High BET lithium-rich manganese-based binary precursor and preparation method and application thereof

Abstract

The invention discloses a high-BET lithium-rich manganese-based binary precursor as well as a preparation method and application thereof. The preparation method comprises the following steps: injecting a nickel-manganese mixed salt solution, a precipitant solution and a complexing agent solution into a reaction base solution in a parallel flow manner to carry out a co-precipitation reaction, stopping introducing protective gas after feeding is started, and introducing air at a first flow rate to carry out a nucleation reaction; after the nucleation reaction is finished, introducing air at a second flow rate; after the particle size reaches the first target particle size, air introduction is stopped, and protective gas is introduced at a third flow speed; after the particle size reaches a second target particle size, feeding is stopped, and a high BET lithium-rich manganese-based binary precursor is obtained through washing and drying; wherein the first flow velocity is smaller than the second flow velocity. According to the preparation method disclosed by the invention, the oxidation degree of the slurry is controlled by controlling the reaction atmospheres at different stages in the precursor preparation process based on a coprecipitation method and matching with the corresponding gas flow rate, so that the micro-powder condition on the surface of the precursor can be well improved, and the precipitate-free high-BET lithium-rich manganese-based precursor is successfully prepared.

Description

Technical Field

[0001] The present invention relates to the technical field of lithium ion batteries, and in particular to a high-BET lithium-rich manganese-based binary precursor and a preparation method and application thereof. Background Art

[0002] Lithium-ion batteries are widely used in mobile phones, laptops, and some storage products due to their high specific energy, pollution-free, and long cycle life. They are also the power source for electric vehicles and power supply equipment. A series of studies on lithium-ion batteries have become a hot topic in the new energy industry in recent years. The control of micropowder in products is a process that needs to be strictly controlled in the production process of lithium-ion batteries. It can not only come from the raw materials that make up lithium-ion batteries, but also from foreign dust in the environment and mechanical dust introduced by equipment friction in the process. The content of micropowder directly determines the storage life of the battery. What is more serious is that the presence of micropowder may cause internal short circuit of the battery, causing the battery to heat up during the charging and discharging process, and eventually cause serious safety accidents such as battery explosion and electric vehicle self-ignition. The presence of micropowder affects the self-discharge of the battery in two ways: first, it increases the side reactions and micro-short circuits inside the battery, and as the amount of micropowder increases, the impact becomes more serious; second, it causes the battery capacity to decay and the internal resistance to increase during storage, accompanied by phenomena such as flatulence. Therefore, in actual production, the generation of micropowder in each process needs to be strictly controlled.

[0003] As one of the four core materials of the battery, the positive electrode material restricts the comprehensive performance of the battery. The positive electrode material can inherit the morphology and structural characteristics of the precursor, so the structure and preparation process of the precursor have a crucial influence on the performance of the positive electrode material. Due to the high manganese content in the lithium-rich manganese-based binary precursor, the oxide formed after manganese oxidation during the precursor reaction will precipitate on the surface of the precursor, and then after washing, drying and other processes, it will form block precipitation on the surface (that is, form micropowder). In the existing preparation process of lithium-rich manganese-based binary precursors, severe oxidation will lead to an increase in manganese precipitates on the surface of the precursor, and insufficient oxidation will lead to a low BET of the precursor.

[0004] Therefore, the preparation of high BET lithium-rich manganese-based binary precursors without precipitates is currently a difficult problem. Summary of the invention

[0005] The purpose of the present invention is to overcome the above-mentioned technical deficiencies, propose a high BET lithium-rich manganese-based binary precursor and its preparation method and application, and solve the technical problem that the degree of oxidation is difficult to control during the preparation of the lithium-rich manganese-based binary precursor in the prior art, resulting in the inability to obtain a high BET lithium-rich manganese-based binary precursor without precipitates.

[0006] In a first aspect, the present invention provides a method for preparing a high BET lithium-rich manganese-based binary precursor, comprising the following steps: Prepare nickel-manganese mixed salt solution, precipitant solution, complexing agent solution and reaction base solution; A nickel-manganese mixed salt solution, a precipitant solution and a complexing agent solution are injected into a reaction base liquid in parallel to carry out a co-precipitation reaction. After the feeding starts, the introduction of protective gas is stopped, and air is introduced at a first flow rate to carry out a nucleation reaction; after the nucleation reaction is completed, air is introduced at a second flow rate; after the particle size reaches a first target particle size, the introduction of air is stopped, and a protective gas is introduced at a third flow rate; after the particle size reaches a second target particle size, the feeding is stopped, and a high-BET lithium-rich manganese-based binary precursor is obtained through washing and drying; wherein the first flow rate is less than the second flow rate.

[0007] In a second aspect, the present invention provides a high BET lithium-rich manganese-based binary precursor, and the high BET lithium-rich manganese-based binary precursor is obtained by the preparation method of the high BET lithium-rich manganese-based binary precursor provided by the first aspect of the present invention.

[0008] In a third aspect, the present invention provides an application of a high BET lithium-rich manganese-based binary precursor, and the high BET lithium-rich manganese-based binary precursor is used to prepare a lithium-rich manganese-based binary positive electrode material.

[0009] Compared with the prior art, the beneficial effects of the present invention include: The present invention is based on the co-precipitation method, by controlling the reaction atmosphere at different stages in the precursor preparation process and coordinating with the corresponding gas flow rate to control the oxidation degree of the slurry, which can well improve the micro-powder situation on the precursor surface and successfully prepare a high-BET lithium-rich manganese-based precursor without precipitates. BRIEF DESCRIPTION OF THE DRAWINGS

[0010] Figure 1 is a SEM image of the high BET lithium-rich manganese-based binary precursor in Example 1 of the present invention; Figure 2 is a SEM image of the high BET lithium-rich manganese-based binary precursor in Example 2 of the present invention; Figure 3 is a SEM image of the high BET lithium-rich manganese-based binary precursor in Example 3 of the present invention; Figure 4 This is a SEM image of the high BET lithium-rich manganese-based binary precursor in Comparative Example 1 of the present invention; Figure 5 This is a SEM image of the high BET lithium-rich manganese-based binary precursor in Comparative Example 2 of the present invention; Figure 6 This is a SEM image of the high BET lithium-rich manganese-based binary precursor in Comparative Example 3 of the present invention; Figure 7This is a SEM image of the high BET lithium-rich manganese-based binary precursor in Comparative Example 4 of the present invention; Figure 8 This is a SEM image of the high BET lithium-rich manganese-based binary precursor in Comparative Example 5 of the present invention; Fig. 9 This is a SEM image of the high BET lithium-rich manganese-based binary precursor in Comparative Example 6 of the present invention. DETAILED DESCRIPTION

[0011] In order to make the purpose, technical solution and advantages of the present invention more clearly understood, the present invention is further described in detail below in conjunction with the accompanying drawings and embodiments. It should be understood that the specific embodiments described herein are only used to explain the present invention and are not intended to limit the present invention.

[0012] In a first aspect, the present invention provides a method for preparing a high BET lithium-rich manganese-based binary precursor, comprising the following steps: S1, preparing nickel-manganese mixed salt solution, precipitant solution, complexing agent solution and reaction base solution; S2. Injecting the nickel-manganese mixed salt solution, the precipitant solution and the complexing agent solution into the reaction base liquid in parallel for a co-precipitation reaction. After the feeding starts, the introduction of the protective gas is stopped, and air is introduced at a first flow rate for a nucleation reaction; after the nucleation reaction is completed, the air is introduced at a second flow rate; after the particle size reaches the first target particle size, the air is stopped from being introduced, and the protective gas is introduced at a third flow rate; after the particle size reaches the second target particle size, the feeding is stopped, and a high-BET lithium-rich manganese-based binary precursor is obtained through washing and drying; wherein the first flow rate is less than the second flow rate.

[0013] In the coprecipitation reaction process of the present invention, the introduction of protective gas is stopped after the feeding starts, and air is introduced at a relatively low flow rate to control the environment of the precursor during nucleation to be in a slightly oxidized state, making the interior loose and porous. After reaching the growth stable period, the ventilation rate is increased, and a large amount of air is introduced to fully oxidize it to improve BET; when the BET of the material tends to be stable (the particle size reaches 8-9μm), the introduction of air is stopped and protective gas is introduced to prevent excessive oxidation from producing small particles of micropowder. Different from the conventional low-ammonia process for preparing high-BET precursors, the present invention controls the oxidation process to form a loose and porous structure inside to improve BET, while preventing the precipitation of manganese oxides from affecting the performance of the back-end battery.

[0014] In this embodiment, in the nickel-manganese mixed salt solution, the molar ratio of nickel to manganese is 1:(1.5-4).

[0015] In this embodiment, the concentration of the nickel-manganese mixed salt in the nickel-manganese mixed salt solution is 85-125 g / L.

[0016] In this embodiment, the nickel-manganese mixed salt solution is obtained by uniformly mixing nickel salt and manganese salt in water.

[0017] Preferably, the nickel salt is at least one of nickel sulfate, nickel chloride, nickel nitrate and nickel acetate.

[0018] Preferably, the manganese salt is at least one of manganese sulfate, manganese chloride, manganese nitrate and manganese acetate.

[0019] In this embodiment, the mass fraction of the precipitant solution is 28%-32%, including but not limited to 28%, 29%, 30%, 31%, 32%, etc.

[0020] In this embodiment, the mass fraction of the complexing agent solution is 16%-20%, including but not limited to 16%, 17%, 18%, 19%, 20%, etc.

[0021] In this embodiment, in the reaction base liquid, the concentration of the precipitant is 0.04%-0.08%, and the concentration of the complexing agent is 1-1.5 g / L.

[0022] In this embodiment, the preparation process of the reaction base liquid includes: adding 4m 3 Pure water, 6-10L of precipitant solution with a mass fraction of 28%-32% and 4-6kg of complexing agent are mixed evenly to obtain the reaction base liquid.

[0023] In this embodiment, before preparing the reaction base liquid, a protective gas is introduced into the reactor in advance to prevent the reaction base liquid from being oxidized.

[0024] Preferably, the protective gas is introduced into the reactor in advance for 1-3 hours.

[0025] In this embodiment, the precipitant is sodium hydroxide and the complexing agent is oxalic acid.

[0026] In this embodiment, the first flow rate is 2-6m 3 / h, including but not limited to 2m 3 / h、3m 3 / h、4m 3 / h、5m 3 / h、6m 3 / h, etc.

[0027] In this embodiment, the time of the nucleation reaction is 22-26 hours, including but not limited to 22 hours, 23 hours, 24 hours, 25 hours, 26 hours, etc.

[0028] In this embodiment, the second flow rate is 6-12m 3 / h, including but not limited to 6m 3 / h、7m 3 / h、8m 3 / h、9m 3 / h、10m3 / h、11m 3 / h、12m 3 / h, etc.

[0029] In this embodiment, the first target particle size D50 is 8-9 μm, including but not limited to 8 μm, 8.5 μm, 9 μm, etc. Within this particle size range, the material BET has stabilized. If the first target particle size is too high, the time to reach the shutdown particle size will be shortened, and there is a risk of small particles being generated during continuous oxidation; if the first target particle size is too low, internal oxidation is insufficient and BET does not meet the requirements.

[0030] In this embodiment, the third flow rate is 0.5-2m 3 / h, including but not limited to 0.5m 3 / h、1m 3 / h、1.5m 3 / h、2m 3 / h, etc.

[0031] In this embodiment, the second target particle size D50 is 10-11 μm, including but not limited to 10 μm, 10.5 μm, 11 μm, etc.

[0032] The present invention does not limit the type of protective gas, and those skilled in the art can select it according to actual conditions. In some specific embodiments of the present invention, the protective atmosphere is at least one of nitrogen, helium, argon, neon, and krypton.

[0033] In this embodiment, during the coprecipitation reaction, every 4-5m 3 The reaction base liquid meter, the flow rate of nickel-manganese mixed salt solution is 280-320L / h, the flow rate of precipitant solution is 100-120L / h, and the flow rate of complexing agent solution is 15-25L / h.

[0034] In this embodiment, during the coprecipitation reaction, the pH is controlled to be 9.9-10.2, and the concentration of the complexing agent is controlled to be 1-3 g / L.

[0035] In this embodiment, during the coprecipitation reaction, the reaction temperature is 60-70°C.

[0036] In this embodiment, during the coprecipitation reaction, the stirring rate is 200-320 r / min.

[0037] In a second aspect, the present invention provides a high BET lithium-rich manganese-based binary precursor, and the high BET lithium-rich manganese-based binary precursor is obtained by the preparation method of the high BET lithium-rich manganese-based binary precursor provided by the first aspect of the present invention.

[0038] In a third aspect, the present invention provides an application of a high BET lithium-rich manganese-based binary precursor, and the high BET lithium-rich manganese-based binary precursor is used to prepare a lithium-rich manganese-based binary positive electrode material.

[0039] Example 1 (1) Mix nickel sulfate, manganese sulfate and water and stir them thoroughly for 3 hours to obtain a nickel-manganese mixed salt solution (the molar ratio of nickel to manganese is 3:7, and the concentration of the nickel-manganese mixed salt is 110 g / L); disperse sodium hydroxide in water to prepare a precipitant solution with a mass fraction of 30%; disperse oxalic acid in water to prepare a complexing agent solution with a mass fraction of 18%; introduce nitrogen into the reactor in advance for 2 hours, and add 4 m 3 Pure water, 8L of base alkali (sodium hydroxide solution with a mass fraction of 30%) and 5kg of oxalic acid were added into the reactor to prepare the reaction base liquid.

[0040] (2) Add the nickel-manganese mixed salt solution, precipitant solution, and complexing agent solution into the reactor prepared with the reaction base solution at flow rates of 300 L / h, 100-120 L / h, and 15-25 L / h, respectively, to carry out a co-precipitation reaction. The pH of the reaction system is controlled to be 9.9-10.2 and the oxalate concentration is controlled to be 1-3 g / L by adjusting the flow rates of the precipitant solution and the complexing agent solution. After starting to feed, stop introducing nitrogen into the reactor and continue to heat the reactor at 3 m / s. 3 Air was introduced into the reactor at a flow rate of 10 m / h for nucleation reaction for 24 hours. 3 / h flow rate into the reactor; when the particle size reaches 8.5μm, stop passing air into the reactor and continue at 1m 3 / h flow rate of nitrogen into the reactor; stop feeding when the particle size reaches 10.5μm, and finally wash and dry to obtain a high BET lithium-rich manganese-based binary precursor. During the coprecipitation reaction, the temperature is 65°C and the stirring rate is 280r / min.

[0041] Example 2 (1) Mix nickel sulfate, manganese sulfate and water and stir them thoroughly for 3 hours to obtain a nickel-manganese mixed salt solution (the molar ratio of nickel to manganese is 4:6, and the concentration of the nickel-manganese mixed salt is 110 g / L); disperse sodium hydroxide in water to prepare a precipitant solution with a mass fraction of 30%; disperse oxalic acid in water to prepare a complexing agent solution with a mass fraction of 18%; introduce nitrogen into the reactor in advance for 2 hours, and add 4 m 3 Pure water, 8L of base alkali (sodium hydroxide solution with a mass fraction of 30%) and 5kg of oxalic acid were added into the reactor to prepare the reaction base liquid.

[0042] (2) Add the nickel-manganese mixed salt solution, precipitant solution, and complexing agent solution into the reactor prepared with the reaction base solution at flow rates of 300 L / h, 100-120 L / h, and 15-25 L / h, respectively, to carry out a co-precipitation reaction. The pH of the reaction system is controlled to be 9.9-10.2 and the oxalate concentration is controlled to be 1-3 g / L by adjusting the flow rates of the precipitant solution and the complexing agent solution. After starting the feeding, stop introducing nitrogen into the reactor and continue at 4 m 3 Air was introduced into the reactor at a flow rate of 12 m / h for nucleation reaction for 24 hours. 3 / h flow rate into the reactor; when the particle size reaches 8.5μm, stop passing air into the reactor and continue at 1m 3 / h flow rate of nitrogen into the reactor; stop feeding when the particle size reaches 10.5μm, and finally wash and dry to obtain a high BET lithium-rich manganese-based binary precursor. During the coprecipitation reaction, the temperature is 65°C and the stirring rate is 280r / min.

[0043] Example 3 (1) Mix nickel sulfate, manganese sulfate and water and stir them thoroughly for 3 hours to obtain a nickel-manganese mixed salt solution (the molar ratio of nickel to manganese is 2.5:7.5, and the concentration of the nickel-manganese mixed salt is 110 g / L); disperse sodium hydroxide in water to prepare a precipitant solution with a mass fraction of 30%; disperse oxalic acid in water to prepare a complexing agent solution with a mass fraction of 18%; introduce nitrogen into the reactor in advance for 2 hours, and add 4 m 3 Pure water, 8L of base alkali (sodium hydroxide solution with a mass fraction of 30%) and 5kg of oxalic acid were added into the reactor to prepare the reaction base liquid.

[0044] (2) Add the nickel-manganese mixed salt solution, precipitant solution, and complexing agent solution into the reactor prepared with the reaction base solution at flow rates of 300 L / h, 100-120 L / h, and 15-25 L / h, respectively, to carry out a co-precipitation reaction. The pH of the reaction system is controlled to be 9.9-10.2 and the oxalate concentration is controlled to be 1-3 g / L by adjusting the flow rates of the precipitant solution and the complexing agent solution. After starting the feeding, stop introducing nitrogen into the reactor and continue at 5 m 3 Air was introduced into the reactor at a flow rate of 7m / h for nucleation reaction for 24 hours. 3 / h flow rate into the reactor; when the particle size reaches 8.5μm, stop passing air into the reactor and continue at 1m 3 / h flow rate of nitrogen into the reactor; stop feeding when the particle size reaches 10.5μm, and finally wash and dry to obtain a high BET lithium-rich manganese-based binary precursor. During the coprecipitation reaction, the temperature is 65°C and the stirring rate is 280r / min.

[0045] Comparative Example 1 Compared with Example 1, the only difference is that during the nucleation reaction, the nitrogen gas into the reactor was stopped and the nitrogen gas was kept at 1 m 3 Air was introduced into the reactor at a flow rate of / h for 24 hours.

[0046] Comparative Example 2 Compared with Example 1, the only difference is that during the nucleation reaction, the nitrogen gas into the reactor was stopped and the nitrogen gas was kept at 8 m 3 Air was introduced into the reactor at a flow rate of / h for 24 hours.

[0047] Comparative Example 3 Compared with Example 1, the only difference is that after the nucleation reaction is completed, before the particle size reaches 8.5 μm, the particle size is 5 μm. 3 Air was introduced into the reactor at a flow rate of / h.

[0048] Comparative Example 4 Compared with Example 1, the only difference is that after the nucleation reaction is completed, the particle size reaches 8.5 μm, and the particle size is 15 μm. 3 Air was introduced into the reactor at a flow rate of / h.

[0049] Comparative Example 5 Compared with Example 1, the only difference is that after the particle size reaches 8.5 μm, the air is stopped from entering the reactor and the air is cooled to 0.1 μm. 3 Nitrogen was introduced into the reactor at a flow rate of / h.

[0050] Comparative Example 6 Compared with Example 1, the only difference is that after the particle size reaches 8.5 μm, the air is stopped from entering the reactor and the air is cooled to 3 m 3 Nitrogen was introduced into the reactor at a flow rate of / h.

[0051] Performance Testing The performance of the lithium-rich manganese-based binary precursors prepared in the above examples and comparative examples was tested. The test results are shown in Tables 1 and Figure 1-9 .

[0052] Table 1

[0053] Please refer to Table 1 and Figure 1-3 , through Table 1 and Figure 1-3 It can be seen that the lithium-rich manganese-based binary precursor prepared in the embodiment of the present invention has a high specific surface area and no small particles or lumps of micropowder are precipitated on the surface.

[0054] See also Figure 4As shown in Table 1, compared with Example 1, during the nucleation reaction of Comparative Example 1, the flow rate of air introduced into the reactor was too low, the degree of oxidation during nucleation was insufficient, the interior was relatively dense, and the BET was low.

[0055] See also Figure 5 As shown in Table 1, compared with Example 1, during the nucleation reaction of Comparative Example 2, the flow rate of air introduced into the reactor was too high, and excessive air was introduced during the nucleation period, resulting in a large number of small particles in the reaction system.

[0056] See also Figure 6 As shown in Table 1, compared with Example 1, before the particle size of Comparative Example 3 reached 8.5 μm, the flow rate of air introduced into the reactor was too low, the degree of oxidation during the growth period was insufficient, the interior was relatively dense, and the BET was low.

[0057] See also Figure 7 As shown in Table 1, compared with Example 1, before the particle size of Comparative Example 4 reached 8.5 μm, the flow rate of air introduced into the reactor was too high, the degree of oxidation during the growth period was excessive, a large amount of fine powder was generated, and the BET was too high.

[0058] See also Figure 8 As shown in Table 1, compared with Example 1, after the particle size of Comparative Example 5 reached 8.5 μm, the flow rate of nitrogen introduced into the reactor was too low, the amount of nitrogen introduced was small, and there was a phenomenon of local overoxidation, resulting in the precipitation of a small amount of micropowder.

[0059] See also Fig. 9 As shown in Table 1, compared with Example 1, after the particle size of Comparative Example 6 reaches 8.5 μm, the flow rate of nitrogen introduced into the reactor is too high, and excess nitrogen has no obvious effect. For cost considerations, the use of excess nitrogen is minimized.

[0060] The specific implementation of the present invention described above does not constitute a limitation on the protection scope of the present invention. Any other corresponding changes and modifications made based on the technical concept of the present invention should be included in the protection scope of the claims of the present invention.

Claims

1. A method for preparing a high BET lithium-rich manganese-based binary precursor, characterized in that: The following steps are involved: Prepare nickel-manganese mixed salt solution, precipitant solution, complexing agent solution and reaction base solution; The nickel-manganese mixed salt solution, the precipitant solution and the complexing agent solution are injected into the reaction base liquid in parallel to carry out a co-precipitation reaction, and after the feeding starts, the introduction of the protective gas is stopped, and air is introduced at a first flow rate to carry out a nucleation reaction; after the nucleation reaction is completed, the air is introduced at a second flow rate; after the particle size reaches the first target particle size, the introduction of the air is stopped, and the protective gas is introduced at a third flow rate; after the particle size reaches the second target particle size, the feeding is stopped, and a high-BET lithium-rich manganese-based binary precursor is obtained through washing and drying; Wherein, the first flow rate is smaller than the second flow rate.

2. The method for preparing a high BET lithium-rich manganese-based binary precursor according to claim 1, characterized in that: In the nickel-manganese mixed salt solution, the molar ratio of nickel to manganese is 1:(1.5-4); and / or, The concentration of nickel-manganese mixed salt is 85-125 g / L; and / or, The nickel salt is at least one of nickel sulfate, nickel chloride, nickel nitrate and nickel acetate; and / or, The manganese salt is at least one of manganese sulfate, manganese chloride, manganese nitrate and manganese acetate.

3. The method for preparing a high BET lithium-rich manganese-based binary precursor according to claim 1, characterized in that: The mass fraction of the precipitant solution is 28%-32%; and / or, The mass fraction of the complexing agent solution is 16%-20%; and / or, In the reaction base solution, the concentration of the precipitant is 0.04%-0.08%, and the concentration of the complexing agent is 1-1.5 g / L; and / or, The precipitant is sodium hydroxide; and / or, The complexing agent is oxalic acid.

4. The method for preparing a high BET lithium-rich manganese-based binary precursor according to claim 1, characterized in that: Before preparing the reaction base solution, a protective gas is introduced into the reaction kettle for 1-3 hours.

5. The method for preparing a high BET lithium-rich manganese-based binary precursor according to claim 1, characterized in that: The first flow rate is 2-6m 3 / h, the second flow rate is 6-12m 3 / h, the third flow rate is 0.5-2m 3 / h.

6. The method for preparing a high BET lithium-rich manganese-based binary precursor according to claim 1, characterized in that: The nucleation reaction time is 22-26 hours; and / or, The D50 of the first target particle size is 8-9 μm; and / or, The D50 of the second target particle size is 10-11 μm.

7. The method for preparing a high BET lithium-rich manganese-based binary precursor according to claim 1, characterized in that: During the coprecipitation reaction, every 4-5 m 3 According to the reaction base solution, the flow rate of the nickel-manganese mixed salt solution is 280-320 L / h, the flow rate of the precipitant solution is 100-120 L / h, and the flow rate of the complexing agent solution is 15-25 L / h.

8. The method for preparing a high BET lithium-rich manganese-based binary precursor according to claim 1, characterized in that: During the coprecipitation reaction, the pH is controlled at 9.9-10.2, the concentration of the complexing agent is controlled at 1-3 g / L, the reaction temperature is controlled at 60-70° C., and the stirring rate is controlled at 200-320 r / min.

9. A high BET lithium-rich manganese-based binary precursor, characterized in that: The high BET lithium-rich manganese-based binary precursor is obtained by the preparation method of the high BET lithium-rich manganese-based binary precursor according to any one of claims 1-8.

10. An application of the high BET lithium-rich manganese-based binary precursor as claimed in claim 9, characterized in that: The high BET lithium-rich manganese-based binary precursor is used to prepare lithium-rich manganese-based binary positive electrode materials.

Images