Lithium-rich manganese-based positive electrode material precursor as well as preparation method and application thereof

Abstract

The invention discloses a lithium-rich manganese-based positive electrode material precursor and a preparation method and application thereof, and belongs to the technical field of battery materials. The chemical general formula of the precursor is MnxNiy (OH) aOb, x is more than or equal to 0.6 and less than or equal to 0.7, y is equal to 1-x, b is equal to 2-a, and a is more than or equal to 0.6 and less than 2; the porosity of the precursor is not less than 6%, the length of the whisker is 0.1-0.4 [mu] m, the thickness is 10-60 nm, the tap density of the precursor is not less than 1.5 g / cm < 3 >, and D50 is 6-12 [mu] m. The precursor is rich in pores, fine and short in whisker and relatively high in tap density, on one hand, full contact with a lithium source and uniform diffusion of lithium ions in the sintering process are facilitated, on the other hand, the finished positive electrode material can inherit the porous characteristic of the precursor, the contact area between the material and an electrolyte is increased, and the migration path of the lithium ions is shortened; more channels are provided for lithium ion transmission, so that the electrochemical performance of the material is improved.

Description

Technical Field

[0001] The present invention relates to the technical field of battery materials, and in particular, to a lithium-rich manganese-based cathode material precursor, a preparation method thereof, and an application thereof. Background Art

[0002] Currently, the lithium-rich manganese-based precursor is usually prepared by two co-precipitation process routes of carbonate and hydroxide.

[0003] Among them, in the carbonate process, metal precipitation is usually incomplete, resulting in component deviation and cost waste, and the tap density of the prepared precursor is low; when using the conventional hydroxide process, due to the high manganese content, the primary flake particles of the precursor are thicker, the pore distribution is uneven, and the secondary sphericity is poor. On the one hand, this precursor morphology has insufficient contact with the lithium source during the sintering process and requires a higher sintering temperature. On the other hand, the primary particles of the sintered product are larger, and the lithium ion transport impedance of the positive electrode sheet is large after being assembled into a battery, and the material capacity and rate performance are poorly exerted.

[0004] In view of this, the present invention is specifically proposed. Summary of the Invention

[0005] The purpose of the present invention is to provide a lithium-rich manganese-based cathode material precursor, a preparation method thereof, and an application thereof to solve or improve the above technical problems.

[0006] The present invention can be implemented as follows:

[0007] In a first aspect, the present invention provides a lithium-rich manganese-based cathode material precursor, and the chemical general formula of the lithium-rich manganese-based cathode material precursor is Mn x Ni y (OH) a O b , wherein, 0.6 ≤ x ≤ 0.7, y = 1 - x, b = 2 - a, 0.6 ≤ a < 2;

[0008] The porosity of the lithium-rich manganese-based cathode material precursor is not less than 6%;

[0009] The length of the whiskers of the lithium-rich manganese-based cathode material precursor is 0.1 μm to 0.4 μm, and the whisker thickness is 10 nm to 60 nm;

[0010] The tap density of the lithium-rich manganese-based cathode material precursor is not less than 1.5 g / cm 3 , preferably 1.5 g / cm 3 ~1.7 g / cm 3 ;

[0011] The D 50 of the lithium-rich manganese-based cathode material precursor is 6 μm to 12 μm.

[0012] In an alternative embodiment, K of the lithium-rich manganese-based cathode material precursor 90 = 0.2 to 0.5, wherein, K 90 =(D 90 - D 10 ) / D 50 .

[0013] In an alternative embodiment, the specific surface area of the lithium-rich manganese-based cathode material precursor is 20 m 2 / g to 40 m 2 / g.

[0014] In a second aspect, the present invention provides a method for preparing a lithium-rich manganese-based cathode material precursor as described in the foregoing embodiments, including a nucleation stage, a crystal nucleus growth stage, and a seed crystal growth stage;

[0015] Wherein, air is introduced in the later stage of crystal nucleus growth;

[0016] No complexing agent is used throughout the preparation process of the lithium-rich manganese-based cathode material precursor.

[0017] In an alternative embodiment, the nucleation stage includes: in a protective gas environment, a mixed salt solution and a sodium hydroxide solution are added to a reaction vessel having a bottom liquid in a co-current manner, and the reaction temperature is controlled to be 55°C to 65°C, and the reaction time is 100 min to 120 min;

[0018] Wherein, the bottom liquid is composed of water and a sodium hydroxide solution, the concentration of the sodium hydroxide solution is 310 g / L to 330 g / L, and the pH value of the bottom liquid is 11.95 to 12.05; the mixed salt solution is an aqueous solution of a soluble nickel salt and a soluble manganese salt; in the mixed salt solution, the total concentration of nickel and manganese metal ions is 120 g / L to 140 g / L.

[0019] In an alternative embodiment, the nucleation stage has at least one of the following characteristics:

[0020] Characteristic 1: The volume of the bottom liquid is 40% to 70% of the volume of the reaction vessel;

[0021] Characteristic 2: Calculated by the total number of moles of nickel and manganese ions in the mixed salt solution corresponding to each liter of the reaction vessel, the feeding flow rate of the mixed salt solution is 0.042 mol / h to 0.045 mol / h;

[0022] Characteristic 3: The flow rate ratio of the sodium hydroxide solution to the mixed salt solution is 0.61:1 to 0.63:1;

[0023] Characteristic 4: The pH value of the nucleation stage is 11.95 to 12.05.

[0024] In an alternative embodiment, the crystal nucleation growth stage includes: lowering the pH value to 8.88 - 9.10, continuously adding the mixed salt solution and the sodium hydroxide solution in parallel flow at the same flow rate as in the nucleation stage, maintaining the introduction of the protective gas at the same flow rate as in the nucleation stage. After reacting for 2 h - 3 h, increasing the flow rates of the mixed salt solution and the sodium hydroxide solution and simultaneously introducing air until a precursor seed crystal with a particle size D 50 of 3.4 μm - 3.6 μm is obtained.

[0025] In an alternative embodiment, the crystal nucleation growth stage has at least one of the following characteristics:

[0026] Characteristic 5: After reacting for 2 h - 3 h, the feeding flow rate of the mixed salt solution is increased to 0.126 mol / h - 0.135 mol / h;

[0027] Characteristic 6: Throughout the nucleation stage and the first 2 h - 3 h of crystal nucleation growth, a protective gas is introduced; after 2 h - 3 h of crystal nucleation growth, the flow rate of the protective gas is decreased and a certain flow rate of air is introduced, keeping the total gas flow rate unchanged, and the volume percentage of oxygen is 1.45% - 1.55%;

[0028] Characteristic 7: The flow rate ratio of the sodium hydroxide solution to the mixed salt solution is 0.54:1 to 0.56:1;

[0029] Characteristic 8: The reaction time of the crystal nucleation growth stage corresponding to the seed crystal particle size reaching D 50 of 3.4 μm - 3.6 μm is 55 h - 65 h.

[0030] In an alternative embodiment, the seed crystal growth stage includes: first feeding the mixed salt solution and the sodium hydroxide solution in parallel flow at a low flow rate, and after reacting for a period of time, increasing the flow rate of the mixed salt solution in a gradient up-flow manner; introducing air and a protective gas during feeding and keeping the total gas flow rate stable until the precursor seed crystal grows to a preset particle size, obtaining a lithium-rich manganese-based cathode material precursor.

[0031] Among them, before up-flow, the feeding flow rate of the mixed salt solution is 0.042 mol / h - 0.045 mol / h; after reacting for 1 h - 2 h, the feeding flow rate of the mixed salt solution is increased to 0.126 mol / h - 0.135 mol / h, and the up-flow time is 10 h - 12 h.

[0032] In an alternative embodiment, the seed crystal growth stage has at least one of the following characteristics:

[0033] Characteristic 9: Before feeding, adjusting the solid content in the reaction vessel to 40 g / L - 120 g / L;

[0034] Characteristic 10: At particle size D 50When it is < 5 μm, the volume percentage of oxygen in the mixed gas introduced is 1.45% - 1.55%; when D 50 > 5 μm, the air flow rate is increased and the protective gas flow rate is decreased by using a gradient up-flow method, so that after 2 - 3 hours of up-flow, the volume percentage of oxygen in the mixed gas introduced reaches 2.5% - 3.5%;

[0035] Characteristic 11: The flow rate ratio of the sodium hydroxide solution to the mixed salt solution is 0.54:1 to 0.56:1;

[0036] Characteristic 12: When the precursor seed grows to D 50 The reaction time corresponding to the seed growth stage when it is 6 μm - 12 μm is 55 h - 65 h.

[0037] In an optional embodiment, during the preparation process of the entire lithium-rich manganese-based cathode material precursor, the total volume of the protective gas and air introduced per hour and the volume of the reaction vessel have a ratio of 1 - 1.2.

[0038] In a third aspect, the present invention provides a lithium-rich manganese-based cathode material, and the preparation raw materials of the lithium-rich manganese-based cathode material include the lithium-rich manganese-based cathode material precursor of the foregoing embodiment.

[0039] In a fourth aspect, the present invention provides a battery, and the preparation raw materials of the battery include the lithium-rich manganese-based cathode material of the foregoing embodiment.

[0040] The beneficial effects of the present invention include:

[0041] The present invention provides a lithium-rich manganese-based cathode material precursor with rich pores, short and thin whiskers, and a relatively high tap density. This precursor can take into account the characteristics of improving the reaction activity and increasing the compaction density, which is beneficial to improving the energy density and rate performance of the cathode material. For example, on the one hand, this precursor is conducive to the full contact with the lithium source and the uniform diffusion of lithium ions during the sintering process. On the other hand, the finished cathode material prepared from this precursor can inherit the porous characteristics of the precursor, increase the contact area between the material and the electrolyte, shorten the migration path of lithium ions, and provide more channels for the transmission of lithium ions, thereby improving the electrochemical performance of the material. Description of the Drawings

[0042] In order to more clearly illustrate the technical solutions of the embodiments of the present invention, the following will briefly introduce the drawings required in the embodiments. It should be understood that the following drawings only show some embodiments of the present invention, and therefore should not be regarded as limiting the scope. For those of ordinary skill in the art, without creative efforts, other related drawings can also be obtained based on these drawings.

[0043] Figure 1SEM image of the overall precursor of the lithium-rich manganese-based cathode material prepared in Example 1 of the present invention;

[0044] Figure 2 SEM image of the cross-section of the precursor of the lithium-rich manganese-based cathode material prepared in Example 1 of the present invention;

[0045] Figure 3 SEM image of the overall precursor of the lithium-rich manganese-based cathode material prepared in Example 2 of the present invention;

[0046] Figure 4 SEM image of the cross-section of the precursor of the lithium-rich manganese-based cathode material prepared in Example 2 of the present invention;

[0047] Figure 5 SEM image of the overall precursor of the lithium-rich manganese-based cathode material prepared in Example 3 of the present invention;

[0048] Figure 6 SEM image of the cross-section of the precursor of the lithium-rich manganese-based cathode material prepared in Example 3 of the present invention. Detailed implementation manners

[0049] To make the objectives, technical solutions, and advantages of the embodiments of the present invention clearer, the technical solutions in the embodiments of the present invention will be clearly and completely described below. For those not specified in the embodiments, they are carried out according to conventional conditions or conditions recommended by the manufacturer. For reagents or instruments without indicating the manufacturer, they are all conventional products that can be obtained through commercial purchase.

[0050] The lithium-rich manganese-based cathode material precursor provided by the present invention, its preparation method, and application will be specifically described below.

[0051] The present invention provides a lithium-rich manganese-based cathode material precursor, and the chemical general formula of the lithium-rich manganese-based cathode material precursor is Mn x Ni y (OH) a O b , where 0.6 ≤ x ≤ 0.7, y = 1 - x, b = 2 - a, and 0.6 ≤ a < 2.

[0052] The porosity of the lithium-rich manganese-based cathode material precursor is not less than 6%. In some alternative embodiments, the porosity of the lithium-rich manganese-based cathode material precursor can be 6% - 10%, such as 6.1% - 7.2%.

[0053] The length of the whiskers of the lithium-rich manganese-based cathode material precursor is 0.1 μm - 0.4 μm. In some alternative embodiments, the length of the whiskers of the lithium-rich manganese-based cathode material precursor is 0.12 μm - 0.36 μm, such as 0.15 μm - 0.221 μm.

[0054] The whisker thickness of the precursor of the lithium-rich manganese-based cathode material is 10 nm to 60 nm. In some alternative embodiments, the whisker thickness of the precursor of the lithium-rich manganese-based cathode material is 13 nm to 58 nm, such as 23 nm to 28 nm.

[0055] The tap density of the precursor of the lithium-rich manganese-based cathode material is not less than 1.5 g / cm 3 . In some alternative embodiments, the tap density of the precursor of the lithium-rich manganese-based cathode material is 1.5 g / cm 3 to 1.7 g / cm 3 , such as 1.54 g / cm 3 to 1.62 g / cm 3 .

[0056] The D 50 of the precursor of the lithium-rich manganese-based cathode material is 6 μm to 12 μm. In some alternative embodiments, the D 50 of the precursor of the lithium-rich manganese-based cathode material is 6.0 μm to 10.0 μm, such as 6.5 μm to 10.0 μm.

[0057] The precursor of the lithium-rich manganese-based cathode material having the above characteristics is rich in pores, with short and thin whiskers, a relatively high tap density, and a uniform particle size distribution, which can balance the performance of improving the reaction activity and increasing the compaction density, and is beneficial to improving the energy density and rate performance of the cathode material. For example, on the one hand, this precursor is conducive to the full contact with the lithium source and the uniform diffusion of lithium ions during the sintering process. On the other hand, the finished cathode material prepared from this precursor can inherit the porous characteristics of the precursor, increase the contact area between the material and the electrolyte, shorten the migration path of lithium ions, and provide more channels for the transmission of lithium ions, thereby improving the electrochemical performance of the material.

[0058] Furthermore, in the precursor of the lithium-rich manganese-based cathode material provided by the present invention, the pore distribution is uniform.

[0059] In some alternative embodiments, the K 90 of the precursor of the lithium-rich manganese-based cathode material is 0.2 to 0.5, such as 0.32 to 0.42, where K 90 =(D 90 -D 10 ) / D 50 . The precursor of the lithium-rich manganese-based cathode material having this K 90 range, combined with the aforementioned D 50 , is beneficial to the setting of the sintering process in the preparation of the cathode material, so as to obtain a better sintering effect. If the particle size distribution of the precursor is uneven, it is easy to cause problems such as overburning or fragmentation of small particles under the process conditions suitable for the sintering of large particles.

[0060] In some alternative embodiments, the specific surface area of the lithium-rich manganese-based cathode material precursor is 20 m 2 / g to 40 m 2 / g, preferably 28 m 2 / g to 40 m 2 / g, such as 28.8 m 2 / g to 38.2 m 2 / g. The lithium-rich manganese-based cathode material precursor with such a specific surface area range is beneficial to improving the sintering reaction activity and avoiding the gas generation problem during the cycling of the cathode material.

[0061] Correspondingly, the present invention also provides a preparation method of the above lithium-rich manganese-based cathode material precursor, including a nucleation stage, a crystal nucleus growth stage, and a seed crystal growth stage;

[0062] Among them, air is introduced in the later stage of crystal nucleus growth;

[0063] No complexing agent is used throughout the preparation process of the lithium-rich manganese-based cathode material precursor.

[0064] The following is an elaboration on each stage:

[0065] S1: Nucleation stage.

[0066] Under a protective gas environment, a mixed salt solution and a sodium hydroxide solution are added to a reaction vessel with a bottom liquid in a parallel flow manner, and the reaction temperature is controlled to be 55°C to 65°C, and the reaction time is 100 min to 120 min.

[0067] Among them, the bottom liquid is composed of water and a sodium hydroxide solution. The concentration of the sodium hydroxide solution can be 310 g / L to 330 g / L, such as 310 g / L, 315 g / L, 320 g / L, 325 g / L, or 330 g / L, etc., or other values within the range of 310 g / L to 330 g / L.

[0068] The pH value of the bottom liquid can be 11.95 to 12.05, such as 11.95, 11.98, 12.00, 12.02, or 12.05, etc., or other values within the range of 11.95 to 12.05.

[0069] The volume of the bottom liquid can be 40% to 70% of the volume of the reaction vessel, such as 40%, 45%, 50%, 55%, 60%, 65%, or 70%, etc., or other values within the range of 40% to 70%.

[0070] The mixed salt solution is an aqueous solution of a soluble nickel salt and a soluble manganese salt. In the mixed salt solution, the total concentration of metal ions is 120 g / L to 140 g / L. In the mixed salt solution, the molar ratio of Mn to Ni is x:y (matching the chemical general formula). Among them, the forms of the soluble nickel salt and the soluble manganese salt can exemplarily but non-limitingly include forms such as sulfates, nitrates, and acetates.

[0071] Based on the total molar number of nickel and manganese ions in the mixed salt solution corresponding to each liter of the reaction vessel, the feeding flow rate of the mixed salt solution is 0.042 mol / h to 0.045 mol / h. In other words, taking the total volume of the reaction vessel as 10 L as an example, the amount of the mixed metal introduced into the reaction vessel per hour is 10×0.042 mol to 10×0.045 mol / h.

[0072] The molar ratio of the sodium hydroxide solution to the mixed salt solution can be 0.61:1 to 0.63:1, such as 0.61:1, 0.62:1, or 0.63:1, etc., or other values within the range of 0.61:1 to 0.63:1.

[0073] In some alternative embodiments, the reaction temperature in the nucleation stage can be 55 °C, 58 °C, 60 °C, 62 °C, or 65 °C, etc., or other values within the range of 55 °C to 65 °C.

[0074] In some alternative embodiments, the reaction time in the nucleation stage can be 100 min, 105 min, 110 min, 115 min, or 120 min, etc., or other values within the range of 100 min to 120 min.

[0075] In some alternative embodiments, the pH value in the nucleation stage is 11.95 to 12.05.

[0076] During actual operation, a protective gas can be introduced into the reaction vessel in advance to evacuate the air in the reaction vessel and the protective gas is continuously introduced during the subsequent reaction to maintain a slightly positive pressure state in the reaction vessel. Water and a sodium hydroxide solution are added to the reaction vessel as the bottom liquid, and the pH of the bottom liquid is adjusted; under stirring conditions, the mixed salt solution and the sodium hydroxide solution are added in a co-current feeding manner for nucleation.

[0077] It should be noted that during the entire preparation process of the lithium-rich manganese-based cathode material precursor, the sodium hydroxide solution and the mixed salt solution used always remain the same and do not change due to different stages. In addition, during the entire preparation process of the lithium-rich manganese-based cathode material precursor, based on the volume of the protective gas introduced corresponding to each liter of the reaction vessel, the feeding flow rate of the protective gas is 1.2 L / h. Among them, the protective gas can exemplarily be nitrogen.

[0078] S2: Crystal nucleus growth stage.

[0079] Compared with the nucleation stage, the pH value is reduced to 8.88 - 9.10, and the mixed salt solution and sodium hydroxide solution are continuously added in parallel at the same flow rate as in the nucleation stage, while maintaining the introduction of the protective gas at the same flow rate as in the nucleation stage. After reacting for 2 - 3 h, the flow rates of the mixed salt solution and sodium hydroxide solution are increased and air is introduced simultaneously until a precursor seed crystal with a particle size D 50 of 3.4 μm - 3.6 μm is obtained.

[0080] By increasing the material flow rate and introducing air during the crystal nucleus growth stage, and controlling the stirring speed simultaneously, the morphology of the precursor of the lithium-rich manganese-based cathode material can be regulated. This is mainly because the morphology of the Mn-based material is affected by the valence state of Mn. Under micro-oxidation conditions, manganese hydroxide is easily converted into sheet-like manganese oxyhydroxide, and nickel hydroxide continues to grow on this template while maintaining the template morphology. Under higher rotation speed conditions, the diffusion of ions can be enhanced, thereby regulating the pore structure between primary particles and also avoiding the adhesion and agglomeration between secondary particles. Therefore, through micro-oxidation and higher rotation speed, a smaller primary sheet-like particle morphology and more pore structures can be obtained, while ensuring a better particle sphericity. Finally, secondary spherical particles are assembled and formed, and the primary particles are in the shape of sheet-like slender.

[0081] In some embodiments, after reacting for 2 - 3 h, the feeding flow rate of the mixed salt solution is increased to 0.126 mol / h - 0.135 mol / h. At this time, the flow rate ratio of the sodium hydroxide solution to the mixed salt solution can be 0.54:1 to 0.56:1, such as 0.54:1, 0.55:1, 0.56:1, etc., or other values within the range of 0.54:1 to 0.56:1.

[0082] In this stage, the stirring speed is controlled so that the reaction time corresponding to the crystal seed particle size reaching D 50 of 3.4 μm - 3.6 μm is 55 h - 65 h (such as 55 h, 58 h, 60 h, 62 h or 65 h, etc.).

[0083] In some embodiments, a protective gas is introduced throughout the nucleation stage and the first 2 - 3 h of crystal nucleus growth; after 2 - 3 h of crystal nucleus growth, the flow rate of the protective gas is reduced and a certain flow rate of air is introduced, while maintaining the total gas flow rate unchanged, and the volume of oxygen in the air accounts for 1.45% - 1.55% of the total volume of the air and the protective gas.

[0084] If the oxygen introduction amount is too high, it is easy to cause over-oxidation, and tetravalent manganese dioxide is locally generated, manifested as an increase in the thickness of primary particles and uneven thickness of whiskers. On the other hand, if a large flow rate of air is introduced in the early stage, the agglomeration effect of particles will be weakened, and it is easy to cause the inner core to be loose and form larger holes.

[0085] For the remaining conditions that are not described, such as the reaction temperature in this stage, they are the same as those in the nucleation stage.

[0086] S3: Seed growth stage.

[0087] First, the mixed salt solution and the sodium hydroxide solution are fed in parallel in a low-flow manner. After reacting for a period of time, the flow rate of the mixed salt solution is increased by a gradient up-flow method; while feeding, air and a protective gas are introduced and the total gas flow rate is kept stable until the precursor seed grows to a preset particle size, obtaining a lithium-rich manganese-based cathode material precursor.

[0088] In some embodiments, before increasing the flow rates of the mixed salt solution and the sodium hydroxide solution, the solid content in the reaction vessel is adjusted to 40 g / L to 120 g / L, such as 40 g / L, 50 g / L, 90 g / L, 110 g / L, or 120 g / L, etc., and it can also be other values within the range of 40 g / L to 120 g / L. Specifically, part of the precursor seeds can be transferred out and the remaining precursor seeds can be diluted with water. For example, it can be diluted to a volume ratio of the slurry accounting for 40% to 70% of the reaction vessel.

[0089] In some embodiments, based on the total molar amount of nickel and manganese ions in the mixed salt solution corresponding to each liter of the reaction vessel, before the up-flow, the feeding flow rate of the mixed salt solution is 0.042 mol / h to 0.045 mol / h; after reacting for 1 h to 2 h (such as 1 h, 1.5 h, or 2 h, etc.), the flow rate is increased by a gradient up-flow method. After 10 h to 12 h (such as 10 h, 10.5 h, 11 h, 11.5 h, or 12 h, etc.) of up-flow, the feeding flow rate of the mixed salt solution is increased to 0.126 mol / h to 0.135 mol / h. The flow rate ratio of the sodium hydroxide solution to the mixed salt solution can also be 0.54:1 to 0.56:1, such as 0.54:1, 0.55:1, 0.56:1, etc., and it can also be other values within the range of 0.54:1 to 0.56:1.

[0090] Air and the protective gas are introduced in the following manner: At particle size D 50 < 5 μm, the volume percentage of oxygen in the mixed gas introduced is 1.45% to 1.55%; when D 50 > 5 μm, a gradient up-flow method is used to increase the air flow rate and decrease the protective gas flow rate, so that after 2 h to 3 h (such as 2 h, 2.5 h, or 3 h, etc.) of up-flow, the volume percentage of oxygen in the mixed gas introduced reaches 2.5% to 3.5%.

[0091] In this stage, for the control of the stirring speed, when the precursor seed grows to D 50 being 6 μm to 12 μm, the corresponding reaction time is 55 h to 65 h (such as 55 h, 58 h, 60 h, 62 h, or 65 h, etc.).

[0092] For the remaining conditions such as the reaction temperature in this stage that are not described, they are the same as those in the crystal nucleation growth stage.

[0093] As described above, the preparation method of the lithium-rich manganese-based cathode material precursor provided by the present invention is simple and easy to control, and can be industrially produced. By adopting the seed process, the total growth time of the particles is indirectly extended through stepwise synthesis, thereby prolonging the repair time of the particle adhesion cracks, enabling the particle adhesion cracks to be fully repaired, and the prepared particles have a plump morphology and good sphericity; during the crystal nucleation growth stage and the seed growth process, measures such as gradient upflow and gradient oxygen increase are adopted to solve problems such as uneven internal pore distribution and uneven whisker thickness in the particles; no complexing agent is used in the whole preparation process.

[0094] In addition, the present invention also provides a lithium-rich manganese-based cathode material, and the preparation raw materials of the lithium-rich manganese-based cathode material include the above-mentioned lithium-rich manganese-based cathode material precursor.

[0095] Furthermore, the present invention also provides a battery, and the preparation raw materials of the battery include the above-mentioned lithium-rich manganese-based cathode material to obtain better electrochemical performance.

[0096] The features and properties of the present invention will be further described in detail below in conjunction with embodiments.

[0097] Example 1

[0098] This example provides a lithium-rich manganese-based cathode material precursor, and its chemical general formula is Mn 0.66 Ni 0.34 (OH) a O b , and its preparation method includes:

[0099] S1: Nucleation stage.

[0100] S11: Nitrogen is introduced into the reaction kettle (with a volume of 500 L) in advance to evacuate the air in the reaction kettle and continuously introduced into the reaction kettle during the subsequent reaction to maintain a slightly positive pressure state in the reaction kettle. Calculated by the volume of nitrogen introduced per liter of the reaction kettle, the introduction rate of nitrogen is 1.2 L / h.

[0101] S12: Add the bottom liquid into the reaction kettle, and the bottom liquid is composed of water and sodium hydroxide solution. The concentration of the sodium hydroxide solution is 320 g / L, the pH value of the bottom liquid is 12, and the volume of the bottom liquid is 55% of the volume of the reaction vessel.

[0102] S13: Under stirring conditions (stirring speed is 460 rpm), add the mixed salt solution and sodium hydroxide solution in parallel flow, control the reaction temperature at 60 °C, and the reaction time at 110 min. The mixed salt solution is an aqueous solution of nickel sulfate and manganese sulfate. In the mixed salt solution, the total concentration of metal ions is 130 g / L, and the molar ratio of Mn to Ni is x:y (matched with the chemical general formula). Based on the total molar number of nickel and manganese ions in the mixed solution corresponding to each liter of the reaction vessel, the feeding rate of the mixed salt solution is 0.043 mol / h. The flow rate ratio of the sodium hydroxide solution to the mixed salt solution is 0.62:1.

[0103] S2: Crystal nucleus growth stage.

[0104] Compared with the nucleation stage, reduce the flow rate ratio of the sodium hydroxide solution to the mixed solution to 0.55:1, adjust the pH value to 9.0 ± 0.02, and continue to add the mixed salt solution and sodium hydroxide solution in parallel flow at the same flow rate as in the nucleation stage. After reacting for 2 h, increase the flow rates of the mixed salt solution and sodium hydroxide solution in a gradient up-flow manner. The up-flow time is 6 h, and the flow rate of the mixed solution after up-flow is 0.129 mol / h and remains basically stable. At the same time, introduce air (the volume of oxygen in the air accounts for 1.5% of the total volume of air and nitrogen) until a precursor seed crystal with a particle size D 50 of 3.5 μm is obtained.

[0105] Among them, the stirring speed is 460 rpm, and the reaction time corresponding to the seed crystal particle size reaching D 50 of 3.5 μm is 60 h.

[0106] For the remaining conditions not described such as the reaction temperature in this stage, they are the same as those in the nucleation stage.

[0107] S3: Seed crystal growth stage.

[0108] S31: Transfer out part of the precursor seed crystals and dilute the remaining precursor seed crystals with water until the volume ratio of the slurry accounts for 55% of the reaction vessel, so that the solid content in the reaction kettle is 40 g / L.

[0109] S32: Compared with the crystal nucleus growth stage, further increase the flow rates of the mixed salt solution and sodium hydroxide solution and introduce air until the precursor seed crystals grow to the preset particle size, obtaining a precursor of the lithium-rich manganese-based cathode material.

[0110] Among them, the initial feeding flow rate is 0.043 mol / h. After reacting for 1 h, increase the flow rate in a gradient up-flow manner. The up-flow time is 12 h, and the feeding rate of the mixed salt solution is increased to 0.129 mol / h. The flow rate ratio of the sodium hydroxide solution to the mixed salt solution is also 0.55:1. In this stage, the stirring speed is 350 rpm, and the precursor seed crystals grow to D 50The reaction time corresponding to 9.8 μm is 60 h.

[0111] In the seed growth stage, a mixed gas of protective gas and air is introduced. The total gas flow rate is kept constant throughout the growth process, and the volume fraction of oxygen is changed by regulating the air flow rate. Among them, when the particle size D 50 <5 μm, the volume fraction of oxygen in the introduced mixed gas is (1.5 ± 0.05)%; when D 50 >5 μm, the air flow rate is increased and the protective gas flow rate is decreased in a gradient up-flow manner. After 2 h of up-flow, the volume fraction of oxygen in the introduced mixed gas reaches 3.5% and remains basically stable.

[0112] For the remaining conditions such as the reaction temperature in this stage that are not described, they are the same as those in the crystal nucleus growth stage.

[0113] Both the above crystal nucleus growth stage and seed growth stage adopt a continuous feeding - discharging method to maintain the basic stability of the slurry volume in the autoclave. During the entire synthesis process of the manganese-rich precursor, the circulation flow rate between the thickener and the reaction vessel relative to the volume of the reaction vessel is 1.2 L / (L·h).

[0114] Example 2

[0115] This example provides a precursor of a lithium-rich manganese-based cathode material, whose chemical general formula is Mn 0.62 Ni 0.38 (OH) a O b , and its preparation method includes:

[0116] S1: Nucleation stage.

[0117] S11: Nitrogen is introduced into the reaction kettle (with a volume of 500 L) in advance to evacuate the air in the reaction kettle and is continuously introduced into the reaction kettle during the subsequent reaction to maintain a slightly positive pressure state in the reaction kettle. Calculated by the volume of nitrogen introduced per liter of the reaction kettle, the introduction rate of nitrogen is 1.0 L / h.

[0118] S12: Add the bottom liquid into the reaction kettle. The bottom liquid is composed of water and sodium hydroxide solution. The concentration of the sodium hydroxide solution is 310 g / L, the pH value of the bottom liquid is 11.95, and the volume of the bottom liquid is 70% of the volume of the reaction vessel.

[0119] S13: Under stirring conditions (stirring speed is 460 rpm), the mixed salt solution and the sodium hydroxide solution are added in parallel flow, controlling the reaction temperature at 55 °C and the reaction time at 120 min. The mixed salt solution is an aqueous solution of nickel sulfate and manganese sulfate. In the mixed salt solution, the total concentration of metal ions is 120 g / L, and the molar ratio of Mn to Ni is x:y (matching the chemical general formula). Calculated by the total molar amount of nickel and manganese ions in the mixed salt solution corresponding to each liter of the reaction vessel, the feeding rate of the mixed salt solution is 0.042 mol / h. The flow rate ratio of the sodium hydroxide solution to the mixed salt solution is 0.61:1.

[0120] S2: Crystal nucleus growth stage.

[0121] Compared with the nucleation stage, the flow rate ratio of the sodium hydroxide solution to the mixed salt solution is reduced to 0.54:1, the pH value is adjusted to 8.9 ± 0.02, and the mixed salt solution and the sodium hydroxide solution are continuously added in parallel flow at the same flow rate as in the nucleation stage. After reacting for 3 h, the flow rates of the mixed salt solution and the sodium hydroxide solution are increased in a gradient up-flow manner, and the up-flow time is 6 h. The flow rate of the metal salt solution after up-flow is 0.126 mol / h and remains basically stable. At the same time, air is introduced (the volume of oxygen in the air accounts for 1.45% of the total volume of air and nitrogen) until a precursor seed crystal with a particle size D 50 of 3.4 μm is obtained.

[0122] Among them, in this stage, the stirring speed is 460 rpm, and the reaction time corresponding to the seed crystal particle size reaching D 50 of 3.4 μm is 55 h.

[0123] For the remaining conditions not described such as the reaction temperature in this stage, they are the same as those in the nucleation stage.

[0124] S3: Seed crystal growth stage.

[0125] S31: Transfer out part of the precursor seed crystal and dilute the remaining precursor seed crystal with water until the volume ratio of the slurry is 70% of the reaction vessel, so that the solid content in the reaction kettle is 120 g / L.

[0126] S32: Compared with the crystal nucleus growth stage, further increase the flow rates of the mixed salt solution and the sodium hydroxide solution and introduce air until the precursor seed crystal grows to the preset particle size, obtaining a precursor of the lithium-rich manganese-based cathode material.

[0127] Among them, the initial feeding flow rate is 0.042 mol / h. After reacting for 2 h, the flow rate is increased in a gradient up-flow manner, and the up-flow time is 10 h. The feeding rate of the mixed salt solution is increased to 0.126 mol / h. The flow rate ratio of the sodium hydroxide solution to the mixed salt solution is also 0.54:1. In this stage, the stirring speed is 350 rpm, and the precursor seed crystal grows to D 50The reaction time corresponding to 6.5 μm is 55 h.

[0128] During the seed crystal growth stage, a mixed gas of protective gas and air is introduced, and the total gas flow rate is kept constant throughout the growth process. The volume ratio of oxygen is changed by regulating the air flow rate. Among them, when the particle size D 50 <5 μm, the volume ratio of oxygen in the introduced mixed gas is (1.5 ± 0.05)%; when D 50 >5 μm, the air flow rate is increased and the protective gas flow rate is decreased in a gradient upflow manner. After 3 h of upflow, the volume ratio of oxygen in the introduced mixed gas reaches 2.5% and remains basically stable.

[0129] For the other conditions such as the reaction temperature in this stage that are not described, they are the same as those in the crystal nucleus growth stage.

[0130] Both the above crystal nucleus growth stage and seed crystal growth stage adopt a continuous feeding - discharging method to maintain the basic stability of the slurry volume in the kettle. During the entire synthesis process of the manganese - rich precursor, the circulation flow rate between the thickener and the reaction vessel relative to the volume of the reaction vessel is 1 L / (L·h).

[0131] Example 3

[0132] This example provides a precursor of a lithium - rich manganese - based cathode material, whose chemical general formula is Mn 0.68 Ni 0.32 (OH) a O b , and its preparation method includes:

[0133] S1: Nucleation stage.

[0134] S11: Nitrogen is introduced into the reaction kettle (with a volume of 500 L) in advance to evacuate the air in the reaction kettle and continuously introduced into the reaction kettle during the subsequent reaction to maintain a slightly positive pressure state in the reaction kettle. Calculated by the volume of nitrogen introduced per liter of the reaction kettle, the introduction rate of nitrogen is 1.2 L / h.

[0135] S12: Add a bottom liquid to the reaction kettle. The bottom liquid is composed of water and sodium hydroxide solution. The concentration of the sodium hydroxide solution is 330 g / L, the pH value of the bottom liquid is 12.05, and the volume of the bottom liquid is 40% of the volume of the reaction vessel.

[0136] S13: Under stirring conditions (stirring speed is 460 rpm), the mixed salt solution and the sodium hydroxide solution are added in parallel, controlling the reaction temperature at 65 °C and the reaction time at 100 min. The mixed salt solution is an aqueous solution of nickel sulfate and manganese sulfate. In the mixed salt solution, the total concentration of metal ions is 140 g / L, and the molar ratio of Mn to Ni is x:y (matched with the chemical general formula). Based on the total molar number of nickel and manganese ions in the mixed solution corresponding to each liter of the reaction vessel, the feeding rate of the mixed salt solution is 0.045 mol / h. The molar ratio of the sodium hydroxide solution to the mixed salt solution is 0.63:1.

[0137] S2: Crystal nucleus growth stage.

[0138] Compared with the nucleation stage, the flow ratio of the sodium hydroxide solution to the mixed salt solution is reduced to 0.56:1, the pH value is adjusted to 9.1 ± 0.02, and the mixed salt solution and the sodium hydroxide solution are continuously added in parallel at the same flow rate as in the nucleation stage. After reacting for 3 h, the flow rates of the mixed salt solution and the sodium hydroxide solution are increased in a gradient up-flow manner, and the up-flow time is 6 h. The flow rate of the metal salt solution after up-flow is 0.135 mol / h and remains basically stable. At the same time, air is introduced (the volume of oxygen in the air accounts for 1.55% of the total volume of air and nitrogen) until the precursor crystal seeds with a particle size D 50 of 3.6 μm are obtained.

[0139] Among them, the stirring speed is 460 rpm, and the reaction time corresponding to the crystal seed particle size reaching D 50 of 3.6 μm is 65 h.

[0140] For the remaining conditions not described such as the reaction temperature in this stage, they are the same as those in the nucleation stage.

[0141] S3: Crystal seed growth stage.

[0142] S31: Transfer out part of the precursor crystal seeds and dilute the remaining precursor crystal seeds with water until the volume ratio of the slurry accounts for 40% of the reaction vessel, so that the solid content in the reaction kettle is 60 g / L.

[0143] S32: Compared with the crystal nucleus growth stage, further increase the flow rates of the mixed salt solution and the sodium hydroxide solution and introduce air until the precursor crystal seeds grow to the preset particle size, obtaining the precursor of the lithium-rich manganese-based cathode material.

[0144] Among them, the initial feeding flow rate is 0.045 mol / L. After reacting for 1.5 h, the flow rate is increased in a gradient up-flow manner, and the up-flow time is 11 h. The feeding rate of the mixed salt solution is increased to 0.135 mol / h. The flow ratio of the sodium hydroxide solution to the mixed salt solution is also 0.56:1. In this stage, the stirring speed is 350 rpm, and the precursor crystal seeds grow to D 50The reaction time corresponding to 10.1 μm is 65 h.

[0145] During the seed growth stage, a mixed gas of protective gas and air is introduced, and the total gas flow rate is kept constant throughout the growth process. The volume fraction of oxygen is changed by regulating the air flow rate. Among them, when the particle size D 50 < 5 μm, the volume fraction of oxygen in the introduced mixed gas is (1.5 ± 0.05)%; when D 50 > 5 μm, the air flow rate is increased and the protective gas flow rate is decreased by means of gradient upflow. After 2.5 h of upflow, the volume fraction of oxygen in the introduced mixed gas reaches 3.0% and remains basically stable.

[0146] For the remaining conditions not described such as the reaction temperature in this stage, they are the same as those in the crystal nucleus growth stage.

[0147] In the above crystal nucleus growth stage and seed growth stage, the continuous feeding - discharging method is adopted to maintain the basic stability of the slurry volume in the kettle. During the whole synthesis process of the manganese - rich precursor, the circulation flow rate between the thickener and the reaction vessel relative to the volume of the reaction vessel is 1 L / (L·h).

[0148] Comparative Example 1

[0149] The difference between this comparative example and Example 1 is that air is not introduced throughout the preparation process of the precursor.

[0150] Comparative Example 2

[0151] The difference between this comparative example and Example 1 is that air is introduced at the very beginning of the nucleation stage.

[0152] Comparative Example 3

[0153] The difference between this comparative example and Example 1 is that in the crystal nucleus growth and seed growth stages, the volume fraction of oxygen in the air accounts for 5% of the total volume of air and protective gas.

[0154] Test Example 1

[0155] ① Taking the lithium - rich manganese - based cathode material precursor obtained in Examples 1 to 3 as an example, SEM observation is carried out on its surface and cross - section, and the results are as Figures 1 to 6 shown.

[0156] From Figures 1 to 6 it can be seen that the porosities of the lithium - rich manganese - based cathode material precursors prepared in Examples 1 to 3 are all relatively high, and the pores are evenly distributed on the surface and inside of the lithium - rich manganese - based cathode material precursor. The whiskers of the lithium - rich manganese - based cathode material precursor are thin, short and have a high sphericity.

[0157] ② Performance tests are carried out on the lithium - rich manganese - based cathode material precursors prepared in Examples 1 to 3 and Comparative Examples 1 to 3.

[0158] Among them, the porosity was analyzed and tested on the particle profile using AVIZO software, the whiskers were measured and tested on the SEM images using length measurement software, the tapped density was tested using a tapped density tester, D 50 , D 10 and D 90 were tested using a Malvern laser particle size analyzer, and the specific surface area was tested using a nitrogen adsorption specific surface area analyzer. The results are shown in Table 1.

[0159] Table 1 Test Results

[0160]

[0161]

[0162] As can be seen from Table 1, the lithium-rich manganese-based cathode material precursor prepared by the method provided in this application has rich pores, uniform particle size distribution, short and thin whiskers, high tapped density, and moderate specific surface area.

[0163] Test Example 2

[0164] The lithium-rich manganese-based cathode material precursors prepared in Examples 1 to 3 and Comparative Examples 1 to 3 above were all prepared into cathode materials and further into batteries according to the following method:

[0165] Cathode material preparation method: The manganese-rich precursor material and lithium carbonate were mixed evenly according to the ratio of n(Li) / [n(Ni)+n(Mn)] = 1.3, placed in a sintering furnace, heated gradientally to 600 °C in an air atmosphere and held for 2 h, then continued to be heated to 800 °C and held for 8 h, taken out after natural cooling, crushed and sieved to obtain the lithium-rich manganese-based cathode material.

[0166] Battery preparation method: The lithium-rich manganese-based cathode material was mixed with acetylene black, binder and organic solvent in proportion to obtain a cathode slurry. After coating, drying and cutting, it was assembled into a button battery in a glove box, and the battery test voltage range was 2.5 V to 4.6 V.

[0167] The test results are shown in Table 2.

[0168] Table 2 Test Results

[0169] Example 1 Example 2 Example 3 Comparative Example 1 Comparative Example 2 Comparative Example 3 0.1C (mAh / g) 249.1 246.7 248.8 238.3 247.2 250.1 Initial efficiency 93.4％ 92.6％ 93.1％ 94.2％ 91.8％ 92.5％ Capacity retention rate after 100 cycles 86.3％ 86.5％ 86.6％ 89.4％ 81.7％ 81.2％

[0170] As can be seen from Table 2, the lithium-rich manganese-based cathode material precursor prepared by the method provided in this application can be further prepared into a battery that can balance capacity, initial efficiency and rate performance.

[0171] In summary, the present invention provides a lithium-rich manganese-based cathode material precursor with rich pores, short and thin whiskers, and a relatively high tap density. This precursor can balance the characteristics of improving the reaction activity and increasing the compaction density, which is beneficial to improving the energy density and rate performance of the cathode material. For example, on the one hand, this precursor is conducive to the full contact with the lithium source and the uniform diffusion of lithium ions during the sintering process. On the other hand, the finished cathode material prepared from this precursor can inherit the porous characteristics of the precursor, increase the contact area between the material and the electrolyte, shorten the migration path of lithium ions, and provide more channels for the transmission of lithium ions, thereby improving the electrochemical performance of the material.

[0172] The foregoing is only a preferred embodiment of the present invention and is not intended to limit the present invention. For those skilled in the art, the present invention may have various modifications and changes. Any modification, equivalent replacement, improvement, etc. made within the spirit and principle of the present invention shall be included within the protection scope of the present invention.

Claims

1. A lithium-rich manganese-based cathode material precursor, characterized in that: The general chemical formula of the lithium-rich manganese-based positive electrode material precursor is Mn x Ni y (OH) a O b , where 0.6≤x≤0.7, y=1-x, b=2-a, 0.6≤a<2; The porosity of the lithium-rich manganese-based positive electrode material precursor is not less than 6%; The length of the whiskers of the lithium-rich manganese-based positive electrode material precursor is 0.1 μm to 0.4 μm, and the thickness of the whiskers is 10 nm to 60 nm; The tap density of the lithium-rich manganese-based positive electrode material precursor is not less than 1.5 g / cm 3 ; The D of the lithium-rich manganese-based cathode material precursor 50 6μm~12μm.

2. The lithium-rich manganese-based cathode material precursor according to claim 1, characterized in that: The K of the lithium-rich manganese-based cathode material precursor 90 =0.2~0.5, where K 90 =(D 90 -D 10 ) / D 50 .

3. The lithium-rich manganese-based positive electrode material precursor according to claim 1 or 2, characterized in that: The specific surface area of ​​the lithium-rich manganese-based positive electrode material precursor is 20 m 2 / g~40m 2 / g.

4. A method for preparing a lithium-rich manganese-based positive electrode material precursor according to any one of claims 1 to 3, characterized in that: It includes the nucleation stage, the crystal nucleus growth stage and the crystal seed growth stage; Among them, air is introduced in the late stage of crystal nucleus growth; No complexing agent is used in the entire preparation process of the lithium-rich manganese-based positive electrode material precursor.

5. The preparation method according to claim 4, characterized in that: The nucleation stage includes: adding a mixed salt solution and a sodium hydroxide solution in parallel to a reaction vessel with a bottom liquid under a protective gas environment, controlling the reaction temperature to be 55° C. to 65° C., and the reaction time to be 100 min to 120 min; The base liquid is composed of water and sodium hydroxide solution, the concentration of the sodium hydroxide solution is 310 g / L to 330 g / L, and the pH value of the base liquid is 11.95 to 12.05; the mixed salt solution is an aqueous solution of soluble nickel salt and soluble manganese salt; in the mixed salt solution, the total concentration of nickel and manganese metal ions is 120 g / L to 140 g / L; Optionally, the nucleation phase has at least one of the following characteristics: Feature 1: The volume of the base liquid is 40% to 70% of the volume of the reaction container; Feature 2: The feed flow rate of the mixed salt solution is 0.042 mol / h to 0.045 mol / h, based on the total molar number of nickel and manganese ions in the mixed salt solution corresponding to each liter of the reaction container; Feature 3: The flow ratio of the sodium hydroxide solution to the mixed salt solution is 0.61:1 to 0.63:1; Feature 4: The pH value in the nucleation stage is 11.95-12.

05.

6. The preparation method according to claim 5, characterized in that: The crystal nucleus growth stage includes: lowering the pH value to 8.88-9.10, continuing to add the mixed salt solution and the sodium hydroxide solution at the same flow rate as the nucleus formation stage, and keeping the protective gas at the same flow rate as the nucleus formation stage. After reacting for 2h-3h, increasing the flow rate of the mixed salt solution and the sodium hydroxide solution and introducing air at the same time until a particle size D is obtained. 50 The precursor seed is 3.4 μm to 3.6 μm; Optionally, the crystal nucleus growth stage has at least one of the following characteristics: Feature 5: After 2h to 3h of reaction, the feed rate of the mixed salt solution is increased to 0.126mol / h to 0.135mol / h; Feature 6: During the entire nucleation stage and the first 2h to 3h of the crystal nucleus growth, protective gas is introduced; after the crystal nucleus grows for 2h to 3h, the protective gas flow rate is reduced and a certain flow rate of air is introduced to keep the total gas flow rate unchanged, and the oxygen volume proportion is 1.45% to 1.55%; Feature 7: The flow ratio of the sodium hydroxide solution to the mixed salt solution is 0.54:1 to 0.56:1; Feature 8: Seed particle size reaches D 50 The reaction time of the crystal nucleus growth stage corresponding to 3.4μm~3.6μm is 55h~65h.

7. The preparation method according to claim 6, characterized in that: Seed crystal growth stage: first, a mixed salt solution and a sodium hydroxide solution are added in parallel at a low flow rate, and after a period of reaction, the flow rate of the mixed salt solution is increased by a gradient upflow method; air and protective gas are introduced simultaneously with the feed and the total gas flow rate is kept stable until the precursor seed crystal grows to a preset particle size, thereby obtaining a lithium-rich manganese-based positive electrode material precursor; Before the rising flow, the feeding flow rate of the mixed salt solution is 0.042mol / h to 0.045mol / h; after reacting for 1h to 2h, the feeding flow rate of the mixed salt solution is increased to 0.126mol / h to 0.135mol / h, and the rising flow time is 10h to 12h; Optionally, the seed growth stage has at least one of the following characteristics: Feature 9: Before adding materials, adjust the solid content in the reaction vessel to 40 g / L to 120 g / L; Feature 10: In particle size D 50 When the diameter of the mixed gas is less than 5 μm, the volume proportion of oxygen in the mixed gas is 1.45% to 1.55%; when D 50 When the particle size is greater than 5μm, the air flow rate is increased by gradient upflow and the protective gas flow rate is reduced, so that after 2h to 3h of upflow, the volume proportion of oxygen in the mixed gas introduced reaches 2.5% to 3.5%; Feature 11: The flow ratio of the sodium hydroxide solution to the mixed salt solution is 0.54:1 to 0.56:1; Feature 12: Precursor seed growth to D 50 The reaction time of the seed growth stage corresponding to 6μm to 12μm is 55h to 65h.

8. The preparation method according to any one of claims 4 to 7, characterized in that: During the entire preparation process of the lithium-rich manganese-based positive electrode material precursor, the ratio of the total volume of the protective gas and air introduced per hour to the volume of the reaction container is 1 to 1.

2.

9. A lithium-rich manganese-based positive electrode material, characterized in that: The raw material for preparing the lithium-rich manganese-based positive electrode material includes the lithium-rich manganese-based positive electrode material precursor according to any one of claims 1 to 3.

10. A battery, characterized in that: The raw materials for preparing the battery include the lithium-rich manganese-based positive electrode material as described in claim 9.

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