention provides a pre-lithiated multi-component precursor comprising a multi-component principal component, wherein the multi-component principal component comprises at least two transition metal elements and wherein the multi-component principal component has pores; the pre-lithiated multi-component precursor further comprises lithium source nanoparticles disposed in the pores of the multi-component principal component.

[0006] In the pre-lithiated multi-component precursor provided by this invention, the lithium source is uniformly distributed in the form of nanoparticles within the internal pores of the multi-component main component particles, rather than merely adhering to the surface. This fully utilizes the porosity and porosity characteristics of the multi-component main components themselves, confining the lithium source within nanoscale pores and achieving true microscale uniform mixing. Since the lithium source is uniformly distributed within the pre-lithiated multi-component precursor, lithium ions can diffuse from the inside out during the subsequent calcination and sintering process to form the cathode material. This is completely opposite to the outside-in diffusion of lithium in precursors obtained through traditional solid-phase mixing processes. Therefore, the pre-lithiated multi-component precursor provided by this invention facilitates a more complete reaction, resulting in lower surface alkali residue in the obtained cathode material, thereby effectively improving the performance of the multi-component cathode material.

[0007] The following are preferred technical solutions of the present invention, but are not intended to limit the technical solutions provided by the present invention. The technical objectives and beneficial effects of the present invention can be better achieved and realized through the following technical solutions.

[0008] As a preferred embodiment of the present invention, the porosity of the multi-component principal component is 30% to 60%, for example, it can be 30%, 35%, 40%, 45%, 50%, 55% or 60%; the pore size range is 5nm to 500nm, for example, it can be 5nm, 10nm, 30nm, 50nm, 80nm, 100nm, 150nm, 200nm, 250nm, 300nm, 350nm, 400nm, 450nm or 500nm.

[0009] Preferably, the multi-component principal component includes at least one of hydroxides, carbonates, or oxides. For example, it can be a composite hydroxide, composite carbonate, or composite oxide corresponding to at least two of the transition metal elements nickel, cobalt, or manganese. Further, when the multi-component principal component is a ternary precursor, the chemical formula of the ternary precursor can be Ni. x Co y Mn z (OH)2, x+y+z=1, 0<x<1, 0<y<1, 0<z<1, x, y, z can all be selected from 0.01, 0.05, 0.08, 0.1, 0.2, 0.3, 0.5, 0.7, 0.8 or 0.9 etc.

[0010] Preferably, the lithium source nanoparticles include lithium hydroxide and / or lithium carbonate.

[0011] Preferably, the size range of the lithium source nanoparticles is 2nm to 200nm, for example, it can be 2nm, 5nm, 8nm, 10nm, 30nm, 50nm, 80nm, 100nm, 130nm, 150nm, 180nm or 200nm, etc.

[0012] Preferably, the ratio of the total molar amount of lithium in the lithium source nanoparticles to the total molar amount of transition metal elements in the multi-component principal components is (1.00~1.08):1, for example, it can be 1.00:1, 1.01:1, 1.02:1, 1.03:1, 1.04:1, 1.05:1, 1.06:1, 1.07:1 or 1.08:1, etc.

[0013] In a second aspect, the present invention provides a method for preparing the pre-lithiated multi-element precursor described in the first aspect, comprising: Prepare or provide porous multi-component principal components; Provide liquid lithium source; The porous multi-component main component is mixed with the liquid lithium source, allowing the liquid lithium source to enter the pores, to obtain a loaded material; The loaded material is dried or cooled to form lithium source nanoparticles in the pores, thus obtaining a pre-lithiated multi-element precursor.

[0014] In the method for preparing the pre-lithiated multi-component precursor provided by this invention, a lithium source is converted into a liquid state (solution or molten liquid), and then mixed with a pre-formed porous multi-component principal component. This allows the lithium source to enter and penetrate the internal pores of the multi-component principal component. Drying or cooling then allows the penetrated liquid lithium source to crystallize in situ as nanoparticles and be loaded onto the internal pores of the matrix. Furthermore, due to mixing in the liquid phase, some lithium source also precipitates and loads on the surface of the multi-component principal component, thereby achieving a more comprehensive and uniform distribution of lithium.

[0015] As a preferred technical solution of the present invention, the method for preparing the multi-component principal component includes: mixing a transition metal element source, a complexing agent and a precipitant, and carrying out a solvothermal reaction.

[0016] Preferably, the transition metal source includes at least one of the nitrate, hydrochloride, or sulfate corresponding to at least two of the elements nickel, cobalt, and manganese.

[0017] Preferably, the complexing agent comprises ammonia; the precipitant comprises sodium hydroxide.

[0018] Preferably, the solvent medium for the solvothermal reaction includes water.

[0019] Preferably, the pH of the solvothermal reaction is 10-12, for example, 10, 10.3, 10.5, 10.8, 11.0, 11.4, 11.6, 11.8 or 12; the temperature is 120℃-180℃, for example, 120℃, 130℃, 140℃, 150℃, 160℃, 170℃ or 180℃; and the time is 60h-80h, for example, 60h, 62h, 65h, 68h, 70h, 73h, 75h, 78h or 80h.

[0020] In this invention, during the solvothermal synthesis of porous multi-component main components, pH, temperature, time, complexing agent, precipitant dropping rate, and metal salt concentration can all control the porosity and pore size. Too low a porosity or too small a pore size can lead to insufficient lithium source loading, difficulty in penetration, and easy pore blockage. Too high a porosity or too large a pore size can lead to excessive lithium source loading and easy agglomeration and growth of nanoparticles. Therefore, by rationally controlling the conditions of solvothermal synthesis, the porosity can be controlled at 30%~60%, and the pore size at 5nm~500nm, which is beneficial for uniform lithium source loading, precise loading amount, and controllable lithium source nanoparticle size.

[0021] As a preferred technical solution of the present invention, the liquid lithium source includes an aqueous lithium source solution or a molten lithium source.

[0022] Preferably, the concentration of lithium source component in the lithium source aqueous solution is 1 mol / L to 10 mol / L, for example, it can be 1 mol / L, 3 mol / L, 5 mol / L, 8 mol / L or 10 mol / L.

[0023] Preferably, the lithium source components in the liquid lithium source include lithium hydroxide (LiOH·H2O) and / or lithium carbonate (Li2CO3).

[0024] Preferably, the temperature of the lithium source melt is 50℃~80℃, for example, it can be 50℃, 55℃, 60℃, 65℃, 70℃, 75℃ or 80℃.

[0025] It should be noted that the lithium source melt described in this invention refers to lithium hydroxide monohydrate (LiOH·H2O) which rapidly releases water of crystallization at 50℃~80℃ to form a high-concentration liquid slurry (i.e., lithium source melt), thereby possessing fluidity and wettability, and can penetrate into the pores of the precursor. Therefore, the temperature range of 50℃~80℃ is the process operating temperature, not the crystal melting point, thus achieving lithium source loading in a low-temperature and gentle liquid system.

[0026] It is worth emphasizing that in the preparation method described in this invention, by controlling and adjusting the concentration or amount of lithium source in the liquid lithium source during mixing, and by adjusting the immersion time of the multi-component main component in the liquid lithium source during mixing, the loading amount of lithium source nanoparticles actually loaded on the multi-component main component can be adjusted. When the loading amount of lithium source nanoparticles makes the ratio of the total molar amount of lithium element to the total molar amount of transition metal in the multi-component main component reach (1.00~1.08):1, it means that the pre-lithiated multi-component precursor has enough lithium source to support the subsequent reaction to generate the cathode material. Therefore, the obtained pre-lithiated multi-component precursor does not need to add additional lithium source during subsequent calcination.

[0027] As a preferred embodiment of the present invention, the mixing is carried out under vacuum.

[0028] In this invention, the liquid lithium source has low surface tension and excellent wettability, allowing it to be automatically drawn into the pores through capillary action. Simultaneously, the stirring process ensures that the particles are completely immersed in the liquid lithium source, achieving full surface contact. Furthermore, applying a vacuum environment during mixing helps to expel air from the pores. Moreover, for the molten lithium source, under normal pressure, some of the molten material tends to adhere only to the surface; applying a vacuum facilitates its penetration into the interior, thus promoting more thorough internal pre-lithiation.

[0029] Preferably, the drying temperature is 100℃~300℃, for example, it can be 100℃, 130℃, 150℃, 180℃, 200℃, 230℃, 250℃, 280℃ or 300℃, etc.; the drying is carried out under vacuum, that is, vacuum drying.

[0030] In this invention, the core purpose of using drying or cooling is to cause the liquid lithium source that enters the pores to precipitate in situ inside the pores to form lithium source nanoparticles. Among them, vacuum drying is more suitable for lithium source aqueous solution systems, which achieves in-situ crystallization of lithium salt through rapid dehydration, while cooling is suitable for lithium source molten liquid systems, which solidifies the lithium source molten liquid to form nanoparticles by cooling down, thereby helping to avoid the growth of lithium source grains that lead to pore blockage and uneven distribution.

[0031] Preferably, the cooling method includes at least one of room temperature air cooling, nitrogen quenching, cold table cooling, or ice-water bath rapid cooling.

[0032] In this invention, the cooling process can be reasonably controlled according to the actual situation to ensure that uniformly sized nanoscale lithium source particles are formed in the pores, thus ensuring the structure and performance of the pre-lithiated multi-element precursor.

[0033] Thirdly, the present invention provides a method for manufacturing a multi-element cathode material, the method comprising: using a pre-lithiated multi-element precursor provided in the first aspect, or a pre-lithiated multi-element precursor obtained by the preparation method provided in the second aspect, without calcination, to obtain a multi-element cathode material.

[0034] Preferably, the manufacturing method does not add any other lithium source, and the pre-lithiated multi-element precursor is directly calcined to obtain a multi-element cathode material.

[0035] As a preferred embodiment of the present invention, the calcination is carried out in an oxygen-containing atmosphere, with a heating rate of 1℃ / min to 10℃ / min, for example, 1℃ / min, 3℃ / min, 5℃ / min, 8℃ / min, or 10℃ / min; the holding temperature is 650℃ to 850℃, for example, 650℃, 680℃, 700℃, 730℃, 750℃, 780℃, 800℃, 820℃, or 850℃; and the holding time is 6h to 24h, for example, 6h, 8h, 12h, 16h, 18h, 20h, or 24h.

[0036] Fourthly, the present invention provides a multi-element cathode material, obtained according to the manufacturing method described in the third aspect.

[0037] Fifthly, the present invention provides a battery comprising the multi-element cathode material described in the fourth aspect.

[0038] It should be noted that, due to space limitations and to avoid redundancy, this invention does not exhaustively list all point values ​​within the above numerical range, but it is not limited to the listed values ​​either; other unlisted values ​​within the above numerical range are also applicable.

[0039] Compared with existing technical solutions, the present invention has at least the following beneficial effects: The pre-lithiated multi-component precursor provided by this invention utilizes the internal pores of the multi-component main components as a nanoscale carrier for the lithium source, setting and confining the lithium source in the form of nanoparticles within the pores, thereby achieving a microscopically uniform distribution of the lithium source within the particles. This pre-lithiated multi-component precursor does not require the addition of additional lithium salts during the sintering process to form the cathode material, which is beneficial for achieving precise control of lithium and reducing surface residual alkali. Furthermore, the lithium source nanoparticles already loaded in the pores can form a lithium diffusion path from the inside out, which can significantly improve the consistency and electrochemical performance of the multi-component cathode material.

[0040] The preparation method of the pre-lithiated multi-component precursor provided by the present invention is simple, easy to implement on a large scale, and does not require solid phase mixing operations such as grinding. This avoids the destruction of the spherical morphology and primary particle stacking structure of the multi-component precursor, and is conducive to achieving uniformity and consistency of lithium distribution in the multi-component precursor in all aspects. Attached Figure Description

[0041] Figure 1 This is a scanning electron microscope (SEM) image of the pre-lithiated multi-component precursor obtained in Example 1.

[0042] Figure 2 This is a scanning electron microscope (SEM) image of the ternary cathode material obtained using the pre-lithiated multi-component precursor obtained in Example 1.

[0043] Figure 3 This is an electron probe microanalysis (EPMA) test image of the pre-lithiated multi-component precursor obtained in Example 1. Detailed Implementation

[0044] The technical solution of the present invention will be further illustrated below through specific embodiments. Those skilled in the art should understand that the embodiments described are merely illustrative of the present invention and should not be construed as limiting the invention in any way.

[0045] The scope of this invention can be defined by lower and upper limits. The selected lower and upper limits define the boundaries of a specific range. The range defined in this way can be defined by the inclusion or exclusion of endpoints. Any endpoint can be independently selected for inclusion or exclusion, and all lower and upper limits can be arbitrarily combined to form new ranges. That is, any lower limit can be combined with any upper limit to form an effective range. For example, if the ranges of 60~120 and 80~110 are listed for specific parameters, it should be understood that the ranges of 60~110 and 80~120 also fall within the scope of this invention. In addition, if the minimum range values ​​1 and 2 are listed, and the maximum range values ​​3, 4 and 5 are also listed, then all ranges of 1~3, 1~4, 1~5, 2~3, 2~4 and 2~5 fall within the scope of this invention. In this invention, the numerical range "a~b" represents a shortened representation of any combination of real numbers between a and b, where a and b are both real numbers. For example, the numerical range "0~5" means that all real numbers between 0 and 5 have been fully listed in this document, and "0~5" is only a shortened representation of this set of numerical combinations. When a parameter is expressed as an integer ≥2, it is equivalent to listing positive integers that meet the requirements, such as 2, 3, 4, 5, 6, 7, 8, 9, 10, etc. When a parameter is expressed as an integer selected from "2~10", it is equivalent to listing any integer among 2, 3, 4, 5, 6, 7, 8, 9, and 10.

[0046] In this invention, "a combination of at least two" refers to a quantity greater than or equal to 2 unless otherwise specified. For example, "any one or a combination of at least two" means that any one of the listed items can be selected, or a combination of at least two of the listed items formed in a manner that does not conflict and enables the implementation of this invention. In this invention, unless otherwise specified, the features or solutions corresponding to "and / or" cover any one of two or more related listed items, as well as any and all combinations of the related listed items. The arbitrary and all combinations include any two related listed items, any more related listed items, or a combination of all related listed items. For example, "A and / or B" means a set consisting of A, B, and combinations of A and B, where "containing A and / or B" can be understood, depending on the context of the statement, as containing A, containing B, or simultaneously containing both A and B. In this invention, "optional" means that the corresponding feature, component, step or solution is not necessary, that is, it is selected from either "with" or "without". If there are multiple "optional" limitations in a technical solution, unless otherwise specified and there is no technical conflict or mutual constraint, each "optional" limitation is independent and does not affect the others.

[0047] In this invention, technical features or solutions described using open-ended terms such as "comprising" or "including" do not exclude additional non-conflicting elements beyond the listed elements unless otherwise specified. They are considered to disclose both closed-ended features or solutions consisting solely of the listed elements and open-ended features or solutions that may include additional non-conflicting elements beyond the listed elements. For example, if A includes a1, a2, and a3, unless otherwise specified, this means that A can consist only of a1, a2, and a3, or it can include other non-conflicting elements based on a1, a2, and a3. This corresponds to the disclosure of technical solutions such as "A consists of a1, a2, and a3," "A is selected from a1, a2, and a3," and "A not only includes a1, a2, and a3, but may also include other non-conflicting elements." All embodiments and optional embodiments of this invention, unless otherwise specified and without technical conflict, can be combined to form new technical solutions, and such combinations fall within the scope of this invention. The term "embodiment" as used in this invention means that a specific feature, structure, or characteristic described in connection with an embodiment may be included in at least one embodiment or implementation of the invention. The appearance of this phrase in various locations throughout the specification does not necessarily refer to the same embodiment, nor is it an independent or alternative embodiment mutually exclusive with other embodiments. Those skilled in the art will understand, explicitly and implicitly, that the embodiments described in this invention can be combined with other embodiments that do not conflict with the technology. The ordinal numbers "first," "second," "third," and "fourth," etc., used in the expressions "first aspect," "second aspect," "third aspect," and "fourth aspect" in this invention are for descriptive purposes only and should not be construed as indicating or implying relative importance or quantity, nor should they be construed as implicitly specifying the importance or quantity of the indicated technical features. They serve only as a non-exhaustive enumeration and do not constitute a closed limitation on quantity.

[0048] In this invention, the order in which the steps are written in the methods described in the various embodiments does not imply a strict execution order. The actual execution order of each step should be determined based on its function and possible internal logic. Unless otherwise specified, all steps of this invention can be executed in the order they are written, or in any order without technical conflict. For example, if the method includes steps (a) and (b), it means that the method may include steps (a) and (b) executed sequentially, or it may include steps (b) and (a) executed sequentially. If the method also includes step (c), then step (c) can be added to the method in any conflict-free order, including but not limited to the execution order of steps (a), (b), and (c), steps (a), (c), and (b), steps (c), (a), and (b), etc.

[0049] Example 1 This embodiment provides a pre-lithiation multi-component precursor, which consists of a porous multi-component principal component and lithium source nanoparticles disposed within the pores; the chemical formula of the multi-component principal component is Ni. 0.8 Co 0.1 Mn 0.1 (OH)2, wherein the lithium source nanoparticles are LiOH·H2O nanoparticles; The preparation method of the pre-lithiated multi-component precursor includes: S1. Using ammonia as a complexing agent and sodium hydroxide as a precipitant, Ni(NO3)2, Co(NO3)2, and Mn(NO3)2 were subjected to a hydrothermal reaction at 120℃ and pH=10~12 for 60h to obtain a porous ternary precursor main component; the porosity of the porous ternary precursor main component was 45%, and the pore size range was 50nm~280nm. S2. Heat the lithium source LiOH·H2O to 80℃ to completely melt it, and it becomes a liquid lithium source. Then, preheat the main component of the ternary precursor to 70℃, and then immerse it in the liquid lithium source. Keep it warm and stir for 1 hour to allow the liquid lithium source to fully penetrate into the pores of the particles and obtain the loaded material. S3. The loading material is rapidly cooled to room temperature (25°C), and the liquid lithium source crystallizes and precipitates in the pores to generate lithium source nanoparticles, thus obtaining a pre-lithiated ternary precursor. The loading amount of lithium source nanoparticles is adjusted by controlling the impregnation time in step S2, so that the ratio of the total molar amount of lithium element in the pre-lithiated ternary precursor to the total molar amount of transition metals nickel, cobalt and manganese is 1.08:1.

[0050] Example 2 This embodiment provides a pre-lithiated multi-element precursor, the preparation method of which includes: S1. Provide the porous ternary precursor principal component obtained in step S1 of Example 1; S2. Prepare a lithium source aqueous solution by mixing lithium source LiOH·H2O with water as a liquid lithium source with a lithium source concentration of 5 mol / L. Then immerse the liquid lithium source in the solution and keep it warm and stirred for 2 hours to allow the liquid lithium source to fully penetrate into the pores of the particles and obtain the loaded material. S3. The loading material is vacuum dried at 200°C to allow the liquid lithium source to crystallize and precipitate in the pores, generating lithium source nanoparticles and obtaining a pre-lithiated ternary precursor. The loading amount of lithium source nanoparticles is adjusted by controlling the impregnation time in step S2 so that the ratio of the total molar amount of lithium element in the pre-lithiated ternary precursor to the total molar amount of transition metals nickel, cobalt and manganese is 1.08:1.

[0051] Example 3 The difference from Example 1 is that at least one of the temperature, pH and time of the hydrothermal reaction in step S1 is adjusted so that the porosity of the ternary precursor main component is 30% and the pore size range is 5nm~100nm. Apart from the above, the other conditions are exactly the same as those in Example 1.

[0052] Example 4 The difference from Example 1 is that at least one of the temperature, pH and time of the hydrothermal reaction in step S1 is adjusted so that the porosity of the ternary precursor main component is 60% and the pore size range is 200nm~500nm. Apart from the above, the other conditions are exactly the same as those in Example 1.

[0053] Example 5 The difference from Example 1 is that the impregnation time in step S2 is adjusted to regulate the loading of lithium source nanoparticles, so that the ratio of the total molar amount of lithium element in the pre-lithiated ternary precursor to the total molar amount of transition metals nickel, cobalt and manganese is 1.00:1. Apart from the above, the other conditions are exactly the same as in Example 1.

[0054] Example 6 The difference from Example 1 is that the impregnation time in step S2 is adjusted to regulate the loading of lithium source nanoparticles, so that the ratio of the total molar amount of lithium element in the pre-lithiated ternary precursor to the total molar amount of transition metals nickel, cobalt and manganese is 1.04:1. Apart from the above, the other conditions are exactly the same as in Example 1.

[0055] Comparative Example 1 This comparative example provides a ternary precursor, the preparation method of which includes: The porous ternary precursor main component obtained in step S1 of Example 1 is provided. It is mixed with lithium source LiOH·H2O powder, and the ratio of the total molar amount of lithium element in the lithium source to the total molar amount of transition metals nickel, cobalt and manganese in the ternary precursor is controlled to be 1.08:1. The mixture is placed in a ball mill jar and mixed at 200 rpm for 2 hours to obtain a mechanically mixed material, which is used as the ternary precursor.

[0056] Comparative Example 2 This comparative example provides a ternary precursor, the preparation method of which includes: using ammonia water as a complexing agent, sodium hydroxide as a precipitant, and LiOH·H2O as a lithium source as a lithium source, and mixing it simultaneously with Ni(NO3)2, Co(NO3)2, and Mn(NO3)2, controlling the amount according to the ratio of the total molar amount of lithium element in the lithium source to the total molar amount of transition metals nickel, cobalt and manganese at 1.08:1, and then carrying out a hydrothermal reaction at 120℃ and pH=10~12 for 60h to obtain the ternary precursor.

[0057] Characterization and testing: The precursors obtained in the examples and comparative examples were heated to 780°C at a heating rate of 2°C / min under an oxygen atmosphere, and sintered for 12 hours. After natural cooling, they were crushed and sieved to obtain the final ternary cathode material.

[0058] I. Figure 1 and Figure 2 The images show scanning electron microscope (SEM) test images of the pre-lithiated multi-element precursor obtained in Example 1 and the ternary cathode material prepared from it. As can be seen from the images, the precursor particles are relatively intact, and the cathode material prepared from them exhibits a morphology of primary sheet structure.

[0059] Figure 3 This is an electron probe microanalysis (EPMA) test image of the pre-lithiated multi-component precursor obtained in the preparation method of Example 1. The image shows that the green lithium source was successfully loaded into the pores of the main component of the multi-component precursor.

[0060] II. The following tests were performed on the ternary cathode material: 1) Residual alkali content test: The free lithium content (including Li2CO3 and LiOH) on the surface of the cathode material is tested by acid-base titration. 2) Electrochemical performance testing: The positive electrode material, conductive carbon black, and PVDF were mixed at a mass ratio of 90:5:5 to form an electrode sheet, which was then assembled into a CR2032 coin cell using a lithium foil as the counter electrode. The specific capacity at 0.1C initial charge / discharge and the capacity retention after 100 cycles at 1C were tested within a voltage range of 2.8V to 4.3V.

[0061] The test results are recorded in Table 1.

[0062] Table 1 As can be seen from Table 1: Compared to Comparative Examples 1-2, in Examples 1-6, the lithium source is uniformly loaded within the pores of the precursor. During high-temperature sintering, the lithium elements are fully integrated into the crystal lattice, reducing the precipitation of free lithium and side reactions with CO2 and H2O, resulting in low residual alkali. Simultaneously, the regular crystal lattice and high lithium utilization rate suppress interfacial side reactions and structural degradation, leading to superior capacity and cycle performance. Comparative Examples 1-2 did not employ this pre-lithiation process; the lithium source only adhered to the surface, making it prone to agglomeration and segregation. The enrichment of free lithium resulted in higher residual alkali, which in turn covered active sites, exacerbated structural damage, and degraded performance. The internal performance gradient in Examples 1-6 can originate from subtle differences in the uniformity of pre-lithiation loading and doping levels.

[0063] In summary, the pre-lithiated multi-component precursor provided by this invention utilizes the internal pores of the multi-component main components as a nanoscale carrier for the lithium source, setting and confining the lithium source in the form of nanoparticles within the pores, thereby achieving a microscopically uniform distribution of the lithium source within the particles. This pre-lithiated multi-component precursor eliminates the need for additional lithium salts during the sintering process to form the cathode material, facilitating precise control of lithium and reducing surface residual alkali. Furthermore, the lithium source nanoparticles already loaded within the pores can form an inward-to-outward lithium diffusion path, significantly improving the consistency and electrochemical performance of the multi-component cathode material.

[0064] The preferred embodiments of the present invention have been described in detail above. However, the present invention is not limited to the specific details in the above embodiments. Within the scope of the technical concept of the present invention, various simple modifications can be made to the technical solution of the present invention, and these simple modifications all fall within the protection scope of the present invention.

[0065] It should also be noted that the various specific technical features described in the above specific embodiments can be combined in any suitable manner without contradiction. In order to avoid unnecessary repetition, the present invention will not describe the various possible combinations separately.

[0066] Furthermore, various different embodiments of the present invention can be combined in any way, as long as they do not violate the spirit of the present invention, they should also be regarded as the content disclosed by the present invention.

Claims

1. A pre-lithiated multi-element precursor, characterized in that, The pre-lithiated multi-component precursor includes at least two transition metal elements and has pores; the pre-lithiated multi-component precursor also includes lithium source nanoparticles disposed in the pores of the multi-component precursor.

2. The pre-lithiated multi-element precursor according to claim 1, characterized in that, The porosity of the multi-component principal component is 30%~60%, and the pore size ranges from 5nm to 500nm. Preferably, the multi-component principal component includes at least one of hydroxide, carbonate, or oxide; Preferably, the lithium source nanoparticles comprise lithium hydroxide and / or lithium carbonate; Preferably, the size range of the lithium source nanoparticles is 2nm~200nm; Preferably, the ratio of the total molar amount of lithium in the lithium source nanoparticles to the total molar amount of transition metal elements in the multi-component principal components is (1.00~1.08):

1.

3. A method for preparing the pre-lithiated multi-component precursor according to claim 1 or 2, characterized in that, include: Prepare or provide porous multi-component principal components; Provide liquid lithium source; The porous multi-component main component is mixed with the liquid lithium source, allowing the liquid lithium source to enter the pores, to obtain a loaded material; The loaded material is dried or cooled to form lithium source nanoparticles in the pores, thus obtaining a pre-lithiated multi-element precursor.

4. The method for preparing the pre-lithiated multi-component precursor according to claim 3, characterized in that, The method for preparing the multi-component principal component includes: mixing a transition metal element source, a complexing agent and a precipitant, and carrying out a solvothermal reaction; Preferably, the transition metal source includes at least one of the nitrate, hydrochloride, or sulfate corresponding to at least two of the elements nickel, cobalt, and manganese; Preferably, the solvent medium for the solvothermal reaction includes water; Preferably, the pH of the solvothermal reaction is 10-12, the temperature is 120℃-180℃, and the time is 60h-80h.

5. The method for preparing the pre-lithiated multi-component precursor according to claim 3 or 4, characterized in that, The liquid lithium source includes an aqueous lithium source solution or a molten lithium source solution; Preferably, the concentration of the lithium source in the lithium source aqueous solution is 1 mol / L to 10 mol / L; Preferably, the lithium source component in the liquid lithium source includes LiOH·H2O; Preferably, the temperature of the lithium source molten liquid is 50℃~80℃.

6. The method for preparing the pre-lithiated multi-component precursor according to any one of claims 3-5, characterized in that, The mixing is carried out under vacuum; Preferably, the drying temperature is 100℃~300℃; the drying is carried out under vacuum; Preferably, the cooling method includes at least one of room temperature air cooling, nitrogen quenching, cold table cooling, or ice-water bath rapid cooling.

7. A method for manufacturing a multi-element cathode material, characterized in that, The manufacturing method includes: calcining the pre-lithiated multi-element precursor provided by claim 1 or 2, or the pre-lithiated multi-element precursor obtained by the preparation method provided by any one of claims 3-6, to obtain a multi-element cathode material.

8. The method for manufacturing the multi-element cathode material according to claim 7, characterized in that, The calcination is carried out in an oxygen-containing atmosphere, with a heating rate of 1℃ / min to 10℃ / min, a holding temperature of 650℃ to 850℃, and a holding time of 6h to 24h.

9. A multi-element cathode material, characterized in that, Obtained by the manufacturing method according to claim 7 or 8.

10. A battery, characterized in that, It contains the multi-element cathode material as described in claim 9.

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