WO2023123713A1 - 三元正极材料前驱体及制备方法、正极材料、正极浆料、锂离子电池及正极和涉电设备 - Google Patents

三元正极材料前驱体及制备方法、正极材料、正极浆料、锂离子电池及正极和涉电设备 Download PDF

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WO2023123713A1
WO2023123713A1 PCT/CN2022/083481 CN2022083481W WO2023123713A1 WO 2023123713 A1 WO2023123713 A1 WO 2023123713A1 CN 2022083481 W CN2022083481 W CN 2022083481W WO 2023123713 A1 WO2023123713 A1 WO 2023123713A1
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positive electrode
ternary
material precursor
cathode material
ion battery
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French (fr)
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訚硕
王乐
张雨英
纪方力
李魁
王一乔
沙金
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CNGR Advanced Material Co Ltd
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CNGR Advanced Material Co Ltd
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Priority to JP2023526665A priority Critical patent/JP7683007B2/ja
Priority to EP22908858.8A priority patent/EP4458774A4/en
Priority to KR1020237021203A priority patent/KR102855474B1/ko
Publication of WO2023123713A1 publication Critical patent/WO2023123713A1/zh
Priority to US18/460,112 priority patent/US20230411608A1/en
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    • H01M4/525—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron of mixed oxides or hydroxides containing iron, cobalt or nickel for inserting or intercalating light metals, e.g. LiNiO2, LiCoO2 or LiCoOxFy
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    • Y02E60/10—Energy storage using batteries

Definitions

  • the present disclosure relates to the field of lithium-ion batteries, in particular to a ternary cathode material precursor and a preparation method, an anode material, an anode slurry, a lithium-ion battery, an anode, and electrical equipment.
  • Lithium-ion batteries are a new generation of high-energy renewable green energy. It has the characteristics of high working voltage, high energy density, good safety performance, long cycle life, low self-discharge rate and no memory effect, and has been widely used in various electric vehicles and large-scale energy storage fields. In recent years, with the rapid development of electric vehicles, the energy density requirements of lithium batteries have been continuously improved; in order to improve the battery life of electric vehicles, it is imminent to develop power batteries with high energy density.
  • the excellent performance of lithium-ion batteries such as cycle stability, capacity, and voltage mainly depends on the preparation of cathode materials.
  • the low capacity of conventional cathode materials restricts the improvement of the overall capacity of lithium-ion batteries. Therefore, the development of cathode materials with high capacity, excellent rate performance, stable cycle performance, and good safety is a hot and difficult point in the current research on lithium-ion batteries.
  • layered ternary positive electrode materials have obvious advantages in terms of higher capacity, better cycle performance, and low cost compared with conventional positive electrode materials. Stable, easy to transform to spinel phase and rock salt phase, resulting in too fast capacity decay in the cycle process; and its thermal stability and safety performance are poor. These disadvantages limit the wide application of layered ternary materials to some extent.
  • the purpose of the present disclosure is to provide a ternary positive electrode material precursor and preparation method, positive electrode material, positive electrode slurry, lithium-ion battery, positive electrode and electrical equipment, so as to solve the above problems.
  • a ternary cathode material precursor comprising a core layer, an intermediate layer and a shell layer, the intermediate layer covering the core layer, the shell layer covering the intermediate layer, the core layer, the intermediate layer , the porosity of the shell layer increases sequentially.
  • the porosity of the core layer is 5.4%-17.1%
  • the porosity of the middle layer is 7.8%-19.2%
  • the porosity of the shell layer is 9%-20.1%;
  • the porosity of the core layer is 7.03%-12.74%
  • the porosity of the middle layer is 8.7%-13.6%
  • the porosity of the shell layer is 14.8%-16.3%
  • the radius of the core layer accounts for 25%-30% of the overall radius
  • the thickness of the intermediate layer accounts for 50%-58.8% of the overall radius
  • the thickness of the shell layer accounts for 11.2%-25% of the overall radius .
  • the half peak width of the 001 crystal plane of the ternary cathode material precursor is 0.4-0.88°, and the half peak width of the 101 crystal plane is 0.25-0.61°;
  • the range of FWHM(I001-I101)/I101 ratio of the ternary cathode material precursor is: 0.1-0.9.
  • the BET/TD ratio of the ternary cathode material precursor is 3.90-6.66.
  • the general chemical formula of the ternary cathode material precursor is Ni x Co y Mn z Me (1-xyz) (OH) 2 , where 0.6 ⁇ x ⁇ 1, 0 ⁇ y ⁇ 1, 0 ⁇ z ⁇ 1, x+y+z ⁇ 1;
  • Me represents a doping element, and the doping element includes one or more of Al, Ti, V, W, Zr, Mg, Ce, Nb, La;
  • the mass percentage content of the doping element is 0.01%-10%.
  • the present disclosure also provides a preparation method of a ternary cathode material precursor, including:
  • the raw materials including nickel source, cobalt source, manganese source, precipitating agent and complexing agent are mixed, and reacted by solution co-precipitation method to obtain the precursor of the ternary cathode material.
  • the nickel source includes nickel sulfate
  • the cobalt source includes cobalt sulfate
  • the manganese source includes manganese sulfate
  • the precipitation agent includes one or more of sodium hydroxide, sodium carbonate, and sodium bicarbonate
  • the complexing agent includes one or more of ammonia water, sodium citrate, EDTA, and oxalic acid.
  • the nickel source, the cobalt source, and the manganese source are pre-mixed to obtain a ternary metal salt solution for use;
  • the concentration of the ternary metal salt solution is 100g/L-130g/L.
  • said mixing comprises:
  • the pH of the reaction bottom liquid is 11-12.
  • a protective gas is introduced into the reaction system.
  • the pH of the system is 10-12, and the supernatant nickel control range is 0-500ppm;
  • the pH of the system gradually decreases from 11.9 to 10.8-10.3.
  • the temperature of the reaction is 40°C-70°C;
  • the stirring speed of the reaction is 100r/min-600r/min.
  • the raw material also includes a doping element solution.
  • the doping elements in the doping element solution include one or more of Al, Ti, V, W, Zr, Mg, Ce, Nb, La;
  • the doping element is W
  • the doping element solution includes sodium tungstate and sodium citrate
  • the mass ratio of the sodium tungstate to the sodium citrate is 1-3:1.
  • the preparation method of the ternary cathode material precursor also includes post-treatment, the post-treatment includes alkali washing, water washing and drying;
  • the drying temperature is 100°C-180°C, and the moisture content is less than or equal to 0.4%.
  • the present disclosure also provides a positive electrode material, including an inner core, a middle region, and an outer shell, the middle area covers the inner core, the outer shell covers the middle area, the inner core, the middle area, and the outer shell
  • the porosity increases sequentially.
  • the present disclosure also provides a positive electrode slurry, the raw material of which includes the above positive electrode material.
  • the present disclosure also provides a positive electrode of a lithium ion battery, the raw material of which includes the positive electrode slurry of the lithium ion battery.
  • the present disclosure also provides a lithium ion battery, the raw material of which includes the positive electrode of the lithium ion battery.
  • the present disclosure also provides an electrical device, including the lithium-ion battery.
  • the beneficial effects of the present disclosure include:
  • the ternary cathode material precursor provided by the present disclosure has a special pore distribution with gradually increasing porosity from the core layer to the middle layer to the shell layer, which can stabilize the structure of the ternary material, effectively improve the generation of material cracks, and inhibit the cycle process
  • the phase transition in the material can prolong the service life of the material, and at the same time, it can improve the cycle performance, rate performance and energy density of the material.
  • the preparation method of the precursor of the ternary cathode material provided by the present disclosure has simple process and low cost, and can realize large-scale industrial production.
  • the positive electrode material, positive electrode slurry, lithium ion battery positive electrode, and lithium ion battery provided by the present disclosure have strong stability, good safety, and excellent electrical performance.
  • the lithium ion battery provided by the present disclosure is widely used.
  • Fig. 1 is the model schematic diagram of gained ternary cathode material precursor
  • Fig. 2 is the SEM figure of the ternary cathode material precursor obtained in embodiment 1;
  • Fig. 3 is the SEM figure of the section of the ternary cathode material precursor obtained in embodiment 1;
  • Fig. 4 is the XRD figure of the ternary cathode material precursor obtained in embodiment 1;
  • Fig. 5 is the mesopore diameter differential distribution curve of the ternary cathode material precursor obtained in Example 1;
  • Fig. 6 is the SEM figure of the ternary cathode material precursor obtained in embodiment 2;
  • Fig. 7 is the XRD figure of the ternary cathode material precursor obtained in embodiment 2;
  • Fig. 8 is the SEM figure of the ternary cathode material precursor obtained in embodiment 3;
  • Fig. 9 is the XRD figure of the ternary cathode material precursor obtained in embodiment 3.
  • Fig. 10 is the SEM figure of the ternary cathode material precursor obtained in embodiment 4.
  • Fig. 11 is the XRD pattern of the ternary cathode material precursor obtained in Example 4.
  • Fig. 12 is the SEM figure of the ternary cathode material precursor obtained in Example 5;
  • Example 13 is an XRD pattern of the ternary cathode material precursor obtained in Example 5.
  • compositions are synonymous with “comprising”.
  • the terms “comprises,” “including,” “has,” “containing,” or any other variation thereof, are intended to cover a non-exclusive inclusion.
  • a composition, step, method, article, or device comprising listed elements is not necessarily limited to those elements, but may include other elements not explicitly listed or inherent to such composition, step, method, article, or device. element.
  • Parts by mass refers to the basic measurement unit that expresses the mass ratio relationship of multiple components, and 1 part can represent any unit mass, such as 1g or 2.689g. If we say that the mass part of A component is a part, and the mass part of B component is b part, it means that the mass ratio of A component to B component is a:b. Alternatively, it means that the mass of component A is aK, and the mass of component B is bK (K is an arbitrary number, representing a multiple factor). It should not be misunderstood that, unlike the parts by mass, the sum of parts by mass of all components is not limited to 100 parts.
  • a and/or B includes (A and B) and (A or B).
  • a ternary cathode material precursor comprising a core layer, an intermediate layer and a shell layer, the intermediate layer covering the core layer, the shell layer covering the intermediate layer, the core layer, the intermediate layer , the porosity of the shell layer increases sequentially.
  • the internal and external pores of the conventional material are very dense, the structure is unstable during the charging and discharging process, and the stability and safety performance are poor.
  • the porosity distribution of the cross section of the precursor of the ternary positive electrode material is inconsistent.
  • the core layer, the intermediate layer, The porosity of the shell layer increases sequentially, which can improve the cycle performance and energy density per unit volume of the ternary positive electrode material, and improve the structural stability of the material and the safety performance of the battery.
  • the porosity of the core layer is 5.4%-17.1%
  • the porosity of the middle layer is 7.8%-19.2%
  • the porosity of the shell layer is 9%-20.1%. ;
  • the porosity of the core layer is 7.03%-12.74%
  • the porosity of the middle layer is 8.7%-13.6%
  • the porosity of the shell layer is 14.8%-16.3%. .
  • this disclosure uses image analysis software (ImageJ) to directly calculate the pore area and cross-sectional area of each region, and calculate the different The porosity of the region, the porosity of the present disclosure, is characterized by this method.
  • the porosity of the core layer can be 5.4%, 6%, 7%, 8%, 9%, 10%, 11%, 12%, 13%, 14%, 15%, 16%, 17% %, 17.1% or any value between 5.4%-17.1%
  • the porosity of the middle layer can be 7.8, 8%, 9%, 10%, 11%, 12%, 13%, 14%, 15% %, 16%, 17%, 18%, 19%, 19.2% or any value between 7.8%-19.2%
  • the porosity of the shell can be 9%, 10%, 11%, 12%, 13%, 14%, 15%, 16%, 17%, 18%, 19%, 20%, 20.1%, or any value between 9% and 20.1%.
  • the pores of the intermediate layer and the shell layer are strip-shaped
  • the widths of the pores of the intermediate layer and the shell layer gradually increase from the inside to the outside, and are distributed radially as a whole.
  • the prepared ternary cathode material can form a lithium ion diffusion channel from the inside to the outside. This channel is conducive to the diffusion of the electrolyte and the ion conduction during the charge and discharge process, thereby It is conducive to the play of capacity, and can also improve the rate performance of the battery to a certain extent.
  • the radius of the core layer accounts for 25%-30% of the overall radius
  • the thickness of the intermediate layer accounts for 50%-58.8% of the overall radius
  • the thickness of the shell layer accounts for 50%-58.8% of the overall radius. 11.2%-25%.
  • the D50 of the ternary cathode material precursor can be 7 ⁇ m, 8 ⁇ m, 9 ⁇ m, 10 ⁇ m, 11 ⁇ m, 12 ⁇ m, 13 ⁇ m, 14 ⁇ m, 15 ⁇ m or any value between 7-15 ⁇ m, (D90-D10)/D50 can be It is 0.6, 0.7, 0.8 or any value between 0.6-0.8.
  • the half-width of the 001 crystal plane of the ternary cathode material precursor is 0.4-0.88°, and the half-peak width of the 101 crystal plane is 0.25-0.61°;
  • the half-width of the 001 crystal plane of the ternary cathode material precursor can be 0.4°, 0.5°, 0.6°, 0.7°, 0.8°, 0.81°, 0.82°, 0.83°, 0.84°, 0.85°, 0.86° °, 0.87°, 0.88° or any value between 0.4-0.88°
  • the half maximum width of the 101 crystal plane can be 0.25°, 0.3°, 0.35°, 0.4°, 0.45°, 0.5°, 0.55°, 0.56° , 0.57°, 0.58°, 0.59°, 0.60°, 0.61° or any value between 0.25-0.61°;
  • the range of the FWHM(I001-I101)/I101 ratio of the ternary cathode material precursor is: 0.1-0.9.
  • the ratio of FWHM(I001-I101)/I101 can be 0.1, 0.2, 0.3, 0.4, 0.5, 0.6, 0.7, 0.8, 0.9 or any value between 0.1-0.9.
  • the crystallinity and structure of the material are improved, so that the primary particles are miniaturized, which can suppress the reduction of particle density and increase the density, which is further conducive to the development of capacity and is effective. It is beneficial to improve the cycle stability of the material, and can also suppress the reduction of energy density.
  • the BET/TD ratio of the ternary cathode material precursor is 3.90-6.66.
  • the ratio of BET to TD has a linear relationship, and the larger the ratio of BET/TD, the larger the porosity of the material, which is conducive to enhancing the safety performance of the battery and improving the rate performance and cycle performance of the battery.
  • the BET/TD ratio can be 3.90, 4, 5, 6, 6.66 or any value between 3.90-6.66.
  • the general chemical formula of the ternary cathode material precursor is Ni x Co y Mn z Me (1-xyz) (OH) 2 , where 0.6 ⁇ x ⁇ 1, 0 ⁇ y ⁇ 1, 0 ⁇ z ⁇ 1, x+y+z ⁇ 1;
  • Me represents a doping element, which includes one or more of Al, Ti, V, W, Zr, Mg, Ce, Nb, La ;
  • the mass percentage content of the doping element is 0.01%-10%.
  • the precursor of the ternary positive electrode material provided by the present disclosure becomes a high-nickel material when the Ni content is greater than or equal to 0.6, and has the advantages of good cycle performance, high energy density, good stability and safety performance.
  • the stability of the material structure is enhanced, thereby improving the safety performance and cycle stability of the material.
  • the mass percentage content of the doping element can be 0.01%, 0.05%, 0.1%, 0.5%, 1%, 2%, 3%, 4%, 5%, 6%, 7%, 8% , 9%, 10%, or any value between 0.01% and 10%.
  • the present disclosure also provides a preparation method of a ternary cathode material precursor, including:
  • the raw materials including nickel source, cobalt source, manganese source, precipitating agent and complexing agent are mixed, and reacted by solution co-precipitation method to obtain the precursor of the ternary cathode material.
  • the nickel source includes nickel sulfate
  • the cobalt source includes cobalt sulfate
  • the manganese source includes manganese sulfate
  • the precipitation agent includes sodium hydroxide, sodium carbonate, and sodium bicarbonate.
  • the complexing agent includes one or more of ammonia water, sodium citrate, EDTA, oxalic acid.
  • the nickel source, the cobalt source, and the manganese source are pre-mixed to obtain a ternary metal salt solution for use;
  • the concentration of the ternary metal salt solution is 100g/L-130g/L.
  • the concentration of the ternary metal salt solution can be 100g/L, 101g/L, 102g/L, 103g/L, 104g/L, 105g/L, 106g/L, 107g/L, 108g/L , 109g/L, 110g/L, 111g/L, 112g/L, 113g/L, 114g/L, 115g/L, 116g/L, 117g/L, 118g/L, 119g/L, 120g/L, 121g /L, 122g/L, 123g/L, 124g/L, 125g/L, 126g/L, 127g/L, 128g/L, 129g/L, 130g/L or any between 100g/L-130g/L one value.
  • the mixing includes:
  • the pH of the reaction bottom liquid is 11-12.
  • the pH of the reaction bottom liquid may be 11.0, 11.1, 11.2, 11.3, 11.4, 11.5, 11.6, 11.7, 11.8, 11.9, 12.0 or any value between 11-12.
  • a protective gas is introduced into the reaction system.
  • the protective gas is preferably nitrogen.
  • the pH of the system is 10-12, and the supernatant nickel control range is 0-500ppm;
  • the pH of the system gradually decreases from 11.9 to 10.8-10.3.
  • the pH of the system can be any value between 10, 10.5, 11, 11.5, 12 or 10-12, and the supernatant nickel control range can be 0ppm, 50ppm, 100ppm, 200ppm , 300ppm, 400ppm, 500ppm or any value between 0-500ppm.
  • the temperature of the reaction is 40°C-70°C;
  • the stirring speed of the reaction is 100r/min-600r/min.
  • the temperature of the reaction can be 40°C, 50°C, 60°C, 70°C or any value between 40-70°C;
  • the stirring speed of the reaction can be 100r/min, 200r/min, 300r/min, 400r/min, 500r/min, 600r/min or any value between 100r/min-600r/min.
  • the raw material also includes a doping element solution.
  • the doping elements in the doping element solution include one or more of Al, Ti, V, W, Zr, Mg, Ce, Nb, La;
  • the doping element is W
  • the doping element solution includes sodium tungstate and sodium citrate
  • the mass ratio of the sodium tungstate to the sodium citrate is 1-3:1.
  • the mass ratio of the sodium tungstate to the sodium citrate can be any value between 1:1, 2:1, 3:1 or 1-3:1.
  • the preparation method of the ternary positive electrode material precursor also includes post-treatment, the post-treatment includes alkali washing, water washing and drying;
  • the drying temperature is 100°C-180°C, and the moisture content is less than or equal to 0.4%.
  • the volume ratio of alkali washing and water washing can be 2:1, 3:1, 4:1, 5:1, 6:1, 7:1, 8:1 or V water washing :
  • V alkali washing (2-8): Any value between 1, the temperature of alkali washing and water washing can be independently any value between 30°C, 40°C, 50°C, 60°C, 70°C or 30-70°C;
  • the drying temperature can be 100°C, 110°C, 120°C, 130°C, 140°C, 150°C, 160°C, 170°C, 180°C or any value between 100°C-180°C, and the moisture can be 0.1% , 0.2%, 0.3%, 0.4% or any value less than or equal to 0.4%.
  • the present disclosure also provides a positive electrode material, including an inner core, a middle region, and an outer shell, the middle area covers the inner core, the outer shell covers the middle area, the inner core, the middle area, and the outer shell
  • the porosity increases sequentially.
  • the present disclosure also provides a positive electrode slurry, the raw material of which includes the above positive electrode material.
  • the present disclosure also provides a positive electrode of a lithium ion battery, the raw material of which includes the positive electrode slurry of the lithium ion battery.
  • the present disclosure also provides a lithium ion battery, the raw material of which includes the positive electrode of the lithium ion battery.
  • the present disclosure also provides an electrical device, including the lithium-ion battery.
  • the electrical equipment referred to here not only refers to itself including the lithium ion battery provided by the present disclosure, but also includes the situation of using the lithium ion battery provided by the present disclosure as an external power supply or energy carrier; that is, A device powered directly or indirectly by the lithium-ion battery provided by the present disclosure, or the device itself serves as a power source to charge the lithium-ion battery provided by the present disclosure.
  • the obtained doped precursor material is mixed and sintered with the lithiated compound under certain conditions to prepare the doped positive electrode material.
  • Figure 1 is a schematic diagram of the model of the obtained ternary cathode material precursor, wherein, the A region represents the core layer, the B region represents the middle layer, and the C region represents the shell layer.
  • Fig. 2 is the SEM figure of the ternary positive electrode material precursor gained in embodiment 1;
  • Fig. 3 is the SEM figure of the section of the ternary positive electrode material precursor gained in embodiment 1;
  • Fig. 4 is the ternary positive electrode material gained in embodiment 1
  • the XRD pattern of the precursor where the abscissa is the angle of the diffraction peak, and the ordinate is the intensity of the diffraction peak.
  • FIG. 5 is the differential distribution curve of the mesopore diameter of the ternary cathode material precursor obtained in Example 1.
  • FIG. 5 is the differential distribution curve of the mesopore diameter of the ternary cathode material precursor obtained in Example 1.
  • the aluminum solution of L, precipitating agent and complexing agent are used as main raw materials and auxiliary materials; pure water, liquid caustic soda (mass concentration 32%), and ammonia water are added into the reaction kettle to form a bottom liquid with a pH range of 11.60-11.70, and the Nitrogen, at a stirring rate of 539r/min, heated to 60°C, and then passed the ternary solution (4L/h), liquid caustic soda (1.6L/h), ammonia water (0.31L/h) and mixed Miscellaneous solution (2L/h);
  • the nickel content in the supernatant is controlled at 50-100ppm, and the stirring frequency is gradually reduced from 539r/min to 462r/min, and the reaction obtains the medium particle size D50
  • Example 234 the finished Ni 0.88 Co 0.09 Mn 0.03 (OH) 2 precursor doped with Al (6000ppm) was obtained.
  • Fig. 6 is the SEM picture of the ternary positive electrode material precursor obtained in Example 2
  • Fig. 7 is the XRD figure of the ternary positive electrode material precursor obtained in Example 2, wherein the abscissa is the diffraction peak angle, and the ordinate is the diffraction peak strength.
  • Example 234 the finished Ni 0.92 Co 0.03 Mn 0.05 (OH) 2 precursor doped with Ti (4000ppm) was obtained.
  • Fig. 8 is the SEM image of the ternary positive electrode material precursor obtained in Example 3
  • Fig. 9 is the XRD pattern of the ternary positive electrode material precursor obtained in Example 3, wherein the abscissa is the diffraction peak angle, and the ordinate is the diffraction peak strength.
  • Fig. 10 is the SEM figure of the ternary positive electrode material precursor obtained in Example 4
  • Fig. 11 is the XRD figure of the ternary positive electrode material precursor obtained in Example 4, wherein the abscissa is the diffraction peak angle, and the ordinate is the diffraction peak strength.
  • Figure 12 is the SEM figure of the ternary cathode material precursor obtained in Example 5
  • Figure 13 is the XRD figure of the ternary cathode material precursor obtained in Example 5, wherein the abscissa is the diffraction peak angle, and the ordinate is the diffraction peak strength.
  • the stirring was adjusted to be at a stirring rate of 616.4r/min, and the feed amount was adjusted to ternary solution (1L/h), liquid caustic soda (0.4L/h), ammonia water (0.05L/h), and other Similar to Example 5, the chemical formula of the obtained precursor product is Ni 0.905 Co 0.057 Mn 0.038 (OH) 2 .
  • the stirring is adjusted to be gradually reduced to 539.7r/min at a stirring rate of 693.7r/min, and the others are the same as in Example 5, and the chemical formula of the finished precursor is Ni 0.905 Co 0.057 Mn 0.038 ( OH) 2 .

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Abstract

本公开提供一种三元正极材料前驱体及制备方法、正极材料、正极浆料、锂离子电池及正极和涉电设备。三元正极材料前驱体，包括核层、中间层和壳层，核层、中间层、壳层的孔隙率依次增大。制备方法：将包括镍源、钴源、锰源、沉淀剂、络合剂在内的原料混合，通过溶液共沉淀法反应。正极材料，其原料包括三元正极材料前驱体。正极浆料，其原料包括正极材料。锂离子电池正极，其原料包括锂离子电池正极浆料。锂离子电池，其原料包括锂离子电池正极。涉电设备，包括锂离子电池。本公开提供的三元正极材料前驱体及正极材料，孔隙的特殊分布，可以稳定材料的结构，改善裂纹的产生，抑制循环过程中的相转变，延长使用寿命，提高材料的循环性能和倍率性能。

Description

三元正极材料前驱体及制备方法、正极材料、正极浆料、锂离子电池及正极和涉电设备
相关申请的交叉引用
本公开要求于2021年12月28日提交中国国家知识产权局的申请号为202111623510.0、名称为“三元正极材料前驱体及制备方法、正极材料、正极浆料、锂离子电池及正极和涉电设备”的中国专利申请的优先权，其全部内容通过引用结合在本公开中。
技术领域
本公开涉及锂离子电池领域，尤其涉及一种三元正极材料前驱体及制备方法、正极材料、正极浆料、锂离子电池及正极和涉电设备。
背景技术
锂离子电池是新一代的高能可再生绿色能源。它具有工作电压高、能量密度大、安全性能好、循环寿命长、自放电率低和无记忆效应等特点，已被广泛应用于各种电动汽车、大规模储能领域中。近年来随着电动汽车的迅速发展，对锂电池能量密度要求不断地提高；为了提高电动汽车的续航能力，开发高能量密度的动力电池已迫在眉睫。
锂离子电池的循环稳定性、容量和电压等优异的性能主要取决于正极材料的制备，常规正极材料的容量低，制约了锂离子电池整体容量的提升。因此，开发容量高、倍率性能优异、循环性能稳定、安全性好的正极材料是当前研究锂离子电池的热点和难点。
在众多的锂离子电池正极材料中，层状三元正极材料相比常规的正极材料，其容量更高，循环性能更好，成本低等方面具有明显优势，但该材料充放电过程中结构不稳定，容易向尖晶石相和岩盐相转变，导致循环过程容量衰减过快；且其热稳定性和安全性能较差。这些缺点在一定程度上限制了层状三元材料的广泛应用。
发明内容
本公开的目的在于提供一种三元正极材料前驱体及制备方法、正极材料、正极浆料、锂离子电池及正极和涉电设备，以解决上述问题。
为实现以上目的，本公开采用以下技术方案：
一种三元正极材料前驱体，包括核层、中间层和壳层，所述中间层包覆所述核层，所述壳层包覆所述中间层，所述核层、所述中间层、所述壳层的孔隙率依次增大。
优选地，所述核层的孔隙率为5.4％-17.1％，所述中间层的孔隙率为7.8％-19.2％，所述壳层的孔隙率为9％-20.1％；
优选地，所述核层的孔隙率为7.03％-12.74％，所述中间层的孔隙率为8.7％-13.6％，所述壳层的孔隙率为14.8％-16.3％；
优选地，所述核层的半径占整体半径的25％-30％，所述中间层的厚度占整体半径的50％-58.8％，所述壳层的厚度占整体半径的11.2％-25％。
优选地，所述三元正极材料前驱体的D50为7-15μm，(D90-D10)/D50＝0.6-0.8。
优选地，所述三元正极材料前驱体的001晶面半峰宽为0.4-0.88°，101晶面半峰宽为0.25-0.61°；
优选地，所述三元正极材料前驱体的FWHM(I001-I101)/I101比值范围为：0.1-0.9。
优选地，所述三元正极材料前驱体的BET/TD比值为3.90-6.66。
优选地，所述三元正极材料前驱体的化学通式为Ni xCo yMn zMe (1-x-y-z)(OH) 2，其中0.6≤x≤1，0＜y≤1，0＜z≤1，x+y+z≤1；Me表示掺杂元素，所述掺杂元素包括Al、Ti、V、W、Zr、Mg、Ce、Nb、La中的一种或多种；
优选地，所述掺杂元素的质量百分比含量为0.01％-10％。
本公开还提供一种三元正极材料前驱体的制备方法，包括：
将包括镍源、钴源、锰源、沉淀剂、络合剂在内的原料混合，通过溶液共沉淀法反应得到所述三元正极材料前驱体。
优选地，所述镍源包括硫酸镍，所述钴源包括硫酸钴，所述锰源包括硫酸锰，所述沉淀剂包括氢氧化钠、碳酸钠、碳酸氢钠中的一种或多种，所述络合剂包括氨水、柠檬酸钠、EDTA、草酸中的一种或多种。
优选地，所述镍源、所述钴源、所述锰源预先混合得到三元金属盐溶液使用；
优选地，所述三元金属盐溶液的浓度为100g/L-130g/L。
优选地，所述混合包括：
先将水、沉淀剂、络合剂混合得到反应底液，然后向所述反应底液中通入所述三元金属盐溶液、络合剂、沉淀剂；
优选地，所述反应底液的pH为11-12。
优选地，所述反应体系中通入保护气体。
优选地，所述反应的过程中，体系pH为10-12，上清液镍控制范围为0-500ppm；
优选地，所述反应的过程中，体系pH从11.9逐渐下降至10.8-10.3。
优选地，所述反应的温度为40℃-70℃；
优选地，所述反应的搅拌速度为100r/min-600r/min。
优选地，所述原料还包括掺杂元素溶液。
优选地，所述掺杂元素溶液中的掺杂元素包括Al、Ti、V、W、Zr、Mg、Ce、Nb、La中的一种或多种；
优选地，所述掺杂元素为W，所述掺杂元素溶液包括钨酸钠和柠檬酸钠；
优选地，所述钨酸钠和所述柠檬酸钠的质量比为1-3:1。
优选地，所述的三元正极材料前驱体的制备方法还包括后处理，所述后处理包括碱洗、水洗和干燥；
优选地，所述碱洗和水洗量体积比为：V 水洗：V 碱洗＝(2-8):1，碱洗和水洗温度各自独立的为30-70℃；
优选地，所述干燥温度为100℃-180℃，水分小于等于0.4％。
本公开还提供一种正极材料，包括内核、中间区域和外壳，所述中间区域包覆所述内核，所述外壳包覆所述中间区域，所述内核、所述中间区域、所述外壳的孔隙率依次增大。
本公开还提供一种正极浆料，其原料包括所述的正极材料。
本公开还提供一种锂离子电池正极，其原料包括所述的锂离子电池正极浆料。
本公开还提供一种锂离子电池，其原料包括所述的锂离子电池正极。
本公开还提供一种涉电设备，包括所述的锂离子电池。
与现有技术相比，本公开的有益效果包括：
本公开提供的三元正极材料前驱体，具有由核层到中间层再到壳层孔隙率逐渐增大的特殊孔隙分布，可以稳定三元材料的结构，有效改善材料裂纹的产生，抑制循环过程中的相转变，从而延长材料的使用寿命，同时可以提高材料的循环性能、倍率性能和能量密度。
本公开提供的三元正极材料前驱体的制备方法，工艺简单、成本低，可实现大规模工业化生产。
本公开提供的正极材料、正极浆料、锂离子电池正极、锂离子电池，稳定性强、安全性好，电性能优异。
本公开提供的锂离子电池，应用广泛。
附图说明
为了更清楚地说明本公开实施例的技术方案，下面将对实施例中所需要使用的附图作简单地介绍，应当理解，以下附图仅示出了本公开的某些实施例，因此不应被看作是对本公开范围的限定。
图1为所得三元正极材料前驱体的模型示意图；
图2为实施例1所得的三元正极材料前驱体的SEM图；
图3为实施例1所得的三元正极材料前驱体的剖面的SEM图；
图4为实施例1所得的三元正极材料前驱体的XRD图；
图5为实施例1所得的三元正极材料前驱体的介孔孔径微分分布曲线；
图6为实施例2所得的三元正极材料前驱体的SEM图；
图7为实施例2所得的三元正极材料前驱体的XRD图；
图8为实施例3所得的三元正极材料前驱体的SEM图；
图9为实施例3所得的三元正极材料前驱体的XRD图；
图10为实施例4所得的三元正极材料前驱体的SEM图；
图11为实施例4所得的三元正极材料前驱体的XRD图；
图12为实施例5所得的三元正极材料前驱体的SEM图；
图13为实施例5所得的三元正极材料前驱体的XRD图。
具体实施方式
如本文所用之术语：
“由……制备”与“包含”同义。本文中所用的术语“包含”、“包括”、“具有”、“含有”或其任何其它变形，意在覆盖非排它性的包括。例如，包含所列要素的组合物、步骤、方法、制品或装置不必仅限于那些要素，而是可以包括未明确列出的其它要素或此种组合物、步骤、方法、制品或装置所固有的要素。
连接词“由……组成”排除任何未指出的要素、步骤或组分。如果用于权利要求中，此短语将使权利要求为封闭式，使其不包含除那些描述的材料以外的材料，但与其相关的常规杂质除外。当短语“由……组成”出现在权利要求主体的子句中而不是紧接在主题之后时，其仅限定在该子句中描述的要素；其它要素并不被排除在作为整体的所述权利要求之外。
当量、浓度、或者其它值或参数以范围、优选范围、或一系列上限优选值和下限优选值限定的范围表示时，这应当被理解为具体公开了由任何范围上限或优选值与任何范围下限或优选值的任一配对所形成的所有范围，而不论该范围是否单独公开了。例如，当公开了范围“1～5”时，所描述的范围应被解释为包括范围“1～4”、“1～3”、“1～2”、“1～2和4～5”、“1～3和5”等。当数值范围在本文中被描述时，除非另外说明，否则该范围意图包括其端值和在该范围内的所有整数和分数。
在这些实施例中，除非另有指明，所述的份和百分比均按质量计。
“质量份”指表示多个组分的质量比例关系的基本计量单位，1份可表示任意的单位质量，如可以表示为1g，也可表示2.689g等。假如我们说A组分的质量份为a份，B组分的质量份为b份，则表示A组分的质量和B组分的质量之比a：b。或者，表示A组分的质量为aK，B组分的质量为bK(K为任意数，表示倍数因子)。不可误解的是，与质量份数不同的是，所有组分的质量份之和并不受限于100份之限制。
“和/或”用于表示所说明的情况的一者或两者均可能发生，例如，A和/或B包括(A和B)和(A或B)。
一种三元正极材料前驱体，包括核层、中间层和壳层，所述中间层包覆所述核层，所述壳层包覆所述中间层，所述核层、所述中间层、所述壳层的孔隙率依次增大。
常规型材料内外孔隙非常致密，充放电过程中结构不稳定，稳定性和安全性能较差，而该三元正极材料前驱体横截面其孔隙率分布不一致，所述核层、所述中间层、所述壳层的孔隙率依次增大，能够改善三元正极材料的循环性能和单位体积内能量密度，提升材料的结构稳定性和电池的安全性能。
在一个可选的实施方式中，所述核层的孔隙率为5.4％-17.1％，所述中间层的孔隙率为7.8％-19.2％，所述壳层的孔隙率为9％-20.1％；
在一个可选的实施方式中，所述核层的孔隙率为7.03％-12.74％，所述中间层的孔隙率为8.7％-13.6％，所述壳层的孔隙率为14.8％-16.3％。
将本公开材料通过HITACHI IM4000设备前处理后，将制得的样品在HITACHI SU8100下拍摄SEM图。为了评价孔隙率的特点，本公开使用图像解析软件(ImageJ)直接求出各个区域孔隙面积和截面积，由(孔隙率＝各区域孔隙面积/各区域截面积×100％)，计算得出不同区域的孔隙率，本公开孔隙率均由该方法表征。
可选的，所述核层的孔隙率可以为5.4％、6％、7％、8％、9％、10％、11％、12％、13％、14％、15％、16％、17％、17.1％或者5.4％-17.1％之间的任一值，所述中间层的孔隙率可以为7.8、8％、9％、10％、11％、12％、13％、14％、15％、16％、17％、18％、19％、19.2％或者7.8％-19.2％之间的任一值，所述壳层的孔隙率可以为9％、10％、11％、12％、13％、14％、15％、16％、17％、18％、19％、20％、20.1％或者9％-20.1％之间的任一值。
在一个可选的实施方式中，所述中间层和所述壳层的孔隙呈长条状；
在一个可选的实施方式中，所述中间层和所述壳层的孔隙的宽度由内向外逐渐增大，且整体呈放射状分布。
因其孔径大小内外不一致，其生长呈现多孔放射状，制备成的三元正极材料能够形成由内向外的锂离子扩散通道，这种通道有利于电解液的扩散以及充放电过程中的离子传导，从而利于容量的发挥，且在一定程度上也能提高电池的倍率性能。
在一个可选的实施方式中，所述核层的半径占整体半径的25％-30％，所述中间层的厚度占整体半径的50％-58.8％，所述壳层的厚度占整体半径的11.2％-25％。
在一个可选的实施方式中，三元正极材料前驱体的D50为7-15μm，(D90-D10)/D50＝0.6-0.8。
可选的，三元正极材料前驱体的D50可以为7μm、8μm、9μm、10μm、11μm、12μm、13μm、14μm、15μm或者7-15μm之间的任一值，(D90-D10)/D50可以为0.6、0.7、0.8或者0.6-0.8之间的任一值。
在一个可选的实施方式中，三元正极材料前驱体的001晶面半峰宽为0.4-0.88°，101晶面半峰宽为0.25-0.61°；
可选的，三元正极材料前驱体的001晶面半峰宽可以为0.4°、0.5°、0.6°、0.7°、0.8°、0.81°、0.82°、0.83°、0.84°、0.85°、0.86°、0.87°、0.88°或者0.4-0.88°之间的任一值，101晶面半峰宽可以为0.25°、0.3°、0.35°、0.4°、0.45°、0.5°、0.55°、0.56°、0.57°、0.58°、0.59°、0.60°、0.61°或者0.25-0.61°之间的任一值；
在一个可选的实施方式中，三元正极材料前驱体的FWHM(I001-I101)/I101比值范围为：0.1-0.9。
可选的，FWHM(I001-I101)/I101比值可以为0.1、0.2、0.3、0.4、0.5、0.6、0.7、0.8、0.9或者0.1-0.9之间的任一值。
通过控制半峰宽以及FWHM(I001-I101)/I101比值，改善材料的结晶度和结构，从而使一次颗粒微细化，可以抑制颗粒密度的降低且增大疏密度，进一步利于容量的发挥且有利于提高材料的循环稳定性，也能够抑制能量密度的降低。
在一个可选的实施方式中，三元正极材料前驱体的BET/TD比值为3.90-6.66。
BET与TD的比值呈线性关系，且随着BET/TD比值越大，材料的孔隙率越大，有利于增强电池的安全性能同时提高电池的倍率性能和循环性能。
可选的，BET/TD比值可以为3.90、4、5、6、6.66或者3.90-6.66之间的任一值。
在一个可选的实施方式中，三元正极材料前驱体的化学通式为Ni xCo yMn zMe (1-x-y-z)(OH) 2，其中0.6≤x≤1，0＜y≤1，0＜z≤1，x+y+z≤1；Me表示掺杂元素，所述掺杂元素包括Al、Ti、V、W、Zr、Mg、Ce、Nb、La中的一种或多种；
在一个可选的实施方式中，所述掺杂元素的质量百分比含量为0.01％-10％。
本公开提供的三元正极材料前驱体，当Ni含量大于等于0.6时，成为高镍材料，具有循环性能好、能量密度大、稳定性和安全性能好的优势。通过引入Al、Ti、V、W、Zr、Mg、Ce、Nb、La等其它金属元素，来增强材料结构的稳定性，从而提高材料的安全性能和循环稳定性等。
可选的，所述掺杂元素的质量百分比含量可以为0.01％、0.05％、0.1％、0.5％、1％、2％、3％、4％、5％、6％、7％、8％、9％、10％或者0.01％-10％之间的任一值。
本公开还提供一种三元正极材料前驱体的制备方法，包括：
将包括镍源、钴源、锰源、沉淀剂、络合剂在内的原料混合，通过溶液共沉淀法反应得到所述三元正极材料前驱体。
在一个可选的实施方式中，所述镍源包括硫酸镍，所述钴源包括硫酸钴，所述锰源包括硫酸锰，所述沉淀剂包括氢氧化钠、碳酸钠、碳酸氢钠中的一种或多种，所述络合剂包括氨水、柠檬酸钠、EDTA、草酸中的一种或多种。
在一个可选的实施方式中，所述镍源、所述钴源、所述锰源预先混合得到三元金属盐 溶液使用；
在一个可选的实施方式中，所述三元金属盐溶液的浓度为100g/L-130g/L。
可选的，所述三元金属盐溶液的浓度可以为100g/L、101g/L、102g/L、103g/L、104g/L、105g/L、106g/L、107g/L、108g/L、109g/L、110g/L、111g/L、112g/L、113g/L、114g/L、115g/L、116g/L、117g/L、118g/L、119g/L、120g/L、121g/L、122g/L、123g/L、124g/L、125g/L、126g/L、127g/L、128g/L、129g/L、130g/L或者100g/L-130g/L之间的任一值。
在一个可选的实施方式中，所述混合包括：
先将水、沉淀剂、络合剂混合得到反应底液，然后向所述反应底液中通入所述三元金属盐溶液、络合剂、沉淀剂；
在一个可选的实施方式中，所述反应底液的pH为11-12。
可选的，所述反应底液的pH可以为11.0、11.1、11.2、11.3、11.4、11.5、11.6、11.7、11.8、11.9、12.0或者11-12之间的任一值。
在一个可选的实施方式中，所述反应体系中通入保护气体。
保护气体优选氮气。
在一个可选的实施方式中，所述反应的过程中，体系pH为10-12，上清液镍控制范围为0-500ppm；
在一个可选的实施方式中，所述反应的过程中，体系pH从11.9逐渐下降至10.8-10.3。
可选的，所述反应的过程中，体系pH可以为10、10.5、11、11.5、12或者10-12之间的任一值，上清液镍控制范围可以为0ppm、50ppm、100ppm、200ppm、300ppm、400ppm、500ppm或者0-500ppm之间的任一值。
在一个可选的实施方式中，所述反应的温度为40℃-70℃；
在一个可选的实施方式中，所述反应的搅拌速度为100r/min-600r/min。
可选的，所述反应的温度可以为40℃、50℃、60℃、70℃或者40-70℃之间的任一值；所述反应的搅拌速度可以为100r/min、200r/min、300r/min、400r/min、500r/min、600r/min或者100r/min-600r/min之间的任一值。
在一个可选的实施方式中，所述原料还包括掺杂元素溶液。
在一个可选的实施方式中，所述掺杂元素溶液中的掺杂元素包括Al、Ti、V、W、Zr、Mg、Ce、Nb、La中的一种或多种；
在一个可选的实施方式中，所述掺杂元素为W，所述掺杂元素溶液包括钨酸钠和柠檬酸钠；
在一个可选的实施方式中，所述钨酸钠和所述柠檬酸钠的质量比为1-3:1。
可选的，所述钨酸钠和所述柠檬酸钠的质量比可以为1：1、2：1、3：1或者1-3:1之 间的任一值。
在一个可选的实施方式中，所述的三元正极材料前驱体的制备方法还包括后处理，所述后处理包括碱洗、水洗和干燥；
在一个可选的实施方式中，所述碱洗和水洗量体积比为：V 水洗：V 碱洗＝(2-8):1，碱洗和水洗温度各自独立的为30-70℃；
在一个可选的实施方式中，所述干燥温度为100℃-180℃，水分小于等于0.4％。
可选的，所述碱洗和水洗量体积比可以为2：1、3：1、4：1、5：1、6：1、7：1、8：1或者V 水洗：V 碱洗＝(2-8):1之间的任一值，碱洗和水洗温度各自独立的可以为30℃、40℃、50℃、60℃、70℃或者30-70℃之间的任一值；所述干燥温度可以为100℃、110℃、120℃、130℃、140℃、150℃、160℃、170℃、180℃或者100℃-180℃之间的任一值，水分可以为0.1％、0.2％、0.3％、0.4％或者小于等于0.4％之间的任一值。
本公开还提供一种正极材料，包括内核、中间区域和外壳，所述中间区域包覆所述内核，所述外壳包覆所述中间区域，所述内核、所述中间区域、所述外壳的孔隙率依次增大。
本公开还提供一种正极浆料，其原料包括所述的正极材料。
本公开还提供一种锂离子电池正极，其原料包括所述的锂离子电池正极浆料。
本公开还提供一种锂离子电池，其原料包括所述的锂离子电池正极。
本公开还提供一种涉电设备，包括所述的锂离子电池。
需要说明的是，此处所指的涉电设备，不仅仅是指其本身包括本公开提供的锂离子电池，还包括使用本公开提供的锂离子电池作为外接电源或能量载体的情形；即，由本公开提供的锂离子电池直接或间接供电的设备，或者该设备本身作为电源给本公开提供的锂离子电池进行充电。
下面将结合具体实施例对本公开的实施方案进行详细描述，但是本领域技术人员将会理解，下列实施例仅用于说明本公开，而不应视为限制本公开的范围。实施例中未注明具体条件者，按照常规条件或制造商建议的条件进行。所用试剂或仪器未注明生产厂商者，均为可以通过市售购买获得的常规产品。
实施例1
①将79.98kg硫酸镍、11.30kg硫酸钴和4.06kg硫酸锰晶体和纯水混合搅匀，配置成(2moL/L)的三元溶液，与定量的钨酸钠和柠檬酸钠配置成0.91g/L的钨溶液，与沉淀剂、络合剂作为主要的原料和辅料；在反应釜内加入纯水、液碱(质量浓度32％)、氨水(质量浓度20.5％)配置成pH范围为11.60-11.70的底液、通入氮气，在539r/min搅拌速率下，加热至60℃，然后按设定的流量通入三元溶液(4L/h)、液碱(1.6L/h)、氨水(0.22L/h)以及掺杂溶液(2L/h)；反应过程中pH控制范围为(11.65-10.50)，上清镍含量控制在 50-100ppm之间，反应得到中粒径D50为10μm的钨掺杂型镍钴锰三元沉淀物。
②将反应产物固液分离后，通过一定量碱洗、水洗，使其Na＜300、2200＜S＜2600后，将滤饼取出保存好。
③将保存好的滤饼分散开后，在鼓风式烘箱中烘干脱水，当水分低于4000ppm后，取出密封保存。
④将得到的干燥料通过过筛、除铁等处理，得到掺钨(2500ppm)的前驱体成品Ni 0.9Co 0.06Mn 0.04(OH) 2。
⑤将得到的掺杂型前驱体材料在一定条件下与锂化物混合烧结制备成掺杂型正极材料。
图1为所得三元正极材料前驱体的模型示意图，其中，A区域代表核层，B区域代表中间层，C区域代表壳层。图2为实施例1所得的三元正极材料前驱体的SEM图；图3为实施例1所得的三元正极材料前驱体的剖面的SEM图；图4为实施例1所得的三元正极材料前驱体的XRD图，其中，横坐标为衍射峰角度，纵坐标为衍射峰强度。图5为实施例1所得的三元正极材料前驱体的介孔孔径微分分布曲线。
实施例2
①将84.82kg硫酸镍、7.15kg硫酸钴和4.67kg硫酸锰晶体和纯水混合搅匀，配置成(2moL/L)的三元溶液，与定量的硫酸铝和氢氧化钠配置成1.47g/L的铝溶液与沉淀剂、络合剂作为主要的原料和辅料；在反应釜内加入纯水、液碱(质量浓度32％)、氨水配置成pH范围为11.60-11.70的底液、通入氮气，在539r/min搅拌速率下，加热至60℃，然后按设定的流量通入三元溶液(4L/h)、液碱(1.6L/h)、氨水(0.31L/h)以及掺杂溶液(2L/h)；反应过程中通过调整pH(11.60-10.55)，将上清镍含量控制在50-100ppm，搅拌频率由539r/min逐渐降至462r/min，反应得到中粒径D50为12μm的铝掺杂型镍钴锰三元沉淀物。
②③④步同实施例1，得到掺Al(6000ppm)前驱体成品Ni 0.88Co 0.09Mn 0.03(OH) 2。
⑤步同实施例1。
图6为实施例2所得的三元正极材料前驱体的SEM图，图7为实施例2所得的三元正极材料前驱体的XRD图，其中，横坐标为衍射峰角度，纵坐标为衍射峰强度。
实施例3
①将88.52kg硫酸镍、5.10kg硫酸钴和3.44kg硫酸锰晶体和纯水混合搅匀，配置成(2moL/L)的三元溶液，与定量的硫酸氧钛、柠檬酸钠和硫酸配置成2.0g/L的钛溶液与沉淀剂、络合剂作为主要的原料和辅料；在反应釜内加入纯水、液碱(质量浓度32％)、氨水配置成pH范围为11.60-11.70的底液、通入氮气，在539r/min搅拌速率下，加热至60℃，然后按设定的流量通入三元溶液(4L/h)、液碱(1.6L/h)、氨水(0.54L/h)以及掺杂溶液(2L/h)； 反应过程通过调整PH(11.65-11.00)，将上清镍含量控制在50-100ppm，搅拌频率由539r/min逐渐降至308r/min，反应得到中粒径D50为16μm的钛掺杂型镍钴锰三元沉淀物。
②③④步同实施例1，得到掺Ti(4000ppm)前驱体成品Ni 0.92Co 0.03Mn 0.05(OH) 2。
⑤步同实施例1。
图8为实施例3所得的三元正极材料前驱体的SEM图，图9为实施例3所得的三元正极材料前驱体的XRD图，其中，横坐标为衍射峰角度，纵坐标为衍射峰强度。
实施例4
①将91.26kg硫酸镍、4.07kg硫酸钴和2.22kg硫酸锰晶体和纯水混合搅匀，配置成(2moL/L)的三元溶液，与定量的硫酸锆、柠檬酸钠和硫酸配置成3.67g/L的锆溶液与沉淀剂、络合剂作为主要的原料和辅料；在反应釜内加入纯水、液碱(质量浓度32％)、氨水配置成pH范围为11.60-11.70的底液、通入氮气，在539r/min搅拌速率下，加热至60℃，然后按设定的流量通入三元溶液(4L/h)、液碱(1.6L/h)、氨水(0.6L/h)以及掺杂溶液(2L/h)；反应过程中通过调整pH(11.65-10.30)，将上清镍控制在0-200ppm，搅拌频率由539r/min逐渐降至231r/min，反应得到中粒径D50为16μm的锆掺杂型镍钴锰三元沉淀物。
②③④步同实施例1，得到掺Zr(10000ppm)前驱体成品Ni 0.94Co 0.04Mn 0.02(OH) 2。
⑤步同实施例1。
图10为实施例4所得的三元正极材料前驱体的SEM图，图11为实施例4所得的三元正极材料前驱体的XRD图，其中，横坐标为衍射峰角度，纵坐标为衍射峰强度。
实施例5
①将85.61kg硫酸镍、6.15kg硫酸钴和2.45kg硫酸锰晶体和纯水混合搅匀，配置成(2moL/L)的三元溶液，与沉淀剂、络合剂作为主要的原料和辅料；在反应釜内加入纯水、液碱(质量浓度32％)、氨水(质量浓度20.5％)配置成pH范围为11.60-11.70的底液、通入氮气，在539r/min搅拌速率下，加热至60℃，然后按设定的流量通入三元溶液(4L/h)、液碱(1.6L/h)、氨水(0.22L/h)以及掺杂溶液(2L/h)；反应过程中pH控制范围为(11.65-10.50)，上清镍含量控制在50-100ppm之间，反应得到中粒径D50为10μm的镍钴锰三元沉淀物。
②③④步同实施例1，得到前驱体成品Ni 0.905Co 0.057Mn 0.038(OH) 2。
⑤步同实施例1。
图12为实施例5所得的三元正极材料前驱体的SEM图，图13为实施例5所得的三元正极材料前驱体的XRD图，其中，横坐标为衍射峰角度，纵坐标为衍射峰强度。
对比例1
①反应过程中将搅拌调整为在616.4r/min搅拌速率下，进料量调整为三元溶液(1L/h)、 液碱(0.4L/h)、氨水(0.05L/h)，其他均同实施例5，得到前驱体成品化学式为Ni 0.905Co 0.057Mn 0.038(OH) 2。
对比例2
①反应过程中将三元溶液流量由1L/h调整为逐渐升至4L/h、液碱流量由0.4L/h逐渐升至1.6L/h、氨水流量由0.12L/h逐渐升至0.16L/h，其他均同实施例5，得到前驱体成品化学式为Ni 0.905Co 0.057Mn 0.038(OH) 2。
对比例3
①反应过程中将三元溶液流量调整为2L/h、液碱流量调整为0.8L/h、氨水流量调整为0.12L/h，其他均同实施例5，得到前驱体成品化学式为Ni 0.905Co 0.057Mn 0.038(OH) 2。
对比例4
①反应过程中将三元溶液流量调整为以2L/h逐渐升至7L/h、液碱流量由0.8L/h升至2.8L/h、氨水由0.12L/h逐渐升至0.28L/h，其他均同实施例5，得到前驱体成品化学式为Ni 0.905Co 0.057Mn 0.038(OH) 2。
对照例1
①反应过程中将氨水流量调整为由0.54L/h逐渐降至0.40L/h，其他均同实施例5，得到前驱体成品化学式为Ni 0.905Co 0.057Mn 0.038(OH) 2。
对照例2
①反应过程中将搅拌调整为由在693.7r/min搅拌速率下，逐渐降至在539.7r/min搅拌速率下，其它均同实施例5，得到前驱体成品化学式为Ni 0.905Co 0.057Mn 0.038(OH) 2。
实施例及对比例所得材料的参数及性能测试结果如下表1所示：
表1前驱体数据
Figure PCTCN2022083481-appb-000001
Figure PCTCN2022083481-appb-000002
表2正极材料数据
Figure PCTCN2022083481-appb-000003
由表1和表2数据可知，实施例1-5中获得了一种具有特殊孔隙的掺杂型高镍三元正极材料，就该实施例制备的前驱体材料而言，A区域孔隙在7.3％-16.9％；B区域孔隙在8.8％-17.6％；C区域孔隙在12.5％-19.8％；XRD半峰宽(I001-I101)/I101在0.397-0.489，BET/TD在4.14-6.04；此外，还确认了基于该正极材料制作的电池容量维持率在97％以上，(1C/0.1C)倍率维持在96以上，具有优良的循环特性和倍率性能；
另一方面则确认了，对比例1-4中也制备了一种具有特殊孔隙的掺杂型高镍三元正极材料，对比例1中，BET/TD在3.90-6.84；XRD半峰宽(I001-I101)/I101在0.1-0.9；A区域孔隙低于5.4％，B区域孔隙低于7.8％，C区域孔隙低于9％；对比例2中，BET/TD在3.90-6.84，XRD半峰宽(I001-I101)/I101在在0.1-0.9；A区域孔隙低于5.4％，B区域孔隙低于7.8％，C区域孔隙低于9％；对比例3中，BET/TD在3.90-6.84；XRD半峰宽(I001-I101) /I101在0.1-0.9；A区域孔隙在5.4％-17.1％，B区域孔隙在7.8％-19.2％，C区域孔隙低于9％；对比例4中，BET/TD在3.90-6.84；XRD半峰宽(I001-I101)/I101在0.1-0.9；A区域孔隙在5.4％-17.1％，B区域孔隙低于7.8％，C区域孔隙在9％-20.1％。此外还确认了，基于该正极材料制作的电池容量维持率在94％以下，(1C/0.1C)倍率维持在93以下，故与实施例1-5相比，循环特性和倍率性能较差。
最后应说明的是：以上各实施例仅用以说明本公开的技术方案，而非对其限制；尽管参照前述各实施例对本公开进行了详细的说明，本领域的普通技术人员应当理解：其依然可以对前述各实施例所记载的技术方案进行修改，或者对其中部分或者全部技术特征进行等同替换；而这些修改或者替换，并不使相应技术方案的本质脱离本公开各实施例技术方案的范围。
此外，本领域的技术人员能够理解，尽管在此的一些实施例包括其它实施例中所包括的某些特征而不是其它特征，但是不同实施例的特征的组合意味着处于本公开的范围之内并且形成不同的实施例。例如，在上面的权利要求书中，所要求保护的实施例的任意之一都可以以任意的组合方式来使用。公开于该背景技术部分的信息仅仅旨在加深对本公开的总体背景技术的理解，而不应当被视为承认或以任何形式暗示该信息构成已为本领域技术人员所公知的现有技术。

Claims (15)

  1. 一种三元正极材料前驱体，其特征在于，包括核层、中间层和壳层，所述中间层包覆所述核层，所述壳层包覆所述中间层，所述核层、所述中间层、所述壳层的孔隙率依次增大。
  2. 根据权利要求1所述的三元正极材料前驱体，其特征在于，所述核层的孔隙率为5.4％-17.1％，所述中间层的孔隙率为7.8％-19.2％，所述壳层的孔隙率为9％-20.1％；
    优选地，所述核层的孔隙率为7.03％-12.74％，所述中间层的孔隙率为8.7％-13.6％，所述壳层的孔隙率为14.8％-16.3％。
  3. 根据权利要求1所述的三元正极材料前驱体，其特征在于，所述核层的半径占整体半径的25％-30％，所述中间层的厚度占整体半径的50％-58.8％，所述壳层的厚度占整体半径的11.2％-25％。
  4. 根据权利要求1所述的三元正极材料前驱体，其特征在于，所述三元正极材料前驱体的D50为7-15μm，(D90-D10)/D50＝0.6-0.8；
    优选地，所述三元正极材料前驱体的001晶面半峰宽为0.4-0.88°，101晶面半峰宽为0.25-0.61°；
    优选地，FWHM(I001-I101)/I101比值范围为：0.1-0.9；
    优选地，所述三元正极材料前驱体的BET/TD比值为3.90-6.66。
  5. 根据权利要求1-4任一项所述的三元正极材料前驱体，其特征在于，所述三元正极材料前驱体的化学通式为Ni xCo yMn zMe (1-x-y-z)(OH) 2，其中0.6≤x≤1，0＜y≤1，0＜z≤1，x+y+z≤1；Me表示掺杂元素，所述掺杂元素包括Al、Ti、V、W、Zr、Mg、Ce、Nb、La中的一种或多种；
    优选地，所述掺杂元素的质量百分比含量为0.01％-10％。
  6. 一种三元正极材料前驱体的制备方法，其特征在于，包括：
    将包括镍源、钴源、锰源、沉淀剂、络合剂在内的原料混合，通过溶液共沉淀法反应得到所述三元正极材料前驱体。
  7. 根据权利要求6所述的三元正极材料前驱体的制备方法，其特征在于，所述镍源包括硫酸镍，所述钴源包括硫酸钴，所述锰源包括硫酸锰，所述沉淀剂包括氢氧化钠、碳酸钠、碳酸氢钠中的一种或多种，所述络合剂包括氨水、柠檬酸钠、EDTA、草酸中的一种或多种；
    优选地，所述镍源、所述钴源、所述锰源预先混合得到三元金属盐溶液使用；
    优选地，所述三元金属盐溶液的浓度为100g/L-130g/L；
    优选地，所述混合包括：
    先将水、沉淀剂、络合剂混合得到反应底液，然后向所述反应底液中通入所述三元金属盐溶液、络合剂、沉淀剂；
    优选地，所述反应底液的pH为11-12；
    优选地，反应体系中通入保护气体。
  8. 根据权利要求6所述的三元正极材料前驱体的制备方法，其特征在于，所述反应的过程中，体系pH为10-12，上清液镍控制范围为0-500ppm；
    优选地，所述反应的过程中，体系pH从11.9逐渐下降至10.8-10.3；
    优选地，所述反应的温度为40℃-70℃；
    优选地，所述反应的搅拌速度为100r/min-600r/min。
  9. 根据权利要求6所述的三元正极材料前驱体的制备方法，其特征在于，所述原料还包括掺杂元素溶液；
    优选地，所述掺杂元素溶液中的掺杂元素包括Al、Ti、V、W、Zr、Mg、Ce、Nb、La中的一种或多种；
    优选地，所述掺杂元素为W，所述掺杂元素溶液包括钨酸钠和柠檬酸钠；
    优选地，所述钨酸钠和所述柠檬酸钠的质量比为1-3:1。
  10. 根据权利要求6-9任一项所述的三元正极材料前驱体的制备方法，其特征在于，所述三元正极材料前驱体的制备方法还包括后处理，所述后处理包括碱洗、水洗和干燥；
    优选地，所述碱洗和水洗量体积比为：V 水洗：V 碱洗＝(2-8):1，碱洗和水洗温度各自独立的为30-70℃；
    优选地，所述干燥温度为100℃-180℃，水分小于等于0.4％。
  11. 一种正极材料，其特征在于，包括内核、中间区域和外壳，所述中间区域包覆所述内核，所述外壳包覆所述中间区域，所述内核、所述中间区域、所述外壳的孔隙率依次增大。
  12. 一种正极浆料，其特征在于，其原料包括权利要求11所述的正极材料。
  13. 一种锂离子电池正极，其特征在于，其原料包括权利要求12所述的正极浆料。
  14. 一种锂离子电池，其特征在于，其原料包括权利要求13所述的锂离子电池正极。
  15. 一种涉电设备，其特征在于，包括权利要求14所述的锂离子电池。
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