High-capacity and high-power doped lithium nickel manganese oxide material, preparation method, application and battery

Abstract

The invention provides a high-capacity and high-power doped lithium nickel manganese oxide material, a preparation method, application and a battery. The preparation method comprises the following steps: (1) calcining a mixture of a manganese source, a nickel source, an M source and a sodium source to obtain a precursor NaNi < 0.5-y > Mn < 1.5-z > M < y + z > O < 4 >; wherein M is selected from one or more of Ti, Cr, Co, Cu, Zn and Fe, and y + z is more than 0 and less than or equal to 0.5; and (2) calcining and washing the mixture of the precursor and a lithium source to obtain the doped lithium nickel manganese oxide material Na < x > Li < 1-x > Ni < 0.5-y > Mn < 1.5-z > M < y + z > O < 4 >, and x is more than or equal to 0 and less than 0.1. The doped lithium nickel manganese oxide material prepared by the invention has excellent specific capacity, high rate characteristic and cycle retention rate, and the preparation method does not need a complex precursor preparation process, and is low in raw material cost and strong in process compatibility.

Description

Technical Field

[0001] This invention specifically relates to a high-capacity, high-power doped lithium nickel manganese oxide material, its preparation method, applications, and batteries. Background Technology

[0002] The new energy industry is experiencing explosive growth, with the rapid development of electric vehicles, large-scale electrochemical energy storage power stations, and smart grids placing unprecedented demands on the performance of energy storage devices. As a core component of energy storage devices, cathode materials directly determine the device's energy density, power density, cycle life, and safety performance. Among these, the synergistic improvement of high power and high energy has become a key challenge in current cathode material research and development. Among numerous cathode materials, spinel-structured manganese-based cathode materials occupy an important position in high-power energy storage scenarios due to their low cost, abundant resources, and excellent structural stability. Lithium nickel manganese oxide (LiNi) is another promising candidate. 0.5 Mn 1.5 O4 as spinel Derivative materials, with their unique crystal structure and electrochemical properties, have become one of the core candidate materials for meeting the needs of high-power and high-energy storage.

[0003] spinel It is the earliest manganese-based cathode material to achieve industrial application. It has an open three-dimensional lithium-ion diffusion channel and a high lithium-ion diffusion coefficient, which gives the material excellent high-rate charge and discharge performance. At the same time, manganese is abundant in the earth's crust, and its preparation cost is significantly lower than that of cobalt-based and nickel-cobalt-manganese ternary materials. It has been widely used in power tools, base station backup power supplies and other fields.

[0004] However, The inherent limitations of this material restrict its application in high-energy scenarios: its charge / discharge voltage platform is only around 4.0V, and its energy density is relatively low, making it difficult to meet the range requirements of electric vehicles and the capacity requirements of energy storage stations; during the charge / discharge process, some Mn in the crystal structure... 3+ Jahn-Teller distortion is prone to occur, leading to material structural collapse, while Mn 3+ It will dissolve into the electrolyte, triggering side reactions such as electrolyte decomposition, significantly reducing the cycle stability of the material. This problem is particularly prominent under high-temperature operating conditions, seriously affecting the service life of energy storage devices.

[0005] To solve To address performance bottlenecks, researchers have modified and optimized lithium nickel manganese oxide (LiNi) materials through elemental doping, surface coating, and structural modulation. One such modification involves partially replacing manganese with nickel. 0.5 Mn 1.5 O4 exhibits exceptionally good performance. LiNi 0.5 Mn 1.5O4 inherits from spinel The material features a three-dimensional lithium-ion diffusion channel, and a quarter of the manganese in its crystal structure is replaced by nickel, resulting in a significant leap in its electrochemical performance: its charge / discharge voltage plateau is increased to approximately 4.7V, compared to... The energy density is significantly increased, and the specific capacity is also slightly higher than that of traditional lithium manganese oxide, perfectly meeting the development needs of high-energy storage devices; the valence state of manganese in the material is stable at +4, fundamentally avoiding the Mn... 3+ It overcomes the problems of dissolution and Jahn-Teller distortion, and maintains good structural stability even under high-temperature operating conditions, resulting in a significantly extended cycle life. The introduction of nickel can also optimize the electronic conductivity of the material, further enhancing its high-rate charge and discharge capability, thus demonstrating great potential in high-power scenarios.

[0006] It is precisely because of these excellent properties that lithium nickel manganese oxide (LiNi) materials... 0.5 Mn 1.5 O4 shows broad application prospects in the field of high-power, high-energy storage devices, and is especially suitable for electric vehicles that need to balance long range and fast charging capabilities, large-scale energy storage power stations that require high capacity and high stability, and portable electronic devices.

[0007] However, lithium nickel manganese oxide (LiNi) 0.5 Mn 1.5 The large-scale application of O4 still faces many technical challenges: the material preparation process is complex. Traditional preparation methods mostly use co-precipitation to prepare precursors. This method is cumbersome, has harsh reaction conditions, and high production costs. Moreover, it is very easy to generate impurity phases such as NiO during subsequent calcination. These impurities will seriously damage the crystal integrity of the material, leading to the obstruction of lithium ion diffusion and significantly reducing the cycle stability and rate performance of the material.

[0008] Currently, some studies also use conventional solid-state synthesis methods to prepare lithium nickel manganese oxide (LiNi). 0.5 Mn 1.5 While the O4 method is relatively simple, the poor uniformity of raw material mixing leads to elemental segregation, resulting in low crystallinity and high impurity content in the product. Consequently, the electrochemical properties, such as capacity and rate performance, fail to meet practical application requirements. Therefore, developing a simple, low-cost method for preparing lithium nickel manganese oxide materials with excellent product performance is crucial for promoting its large-scale application in high-power, high-energy storage devices. Summary of the Invention

[0009] This invention addresses the shortcomings of existing preparation technologies by providing a high-capacity, high-power doped lithium nickel manganese oxide material, its preparation method, applications, and batteries. The doped lithium nickel manganese oxide material prepared by this invention possesses a pure spinel structure and exhibits excellent specific capacity, high rate capability, and cycle retention in batteries. Furthermore, the preparation method eliminates the need for complex precursor preparation processes, resulting in low raw material costs, strong process compatibility, and significantly improved production efficiency, thus supporting the large-scale application of high-power, high-energy storage devices.

[0010] This invention abandons the complex co-precipitation precursor preparation process and innovatively uses an ion exchange method to prepare spinel Na. x Li 1-x Ni 0.5-y Mn 1.5-z M y+z O4 achieves multiple performance optimizations through process design: Compared to the common solid-phase direct synthesis method, which is prone to NiO impurities due to uneven raw material mixing and elemental segregation, this invention first prepares uniformly composed NaNi 0.5- y Mn 1.5-z M y+z O4 precursor, then through Li + with Na + Directed ion exchange completes lithiation. The ion-level reaction effectively avoids the local enrichment of nickel to form NiO impurity phase, ensuring the integrity of the material's crystal structure from the source, significantly reducing the negative impact of impurities on cycle performance, and significantly improving the material's cycle stability. Trace amounts of residual Na doping are also eliminated during the ion exchange process. + It can serve as a "pillar" of the crystal structure, further stabilizing the three-dimensional lithium-ion diffusion channels of spinel, reducing the volume distortion of the structure during charging and discharging, and reducing the lithium-ion diffusion resistance, thereby significantly improving the high-rate charge and discharge performance of the material. The present invention adopts a "top-down" preparation path. During the ion exchange phase transition process from precursor to target product, an appropriate amount of lattice defects will naturally form inside the crystal. The lattice spacing will be larger near these defects. These defects can not only provide more active sites for lithium-ion insertion and extraction and improve the specific capacity of the material, but also construct additional ion transport paths to further optimize the rate performance, and finally achieve a synergistic improvement in material capacity and rate performance.

[0011] The present invention solves the above-mentioned technical problems through the following technical solutions:

[0012] This invention provides a method for preparing high-capacity, high-power doped lithium nickel manganese oxide materials, comprising the following steps:

[0013] (1) A mixture of manganese source, nickel source, M source and sodium source was calcined to obtain the precursor NaNi. 0.5-y Mn 1.5-z My+z O4; wherein M is selected from one or more of Ti, Cr, Co, Cu, Zn and Fe, and 0 < y + z ≤ 0.5;

[0014] (2) The mixture of the precursor and the lithium source is calcined and washed to obtain the doped lithium nickel manganese oxide material Na. x Li 1-x Ni 0.5-y Mn 1.5-z M y+z O4, 0 ≤ x < 0.1.

[0015] In step (1), the amounts of manganese source, nickel source, M source and sodium source can be conventional in the art, and can generally be added according to the stoichiometric ratio. Preferably, the molar ratio of manganese in the manganese source, nickel in the nickel source, M in the M source and sodium in the sodium source can be (1.5-z):(0.5-y):(y+z):(0.9-1.2), for example 1.45:0.45:0.1:1.

[0016] In step (1), the manganese source can be conventional in the art, preferably one or more of manganese carbonate, manganese dioxide, and manganese nitrate tetrahydrate. The nickel source can be conventional in the art, preferably one or more of nickel oxide, nickel carbonate, and nickel nitrate hexahydrate. The M source can be one or more of carbonates, acetates, nitrates, and oxides containing metal M, preferably... , , , CuO, ZnO and One or more of the following. The sodium source can be conventional in the art, and preferably one or more of sodium carbonate, sodium hydroxide, and sodium nitrate.

[0017] In step (1), the preparation method of the mixture of manganese source, nickel source, M source and sodium source can be conventional in the art, such as grinding each raw material into uniform powder.

[0018] In step (1), the calcination atmosphere is generally air; the calcination can be carried out in a muffle furnace or a tube furnace; the rate of heating to the calcination temperature can be... For example, The calcination temperature can be 400-600℃, for example 450℃, 480℃, 500℃, 520℃ or 550℃, preferably 480-520℃; the calcination holding time can be 4-18h, for example 6h, 8h, 10h or 12h, preferably 8-12h.

[0019] In step (1), after the calcination is completed, it is generally necessary to cool naturally to room temperature.

[0020] In step (2), in the doped lithium nickel manganese oxide material, x is preferably 0 < x < 0.06, for example, 0.02, 0.03, or 0.05; y can be 0 < y < 0.3, preferably 0 < y ≤ 0.2, for example, 0.02, 0.03, 0.05, 0.1, 0.15, or 0.18; z can be 0 < z < 0.3, preferably 0 < z ≤ 0.2, for example, 0.02, 0.03, 0.05, 0.1, 0.15, or 0.18; 0 < y + z ≤ 0.3, for example, 0.05, 0.1, or 0.2. In step (2), the meaning and range of y and z in the doped lithium nickel manganese oxide material are the same as in step (1).

[0021] In step (2), the lithium source can be LiCl, , and One or more of them.

[0022] In step (2), the molar ratio of sodium in the precursor to lithium in the lithium source can be 1:(0.9-1.2), for example 1:1.

[0023] In step (2), the preparation method of the mixture of precursor and lithium source can be conventional in the art, such as grinding each raw material into a uniform powder.

[0024] In step (2), the calcination atmosphere is generally air; the calcination can be carried out in a muffle furnace or a tube furnace. The calcination temperature can be 400-800℃, for example 450℃, 500℃, 520℃, 550℃, 580℃, 600℃, 620℃, 650℃, 680℃, or 700℃; the calcination time can be 1-8h, for example 2h, 2.5h, 3h, 4h, or 6h; the rate of heating to the calcination temperature can be... ,For example After calcination, the material should generally be allowed to cool naturally to room temperature.

[0025] In some specific implementations, in step (2), the calcination temperature is 600°C and the calcination time is 4 hours.

[0026] In step (2), the solvent used for washing is generally deionized water; preferably, the washing involves repeated rinsing with deionized water until the filtrate is neutral, in order to remove unreacted lithium source and byproducts. After washing, vacuum filtration is generally required. Vacuum filtration can be performed using a Buchner funnel in conjunction with a circulating water vacuum pump.

[0027] In step (2), drying is generally required after washing. The drying process ensures that the moisture content of the solid product is below 0.5%.

[0028] The drying method can be conventional in the art, such as drying and / or calcination.

[0029] The drying is generally carried out in a forced-air drying oven; the drying temperature can be 80-120℃, for example 90℃ or 100℃; the drying time can be 6-24 hours, for example 8 hours, 10 hours, or 12 hours. The calcination atmosphere is generally air; the calcination can be carried out in a muffle furnace or a tube furnace. The rate of heating to the calcination temperature can be... ,For example The calcination temperature can be 500-900℃, for example 550℃, 600℃, 650℃, 700℃, 800℃ or 850℃; the calcination holding time can be 8-12h, for example 10h.

[0030] In some specific embodiments, the drying preferably includes the following process: first drying the washed material, and then calcining it.

[0031] The present invention also provides a high-capacity, high-power doped lithium nickel manganese oxide material prepared by the preparation method described above.

[0032] This invention also provides a high-capacity, high-power doped lithium nickel manganese oxide material with the chemical formula Na. x Li 1-x Ni 0.5- y Mn 1.5-z M y+z O4 has a pure spinel structure, and the crystal structure of the doped lithium nickel manganese oxide material contains dislocation defects; wherein M is selected from one or more of Ti, Cr, Co, Cu, Zn and Fe, and 0≤x<0.1, 0<y+z≤0.5.

[0033] In this invention, the high-capacity, high-power doped lithium nickel manganese oxide material is preferably free of NiO impurity phase. The particle size D of the high-capacity, high-power doped lithium nickel manganese oxide material is... 50 It can be 1-5μm.

[0034] In this invention, x in the chemical formula is preferably 0 < x < 0.06, for example 0.01, 0.02, 0.03 or 0.05.

[0035] In this invention, y in the chemical formula can be 0 < y < 0.3, preferably 0 < y ≤ 0.2, for example 0.02, 0.03, 0.05, 0.1, 0.15 or 0.18.

[0036] In this invention, z in the chemical formula can be 0 < z < 0.3, preferably 0 < z ≤ 0.2, for example 0.02, 0.03, 0.05, 0.1, 0.15 or 0.18.

[0037] In this invention, in the chemical formula, 0 < y + z ≤ 0.3, for example, 0.05, 0.1 or 0.2.

[0038] In this invention, when M is two or more metals in the chemical formula, the molar amount of each metal can be the same or different, as long as the total molar amount satisfies the range of y+z.

[0039] When M includes Co and Cr, the molar ratio of Co and Cr can be 1:(0.5-1.5), for example 1:0.8, 1:1 or 1:1.2.

[0040] In some specific implementation schemes, the chemical formula is Na. 0.02 Li 0.98 Ni 0.45 Co 0.05 Mn 1.45 Cr 0.05 O4.

[0041] In this invention, the dislocation defect refers to a linear atomic arrangement defect present in the crystal structure of the material. The dislocation defect is caused by the shrinkage of the unit cell volume during the transformation from a sodium-based matrix structure to a spinel structure, resulting in a larger lattice spacing near these defects. The interplanar spacing of the (111) plane in the vicinity of the dislocation defect is preferably 0.48-0.52 nm, for example, 0.49 nm, 0.495 nm, 0.50 nm, 0.503 nm, 0.505 nm, or 0.51 nm.

[0042] In this invention, the 1C rate specific capacity of the high-capacity, high-power doped lithium nickel manganese oxide material is preferably 112-140 mAh / g, for example 115 mAh / g, 120 mAh / g, 126 mAh / g, 128 mAh / g, 129 mAh / g, 130 mAh / g, 131 mAh / g, 132 mAh / g or 135 mAh / g.

[0043] In this invention, the 5C rate specific capacity of the high-capacity, high-power doped lithium nickel manganese oxide material is preferably 90-135 mAh / g, for example 95 mAh / g, 98 mAh / g, 105 mAh / g, 110 mAh / g, 112 mAh / g, 115 mAh / g, 116 mAh / g, 118 mAh / g, 119 mAh / g, 120 mAh / g, or 130 mAh / g.

[0044] In this invention, the capacity retention rate of the high-capacity, high-power doped lithium nickel manganese oxide material after 100 cycles of 1C is preferably 85%-100%, for example 88%, 90%, 92%, 95%, 96%, 97%, 98% or 99%.

[0045] The present invention also provides an application of the high-capacity, high-power doped lithium nickel manganese oxide material as described above in batteries.

[0046] The present invention also provides a battery comprising a positive electrode, a negative electrode, and an electrolyte, wherein the positive electrode comprises the high-capacity, high-power doped lithium nickel manganese oxide material.

[0047] In this invention, the battery may be a lithium-ion battery or a solid-state lithium battery.

[0048] Based on common knowledge in the field, the above-mentioned preferred conditions can be combined arbitrarily to obtain various preferred embodiments of the present invention.

[0049] The reagents and raw materials used in this invention are all commercially available.

[0050] The positive and progressive effects of this invention are as follows:

[0051] Na prepared by this invention x Li 1-x Ni 0.5-y Mn 1.5-z M y+z O4 cathode material has a pure spinel structure, which can effectively avoid the formation of NiO impurity phase, resulting in better specific capacity, high rate performance and cycle retention. Moreover, the preparation method does not require complex precursor preparation process, has low raw material cost and strong process compatibility, which can significantly improve production efficiency and provide support for the large-scale application of high-power and high-energy energy storage devices. Attached Figure Description

[0052] Figure 1 SEM image of the doped lithium nickel manganese oxide material prepared in Example 1;

[0053] Figure 2 HRTEM image of the doped lithium nickel manganese oxide material prepared in Example 1;

[0054] Figure 3 XRD patterns of the precursors doped with sodium nickel manganate and lithium nickel manganate prepared in Example 1;

[0055] Figure 4 A comparison chart of the cycling performance of the doped lithium nickel manganese oxide material prepared in Example 1 and the lithium nickel manganese oxide material prepared in Comparative Example 1 under 1C conditions;

[0056] Figure 5The graph shows a comparison of the rate performance of the doped lithium nickel manganese oxide material prepared in Example 1 and the lithium nickel manganese oxide material prepared in Comparative Example 1. Detailed Implementation

[0057] The present invention is further illustrated below by way of embodiments, but the invention is not limited to the scope of the embodiments described herein. Experimental methods in the following embodiments that do not specify specific conditions were performed according to conventional methods and conditions, or as selected according to the product instructions.

[0058] Example 1

[0059] Step (1): Weigh 3.380 g (Chinese medicine, analytical grade, model AR), 0.672 g NiO (Aladdin, 99.9% purity), 0.073 g (Aladdin, 99.9% purity), 0.076 g (Aladdin, 99.9% purity) and 1.060 g (Analytical grade, model AR) was placed in a mortar and thoroughly mixed and ground into a uniform powder. The powder was then transferred to a muffle furnace (Shanghai Yiheng, model SX2-4-10) for further grinding. The temperature was increased to 500℃ at a heating rate and held at this temperature for 10 h. After the holding period, the temperature was naturally cooled to room temperature to obtain the precursor doped sodium nickel manganate (NaNi). 0.45 Co 0.05 Mn 1.45 Cr 0.05 O4).

[0060] Step (2): The precursor doped sodium nickel manganate prepared in step (1) was mixed and ground evenly with 0.848 g of LiCl (Shanghai Maclean, analytical grade) in a mortar. The ground mixture was then placed in a muffle furnace and calcined at 600 °C for 4 h for ion exchange. After calcination, the mixture was cooled to room temperature. The cooled product was washed in deionized water to remove soluble sodium salt byproducts (such as NaCl) and excess lithium salt. Then, it was filtered using a Buchner funnel and a circulating water vacuum pump (model SHB-III). The solid product obtained by filtration was placed in a forced-air drying oven (Chongqing Sida, model 101-1AB) and dried (80 °C, 8 h). Finally, high-temperature annealing was performed. The dried solid sample was placed in a muffle furnace and calcined at 800 °C for 10 h. After calcination, the sample was naturally cooled to room temperature with the furnace to obtain the doped lithium nickel manganate material Na. 0.02 Li 0.98 Ni 0.45 Co 0.05 Mn 1.45 Cr 0.05 O4.

[0061] Example 2

[0062] Except for converting 0.848 g LiCl to 1.379 g Except for (Shanghai Maclean's, analytical grade), all other conditions remain unchanged.

[0063] Example 3

[0064] Except for converting 0.848 g LiCl to 0.739 g Except for (Chinese medicine, analytical grade), all other conditions remain unchanged.

[0065] Example 4

[0066] Except for converting 0.848 g LiCl to 0.839 g Except for Aladdin (analytical grade), all other conditions remain unchanged.

[0067] Example 5

[0068] Compared with Example 1, except that the calcination temperature of ion exchange in step (2) is changed to 550°C, all other operations and conditions are the same as in Example 1.

[0069] Example 6

[0070] Compared with Example 1, except that the calcination temperature of ion exchange in step (2) is changed to 650°C, all other operations and conditions are the same as in Example 1.

[0071] Example 7

[0072] Compared with Example 1, except that the calcination time for ion exchange in step (2) is changed to 2h, all other operations and conditions are the same as in Example 1.

[0073] Comparative Example 1

[0074] A method for preparing LiNi using conventional solid-state synthesis 0.5 Mn 1.5 The specific steps for preparing O4 are as follows: Weigh 0.370 g Li2CO3 (Sinopharm, analytical grade), 3.450 g MnCO3 (Sinopharm, analytical grade), and 0.747 g NiO (Aladdin, 99.9% purity). Place all the above raw materials together in a mortar, add a small amount of anhydrous ethanol as a dispersant, and grind thoroughly for 30 min until a uniform and fine slurry is formed. Then, place the slurry in a forced-air drying oven (Chongqing Sida, model 101-1AB) and dry it at 80 ℃ until the ethanol is completely evaporated, obtaining a dry mixed powder. Transfer the mixed powder to a muffle furnace and... The temperature was increased to 650 °C at a heating rate, and pre-calcined at this temperature for 6 h. After pre-calcination, the sample was allowed to cool naturally to room temperature. The sample was then removed and ground again in a mortar for 15 min. The powder after the second grinding was then placed back into the muffle furnace and ground further at a heating rate of [missing information]. The temperature was increased to 850 °C at a heating rate, held at that temperature for 12 h for high-temperature calcination, and then cooled to room temperature with the furnace after calcination to directly obtain the product LiNi. 0.5 Mn 1.5 O4.

[0075] Effect Example

[0076] (1) Characterization of material properties

[0077] according to Figure 1 It can be seen that the doped lithium nickel manganese oxide material prepared in Example 1 did not form large primary or secondary particles; according to Figure 2 It is known that the doped lithium nickel manganese oxide material prepared in Example 1 has many defects, mainly dislocation defects. These defects are caused by the shrinkage of the unit cell volume during the transformation from a sodium-based matrix structure to a spinel structure. The lattice spacing is larger near these defects. The standard interplanar spacing of the spinel lithium nickel manganese oxide (111) plane is 0.472 nm, while the lattice spacing near the defects is 0.503 nm. The larger lattice spacing provides a wider and faster channel for lithium-ion transport. Figure 3 It can be seen that the doped lithium nickel manganese oxide material prepared in Example 1 has a pure spinel structure and does not contain impurities such as nickel oxide.

[0078] (2) ICP: After dissolving the product in hydrochloric acid, ICP-MS was performed to obtain the elemental composition, thereby calculating the specific molecular composition of the doped lithium nickel manganese oxide prepared in each embodiment.

[0079] (3) Electrochemical performance testing

[0080] The doped lithium nickel manganese oxide materials prepared in Examples 1-7 and Comparative Example 1, along with SuperP and polyvinylidene fluoride, were uniformly mixed in a mass ratio of 8:1:1. NMP solvent was added to prepare an electrode slurry. The electrode slurry was then uniformly coated onto aluminum foil using a coating machine and dried under vacuum at 120°C for 12 hours. Finally, positive electrode sheets with a 12mm diameter hole were punched on a tablet press. The loading of active material on the electrode sheets was approximately... Additionally, using lithium metal as the negative electrode, The electrolyte was EC:DMC:EMC = 1:1:1 (volume ratio), and the separator was Celgard 2400. A CR2032 coin cell was assembled and charged / discharge tested within the 2.5-4.9 V voltage range. Performance indicators included 1C rate specific capacity, 5C high-rate specific capacity, capacity retention after 100 cycles at 1C rate, and rate performance. Specific test results are shown in Table 1. Figure 4 and Figure 5 As shown, the theoretical value of 1C is 147 mAh / g.

[0081] Table 1

[0082]

[0083] Based on the above experimental results, it can be seen that the specific capacity, high-rate performance and cycle life of the lithium nickel manganese oxide prepared by the present invention are significantly better than those of lithium nickel manganese oxide synthesized by traditional solid phase synthesis.

[0084] Comparison of the rate performance of Example 1 and Comparative Example 1 Figure 5 As shown, dislocation defects and the relatively large lattice spacing near the defects provide a fast channel for lithium-ion migration, resulting in a significant improvement in rate performance.

[0085] While specific embodiments of the present invention have been described above, those skilled in the art should understand that these are merely illustrative examples, and the scope of protection of the present invention is defined by the appended claims. Those skilled in the art can make various changes or modifications to these embodiments without departing from the principles and essence of the present invention, but all such changes and modifications fall within the scope of protection of the present invention.

Claims

1. A method for preparing a high-capacity, high-power doped lithium nickel manganese oxide material, characterized in that, Includes the following steps: (1) A mixture of manganese source, nickel source, M source and sodium source was calcined to obtain the precursor NaNi. 0.5-y Mn 1.5-z M y+z O4; wherein M is selected from one or more of Ti, Cr, Co, Cu, Zn and Fe, and 0 < y + z ≤ 0.5; (2) The mixture of the precursor and the lithium source is calcined and washed to obtain the doped lithium nickel manganese oxide material Na. x Li 1- x Ni 0.5-y Mn 1.5-z M y+z O4, 0 ≤ x < 0.

1.

2. The preparation method of the high-capacity, high-power doped lithium nickel manganese oxide material as described in claim 1, characterized in that, Step (2) satisfies one or more of the following conditions: (1) In the doped lithium nickel manganese oxide material, 0 < x < 0.06, for example 0.02, 0.03 or 0.05; (2) The lithium source is LiCl, , and One or more of the following; (3) The molar ratio of sodium in the precursor to lithium in the lithium source is 1:(0.9-1.2).

3. The preparation method of the high-capacity, high-power doped lithium nickel manganese oxide material as described in claim 1, characterized in that, In step (2), the calcination temperature is 400-800℃, for example 450℃, 500℃, 520℃, 550℃, 580℃, 600℃, 620℃, 650℃, 680℃ or 700℃; And / or, in step (2), the calcination time is 1-8h, for example 2h, 2.5h, 3h, 4h or 6h.

4. The preparation method of the high-capacity, high-power doped lithium nickel manganese oxide material as described in claim 1, characterized in that, In step (2), drying is required after washing; The drying method is preferably drying and / or calcination; the calcination temperature is preferably 500-900℃; and the calcination holding time is preferably 8-12h.

5. The method for preparing high-capacity, high-power doped lithium nickel manganese oxide material as described in claim 1, characterized in that, Step (1) satisfies one or more of the following conditions: (1) The amounts of the manganese source, nickel source, doping element source and sodium source are added according to the stoichiometric ratio; (2) The manganese source is one or more of manganese carbonate, manganese dioxide, and manganese nitrate tetrahydrate; (3) The nickel source is one or more of nickel oxide, nickel carbonate, and nickel nitrate hexahydrate; (4) The M source is one or more of carbonates, acetates, nitrates, and oxides containing metal M, preferably... , , , CuO, ZnO and One or more of the following; (5) The sodium source is one or more of sodium carbonate, sodium hydroxide, and sodium nitrate; (6) The calcination temperature is 400-600℃, for example 450℃, 480℃, 500℃, 520℃ or 550℃; (7) The calcination holding time is 4-18h, for example 6h, 8h, 10h or 12h; (8) In the precursor, y is 0 < y < 0.3, preferably 0 < y ≤ 0.2, for example 0.02, 0.03, 0.05, 0.1, 0.15 or 0.18; (9) In the precursor, z is 0 < z < 0.3, preferably 0 < z ≤ 0.2, for example 0.02, 0.03, 0.05, 0.1, 0.15 or 0.18; (10) 0 < y + z ≤ 0.3, for example 0.05, 0.1 or 0.

2.

6. A high-capacity, high-power doped lithium nickel manganese oxide material prepared by a method according to any one of claims 1-5.

7. A high-capacity, high-power doped lithium nickel manganese oxide material, characterized in that, The chemical formula is Na x Li 1-x Ni 0.5-y Mn 1.5- z M y+z O4 has a pure spinel structure, and the crystal structure of the doped lithium nickel manganese oxide material contains dislocation defects; wherein M is selected from one or more of Ti, Cr, Co, Cu, Zn and Fe, and 0≤x<0.1, 0<y+z≤0.

5.

8. The high-capacity, high-power doped lithium nickel manganese oxide material as described in claim 7, characterized in that, The doped lithium nickel manganese oxide material satisfies one or more of the following conditions: (1) The high-capacity, high-power doped lithium nickel manganese oxide material is free of NiO impurity phase; (2) The particle size D of the high-capacity, high-power doped lithium nickel manganese oxide material 50 1-5μm; (3) In the chemical formula, x is 0 < x < 0.06; (4) In the chemical formula, y is 0 < y < 0.3; (5) In the chemical formula, z is 0 < z < 0.3; (6) In the chemical formula, 0 < y + z ≤ 0.3; (7) The interplanar spacing of the (111) plane in the vicinity of the dislocation defect is 0.48-0.52 nm, for example 0.49 nm, 0.495 nm, 0.50 nm, 0.503 nm or 0.51 nm; (8) The 1C rate specific capacity of the high-capacity, high-power doped lithium nickel manganese oxide material is 112-140 mAh / g; (9) The 5C rate specific capacity of the high-capacity, high-power doped lithium nickel manganese oxide material is 90-135 mAh / g; (10) The capacity retention rate of the high-capacity, high-power doped lithium nickel manganese oxide material after 100 cycles of 1C is 85%-100%.

9. The application of a high-capacity, high-power doped lithium nickel manganese oxide material as described in any one of claims 6-8 in a battery.

10. A battery, characterized in that, It includes a positive electrode, a negative electrode, and an electrolyte, wherein the positive electrode comprises a high-capacity, high-power doped lithium nickel manganese oxide material as described in any one of claims 6-8.

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