CN116282204A - Positive electrode nickel-manganese material precursor, and preparation method and application thereof - Google Patents

Positive electrode nickel-manganese material precursor, and preparation method and application thereof Download PDF

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CN116282204A
CN116282204A CN202211313676.7A CN202211313676A CN116282204A CN 116282204 A CN116282204 A CN 116282204A CN 202211313676 A CN202211313676 A CN 202211313676A CN 116282204 A CN116282204 A CN 116282204A
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solution
nickel
positive electrode
manganese
concentration
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张坤
贡正杰
李聪
许开华
薛晓斐
李雪倩
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GEM Co Ltd China
Jingmen GEM New Material Co Ltd
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Jingmen GEM New Material Co Ltd
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Abstract

The invention provides a positive electrode nickel-manganese material precursor, a preparation method and application thereof, wherein the positive electrode nickel-manganese material precursor comprises a core and a shell arranged on the surface of the core, the core comprises a P element, the shell comprises a transition metal element, and the transition metal element comprises any one or a combination of at least two of W, al, cu, fe, cr, zr and Sr. The precursor particles prepared by the method have the advantages that the P element in the core layer is uniformly doped, the metal element is doped in the shell layer, and the positive electrode material obtained after sintering the precursor has higher gram capacity and has excellent cycle performance and multiplying power performance when working in the range of 3.5-4.9V of high voltage.

Description

Positive electrode nickel-manganese material precursor, and preparation method and application thereof
Technical Field
The invention belongs to the technical field of lithium ion batteries, and relates to a positive electrode nickel-manganese material precursor, a preparation method and application thereof.
Background
Lithium ion batteries have been widely used in the fields of electric automobiles, electric tools, and the like, and in addition to safety, high energy density and power density are essential performance indexes that need to be satisfied. Generally, the improvement of the energy density of lithium ion batteries is mainly achieved by increasing the gram capacity and voltage of materials. Nickel cobalt manganese ternary layered oxides have been widely studied over the last two decades and have shown high capacity and good capacity retention. The high cost of cobalt raw materials and uncertainty in the supply chain has driven a strong need to find alternative cathode materials. Just spinel type lithium nickel manganese oxide has a voltage of up to 4.8V (vs Li/Li + ) The lithium ion battery positive electrode material has high working voltage, high energy and power density and no cobalt element, is an ideal power lithium ion battery positive electrode material, and has great potential to replace ternary positive electrode materials.
Spinel type lithium nickel manganese oxide (LiNi) 0.5 Mn 1.5 O 4 ) The positive electrode material has two problems in practical application, namely (1) manganese ions undergo disproportionation reaction in electrolyte to cause ion dissolution, so that the electrochemical cycle performance of the material is poor; (2) Instability of the electrode-electrolyte interface causes thicker SEI films to form during cycling, thereby increasing interface resistance.
CN104538604a discloses a surface modification method of a lithium nickel manganese oxide positive electrode material, which comprises the following steps: (1) Immersing lithium nickel manganese oxide powder in the activation solution for 10-60 min, and washing with water to neutrality; (2) Heating the activated lithium nickel manganese oxide in a constant-temperature electric heating box at 300-350 ℃ for 20-40 min to obtain a lithium nickel manganese oxide matrix with elemental nickel on the surface; (3) Pouring the treated nickel lithium manganate matrix with the simple substance nickel on the surface into chemical plating solution, magnetically stirring or ultrasonically dispersing the nickel lithium manganate matrix for 20-60 min, and then carrying out suction filtration, washing and vacuum drying to obtain the nickel-coated nickel lithium manganate material.
CN106025267a discloses a method for modifying micron-sized lithium nickel manganese oxide with core-shell structure, which comprises the following steps: activating and preprocessing a lithium nickel manganese oxide material; preparing electroless copper plating solution; adding the pretreated and activated lithium nickel manganese oxide material into plating solution to carry out electroless copper plating; agNO is to be carried out 3 Adding the solution into the reaction solution with complete reaction in a spray mode; and filtering, washing and drying the reaction liquid to generate a layer of nano silver/nano copper coating on the surface of the micron-sized lithium nickel manganese oxide material, thereby forming the anode material with a nano silver/nano copper/lithium nickel manganese oxide three-layer core-shell structure.
At present, the method mainly comprises the following steps of 0.5 Mn 1.5 O 4 The anode material is modified by ion doping and coating with various coating materials in post-treatment, and the methods can improve the LiNi to a certain extent 0.5 Mn 1.5 O 4 And the discharge capacity and cycle stability of the same. However, these processes are relatively complex to operate and have high industrialization costs.
Disclosure of Invention
The invention aims to provide a precursor of a positive electrode nickel-manganese material, a preparation method and application thereof, wherein the precursor prepared by the method has the advantages that the P element in a core layer of particles is uniformly doped, any one of metal elements such as W, al, cu, fe, cr, zr, sr is doped in a shell layer, the positive electrode material obtained after sintering the precursor has higher gram capacity, and the positive electrode material has excellent cycle performance and multiplying power performance when working in a high voltage range of 3.5-4.9V.
In order to achieve the aim of the invention, the invention adopts the following technical scheme:
in a first aspect, the present invention provides a positive electrode nickel-manganese material precursor, which includes a core and a shell disposed on a surface of the core, the core includes a P element, the shell includes a transition metal element, and the transition metal element includes any one or a combination of at least two of W, al, cu, fe, cr, zr or Sr.
The invention directly carries out element doping in the precursor coprecipitation stage, and compared with a doping method of mixed calcination, the invention can simplify the preparation process of the anode material and reduce the energy consumption in the preparation of the material.
After P is doped in the inner core of the precursor of the positive electrode nickel-manganese material, more Mn is generated in the positive electrode material 3+ Ions, strengthen LiNi 0.5 Mn 1.5 O 4 Such disordered arrangement of transition metal ions can significantly improve the conductivity of lithium ions and electrons. In addition, the doped P nickel manganese positive electrode material presents more {111} crystal faces, and the {111} crystal faces help to protect the bulk material from further reaction with electrolyte under high working voltage, so that higher capacity retention rate is presented.
According to the anode nickel manganese material precursor, metal elements such as W, al, cu, fe, cr, zr, sr are doped in the shell structure, so that on one hand, the transmission rate of lithium ions can be improved, and the accumulation of the lithium ions on the surface of particles is reduced, so that the polarization and stable crystal structure are reduced, on the other hand, part of metal ions doped in the shell layer can segregate to the outer surface of the particles to form a stable SEI film, and the occurrence of harmful interface side reactions is restrained, so that the cycle performance of the material is improved.
Preferably, the inner core has the chemical formula of Ni 0.5 Mn 1.5 [PO 4 ] x (OH) 4-3x Wherein 0.001. Ltoreq.x.ltoreq.0.020, for example: 0.001, 0.005, 0.01, 0.015, 0.02, etc.
Preferably, the shell has the chemical formula of Ni 0.5-y M 2y Mn 1.5-y (OH) 4 Wherein 0.001. Ltoreq.y.ltoreq.0.020, for example: 0.001, 0.005, 0.01, 0.015, or 0.02, etc., M includes any one or a combination of at least two of W, al, cu, fe, cr, zr or Sr.
Preferably, the thickness of the shell is 0.4-1 μm, for example: 0.4 μm, 0.6 μm, 0.7 μm, 0.8 μm or 1 μm, etc.
In a second aspect, the present invention provides a method for preparing the precursor of the positive electrode nickel manganese material according to the first aspect, the method comprising the following steps:
(1) Adding nickel-manganese mixed salt solution, phosphorus source solution, precipitant solution and complexing agent solution into base solution in parallel flow, and regulating pH value to perform one-step coprecipitation reaction;
(2) Changing the phosphorus source solution in the step (1) into a doped metal salt solution, and carrying out two-step coprecipitation reaction under other conditions without change;
(3) And (3) washing the coprecipitation reaction product obtained in the step (2) to obtain the anode nickel-manganese material precursor.
Preferably, the total concentration of metal ions in the nickel manganese mixed salt solution in the step (1) is 0.1-5 mol/L, for example: 0.1mol/L, 0.5mol/L, 1mol/L, 2mol/L, 5mol/L, etc.
Preferably, the feeding speed of the nickel-manganese mixed salt solution is 4-100L/h, for example: 4L/h, 5L/h, 10L/h, 20L/h, 50L/h, 100L/h, etc.
Preferably, the phosphorus source solution comprises a diammonium phosphate solution.
Preferably, the concentration of the solute in the phosphorus source solution is 0.01 to 0.5mol/L, for example: 0.01mol/L, 0.05mol/L, 0.1mol/L, 0.2mol/L or 0.5mol/L, etc.
Preferably, the feeding rate of the phosphorus source solution is 0.4 to 10L/h, for example: 0.4L/h, 0.5L/h, 1L/h, 2L/h, 5L/h, 10L/h, etc.
Preferably, the precipitant solution comprises sodium hydroxide solution.
Preferably, the concentration of solute in the precipitant solution is 2-15 mol/L, for example: 2mol/L, 5mol/L, 8mol/L, 10mol/L, 15mol/L, etc.
Preferably, the feed rate of the precipitant solution is 1 to 20L/h, for example: 1L/h, 2L/h, 5L/h, 10L/h, 20L/h, etc.
Preferably, the complexing agent solution comprises aqueous ammonia.
Preferably, the concentration of the solute in the complexing agent solution is 4-12 mol/L, for example: 4mol/L, 6mol/L, 8mol/L, 10mol/L, 12mol/L, etc.
Preferably, the complexing agent solution is fed at a rate of 0.5 to 10L/h, for example: 0.5L/h, 1L/h, 2L/h, 5L/h, 10L/h, etc.
Preferably, the pH is adjusted to 9 to 13, for example: 9. 10, 11, 12 or 13, etc.
Preferably, the temperature of the one-step coprecipitation reaction is 40 to 80 ℃, for example: 40 ℃, 50 ℃, 60 ℃, 70 ℃ or 80 ℃ and the like.
Preferably, the atmosphere of the one-step coprecipitation reaction is an inert atmosphere.
Preferably, the median particle diameter D50 of the material after the one-step coprecipitation reaction is 7 to 9 μm, for example: 7 μm, 7.5 μm, 8 μm, 8.5 μm or 9 μm, etc.
Preferably, the solute of the doped metal salt solution of step (2) comprises any one or a combination of at least two of W, al, cu, fe, cr, zr or Sr salts.
Preferably, the concentration of the solute in the doped metal salt solution is 0.01 to 0.5mol/L, for example: 0.01mol/L, 0.05mol/L, 0.1mol/L, 0.2mol/L or 0.5mol/L, etc.
Preferably, the feeding speed of the doped metal salt solution is 0.4-10L/h, for example: 0.4L/h, 0.5L/h, 1L/h, 2L/h, 5L/h, 10L/h, etc.
Preferably, the median particle diameter D50 of the material after the two-step coprecipitation reaction is 8 to 10 μm, for example: 8 μm, 8.5 μm, 9 μm, 9.5 μm or 10 μm, etc.
Preferably, the washing treatment of step (3) comprises alkali washing followed by water washing.
Preferably, the volume of alkali liquor used per 100kg of materials in the alkaline washing process is 1-3 m 3 For example: 1m 3 、1.5m 3 、2m 3 、2.5m 3 Or 3m 3 Etc.
Preferably, the volume of water used per 100kg of material in the water washing process is 1-5 m 3 For example: 1m 3 、2m 3 、3m 3 、4m 3 Or 5m 3 Etc.
In a third aspect, the invention provides a positive electrode nickel-manganese material, which is obtained by sintering the positive electrode nickel-manganese material precursor in the first aspect and mixing and sintering a lithium source.
In a fourth aspect, the present invention provides a positive electrode sheet comprising the positive electrode nickel manganese material according to the third aspect.
In a fifth aspect, the present invention provides a lithium ion battery comprising the positive electrode sheet according to the fourth aspect.
Compared with the prior art, the invention has the following beneficial effects:
(1) The precursor particles prepared by the method have the advantages that the P element in the core layer is uniformly doped, any one of metal elements such as W, al, cu, fe, cr, zr, sr and the like is doped in the shell layer, and the positive electrode material obtained after the precursor is sintered has higher gram capacity and has excellent cycle performance and multiplying power performance when working in a high voltage range of 3.5-4.9V.
(2) The invention directly carries out element doping in the precursor coprecipitation stage, and compared with a doping method of mixed calcination, the invention can simplify the preparation process of the anode material and reduce the energy consumption in the preparation of the material.
(3) After P is doped in the inner core of the precursor of the positive electrode nickel-manganese material, more Mn is generated in the positive electrode material 3+ Ions, strengthen LiNi 0.5 Mn 1.5 O 4 Such disordered arrangement of transition metal ions can significantly improve the conductivity of lithium ions and electrons. In addition, the doped P nickel manganese positive electrode material presents more {111} crystal faces, and the {111} crystal faces help to protect the bulk material from further reaction with electrolyte under high working voltage, so that higher capacity retention rate is presented.
(4) According to the anode nickel manganese material precursor, metal elements such as W, al, cu, fe, cr, zr, sr are doped in the shell structure, so that on one hand, the transmission rate of lithium ions can be improved, and the accumulation of the lithium ions on the surface of particles is reduced, so that the polarization and stable crystal structure are reduced, on the other hand, part of metal ions doped in the shell layer can segregate to the outer surface of the particles to form a stable SEI film, and the occurrence of harmful interface side reactions is restrained, so that the cycle performance of the material is improved. .
Drawings
Fig. 1 is an SEM image of a positive nickel manganese material precursor described in example 1.
Detailed Description
The technical scheme of the invention is further described by the following specific embodiments. It will be apparent to those skilled in the art that the examples are merely to aid in understanding the invention and are not to be construed as a specific limitation thereof.
Example 1
The embodiment provides a positive electrode nickel-manganese material precursor, which is prepared by the following steps:
(1) The mixed salt solution with the total concentration of metal ions being 2mol/L (nickel-manganese molar ratio is 1:3), the monoammonium phosphate solution with the concentration of 0.1mol/L, the sodium hydroxide solution with the concentration of 10mol/L and the ammonia water with the concentration of 8mol/L are added into the base solution with the pH value being 11.4 and the ammonia concentration being 0.4mol/L in parallel flow. In the parallel flow adding process, the feeding speed of the mixed salt solution of nickel, cobalt and manganese is 20L/h, the feeding speed of the ammonium dihydrogen phosphate solution is 1L/h, the pH value of a reaction system is controlled to be 10.5, the concentration of a complexing agent is controlled to be 0.40mol/L by controlling the flow of a precipitator and the flow of a complexing agent solution, the coprecipitation reaction is carried out at the reaction temperature of 58 ℃ under the protection of nitrogen, the reaction is carried out for 50h, the average grain diameter reaches 7.5 mu m, and the reaction in the first stage is stopped;
(2) And adding a mixed salt solution with the total concentration of metal ions of 2mol/L (nickel-manganese molar ratio of 1:3), an ammonium tungstate solution with the concentration of 0.1mol/L, a sodium hydroxide solution with the concentration of 10mol/L and an ammonia water with the concentration of 8mol/L into the mixed solution after the first-stage reaction in parallel. In the parallel flow adding process, the feeding speed of the mixed salt solution of nickel, cobalt and manganese is 20L/h, the feeding speed of the ammonium tungstate solution is 2L/h, the pH value of a reaction system is controlled to be between 10.4 and 10.7, the concentration of a complexing agent is controlled to be between 0.40mol/L by controlling the flow of a precipitator and the flow of a complexing agent solution, the coprecipitation reaction is carried out at the reaction temperature of 58 ℃ under the protection of nitrogen, the reaction is carried out for 5h, the average particle size reaches 8.0 mu m, and the reaction is stopped;
(3) Centrifugal washing is carried out on the product of the coprecipitation reaction after the reaction is finished, and the product is dried for 24 hours at 100 ℃ to obtain the anode nickel-manganese materialA precursor, the chemical formula is Ni 0.5 Mn 1.5 [PO 4 ] 0.005 (OH) 3.985 @[Ni 0.495 M 0.01 Mn 1.495 ](OH) 4 The thickness of the shell in the positive electrode nickel-manganese material precursor is 0.5 mu m.
As can be seen from an SEM image of the precursor of the positive nickel-manganese material shown in FIG. 1, the multielement precursor prepared by the embodiment has good sphericity, uniform size and compact surface.
Example 2
(1) The mixed salt solution with the total concentration of metal ions being 2mol/L (nickel-manganese molar ratio is 1:3), the monoammonium phosphate solution with the concentration of 0.1mol/L, the sodium hydroxide solution with the concentration of 10mol/L and the ammonia water with the concentration of 8mol/L are added into the base solution with the pH value being 11.2 and the ammonia concentration being 0.4mol/L in parallel flow. In the parallel flow adding process, the feeding speed of the mixed salt solution of nickel, cobalt and manganese is 20L/h, the feeding speed of the ammonium dihydrogen phosphate solution is 2L/h, the pH value of a reaction system is controlled to be 10.4, the concentration of a complexing agent is controlled to be 0.35mol/L by controlling the flow of a precipitator and the flow of a complexing agent solution, the coprecipitation reaction is carried out at the reaction temperature of 52 ℃ under the protection of nitrogen, the reaction is carried out for 60h, the average particle size reaches 8.5 mu m, and the reaction in the first stage is stopped;
(2) The mixed salt solution with the total concentration of metal ions being 2mol/L (nickel-manganese molar ratio is 1:3), the zirconium sulfate solution with the concentration of 0.1mol/L, the sodium hydroxide solution with the concentration of 10mol/L and the ammonia water with the concentration of 8mol/L are added into the mixed solution after the first-stage reaction in parallel flow. In the parallel flow adding process, the feeding speed of the mixed salt solution of nickel, cobalt and manganese is 20L/h, the feeding speed of the zirconium sulfate solution is 4L/h, the pH value of a reaction system is controlled to be 10.4, the concentration of a complexing agent is controlled to be 0.35mol/L by controlling the flow of a precipitator and the flow of a complexing agent solution, the coprecipitation reaction is carried out at the reaction temperature of 52 ℃ under the protection of nitrogen, the reaction is carried out for 5h, the average grain diameter reaches 9.0 mu m, and the reaction is stopped;
(3) Centrifugally washing the product of the coprecipitation reaction after the reaction is completed, and drying at 100 ℃ for 24 hours to obtain the positive electrode nickel-manganese material precursor, wherein the chemical formula is Ni 0.5 Mn 1.5 [PO 4 ] 0.01 (OH) 3.97 @[Ni 0.49 M 0.02 Mn 1.49 ](OH) 4 The thickness of the shell in the positive electrode nickel-manganese material precursor is 0.5 mu m.
Example 3
This example differs from example 1 only in that the feeding rate of the phosphorus source solution in step (1) was 0.2L/h, and other conditions and parameters were exactly the same as in example 1.
Example 4
This example differs from example 1 only in that the feeding rate of the phosphorus source solution in step (1) was 15L/h, and other conditions and parameters were exactly the same as in example 1.
Example 5
This example differs from example 1 only in that the ammonium tungstate solution in step (2) is fed at a rate of 0.2L/h, and other conditions and parameters are exactly the same as in example 1.
Example 6
This example differs from example 1 only in that the ammonium tungstate solution in step (2) is fed at a rate of 15L/h, and other conditions and parameters are exactly the same as in example 1.
Example 7
This example differs from example 1 only in that the thickness of the coating layer was controlled to be 0.2 μm, and other conditions and parameters were exactly the same as those of example 1.
Example 8
This example differs from example 1 only in that the thickness of the coating layer was controlled to be 1.2 μm, and other conditions and parameters were exactly the same as those of example 1.
Comparative example 1
This comparative example differs from example 1 only in that step (1) does not add a phosphorus source, and other conditions and parameters are exactly the same as example 1.
Comparative example 2
This comparative example differs from example 1 only in that no ammonium tungstate was added in step (2), and other conditions and parameters were exactly the same as in example 1.
Comparative example 3
This comparative example differs from example 1 only in that step (1) does not add a phosphorus source, step (2) does not add ammonium tungstate, and other conditions and parameters are exactly the same as example 1.
Performance test:
fully mixing the prepared multielement precursor with lithium hydroxide according to Li/M=1.02, sintering in a tube furnace under the flow of oxygen, pre-sintering for 5 hours at 400 ℃, then calcining for 15 hours at a high temperature of 850 ℃, and grinding and screening to obtain the doped positive electrode material. Under the condition of 25 ℃, the anode material is used as an anode main material, a metal lithium sheet is used as a cathode, CR2032 button cell is respectively assembled, and then the cycle performance test is carried out under the voltage range of 3.5-4.9V and the temperature of 0.1C, and the test results are shown in Table 1:
TABLE 1
Gram Capacity for first discharge (mAh/g) Capacity retention after 300 cycles (%)
Example 1 131.4 94.3
Example 2 130.6 95.6
Example 3 130.3 87.6
Example 4 129.8 90.7
Example 5 130.4 86.8
Example 6 129.4 89.9
Example 7 130.5 78.4
Example 8 130.2 81.6
Comparative example 1 129.1 74.2
Comparative example 2 128.5 79.4
Comparative example 3 126.5 69.1
As can be seen from Table 1, the positive electrode nickel-manganese material precursor prepared by the method can reach a gram capacity of 130.6mAh/g or more for initial discharge, and a capacity retention rate of 94.3% or more after 300 cycles.
As can be seen from comparison of examples 1 and 3-4, in the preparation process of the precursor of the anode nickel manganese material, the feeding speed of the phosphorus source solution in the step (1) affects the proportion of phosphorus element in the material, so as to affect the performance of the precursor of the anode nickel manganese material, the feeding speed of the phosphorus source solution is controlled to be 0.4-10L/h, the performance of the precursor of the anode nickel manganese material is better, if the feeding speed of the phosphorus source solution is too fast, the conductivity of the material is reduced due to excessive P doping of a nuclear layer, the multiplying power performance is poor, meanwhile, the stability of a crystal structure is damaged, and the cycle performance is further reduced; if the feeding rate of the phosphorus source solution is too slow, the core layer is too little doped with P, so that a sufficient {111} crystal plane cannot be formed, the stability of the cathode material is affected, and the cycle performance is also deteriorated.
As can be seen from comparison between the embodiment 1 and the embodiment 5-6, in the preparation process of the precursor of the anode nickel-manganese material, the feeding speed of the doped metal source solution in the step (2) influences the proportion of doped metal, so that the performance of the precursor of the anode nickel-manganese material is influenced, the feeding speed of the doped metal source solution is controlled to be 0.4-10L/h, the performance of the precursor of the anode nickel-manganese material is better, if the feeding speed of the doped metal source solution is too fast, a thicker SEI film is formed after the excessive doping of other metal elements of the shell layer is segregated, so that the electrochemical performances such as cycle performance, capacity and multiplying power performance are reduced, and if the feeding speed of the doped metal source solution is too slow, the stable SEI film cannot be formed after the excessive doping of the other metal elements of the shell layer, so that the internal anode material cannot be protected, and the cycle performance is not ideal.
As can be seen from comparison of examples 1 and examples 7-8, the shell thickness of the precursor of the positive electrode nickel-manganese material provided by the invention affects the performance, the shell thickness of the precursor of the positive electrode nickel-manganese material is controlled to be 0.4-1 mu m, the performance of the precursor of the positive electrode nickel-manganese material is better, if the shell is too thin, a better protection effect can not be achieved on a core layer, the stability of the material is poor, the cycle performance is poor, and if the shell is too thick, the precursor of the positive electrode nickel-manganese material is similar to other metal elements doped with too many shell layers, the overall reduction of the electrochemical performance is caused.
As can be obtained by comparing example 1 with comparative example 1, the positive electrode nickel manganese material precursor of the invention has the inner core doped with PThere will be more Mn in the material 3+ Ions, strengthen LiNi 0.5 Mn 1.5 O 4 Such disordered arrangement of transition metal ions can significantly improve the conductivity of lithium ions and electrons. In addition, the doped P nickel manganese positive electrode material presents more {111} crystal faces, and the {111} crystal faces help to protect the bulk material from further reaction with electrolyte under high working voltage, so that higher capacity retention rate is presented.
By comparing the embodiment 1 with the comparative example 2, the shell structure of the anode nickel manganese material precursor is doped with W, al, cu, fe, cr, zr, sr and other metal elements, so that on one hand, the transmission rate of lithium ions can be improved, the accumulation of the lithium ions on the surface of particles is reduced, and therefore, the polarization and stable crystal structure are reduced, on the other hand, part of metal ions doped with a shell layer can segregate to the outer surface of the particles to form a stable SEI film, and the occurrence of harmful interface side reactions is restrained, so that the cycle performance of the material is improved.
The comparison between the embodiment 1 and the comparative example 3 shows that the precursor particle prepared by the invention has the advantages that the P element in the core layer is uniformly doped, any one of metal elements such as W, al, cu, fe, cr, zr, sr and the like is doped in the shell layer, the positive electrode material obtained after the sintering of the precursor has higher gram capacity, and the positive electrode material has excellent cycle performance and multiplying power performance when working in the high voltage range of 3.5-4.9V.
The applicant declares that the above is only a specific embodiment of the present invention, but the scope of the present invention is not limited thereto, and it should be apparent to those skilled in the art that any changes or substitutions that are easily conceivable within the technical scope of the present invention disclosed by the present invention fall within the scope of the present invention and the disclosure.

Claims (10)

1. The positive electrode nickel-manganese material precursor is characterized by comprising a core and a shell arranged on the surface of the core, wherein the core comprises a P element, the shell comprises a transition metal element, and the transition metal element comprises any one or a combination of at least two of W, al, cu, fe, cr, zr and Sr.
2. The positive nickel manganese material precursor according to claim 1, wherein the inner core has a chemical formula of Ni 0.5 Mn 1.5 [PO 4 ] x (OH) 4-3x Wherein x is more than or equal to 0.001 and less than or equal to 0.020.
3. The positive electrode nickel manganese material precursor according to claim 1 or 2, wherein the shell has a chemical formula of Ni 0.5-y M 2y Mn 1.5-y (OH) 4 Wherein y is more than or equal to 0.001 and less than or equal to 0.020, and M comprises any one or a combination of at least two of W, al, cu, fe, cr, zr and Sr;
preferably, the thickness of the housing is 0.4 to 1 μm.
4. A method for preparing the positive electrode nickel manganese material precursor according to any one of claims 1 to 3, wherein the preparation method comprises the following steps:
(1) Adding nickel-manganese mixed salt solution, phosphorus source solution, precipitant solution and complexing agent solution into base solution in parallel flow, and regulating pH value to perform one-step coprecipitation reaction;
(2) Changing the phosphorus source solution in the step (1) into a doped metal salt solution, and carrying out two-step coprecipitation reaction under other conditions without change;
(3) And (3) washing the coprecipitation reaction product obtained in the step (2) to obtain the anode nickel-manganese material precursor.
5. The preparation method according to claim 4, wherein the total concentration of metal ions in the nickel-manganese mixed salt solution in the step (1) is 0.1 to 5mol/L;
preferably, the feeding speed of the nickel-manganese mixed salt solution is 4-100L/h;
preferably, the phosphorus source solution comprises a diammonium phosphate solution;
preferably, the concentration of the solute in the phosphorus source solution is 0.01-0.5 mol/L;
preferably, the feeding speed of the phosphorus source solution is 0.4-10L/h;
preferably, the precipitant solution comprises sodium hydroxide solution;
preferably, the concentration of the solute in the precipitant solution is 2-15 mol/L;
preferably, the feeding speed of the precipitant solution is 1-20L/h;
preferably, the complexing agent solution comprises aqueous ammonia;
preferably, the concentration of the solute in the complexing agent solution is 4-12 mol/L;
preferably, the feeding speed of the complexing agent solution is 0.5-10L/h;
preferably, the pH is adjusted to 9-13;
preferably, the temperature of the one-step coprecipitation reaction is 40-80 ℃;
preferably, the atmosphere of the one-step coprecipitation reaction is an inert atmosphere;
preferably, the median particle diameter D50 of the material after the one-step coprecipitation reaction is 7-9 μm.
6. The method of claim 4 or 5, wherein the solute of the doped metal salt solution of step (2) comprises any one or a combination of at least two of W, al, cu, fe, cr, zr or Sr salts;
preferably, the concentration of the solute in the doped metal salt solution is 0.01-0.5 mol/L;
preferably, the feeding speed of the doped metal salt solution is 0.4-10L/h;
preferably, the median particle diameter D50 of the material after the two-step coprecipitation reaction is 8-10 mu m.
7. The method of any one of claims 4 to 6, wherein the washing treatment of step (3) comprises alkali washing followed by water washing;
preferably, the volume of alkali liquor used per 100kg of materials in the alkaline washing process is 1-3 m 3 ；
Preferably, every 100kg of the material is washed with waterThe volume of water used in the material is 1-5 m 3 。
8. A positive nickel-manganese material, which is obtained by mixing and sintering the positive nickel-manganese material precursor according to any one of claims 1-3 with a lithium source.
9. A positive electrode sheet comprising the positive electrode nickel manganese material according to claim 8.
10. A lithium ion battery comprising the positive electrode sheet of claim 9.
CN202211313676.7A 2022-10-25 2022-10-25 Positive electrode nickel-manganese material precursor, and preparation method and application thereof Pending CN116282204A (en)

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CN103151520A (en) * 2013-03-20 2013-06-12 东莞市力嘉电池有限公司 Lithium ion battery anode material and preparation method thereof
CN103794783A (en) * 2014-03-07 2014-05-14 哈尔滨工业大学 High voltage Li-ion battery cathode materials with core-shell structure and preparation method thereof
CN107978755A (en) * 2016-10-25 2018-05-01 中国科学院化学研究所 A kind of method and its product and application in material surface Uniform Doped metal ion
CN114314546A (en) * 2021-12-21 2022-04-12 万向一二三股份公司 Phosphate anode material and preparation method thereof
CN114361440A (en) * 2022-01-07 2022-04-15 巴斯夫杉杉电池材料有限公司 High-voltage ternary cathode material with core-shell structure and preparation method thereof
CN114512660A (en) * 2020-11-17 2022-05-17 松山湖材料实验室 Positive electrode active material precursor, preparation method thereof and positive electrode active material
CN115057482A (en) * 2022-05-18 2022-09-16 中南大学 Positive electrode material and precursor of sodium-ion battery and preparation method

Patent Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN103151520A (en) * 2013-03-20 2013-06-12 东莞市力嘉电池有限公司 Lithium ion battery anode material and preparation method thereof
CN103794783A (en) * 2014-03-07 2014-05-14 哈尔滨工业大学 High voltage Li-ion battery cathode materials with core-shell structure and preparation method thereof
CN107978755A (en) * 2016-10-25 2018-05-01 中国科学院化学研究所 A kind of method and its product and application in material surface Uniform Doped metal ion
CN114512660A (en) * 2020-11-17 2022-05-17 松山湖材料实验室 Positive electrode active material precursor, preparation method thereof and positive electrode active material
CN114314546A (en) * 2021-12-21 2022-04-12 万向一二三股份公司 Phosphate anode material and preparation method thereof
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