WO2022207010A1 - 多元正极材料及其制备方法与应用 - Google Patents

多元正极材料及其制备方法与应用 Download PDF

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WO2022207010A1
WO2022207010A1 PCT/CN2022/092619 CN2022092619W WO2022207010A1 WO 2022207010 A1 WO2022207010 A1 WO 2022207010A1 CN 2022092619 W CN2022092619 W CN 2022092619W WO 2022207010 A1 WO2022207010 A1 WO 2022207010A1
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positive electrode
electrode material
additive
component
cathode material
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French (fr)
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王余
岳鹏
刘亚飞
陈彦彬
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Beijing Easpring Material Technology Co Ltd
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Beijing Easpring Material Technology Co Ltd
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Priority to EP22779190.2A priority Critical patent/EP4156342A4/en
Priority to KR1020227046138A priority patent/KR102646171B1/ko
Priority to JP2022581594A priority patent/JP7374358B2/ja
Publication of WO2022207010A1 publication Critical patent/WO2022207010A1/zh
Priority to US18/091,878 priority patent/US20230174389A1/en
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    • C01G53/50—Complex oxides containing nickel and at least one other metal element containing alkali metals, e.g. LiNiO2 containing manganese of the type (MnO2)n-, e.g. Li(NixMn1-x)O2 or Li(MyNixMn1-x-y)O2
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    • H01M4/505—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of manganese of mixed oxides or hydroxides containing manganese for inserting or intercalating light metals, e.g. LiMn2O4 or LiMn2OxFy
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    • H01M2004/026—Electrodes composed of, or comprising, active material characterised by the polarity
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    • Y02E60/10—Energy storage using batteries

Definitions

  • the invention relates to the field of lithium ion batteries, in particular to a multi-element positive electrode material and a preparation method and application thereof.
  • cathode materials Due to the continuous improvement of the energy density and cycle life requirements of lithium-ion batteries in the power market in recent years, and the key role of cathode materials on the energy density and cycle life of lithium-ion batteries, multi-component cathode materials as a research hotspot continue to attract the attention of researchers and the market.
  • Improving the energy density of the positive electrode of lithium-ion batteries is mainly achieved by increasing the gram capacity of active materials, which can generally be achieved by increasing the charge-discharge voltage window.
  • increasing the charge-discharge voltage puts forward more stringent requirements on the structural stability of the cathode material and the control of the surface-interface reactivity. If the cathode material cannot meet the requirements, blindly increasing the voltage window may lead to serious degradation of the battery cycle performance and safety. Sexual decline, etc.
  • the main reasons are: (1) If the structural stability of the material is insufficient, when the charging voltage is high, the lithium ions will be extracted from the layered structure of the positive electrode material, resulting in partial collapse of the layered structure, and the lithium ions cannot be returned during the discharge process.
  • doping and coating the positive electrode material By doping and coating the positive electrode material with specific elements and compounds, the structural stability of the material can be greatly improved, and the reactivity of the material surface interface and the electrolyte can be reduced; Maintain the stability of the layered structure of the material and the surface interface.
  • doping and coating additives in the industry are mostly introduced in the form of oxygen-containing compounds such as oxides, hydroxides or oxo-acid salts of additive elements, and finally exist in the form of oxides or composite oxides formed with lithium oxide. . Since the additive compound itself contains oxygen elements, it is difficult for the additive elements to re-combine with the oxygen in the structure and surface of the positive electrode material, and it is difficult to form a stable and effective bond with the structure and surface of the positive electrode material.
  • the improvement effect of voltage characteristics and the like is limited, and the significant effect of the additive element cannot be fully exerted.
  • the purpose of the present invention is to overcome the poor structural stability of the oxygen-containing compound doped and/or coated positive electrode material in the prior art and the serious side reaction with the electrolyte in the high delithiation state, which cannot meet the application under high voltage conditions.
  • the problem of demand is to provide a multi-component positive electrode material and its preparation method and application.
  • the multi-component positive electrode material has a specific structure, thereby significantly improving the structural stability of the positive electrode material, improving the problem of oxygen evolution in a high delithiation state, and reducing
  • the degree of side reactions between the cathode material and the electrolyte under high voltage conditions improves the electrochemical performance and safety of lithium-ion batteries.
  • the first aspect of the present invention provides a multi-element positive electrode material, characterized in that the peak intensity of the (006) crystal plane of the positive electrode material obtained by XRD I (006) and the peak intensity of the (012) crystal plane The ratio of I (012) I (006) /I (012) ⁇ 0.8;
  • the ratio of the peak area A (006) of the (006) crystal plane to the peak area A (012) of the (012) crystal plane obtained by XRD of the positive electrode material is A (006) /A (012) ⁇ 0.5.
  • a second aspect of the present invention provides a method for preparing a multi-element positive electrode material, characterized in that the method comprises the following steps:
  • At least one of the first additive, the second additive and the third additive is included.
  • a third aspect of the present invention provides a multi-component positive electrode material prepared by the above preparation method.
  • a fourth aspect of the present invention provides the application of the above-mentioned multi-component positive electrode material in a lithium ion battery.
  • the multi-element positive electrode material provided by the present invention and its preparation method and application obtain the following beneficial effects:
  • the multi-component cathode material provided by the present invention has a specific structure, and the ratio of peak intensity obtained by XRD I (006) /I (012) ⁇ 0.8, and the ratio of peak area I (006) / I (012) ⁇ 0.5.
  • the diffraction peak of the (003) crystal plane between the crystal phases corresponds to the peak of the (006) crystal plane, and the ratio of the peak intensity of the multi-component cathode material with this specific structure in the present invention is I (006) /I (012) ⁇ 0.8, and the peak area is
  • the multi-component cathode material with ratio A (006) /A (012) ⁇ 0.5 has a better (003) crystal plane orientation, the M'-O bond length increases, the bond energy is weakened, and the covalentity is reduced (M' is the multi-component cathode.
  • the O element can remain stable in a wider range of M' valence, so as not to generate electron holes in the 2p energy band, resulting in the evolution of oxygen. Therefore, in the present invention, the structural stability of the multi-component positive electrode material is improved, and the problem of oxygen evolution in the state of high delithiation can be improved, and the degree of side reactions between the positive electrode material and the electrolyte under high voltage conditions can be reduced, and the electric power of the lithium ion battery can be improved. Chemical Properties and Safety.
  • the present invention provides a preferred example of a multi-component positive electrode material with the above-mentioned specific structure
  • the multi-component positive electrode material contains Q element and M element, and the two can interact with the internal and/or surface of the positive electrode material during the roasting or calcination process.
  • the oxygen element forms an effective bond, thereby forming a specific structure in the multi-component cathode material.
  • This specific structure can significantly improve the stability of the cathode material and improve the oxygen evolution problem in the high delithiation state. At the same time, it can greatly reduce the material surface.
  • the number of dangling bonds that are not involved in bonding and the number of oxygen active sites at the interface significantly reduce the degree of side reactions between the multi-component cathode material and the electrolyte under high voltage.
  • M element and/or Q element can be introduced into the cathode material and/or in the coating layer, so that the structure and surface and interface stability of the prepared cathode material are remarkable.
  • the preparation method enables the introduction of M and/or Q elements into different kinds of multicomponent materials, such as NCM111, NCM523, NCM622, NCM811, NCA, NCMA, and the like. And the preparation process is simple, and can be suitable for large-scale production.
  • the multi-component cathode material provided by the present invention has a high working voltage window, and when it is used in a lithium ion battery, the gram capacity, cycle life, DC resistance (DCR) increase and safety of the lithium ion battery can be significantly improved.
  • Fig. 1 is the XRD pattern of the multi-element positive electrode material of embodiment 1 and comparative example 1;
  • Example 2 is a graph of the cycle capacity retention rate of batteries prepared from the multi-component cathode materials of Example 1, Example 4, Example 5 and Comparative Example 1;
  • FIG. 3 is a cycle process DCR diagram of batteries prepared from the multi-component cathode materials of Example 1, Example 4, Example 5 and Comparative Example 1.
  • FIG. 3 is a cycle process DCR diagram of batteries prepared from the multi-component cathode materials of Example 1, Example 4, Example 5 and Comparative Example 1.
  • a first aspect of the present invention provides a multi-component positive electrode material, characterized in that, the multi-component positive electrode material has a peak intensity I (006) of the (006) crystal plane and a peak intensity I ( 012) of the (012) crystal plane obtained by XRD.
  • the ratio of the peak area A (006) of the (006) crystal plane to the peak area A (012) of the (012) crystal plane obtained by XRD of the multi-component cathode material is A (006) /A (012) ⁇ 0.5.
  • the inventor's research found that the framework transition metal elements M' (Ni, Co, Mn, etc.) in conventional multi-element cathode materials have strong covalentity with oxygen elements, which will promote the 2p energy band of oxygen to generate electron holes, and This leads to the evolution of oxygen from the multi-component cathode material in a high delithiation state, which makes it difficult to apply the multi-component cathode material at high voltages.
  • controlling the growth rate of the (003) crystal plane and/or controlling the growth rate of the (012) crystal plane of the multi-element cathode material keeps the growth rate of the (003) crystal plane significantly higher than the growth rate of the (012) crystal plane, so that the It has a specific structure in which the (003) crystal plane grows preferentially, and the diffraction peak of the (003) crystal plane between the crystal phases corresponds to the peak of the (006) crystal plane. Therefore, the multi-component cathode material is specifically expressed as the peak intensity of the (006) crystal plane obtained by XRD.
  • This can improve the structural stability of the cathode material, significantly improve the oxygen evolution problem under high delithiation conditions, reduce the degree of side reactions between the cathode material and the electrolyte under high voltage conditions, and improve the electrochemical performance of lithium-ion batteries. .
  • the 2 ⁇ of the (006) characteristic diffraction peak obtained by XRD of the multi-element cathode material is 37.2-39.5°
  • the 2 ⁇ of the (012) characteristic diffraction peak is 37.2-39.5°.
  • the multi-component positive electrode material has the composition shown in the general formula I:
  • M is at least one of W, Mo, V, Ca, Al, Si, Ni, Mn, Hf, Ta, Y, Sr, Ba, Er, Ga, Mg, Ti, Zr, La, Ce, Co, and Nb ;
  • Q is at least one of B, P and Si.
  • the inventors found that the introduction of boron element, phosphorus element or silicon element into the multi-element positive electrode material is to obtain the above-mentioned ratio of peak intensity I (006) /I (012) ⁇ 0.8, peak area ratio A ( 006) /A (012) ⁇ 0.5, one of the possible embodiments of the multi-component cathode material.
  • the present invention does not limit this, but the ratio of the peak intensity I (006) / I ( 012) ⁇ 0.8 and the ratio of peak area A (006) /A (012) ⁇ 0.5 are all within the protection scope of the present invention.
  • introducing boron element, phosphorus element or silicon element, coating and/or doping the multi-element positive electrode material can form an effective bond with the oxygen element inside and on the surface of the positive electrode material, especially, after combining with the internal oxygen element , the original M'-O bond length increases, the covalency between M' and O elements weakens, the M'-M' interlayer spacing in the crystal structure increases significantly, the (003) crystal plane shows a growth rate advantage, and the crystal phase
  • the (003) crystal plane diffraction peak corresponds to the (006) crystal plane peak, so the ratio of the (006) peak intensity I (006) to the (012) crystal plane peak intensity I (012) and the (006) crystal plane in the XRD test crystal structure
  • the ratio A (006) /A (012) of the peak area A (006) of the crystal face and the peak area A (012) of the (012) crystal face increased significantly, and the M' valence state changed greatly during the process of lithium deintercalation.
  • the effect on the O-2p band electronic structure is reduced, which can significantly improve the stability of the cathode material and improve the problem of oxygen evolution in the high delithiation state; after combining with the oxygen element on the surface, it can greatly reduce the surface and interface of the cathode material.
  • the number of dangling bonds involved in bonding and the number of oxygen active sites significantly reduce the degree of side reactions between the multi-component cathode material and the electrolyte under high voltage.
  • the ratio of peak intensity of Q element doping and/or coating I (006) /I (012) ⁇ 0.8, the ratio of peak area A (006) / A (012) ⁇ 0.5 multivariate Cathode materials can not only effectively improve the structure and surface interface stability of cathode materials, but also have a wide range of applications: NCM111, NCM523, NCM622, NCM811, NCA, NCMA and other multi-component materials and LFP, lithium-rich and other lithium-ion batteries positive electrode material.
  • M is one or more of W, Mo, V, Ca, Al, Si, Ni, Mn, Hf, Ta, Y, Sr, Ba, Ga and Er.
  • M is at least one of W, Al, Si, Ta, Y, Sr, Ga, Mg, Ti, Zr, Co and Nb;
  • the M is introduced in the form of one kind of boron compound, phosphorus compound or silicon compound of M or in the form of multiple M compound borides, compound phosphides or compound silicides.
  • the median particle size of the multi-component cathode material is 3-20 ⁇ m, preferably 4-17 ⁇ m.
  • the angle of repose of the multi-component cathode material is ⁇ 35°, preferably ⁇ 30°.
  • the cycle retention rate of the multi-component positive electrode material of the present invention is increased by more than 5 percentage points, as shown in FIG. 2 for details.
  • the DCR of the multi-component positive electrode material of the present invention is reduced by more than 10 percentage points and the DCR increase rate is reduced by more than 5 percentage points after 80 weeks of circulation, as shown in FIG. 3 .
  • the content of LiOH is 1000-3000 ppm, preferably 1200-2500 ppm.
  • the preparation method of the above-mentioned product includes roasting and calcining process, wherein the heating process of the roasting process below 600 ° C adopts an oxygen-depleted or oxygen-free atmosphere with an oxygen content of ⁇ 20vol%, and at 600 ° C and above, an oxygen content of ⁇ 20vol% is used. Air and/or oxygen atmosphere.
  • a second aspect of the present invention provides a method for preparing a multi-element positive electrode material, characterized in that the method comprises the following steps:
  • At least one of the first additive, the second additive and the third additive is included; at least one of the first additive, the second additive and the third additive is a Q compound.
  • the first additive mixture may be a first additive solution, a first additive sol or a first additive suspension.
  • the above-mentioned preparation method is adopted, and specifically, the Q-containing compound is added as the first additive, the second additive or the third additive at different stages of the preparation process of the positive electrode material, so that the prepared positive electrode material can have the present invention.
  • the specific structure can significantly improve the stability of the cathode material, significantly improve the problem of oxygen evolution under high delithiation state, and reduce the degree of side reactions between the cathode material and the electrolyte under high voltage conditions, and improve the lithium-ion battery. electrochemical performance.
  • the positive electrode material prepared by the above method has more excellent fluidity, high sieving and demagnetization efficiency, and excellent processing performance. Specifically, with respect to the multi-element cathode without boron, phosphorus or silicon, the ratio of peak intensity I (006) /I (012) ⁇ 0.8 and the ratio of peak area A (006) /A (012) ⁇ 0.5 In terms of materials, the multi-component cathode material of the present invention has better fluidity, and the angle of repose can be reduced by more than 3°.
  • the multi-element cathode material of the present invention has higher screening and demagnetization efficiency, and the production capacity can be increased by more than 20%.
  • the ratio of the peak intensity I (006) of the (006) crystal plane to the peak intensity I (012) of the (012) crystal plane obtained by XRD of the multi-component cathode material is I (006) /I (012) ⁇ 0.8, preferably, I (006) /I (012) ⁇ 1;
  • the ratio of the peak area A (006) of the (006) crystal plane to the peak area A (012) of the (012) crystal plane obtained by XRD of the multi-component cathode material is A (006) /A (012) ⁇ 0.5, preferably , A (006) /A (012) ⁇ 0.8.
  • the multi-component positive electrode material has the composition shown in the general formula I:
  • M is at least one of W, Mo, V, Ca, Al, Si, Ni, Mn, Hf, Ta, Y, Sr, Ba, Er, Ga, Mg, Ti, Zr, La, Ce, Co, and Nb ;
  • Q is at least one of B, P and Si.
  • M is at least one of W, Al, Si, Ta, Y, Sr, Ga, Mg, Ti, Zr, Co and Nb;
  • the first additive, the second additive and the third additive are each independently selected from one or more of compounds capable of providing M and/or Q.
  • the compound capable of providing M and/or Q is a boride, phosphide or silicide containing M element.
  • the inventor found that the ratio of peak intensity obtained by XRD I (006) /I (012) ⁇ 0.8, the ratio of peak area A (006) /A (012) ⁇ 0.5 compared to the multi-component cathode material
  • the multi-component cathode material has a better (003) crystal plane orientation, and the M'-O bond length increases. Larger, weaker bond energy, lower covalency, the O element can remain stable in a larger range of M' valence, and will not generate electron holes in the 2p energy band, resulting in the evolution of oxygen.
  • One of the preferred examples of obtaining the above-mentioned multi-element cathode material with a specific peak intensity ratio and peak area ratio is to introduce M element into the multi-element cathode material in the form of boron compound, phosphorus compound or silicon compound as doping and/or coating
  • Additives, boron compounds, phosphorus compounds or silicon compounds containing M element are combined with oxygen in the interior and/or surface of the positive electrode material to form stable oxides of additive element M after the reaction (or composite oxides formed together with lithium oxide) compound), boron oxide (or lithium borate, etc.), phosphorus oxide (or lithium phosphate) or silicon oxide (or lithium silicate), which can effectively stabilize the internal structure of the material and the oxygen element in the surface interface, so as to improve the structure and surface of the material. the purpose of interfacial stability.
  • the boron compound containing M element is selected from at least one of the following compounds:
  • the phosphorus compound containing M element is selected from at least one of the following compounds:
  • the silicon compound containing M element is selected from at least one of the following compounds:
  • the content of LiOH is 1000-3000 ppm, preferably 1200-2500 ppm.
  • the first additive is selected from one or more of soluble compounds capable of providing M and/or Q.
  • the second additive and the third additive are each independently selected from one or more of compounds capable of providing M and Q.
  • the second additive and the third additive are independently W, Al, Si, Ta, Y, Sr, Mo, V, Mn, Ca, Ni, Hf, Ba, Er, Ga and B, Compounds formed by P or Si.
  • the nickel salt, cobalt salt and manganese salt are selected from one or more of nickel, cobalt and manganese sulfate, chloride, nitrate and acetate.
  • the precipitating agent is selected from one or more of sodium hydroxide, potassium hydroxide and lithium hydroxide.
  • the complexing agent is selected from one or more of ammonia water, disodium EDTA, ammonium nitrate, ammonium chloride and ammonium sulfate.
  • the dispersing agent is selected from one or more of polyethylene glycol PEG, polyvinyl alcohol PVA and polyglycerol.
  • the conditions of the reaction include: the reaction temperature is 40-80° C.; the pH value of the reaction is controlled in the range of 10-13.
  • the aging time is 2-8h.
  • the drying conditions include: a drying temperature of 100-130° C. and a time of 2-5 hours.
  • the preparation method further includes: after performing low temperature heat treatment on the product after the filter cake is washed and dried, the precursor of the multi-element positive electrode material is obtained.
  • the calcination yield of the multi-component cathode material and the productivity of the calcination process can be further improved, and specifically, the calcination yield can be increased by more than 10%.
  • the conditions of the low-temperature heat treatment include: treatment at a temperature of 300-700° C. for 3-12 hours in the presence of air and/or oxygen.
  • the conditions of the low-temperature heat treatment include: treatment at a temperature of 400-600° C. for 4-8 hours in the presence of air and/or oxygen.
  • the amounts of the multi-component cathode material precursor, the lithium source and the second additive are such that 0.9 ⁇ n(Li)/[n(Ni)+n(Co)+n(Mn)+n( M)+n(Q)] ⁇ 1.3;
  • the amounts of the multi-component cathode material precursor, the lithium source and the second additive are such that 1 ⁇ n(Li)/[n(Ni)+n(Co)+n(Mn)+n(M )+n(Q)] ⁇ 1.2;
  • the lithium source is selected from one or more of lithium carbonate, lithium chloride, lithium hydroxide, lithium fluoride and lithium nitrate.
  • the roasting conditions include: the roasting temperature is 600-1100° C., and the roasting time is 4-18 h.
  • roasting process adopts the oxygen-depleted or oxygen-free atmosphere with oxygen content ⁇ 20vol% in the heating stage below 600 °C, and the roasting process (heating, constant temperature, cooling stage) of 600 °C and above adopts oxygen content ⁇ 20vol % air and/or oxygen atmosphere.
  • the roasting conditions include: the roasting temperature is 700-1000°C, and the roasting time is 6-15h.
  • the amount of the multi-component cathode material process product and the third additive is such that 0 ⁇ n(M)/[n(Ni)+n(Co)+n(Mn)+n(M)+n( Q)] ⁇ 0.04;
  • the amount of the multi-component cathode material process product and the third additive is such that 0 ⁇ n(M)/[n(Ni)+n(Co)+n(Mn)+n(M)+n(Q )] ⁇ 0.03;
  • the calcination conditions include: the calcination temperature is 300-1000°C, and the calcination time is 4-12h.
  • the calcination conditions include: the calcination temperature is 400-900°C, and the calcination time is 6-10h.
  • the third aspect of the present invention provides the multi-component positive electrode material prepared by the above preparation method.
  • the fourth aspect of the present invention provides the application of the multi-component positive electrode material in the lithium ion battery.
  • the XRD parameters were measured by the X-ray diffractometer method.
  • the instrument used was an X-ray diffractometer (Riku, Smart Lab 9KW).
  • the test conditions were: the X-ray source was Cu K ⁇ ray, the scanning range was 10°-80°, and the scanning rate was is 2°/min, and the scan step is 0.02°;
  • the particle size is measured by the laser scattering method, and the instrument used is a laser particle size analyzer (Malvern, Mastersizer 2000), and the test conditions are the rotational speed of 2850rpm and the shading degree of 10%-20%;
  • the angle of repose of the material is tested by the injection limited bottom surface method.
  • the angle of repose tester used is XF-4324, the test condition is 25 ⁇ 3°C, and the feeding rate is 30g/min;
  • the content of each element in the positive electrode material was measured by ICP method.
  • the instrument used was PE Optima 7000DV.
  • the test condition was that 0.1g of the sample was completely dissolved in a mixed acid solution of 3mL HNO 3 +9mL HCl, and diluted to 250mL for testing;
  • the LiOH content parameter of the positive electrode material was measured by potentiometric titration method, the instrument used was Metrohm 848 potentiometric titrator, and the test condition was 25°C;
  • the capacity of sieving and demagnetization is calculated by the statistics of the weight of the materials produced per unit time in the sieving and demagnetization process;
  • the roasting yield was calculated by weighing the samples before and after roasting
  • the first discharge capacity and cycle performance of the cathode material were measured by the button battery method. V or 0.2C@3.0-4.45V, 25°C, the larger the discharge capacity, the higher the specific capacity of the material and the higher the energy density of the battery system; the cycle performance test conditions are 1.0C@3-4.45V or 1.0C@3- 4.50V, 45°C, the smaller the capacity decay during the cycle, the higher the stability of the material and the better the cycle performance of the battery system.
  • the button battery is made according to the following steps:
  • the negative electrode uses a Li metal sheet with a diameter of 17 mm and a thickness of 1 mm; the separator uses a polyethylene porous membrane with a thickness of 25 ⁇ m; the electrolyte uses 1 mol/L LiPF 6 as the electrolyte of ethylene carbonate (EC) and diethyl carbonate ( DEC) in equal volumes.
  • EC ethylene carbonate
  • DEC diethyl carbonate
  • the positive electrode, separator, negative electrode and electrolyte were assembled into a 2025 type button cell in an Ar gas glove box with water content and oxygen content less than 5 ppm.
  • test steps of the cycle performance of the cathode material are as follows:
  • the coin cell was activated by constant current and constant voltage charge-discharge cycles in the range of 3-4.4V.
  • the charging and discharging system is as follows: charge to 4.4V with a constant current and constant voltage at a rate of 0.2C, the cut-off current for constant voltage charging is 0.02C, and discharge to 3V with a constant current rate of 0.2C. Charge and discharge according to this system for 2 weeks, and this battery is regarded as an activated battery.
  • the charge-discharge cycle test was performed at a current density of 1C in the voltage range of 3-4.45V or 3-4.5V, the temperature was 45°C, and the cycle retention rate and DCR increase of the cathode material were investigated for 80 cycles.
  • the raw materials used in the examples and comparative examples are all commercially available products.
  • Fully mixed in a high-speed mixer calcined at 800 °C for 8 hours in a dry air atmosphere, cooled naturally, and passed through a 400-mesh sieve to obtain a multi-component cathode material A1, whose composition is Li 1.05 Ni 0.5 Co 0.2 Mn 0.286 Al 0.003 Y 0.002 B 0.009 O 2 .
  • Table 2 shows the composition, particle size D 50 , LiOH content, angle of repose, I (006) /I (012) and A (006) /A (012) of the positive electrode material A1.
  • the XRD results of the positive electrode material A1 are shown in FIG. 1 .
  • Table 3 shows the gram capacity of the coin cell made from the positive electrode material A1 at a voltage of 4.45V, as well as the cycle retention rate and DCR increase in the voltage range of 3-4.5V.
  • the cycle retention rate and DCR result of the button battery prepared from the positive electrode material A1 are shown in Fig. 2 and Fig. 3, respectively.
  • Table 2 shows the composition, particle size D 50 , LiOH content, angle of repose, I (006) /I (012) and A (006) /A (012) of the positive electrode material A2.
  • Table 3 shows the gram capacity of the coin cell made from the positive electrode material A2 at a voltage of 4.45V, as well as the cycle retention rate and DCR increase in the voltage range of 3-4.5V.
  • Table 2 shows the composition, particle size D 50 , LiOH content, angle of repose, I (006) /I (012) and A (006) /A (012) of the positive electrode material A3.
  • Table 3 shows the gram capacity of the coin cell made from the positive electrode material A3 at a voltage of 4.45V, as well as the cycle retention rate and DCR increase in the voltage range of 3-4.5V.
  • the multi-component positive electrode material A4 was prepared according to the method of Example 1, except that:
  • step S1 after the reaction is completed, it is aged for 6 hours, and then subjected to pressure filtration, washing, drying at 110°C, and sieving, and then not heat-treated at 500°C in an air atmosphere;
  • YB 2 yttrium diboride
  • the positive electrode material A4 was prepared, and its composition was Li 1.05 Ni 0.5 Co 0.2 Mn 0.286 Al 0.003 Y 0.002 B 0.009 O 2 , which was the same as that of the positive electrode material A1.
  • the cycle retention rate and DCR result of the positive electrode material A4 are shown in Fig. 2 and Fig. 3, respectively.
  • Table 2 shows the composition, particle size D 50 , LiOH content, angle of repose, I (006) /I (012) and A (006) /A (012) of the positive electrode material A4.
  • Table 3 shows the gram capacity of the button battery made from the positive electrode material A4 at a voltage of 4.45V, as well as the cycle retention rate and DCR increase in the voltage range of 3-4.5V.
  • step S1 after the reaction is completed, it is aged for 6 hours, and then subjected to pressure filtration, washing, drying at 110°C, and sieving, and then not heat-treated at 500°C in an air atmosphere;
  • step S2 yttrium diboride (YB 2 ) is not added;
  • a positive electrode material A5 was prepared, and its composition was Li 1.05 Ni 0.5 Co 0.2 Mn 0.286 Al 0.003 Y 0.002 B 0.009 O 2 , which was the same as that of the positive electrode material A1.
  • the cycle retention rate and DCR result of the positive electrode material A5 are shown in Fig. 2 and Fig. 3, respectively.
  • Table 2 shows the composition, particle size D 50 , LiOH content, angle of repose, I (006) /I (012) and A (006) /A (012) of the positive electrode material A5.
  • Table 3 shows the gram capacity of the coin cell made from the positive electrode material A5 at a voltage of 4.45V, as well as the cycle retention rate and DCR increase in the voltage range of 3-4.5V.
  • the above is switched to a dry air atmosphere with an oxygen content of 21 vol%, after natural cooling, after crushing and sieving, the multi-component positive electrode material process product I is obtained.
  • Table 2 shows the composition, particle size D 50 , LiOH content, angle of repose, I (006) /I (012) and A (006) /A (012) of the positive electrode material A6.
  • Table 3 shows the gram capacity of the button battery made from the positive electrode material A6 at a voltage of 4.40V, as well as the cycle retention rate and DCR increase in the voltage range of 3-4.45V.
  • Table 2 shows the composition, particle size D 50 , LiOH content, angle of repose, I (006) /I (012) and A (006) /A (012) of the positive electrode material A7.
  • Table 3 shows the gram capacity of the coin cell made from the positive electrode material A7 at a voltage of 4.40V, as well as the cycle retention rate and DCR increase in the voltage range of 3-4.45V.
  • the multi-component positive electrode material A8 was prepared according to the method of Example 7, except that:
  • step S1 except for nickel-cobalt-manganese sulfate mixed solution, NaOH solution, ammonia water, and PEG1000 dispersant solution, the first reactants were simultaneously fed into the reaction kettle with 0.1 mol/L of acid barium metaborate in a cocurrent manner.
  • step S1 after the first reaction is completed, pressure filtration, washing, drying at 110°C, and sieving are not performed under low temperature heat treatment at 500°C in an air atmosphere;
  • step S2 barium diboride (BaB 2 ) is not added;
  • a positive electrode material A8 was prepared, and its composition was Li 1.08 Ni 0.8 Co 0.1 Mn 0.091 Ba 0.001 Zr 0.002 B 0.006 O 2 , which was the same as that of the positive electrode material A7.
  • Table 2 shows the composition, particle size D 50 , LiOH content, angle of repose, I (006) /I (012) and A (006) /A (012) of the positive electrode material A8.
  • Table 3 shows the gram capacity of the coin cell made from the positive electrode material A8 at a voltage of 4.40V, as well as the cycle retention rate and DCR increase in the voltage range of 3-4.45V.
  • the multi-component positive electrode material A9 was prepared according to the method of Example 7, except that:
  • step S1 the first reaction is completed by pressure filtration, washing, drying at 110°C, and sieving, without performing low-temperature heat treatment under the condition of 500°C in an air atmosphere;
  • step S3 zirconium dioxide (ZrO 2 ) is used as the third additive to replace zirconium diboride (ZrB 2 ), and the addition amount of Zr element is the same as that of Example 7.
  • a positive electrode material A9 was prepared, and its composition was Li 1.08 Ni 0.8 Co 0.1 Mn 0.095 Ba 0.001 Zr 0.002 B 0.002 O 2 .
  • Table 2 shows the composition, particle size D 50 , LiOH content, angle of repose, I (006) /I (012) and A (006) /A (012) of the positive electrode material A9.
  • Table 3 shows the gram capacity of the button battery made from the positive electrode material A9 at a voltage of 4.40V, as well as the cycle retention rate and DCR increase in the voltage range of 3-4.45V.
  • the multi-component positive electrode material A10 was prepared according to the method of Example 7, except that:
  • step S1 after the first reaction is completed, pressure filtration, washing, drying at 110°C, and sieving are not performed under low temperature heat treatment at 500°C in an air atmosphere;
  • the positive electrode material A10 was prepared, and its composition was Li 1.03 Ni 0.8 Co 0.1 Mn 0.092 Ti 0.001 B 0.007 O 2 .
  • Table 2 shows the composition, particle size D 50 , LiOH content, angle of repose, I (006) /I (012) and A (006) /A (012) of the positive electrode material A10.
  • Table 3 shows the gram capacity of the coin cell made from the positive electrode material A10 at a voltage of 4.40V, as well as the cycle retention rate and DCR increase in the voltage range of 3-4.45V.
  • Table 2 shows the composition, particle diameter D 50 , LiOH content, angle of repose, I (006) /I (012) and A (006) /A (012) of the positive electrode material A11.
  • Table 3 shows the gram capacity of the coin cell made from the positive electrode material A11 at a voltage of 4.60V, as well as the cycle retention rate and DCR increase in the voltage range of 3-4.5V.
  • the multi-component positive electrode material A12 was prepared according to the method of Example 7, except that:
  • step S1 the first reaction is completed by pressure filtration, washing, drying at 110°C, and sieving, without performing low-temperature heat treatment under the condition of 500°C in an air atmosphere;
  • step S2 barium diboride (BaB 2 ) is not added;
  • the positive electrode material A12 was prepared, and its composition was Li 1.08 Ni 0.8 Co 0.1 Mn 0.096 Ga 0.002 P 0.002 O 2 .
  • Table 2 shows the composition, particle size D 50 , LiOH content, angle of repose, I (006) /I (012) and A (006) /A (012) of the positive electrode material A12.
  • Table 3 shows the gram capacity of the coin cell made from the positive electrode material A12 at a voltage of 4.40V, as well as the cycle retention rate and DCR increase in the voltage range of 3-4.45V.
  • the multi-component positive electrode material A13 was prepared according to the method of Example 7, except that:
  • step S1 after the first reaction is completed, pressure filtration, washing, drying at 110°C, and sieving are not performed under low temperature heat treatment at 500°C in an air atmosphere;
  • the positive electrode material A13 was prepared, and its composition was Li 1.08 Ni 0.8 Co 0.1 Mn 0.096 Ba 0.001 Zr 0.002 B 0.002 Si 0.004 O 2 .
  • Table 2 shows the composition, particle size D 50 , LiOH content, angle of repose, I (006) /I (012) and A (006) /A (012) of the positive electrode material A13.
  • Table 3 shows the gram capacity of the coin cell made from the positive electrode material A12 at a voltage of 4.40V, as well as the cycle retention rate and DCR increase in the voltage range of 3-4.45V.
  • the multi-component positive electrode material A14 was prepared according to the method of Example 7, except that:
  • the positive electrode material A14 was prepared, and its composition was Li 1.08 Ni 0.8 Co 0.1 Mn 0.09 Mg 0.001 Y 0.001 B 0.008 O 2 .
  • Table 2 shows the composition, particle size D 50 , LiOH content, angle of repose, I (006) /I (012) and A (006) /A (012) of the positive electrode material A14.
  • Table 3 shows the gram capacity of the button battery made from the positive electrode material A14 at a voltage of 4.40V, as well as the cycle retention rate and DCR increase in the voltage range of 3-4.45V.
  • the multi-component positive electrode material A15 was prepared according to the method of Example 7, except that:
  • the positive electrode material A15 was prepared, and its composition was Li 1.08 Ni 0.8 Co 0.1 Mn 0.086 Ba 0.001 La 0.001 B 0.012 O 2 .
  • Table 2 shows the composition, particle size D 50 , LiOH content, angle of repose, I (006) /I (012) and A (006) /A (012) of the positive electrode material A15.
  • Table 3 shows the gram capacity of the coin cell made from the positive electrode material A15 at a voltage of 4.40V, as well as the cycle retention rate and DCR increase in the voltage range of 3-4.45V.
  • the XRD, cycle retention, and DCR results of the positive electrode material D1 are shown in Figure 1, Figure 2, and Figure 3, respectively.
  • Table 2 shows the composition, particle size D 50 , LiOH content, angle of repose, I (006) /I (012) and A (006) /A (012) of the positive electrode material D1.
  • Table 3 shows the gram capacity of the coin cell made from the positive electrode material D1 at 4.40V and 4.45V, as well as the cycle retention and DCR increase in the voltage range of 3-4.5V.
  • Table 2 shows the composition, particle size D 50 , LiOH content, angle of repose, I (006) /I (012) and A (006) /A (012) of the positive electrode material D2.
  • Table 3 shows the gram capacity of the coin cell made from the positive electrode material D2 at voltages of 4.35V and 4.40V, as well as the cycle retention rate and DCR increase in the voltage range of 3-4.45V.
  • the multi-component positive electrode material D3 was prepared according to the method of Example 7, except that:
  • the positive electrode material D3 was prepared, and its composition was Li 1.08 Ni 0.8 Co 0.1 Mn 0.03 Ba 0.005 Zr 0.005 B 0.06 O 2 .
  • Table 2 shows the composition, particle size D 50 , LiOH content, angle of repose, I (006) /I (012) and A (006) /A (012) of the positive electrode material D3.
  • Table 3 shows the gram capacity of the coin cell made from the positive electrode material D3 at a voltage of 4.40V, as well as the cycle retention rate and DCR increase in the voltage range of 3-4.45V.
  • the multi-component positive electrode material D4 was prepared according to the method of Example 7, except that:
  • step S2 the roasting temperature is 550°C, and the roasting time is 30h;
  • the positive electrode material D4 was prepared, and its composition was Li 1.08 Ni 0.8 Co 0.1 Mn 0.091 Ba 0.001 Zr 0.002 B 0.006 O 2 .
  • Table 2 shows the composition, particle size D 50 , LiOH content, angle of repose, I (006) /I (012) and A (006) /A (012) of the positive electrode material D4.
  • Table 3 shows the gram capacity of the coin cell made from the positive electrode material D4 at a voltage of 4.40V, as well as the cycle retention rate and DCR increase in the voltage range of 3-4.45V.
  • Example 4 74.5 310
  • Example 6 83.9
  • Example 7 84.1 305
  • Example 9 72.2 273
  • Example 10 72.0 297
  • Example 11 83.5
  • Example 12 72.3 305
  • Example 13 72.2 287
  • Example 1 Compared with Comparative Example 1, the implementation of introducing B element, peak intensity ratio I (006) /I (012) ⁇ 0.8, and peak area ratio A (006) / A (012) ⁇ 0.5 is adopted in the present invention
  • Example 2 Example 3, Example 4, Example 5 have significantly higher sieving and demagnetization capacity, and the prepared multi-component cathode material has a smaller angle of repose, higher LiOH content, and
  • the battery has higher gram capacity, better cycle retention rate, lower DCR increase and the like.
  • the S3 step of the positive electrode material in the present invention includes the introduction of B element and/or P element and/or Si element in the calcination process, and the ratio of peak intensity I (006) /I (012) ⁇ 0.8 , Embodiment 7, Embodiment 8, Embodiment 9, Embodiment 10, Embodiment 12, Embodiment 13 with the ratio of peak area A (006) /A (012) ⁇ 0.5 have significantly higher sieving and demagnetization capacity , and the prepared multi-component cathode material has a smaller angle of repose.
  • the battery has a higher gram capacity, a better cycle retention rate, and a lower DCR increase.
  • the parameter 0 ⁇ a ⁇ 0.03, the parameter 0 ⁇ b ⁇ 0.04, the parameter 0 ⁇ b/a ⁇ 5, and the peak intensity ratio I ( 006) /I (012) ⁇ 0.8, and the ratio of peak areas A (006) /A (012) ⁇ 0.5 in Example 7, Example 8, Example 9, Example 10, Example 12, and Example 13 have Significantly higher sieving and demagnetization capacity, and the prepared multi-component positive electrode material has a smaller angle of repose.
  • the battery has a higher gram capacity, better cycle retention rate, and better performance. Low DCR increase, etc.
  • Example 7, Example 8, Example 9, Example 10, Example 12, Example 13 have significantly higher sieving and demagnetization capacity, and the prepared multi-component positive electrode material has a smaller angle of repose
  • the battery has a significantly higher gram capacity, a significantly better cycle retention rate, and a significantly lower DCR increase.
  • Example 1, Example 2, and Example 3 including the low-temperature heat treatment process of the present invention has the effect of significantly improving the calcination yield compared with Example 4, Example 5, and Comparative Example 1 that do not include the low-temperature heat treatment process.
  • the embodiment 7 of the present invention including the low temperature heat treatment process is less than the embodiment 8, embodiment 9, embodiment 10, embodiment 12, embodiment 13, comparative example 2, comparative example 3, comparative example
  • the ratio 4 has the effect of significantly improving the calcination yield.
  • the battery prepared by using the multi-component cathode material of Example 8 containing the preferred first additive of the present invention has a higher cycle retention rate.
  • the battery prepared by using the multi-component cathode material of Example 7 containing the preferred second additive of the present invention has a higher cycle retention rate.
  • Example 1 Compared with Example 4 using the non-preferred second additive and Example 5 not containing the second additive, Example 1, Example 2, and Example using the present invention containing the preferred second and third additives
  • the battery made of the multi-component cathode material of 3 has higher gram capacity and cycle retention rate.
  • the battery prepared by using the multi-component cathode material of Example 7 containing the preferred third additive of the present invention has a higher cycle retention rate.
  • the multi-component cathode materials of Embodiment 7, Embodiment 8 and Embodiment 9 with smaller b/a value of the present invention are used.
  • the resulting battery has higher cycle retention and lower DCR increase.

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Abstract

本发明涉及锂离子电池技术领域，公开了一种多元正极材料及其制备方法与应用。所述多元正极材料通过XRD获得的(006)晶面的峰强度I (006)与(012)晶面的峰强度I (012)之比I (006)/I (012)≥0.8；所述多元正极材料通过XRD获得的(006)晶面的峰面积A (006)与(012)晶面的峰面积A (012)之比A (006)/A (012)≥0.5。该多元正极材料具有特定的结构，由此显著提高正极材料的结构稳定性，改善高脱锂状态下的析氧问题，并降低高电压条件下正极材料与电解液之间副反应发生的程度，提高锂离子电池的电化学性能和安全性。

Description

多元正极材料及其制备方法与应用
相关申请的交叉引用
本申请要求2021年12月07日提交的中国专利申请202111486692.1的权益，该申请的内容通过引用被合并于本文；
2021年12月24日提效的中国专利申请202111599369.5的权益，该申请的内容通过引用被合并于本文。
技术领域
本发明涉及锂离子电池领域，具体涉及一种多元正极材料及其制备方法与应用。
背景技术
由于近年来动力市场对锂离子电池能量密度和循环寿命要求的不断提高，以及正极材料对锂离子电池能量密度、循环寿命的关键作用，多元正极材料作为研究热点持续受到研究者及市场的关注。
提升锂离子电池正极的能量密度主要通过提高活性物质的克容量来实现，提高活性物质的克容量一般又可以通过提高充放电电压窗口来实现。但提高充放电电压对正极材料的结构稳定性和表界面反应活性的控制都提出了更为苛刻的要求，若正极材料不能满足需求，盲目提高电压窗口，可能会导致电池循环性能严重衰减、安全性降低等问题。主要原因在于：①若材料的结构稳定性不足，则在充电电压较高时，锂离子从正极材料层状结构中脱出较多，导致层状结构部分坍塌，放电过程中锂离子无法返回，容量大幅衰减；②若材料表界面反应活性较高，在高电压下易与电解液发生一系列副反应，导致产气严重，活性物质与电解液接触不充分，容量骤降；同时产气还造成了严重的安全隐患。
通过对正极材料进行特定元素及化合物的掺杂、包覆可大幅改善材料的结构稳定性，降低材料表界面与电解液的反应活性；即使在锂离子脱嵌程度相对较高的条件下也能够维持材料层状结构及表界面的稳定。然而，目前行业内掺杂、包覆添加剂多以添加剂元素的氧化物、氢氧化物或者含氧酸盐等含氧化合物的形式引入，最终以氧化物或与氧化锂形成复合氧化物的形式存在。由于添加剂化合物本身含有氧元素，所以添加剂元素难以重新与正极材料结构、表面中的氧结合，最终难以与正极材料结构、表面之间形成稳定、有效的键合，导致对正极材料循环性能、高电压特性等的改善作用有限，不能充分发挥出添加剂元素的显著作用。
发明内容
本发明的目的是为了克服现有技术存在的含氧化合物掺杂和/或包覆正极材料的结构稳定性差且在高脱锂态下与电解液副反应严重，无法满足高电压条件下的应用需求的问题，提供一种多元正极材料及其制备方法和应用，该多元正极材料具有特定的结构，由此显著提高正极材料的结构稳定性，改善高脱锂状态下的析氧问题，并降低高电压条件下正极材料与电解液之间副反应发生的程度，提高锂离子电池的电化学性能和安全性。
为了实现上述目的，本发明第一方面提供一种多元正极材料，其特征在于，所述正极材料通过XRD获得的(006)晶面的峰强度I (006)与(012)晶面的峰强度I (012)之比I (006)/I (012)≥0.8；
所述正极材料通过XRD获得的(006)晶面的峰面积A (006)与(012)晶面的峰面积A (012)之比A (006)/A (012)≥0.5。
本发明第二方面提供一种多元正极材料的制备方法，其特征在于，所述方法包括以下步骤：
(1)将镍盐、钴盐、锰盐按照n(Ni):n(Co):n(Mn)＝x:y:(1-x-y-a-b)的摩尔比配制混合盐溶液；将沉淀剂、络合剂、分散剂和可选地第一添加剂，分别配制为沉淀剂溶液、络合剂溶液、分散剂溶液和可选地第一添加剂混合物；
(2)将所述混合盐溶液、沉淀剂溶液、络合剂溶液、分散剂溶液和可选地第一添加剂混合物同时、分别通入反应釜，进行反应、陈化，得到固液混合物；
(3)将所述固液混合物进行压滤，得到滤饼，将滤饼进行洗涤、烘干得到多元正极材料前驱体；
(4)将所述多元正极材料前驱体、锂源和可选地第二添加剂进行混合，得到混合物I；
(5)将所述混合物I进行焙烧、冷却、破碎、筛分，得到多元正极材料过程品；
(6)将所述多元正极材料过程品与可选地第三添加剂进行混合，得到混合物II；
(7)将混合物II进行煅烧、冷却、筛分、除磁，得到所述多元正极材料；
其中，至少包括所述第一添加剂、所述第二添加剂和所述第三添加剂中的一种。
本发明第三方面提供一种由上述制备方法制得的多元正极材料。
本发明第四方面提供上述多元正极材料在锂离子电池中的应用。
通过上述技术方案，本发明提供的多元正极材料及其制备方法与应用获得以下有益的效果：
本发明提供的多元正极材料具有特定的结构，其通过XRD获得的峰强度之比I (006)/I (012)≥0.8、峰面积之比I (006)/I (012)≥0.5。晶体相间(003)晶面衍射峰对应(006)晶面峰，本发明中具有该特定结构的多元正极材料相比于峰强度之比I (006)/I (012)＜0.8、峰面积之比A (006)/A (012)＜0.5的多元正极材料具有较优的(003)晶面取向，M’-O键长增大、键能减弱、共价性降低(M’为多元正极材料中的骨架过渡金属元素Ni、Co、Mn等)，O元素可在M’化合价更大的变化范围内保持稳定，而不至于在2p能带产生电子空穴，导致析出氧气。故本发明中多元正极材料结构稳定性提高，并且能够改善高脱锂状态下的析氧问题，并降低高电压条件下正极材料与电解液之间副反应发生的程度，提高锂离子电池的电化学性能和安全性。
进一步地，本发明提供一种具有上述特定结构的多元正极材料的优选示例，该多元正极材料中包含Q元素和M元素，在焙烧或煅烧过程中二者能够与正极材料内部和/或表面的氧元素形成有效键合，从而在多元正极材料中形成特定的结构，该特定结构能够明显提高正极材料的稳定性，改善高脱锂状态下的析氧问题，与此同时，能够大幅减少材料表界面存在的未参与键合的悬键以及氧活性位点数量，明显降低高电压下多元正极材料与电解液间副反应发生的程度。
进一步地，采用本发明提供的多元正极材料的制备方法，能够在正极材料内部和/或包覆层中引入M元素和/或Q元素，使得制得的正极材料的结构以及表界面稳定性显著提升，特别地，所述制备方法能够实现在不同种类的多元材料，例如NCM111、NCM523、NCM622、NCM811、NCA、NCMA等中引入M元素和/或Q元素。且制备工艺简单，能够适用于规模化生产。
进一步地，本发明提供的多元正极材料具有高的使用电压窗口，将其用于锂离子电池时，能够显著改善锂离子电池的克容量、循环寿命、直流电阻(DCR)增幅以及安全性。
附图说明
图1是实施例1以及对比例1的多元正极材料的XRD图；
图2是由实施例1、实施例4、实施例5以及对比例1的多元正极材料制得的电池的循环容量保持率图；
图3是由实施例1、实施例4、实施例5以及对比例1的多元正极材料制得的电池的循环过程DCR图。
具体实施方式
在本文中所披露的范围的端点和任何值都不限于该精确的范围或值，这些范围或值应当理解为包含接近这些范围或值的值。对于数值范围来说，各个范围的端点值之间、各个范围的端点值和单独的点值之间，以及单独的点值之间可以彼此组合而得到一个或多个新的数值范围，这些数值范围应被视为在本文中具体公开。
本发明第一方面提供一种多元正极材料，其特征在于，所述多元正极材料通过XRD获得的(006)晶面的峰强度I (006)与(012)晶面的峰强度I (012)之比I (006)/I (012)≥0.8；
所述多元正极材料通过XRD获得的(006)晶面的峰面积A (006)与(012)晶面的峰面积A (012)之比A (006)/A (012)≥0.5。
发明人研究发现，常规的多元正极材料中的骨架过渡金属元素M’(Ni、Co、Mn等)与氧元素具有较强共价性，这会促进氧的2p能带产生电子空穴，并导致多元正极材料在高脱锂态下析出氧气，导致多元正极材料难以在高电压下应用。
而发明人研究发现，控制多元正极材料(003)晶面生长速率，和/或控制(012)晶面生长速率，保持(003)晶面生长速率明显高于(012)晶面生长速率，使其具有(003)晶面优先生长的特定结构，而晶体相间(003)晶面衍射峰对应(006)晶面峰，因此多元正极材料具体表现为通过XRD获得的(006)晶面的峰强度I (006)与(012)晶面的峰强度I (012)之比I (006)/I (012)≥0.8，(006)晶面的峰面积A (006)与(012)晶面的峰面积A (012)之比A (006)/A (012)≥0.5。由此可提高正极材料的结构稳定性，显著改善高脱锂状态下的析氧问题，并降低高电压条件下正极材料与电解液之间副反应发生的程度，提高锂离子电池的电化学性能。
进一步地，I (006)/I (012)≥1；A (006)/A (012)≥0.8。
本发明中，所述多元正极材料通过XRD获得的(006)特征衍射峰的2θ为37.2-39.5°，(012)特征衍射峰的2θ为37.2-39.5°。
根据本发明，所述多元正极材料具有通式I所示的组成：
Li nNi xCo yMn 1-x-y-a-bM aQ bO 2式I；
其中，0.9≤n≤1.3，0≤x＜1，0≤y＜1，0≤a≤0.04，0＜b≤0.05，0＜b/a≤100；
M为W、Mo、V、Ca、Al、Si、Ni、Mn、Hf、Ta、Y、Sr、Ba、Er、Ga、Mg、Ti、Zr、La、Ce、Co和Nb中的至少一种；
Q为B、P和Si中的至少一种。
本发明中，发明人研究发现，在多元正极材料中引入硼元素、磷元素或硅元素，是获得上述具有峰强度之比I (006)/I (012)≥0.8、峰面积之比A (006)/A (012)≥0.5的多元正极材料的可实施方式之一。当然地，本领域技术人员也可以通过其他方式使所得多元正极材料的峰强度之比和峰面积之比满足上述条件，本发明对此不作限定，但是峰强度之比I (006)/I (012)≥0.8、峰面积之比A (006)/A (012)≥0.5的多元正极材料都在本发明的保护范围之内。
本发明中，引入硼元素、磷元素或硅元素，对多元正极材料进行包覆和/或掺杂能够与正极材料内部和表面的氧元素形成有效键合，特别地，与内部氧元素结合后，原M’-O键长增大，M’与O元素的共价性减弱，晶体结构中的M’-M’层间距显著增大，(003)晶面表现出生长速率优势，晶体相间(003)晶面衍射峰对应(006)晶面峰，因此XRD测试晶体结构中(006)峰强度I (006)与(012)晶面的峰强度I (012)之比及(006)晶面的峰面积A (006)与(012)晶面的峰面积A (012)之比A (006)/A (012)均明显增大，脱嵌锂过程中M’价态变化较大，对O-2p能带电子结构的影响降低，能够明显提高正极材料的稳定性，改善高脱锂状态下的析氧问题；与表面的氧元素结合后，能够大幅减少正极材料表界面存在的未参与键合的悬键以及氧活性位点数量，明显降低高电压下多元正极材料与电解液间副反应发生的程度。
进一步地，本发明中包含Q元素掺杂和/或包覆的峰强度之比I (006)/I (012)≥0.8、峰面积之比A (006)/A (012)≥0.5的多元正极材料不仅能够有效提升正极材料的结构及表界面稳定性，而且使用范围也非常广泛：NCM111、NCM523、NCM622、NCM811、NCA、NCMA等不同组成多元材料以及LFP、富锂等多种锂离子电池正极材料。
本发明的一个具体实施方式中，式I中，其中，0.9≤n≤1.3，0≤x＜1，0≤y＜1，0＜a≤0.04，0＜b≤0.05，0＜b/a≤100，M为W、Mo、V、Ca、Al、Si、Ni、Mn、Hf、Ta、Y、Sr、Ba、Ga和Er中的一种或多种。
进一步地，式I中，1≤n≤1.2，0≤x＜1，0≤y＜1，0＜a≤0.03，0＜b≤0.04，0＜b/a≤20；
M为W、Al、Si、Ta、Y、Sr、Ga、Mg、Ti、Zr、Co和Nb中的至少一种；
Q为B；
进一步优选地，0＜b/a≤5。
本发明中，所述M以一种M的硼化合物、磷化合物或硅化合物的形式或多种M的复合硼化物、复合磷化物或复合硅化物的形式引入。
根据本发明，所述多元正极材料的中值粒径为3-20μm，优选为4-17μm。
根据本发明，所述多元正极材料的安息角为≤35°，优选为≤30°。
本发明中，相对于不含硼元素、磷元素或硅元素，峰强度之比I (006)/I (012)＜0.8、峰面积之比A (006)/A (012)＜0.5的多元正极材料而言，本发明的多元正极材料的循环保持率提升5个百分点以上，详见附图2。
本发明中，相对于不含硼元素、磷元素或硅元素，峰强度之比I (006)/I (012)＜0.8、峰面积之比A (006)/A (012)＜0.5的多元正极材料而言，本发明的多元正极材料循环80周后DCR降低10个百分点以上，DCR增幅降低5个百分点以上，详见附图3。
根据本发明，以所述多元正极材料的总重量为基准，LiOH的含量为1000-3000ppm，优选为1200-2500ppm。
上述产品的制备方法包括焙烧和煅烧过程，其中所述焙烧过程在600℃以下的升温过程采用的是氧气含量＜20vol％的贫氧或无氧气氛，600℃及以上采用氧气含量≥20vol％的空气和/或氧气气氛。
本发明第二方面提供一种多元正极材料的制备方法，其特征在于，所述方法包括以下步骤：
(1)将镍盐、钴盐、锰盐按照n(Ni):n(Co):n(Mn)＝x:y:(1-x-y-a-b)的摩尔比配制混合盐溶液；将沉淀剂、络合剂、分散剂和可选地第一添加剂，分别配制为沉淀剂溶液、络合剂溶液、分散剂溶液和可选地第一添加剂混合物；
(2)将所述混合盐溶液、沉淀剂溶液、络合剂溶液、分散剂溶液和可选地第一添加剂混合物同时、分别通入反应釜，进行反应、陈化，得到固液混合物；
(3)将所述固液混合物进行压滤，得到滤饼，将滤饼进行洗涤、烘干得到多元正极材料前驱体；
(4)将所述多元正极材料前驱体、锂源和可选地第二添加剂进行混合，得到混合物I；
(5)将所述混合物I进行焙烧、冷却、破碎、筛分，得到多元正极材料过程品；
(6)将所述多元正极材料过程品与可选地第三添加剂进行混合，得到混合物II；
(7)将混合物II进行煅烧、冷却、筛分、除磁，得到所述多元正极材料；
其中，至少包括所述第一添加剂、所述第二添加剂和所述第三添加剂中的一种；所述第一添加剂、所述第二添加剂和所述第三添加剂中的至少一种为含Q化合物。
本发明中，所述第一添加剂混合物可以为第一添加剂溶液、第一添加剂溶胶或第一添加剂悬浮液。
本发明中，采用上述制备方法，具体地，在正极材料的制备过程的不同阶段添加含Q化合物作为第一添加剂、第二添加剂或第三添加剂，由此能够使得制得的正极材料具有本发明特定的结构，由此能够显著提高正极材料的稳定性，显著改善高脱锂状态下的析氧问题，并降低高电压条件下正极材料与电解液之间副反应发生的程度，提高锂离子电池的电化学性能。
进一步地，采用上述方法制得的正极材料具有更为优异的流动性，并且筛分、除磁效率高，加工性能优异。具体地，相对于不含硼元素、磷元素或硅元素，峰强度之比I (006)/I (012)＜0.8、峰面积之比A (006)/A (012)＜0.5的多元正极材料而言，本发明的多元正极材料流动性更优，安息角能够降低3°以上。
相对于不含硼元素、磷元素或硅元素，峰强度之比I (006)/I (012)＜0.8、峰面积之比A (006)/A (012)＜0.5的多元正极材料而言，本发明的多元正极材料筛分及除磁效率更高，产能能够提升20％以上。
根据本发明，所述多元正极材料通过XRD获得的(006)晶面的峰强度I (006)与(012)晶面的峰强度I (012)之比I (006)/I (012)≥0.8，优选地，I (006)/I (012)≥1；
所述多元正极材料通过XRD获得的(006)晶面的峰面积A (006)与(012)晶面的峰面积A (012)之比A (006)/A (012)≥0.5，优选地，A (006)/A (012)≥0.8。
根据本发明，所述多元正极材料具有通式I所示的组成：
Li nNi xCo yMn 1-x-y-a-bM aQ bO 2式I；
其中，0.9≤n≤1.3，0≤x＜1，0≤y＜1，0≤a≤0.04，0＜b≤0.05，0＜b/a≤100；
M为W、Mo、V、Ca、Al、Si、Ni、Mn、Hf、Ta、Y、Sr、Ba、Er、Ga、Mg、Ti、Zr、La、Ce、Co和Nb中的至少一种；
Q为B、P和Si中的至少一种。
进一步地，式I中，1≤n≤1.2，0≤x＜1，0≤y＜1，0＜a≤0.03，0＜b≤0.04，0＜b/a≤20；
M为W、Al、Si、Ta、Y、Sr、Ga、Mg、Ti、Zr、Co和Nb中的至少一种；
Q为B；
进一步优选地，0＜b/a≤5。
根据本发明，所述第一添加剂、所述第二添加剂和所述第三添加剂各自独立地选自能够提供M和/或Q的化合物中的一种或多种。
优选地，所述能够提供M和/或Q的化合物为含M元素的硼化物、磷化物或硅化物。
本发明中，发明人研究发现，通过XRD获得的峰强度之比I (006)/I (012)≥0.8、峰面积之比A (006)/A (012)≥0.5的多元正极材料相比于I (006)/I (012)＜0.8、峰面积之比A (006)/A (012)＜0.5的多元正极材料具有较优的(003)晶面取向，M’-O键长增大、键能减弱、共价性降低，O元素可在M’化合价更大的范围内保持稳定，而不至于在2p能带产生电子空穴，导致析出氧气。
获得上述具有特定峰强度之比、峰面积之比的多元正极材料的优选示例之一是采用硼化合物、磷化合物或硅化合物的的形式将M元素引入多元正极材料作为掺杂和/或包覆添加剂，含M元素的硼化合物、磷化合物或硅化合物的与正极材料内部和/或表界面中的氧结合，反应后形成稳定的添加剂元素M的氧化物(或与氧化锂共同形成的复合氧化物)、氧化硼(或硼酸锂等)、氧化磷(或磷酸锂)或氧化硅(或硅酸锂)，能够有效稳定材料内部结构及表界面中的氧元素，达到提高材料的结构及表界面稳定性的目的。
本发明中，所述含M元素的硼化合物选自以下化合物中的至少一种：
MgB 2、MgB 4、MgB 6、MgB 12；
AlB 2、AlB 10、AlB 12；
Si 11B 31、SiB 4、SiB 6、SiB 14、SiB 18；
CaB 6；
TiB、Ti 3B 4、TiB 2、Ti 2B 5、TiB 12、TiB 25、TiB 55、TiB 100；
V 3B 2、VB、V 5B 6、V 3B 4、V 2B 3、VB 2；
Mn 2B、MnB、MnB 2、MnB 4、MnB 12；
Co 4B、Co 23B 6、Co 3B、Co 2B、Co 13B 7、Co 3B 2、CoB；
Ni 3B、Ni 2B、Ni 4B 3、NiB、NiB 12；
SrB 6；
YB 2、YB 4、YB 6、YB 12、YB 25、YB 50、YB 66；
ZrB 2、ZrB 12；
Nb 3B 2、NbB、Nb 5B 6、NbB 2；
Mo 2B、MoB、MoB 2、Mo 2B 5、Mo 4B 15、MoB 4；
BaB 2、BaB 6；
LaB 4、LaB 6；
HfB、HfB 2、HfB 12；
Ta 2B、Ta 3B 2、TaB、Ta 5B 6、Ta 3B 4、TaB 2；
W 2B、WB、WB 2、W 2B 5、WB 4；
CeB 4、CeB 6；
ErB 2、ErB 4、ErB 12、ErB 25、ErB 50、ErB 66。
本发明中，所述含M元素的磷化合物选自以下化合物中的至少一种：
Mg 3P 2、MgP 4；
Ca 3P 2、CaP、Ca 5P 8；
Sr 3P 2、SrP、Sr 4P 5、Sr 3P 4、SrP 3、Sr 3P 14；
Ba 3P 2、Ba 4P 5、Ba 3P 4、BaP 10；
YP；
LaP、LaP 2、LaP 5、LaP 7；
Ti 5P 3、Ti 4P 3、Ti 17P 10、TiP 2；
Zr 2P、Zr 5P 3、ZrP；
Hf 3P 2、HfP；
V 3P、V 2P、V 4P 3、VP、V 4P 7、VP 2、VP 4；
Nb 5P 3、Nb 8P 5、NbP；
Ta 3P、Ta 2P；
CeP、CeP 2；
Mo 8P 5、Mo 4P 3、MoP、MoP 2、MoP 4；
WP、WP 2、WP 4；
Mn 2P、MnP、MnP 2、MnP 4；
Co 2P、CoP、CoP 2、CoP 3、CoP 4；
Ni 3P、Ni 5P 2、Ni 7P 3、Ni 2P、Ni 5P 4、NiP、NiP 2、Ni1 2P 5；
AlP；
GaP；
SiP、SiP 2、Si1 2P 5；
B 13P、B 12P 2、BP。
本发明中，所述含M元素的硅化合物选自以下化合物中的至少一种：
Mg 2Si；
Ca 2Si、CaSi、CaSi 2；
Sr 2Si、SrSi、Sr 2Si 3、SrSi 2；
Ba 2Si、Ba 5Si 3、BaSi、BaSi 2；
Y 5Si 3、YSi、YSi 2；
La 5Si 3、La 3Si 2、La 5Si 4、LaSi、LaSi 2；
Ti 5Si 3、Ti 5Si 4、TiSi、TiSi 2；
Zr 5Si 3、Zr 3Si 2、Zr 5Si 4、ZrSi、ZrSi 2；
Hf 2Si、Hf 5Si 3、Hf 3Si 2、Hf 5Si 4、HfSi、HfSi 2；
V 3Si、V 5Si 3、V 6Si 5、VSi 2；
Nb 3Si、Nb 5Si 3、Nb 3Si 2、NbSi 2；
Ta 3Si、Ta 5Si 2、Ta 2Si、Ta 5Si 3；
Ce 5Si 3、CeSi、CeSi 2；
Mo 3Si、Mo 5Si 3、MoSi 2；
W 5Si 3、WSi 2；
Mn 6Si、Mn 5Si 2、MnSi、Mn 3Si 5、Mn 15Si 26、Mn 27Si 47；
Co 2Si、CoSi、Co 2Si 3、CoSi 2；
Ni 3Si、Ni 74Si 26、Ni 31Si 12、Ni 2Si、Ni 3Si 2、NiSi、NiSi 2；
Al 4Si
Er 5Si 3、ErSi、ErSi 2；
B 18Si、B 14Si、B 6Si、B 4Si、B 31Si 11。
根据本发明，以所述多元正极材料的重量为基准，LiOH的含量为1000-3000ppm，优选为1200-2500ppm。
根据本发明，所述第一添加剂选自能够提供M和/或Q的可溶性化合物中的一种或多种。
根据本发明，所述第二添加剂和所述第三添加剂各自独立地选自能够提供M和Q的化合物中的一种或多种。
进一步地，所述第二添加剂和所述第三添加剂各自独立地为W、Al、Si、Ta、Y、Sr、Mo、V、Mn、Ca、Ni、Hf、Ba、Er、Ga与B、P或Si形成的化合物。
本发明中，所述镍盐、钴盐、锰盐选自镍、钴、锰的硫酸盐、氯化盐、硝酸盐和醋酸盐中的一种或几种。
本发明中，所述沉淀剂选自氢氧化钠、氢氧化钾和氢氧化锂中的一种或几种。
本发明中，所述络合剂选自氨水、乙二胺四乙酸二钠、硝酸铵、氯化铵和硫酸铵中的一种或几种。
本发明中，所述分散剂选自聚乙二醇PEG、聚乙烯醇PVA和聚甘油中的一种或几种。
本发明中，所述混合盐溶液、所述沉淀剂溶液、所述络合剂溶液与所述第一添加剂的用量使得n(Ni):n(Co):n(Mn):n(沉淀剂):n(络合剂)＝x:y:(1-x-y-a-b):1.2:0.3；
0≤n(M)/[n(Ni)+n(Co)+n(Mn)+n(M)+n(Q)]≤0.04；
0≤n(Q)/[n(Ni)+n(Co)+n(Mn)+n(M)+n(Q)]≤0.05。
进一步地，所述混合盐溶液、所述沉淀剂溶液、所述络合剂溶液与所述第一添加的用量使得n(Ni):n(Co):n(Mn):n(沉淀剂):n(络合剂)＝x:y:(1-x-y-a-b):1.1:0.2；
0.0001≤n(M)/[n(Ni)+n(Co)+n(Mn)+n(M)+n(Q)]≤0.03；
0.0001≤n(Q)/[n(Ni)+n(Co)+n(Mn)+n(M)+n(Q)]≤0.04。
根据本发明，所述反应的条件包括：反应温度为40-80℃；反应的pH值控制范围为10-13。
根据本发明，所述陈化的时间为2-8h。
本发明中，所述步骤(3)中，所述烘干的条件包括：烘干温度为100-130℃，时间为2-5h。
根据本发明，所述制备方法还包括：对滤饼洗涤、烘干后的产物进行低温热处理后，得到所述多元正极材料前驱体。
本发明中，采用上述低温热处理后，能够进一步改善多元正极材料的焙烧产率以及焙烧工序的产能，具体地，能够使得焙烧产率提升10％以上。
根据本发明，所述低温热处理的条件包括：在空气和/或氧气的存在下，在300-700℃的温度下处理3-12h。
进一步地，所述低温热处理的条件包括：在空气和/或氧气的存在下，在400-600℃的温度下处理4-8h。
根据本发明，所述多元正极材料前驱体、所述锂源和所述第二添加剂的用量使得0.9≤n(Li)/[n(Ni)+n(Co)+n(Mn)+n(M)+n(Q)]≤1.3；
0≤n(M)/[n(Ni)+n(Co)+n(Mn)+n(M)+n(Q)]≤0.04
0≤n(Q)/[n(Ni)+n(Co)+n(Mn)+n(M)+n(Q)]≤0.05。
优选地，所述多元正极材料前驱体、所述锂源和所述第二添加剂的用量使得1≤n(Li)/[n(Ni)+n(Co)+n(Mn)+n(M)+n(Q)]≤1.2；
0＜n(M)/[n(Ni)+n(Co)+n(Mn)+n(M)+n(Q)]≤0.03；
0＜n(Q)/[n(Ni)+n(Co)+n(Mn)+n(M)+n(Q)]≤0.04。
本发明中，所述锂源选自碳酸锂、氯化锂、氢氧化锂、氟化锂和硝酸锂中的一种或几种。
根据本发明，所述焙烧的条件包括：焙烧温度为600-1100℃，焙烧时间为4-18h。
进一步地，所述焙烧过程在600℃以下的升温阶段采用的是氧气含量＜20vol％的贫氧或无氧气氛，600℃及以上的焙烧过程(升温、恒温、降温阶段)采用氧含量≥20vol％的空气和/或氧气气氛。
进一步地，所述焙烧的条件包括：焙烧温度为700-1000℃，焙烧时间为6-15h。
根据本发明，所述多元正极材料过程品与所述第三添加剂的用量使得0≤n(M)/[n(Ni)+n(Co)+n(Mn)+n(M)+n(Q)]≤0.04；
0≤n(Q)/[n(Ni)+n(Co)+n(Mn)+n(M)+n(Q)]≤0.05。
优选地，所述多元正极材料过程品与所述第三添加剂的用量使得0＜ n(M)/[n(Ni)+n(Co)+n(Mn)+n(M)+n(Q)]≤0.03；
0＜n(Q)/[n(Ni)+n(Co)+n(Mn)+n(M)+n(Q)]≤0.04。
根据本发明，所述煅烧的条件包括：煅烧温度为300-1000℃，煅烧时间为4-12h。
进一步地，所述煅烧的条件包括：煅烧温度为400-900℃，煅烧时间为6-10h。
本发明第三方面提供由上述制备方法制得的多元正极材料。
本发明第四方面提供多元正极材料在锂离子电池中的应用。
以下将通过实施例对本发明进行详细描述。以下实施例中，
XRD参数通过X射线衍射仪方法测得，所用仪器为X射线衍射仪(理学，Smart Lab 9KW)，测试条件为：X射线源为Cu的Kα射线，扫描范围为10°-80°，扫描速率为2°/min，扫描步长为0.02°；
粒径采用激光散射方法测得，所使用仪器为激光粒度仪(马尔文，Mastersizer 2000)，测试条件为转速2850rpm，遮光度10％-20％；
材料安息角采用注入限定底面法测试，所用安息角测定仪为XF-4324，测试条件为25±3℃，下料速率为30g/min；
正极材料中各元素的含量采用ICP方法测试得到，所用仪器为PE Optima 7000DV，测试条件为0.1g样品完全溶解于3mL HNO 3+9mL HCl的混合酸溶液中，稀释至250mL进行测试；
正极材料的LiOH含量参数通过电位滴定方法测得，所用仪器为瑞士万通Metrohm 848电位滴定仪，测试条件为25℃；
过筛除磁产能采用过筛除磁工序单位时间内产出物料重量统计计算得到；
焙烧产率采用称取焙烧前、后样品质量的方法计算得到；
正极材料的首次放电容量、循环性能采用扣式电池方法测得，所用仪器为新威电池测试柜(CT3008)，首次充放电容量测试条件为0.2C@3-4.35V或0.2C@3-4.40V或0.2C@3.0-4.45V，25℃，放电容量越大，表明材料比容量越高，电池体系能量密度越高；循环性能测试条件为1.0C@3-4.45V或1.0C@3-4.50V，45℃，循环过程中容量衰减越小，表明材料稳定性越高，电池体系循环性能越好。
扣式电池按照以下步骤制作：
将9.2g正极材料、0.4g乙炔黑及0.4g聚偏二氟乙烯(PVDF)进行混合，涂覆在铝箔上并进行烘干处理，用100MPa的压力冲压成型，得到直径为12mm，厚度为120μm的正极极片，然后将该正极极片放入真空烘干箱中在120℃下烘干12h。
负极使用直径为17mm，厚度为1mm的Li金属片；隔膜使用厚度为25μm的聚乙烯多孔膜；电解液使用以1mol/L的LiPF 6为电解质的碳酸乙烯酯(EC)和碳酸二乙酯(DEC)的等量混合液。
将正极极片、隔膜、负极极片及电解液在水含量与氧含量均小于5ppm的Ar气手套箱内组装成2025型扣式电池。
正极材料循环性能测试步骤如下：
将扣式电池在3-4.4V的范围内进行恒流恒压充放电循环活化。充放电制度如下：以0.2C倍率恒流恒压充电至4.4V，恒压充电截止电流为0.02C，以0.2C倍率恒流放电至3V。按此制度进行充放电2周，此电池作为已活化电池。
使用已活化电池，以1C的电流密度在3-4.45V或3-4.5V的电压区间进行充放电循环测试，温度为45℃，循环80次考察正极材料的循环保持率和DCR增幅。
实施例以及对比例所用原料均为市售品。
实施例1
S1、配制2mol/L的镍钴锰硫酸盐混合溶液(摩尔比Ni:Co:Mn＝50:19:28.6)，2.5mol/L的NaOH溶液，3mol/L的氨水，20g/L的PEG1000分散剂水溶液，1mol/L的Al 2(SO 4) 3溶液，将上述几种溶液以并流的方式通入反应釜中，其中Al 2(SO 4) 3通入量为[n(Ni)+n(Co)+n(Mn)]:n(Al)＝0.976:0.003，保持反应温度为60℃，反应pH值为12.0。反应完成后陈化6h，然后经压滤、洗涤、110℃烘干、过筛，继续在空气气氛中500℃条件下热处理8h，得到多元正极材料前驱体。
S2、将所述多元正极材料前驱体、碳酸锂、二硼化钇(YB 2)，按照 [n(Ni)+n(Co)+n(Mn)]:n(Li):n(Y)＝0.976:1.05:0.002的比例，在高混机中充分混合，1000℃温度下焙烧12h，其中，焙烧过程在600℃以下的升温过程采用的是氧气含量为15vol％的氮气和空气混合气氛，600℃以上切换为氧气含量为21vol％的干燥空气气氛，经自然冷却降温，经破碎、过筛后，得到多元正极材料过程品I。
S3、将该多元正极材料过程品I、硼化二钴(Co 2B)按照[n(Ni)+n(Co)+n(Mn)]:n(Co)＝0.976:0.010的比例，在高混机中充分混合，干燥空气气氛中800℃煅烧8h，自然冷却降温，过400目筛后得到多元正极材料A1，其组成为Li 1.05Ni 0.5Co 0.2Mn 0.286Al 0.003Y 0.002B 0.009O 2。
其中，该正极材料A1的焙烧产率以及过筛、除磁产能如表1所示。
该正极材料A1的组成、粒径D 50、LiOH含量、安息角、I (006)/I (012)以及A (006)/A (012)如表2所示。该正极材料A1的XRD结果详见附图1。由该正极材料A1制得扣式电池在4.45V电压下的克容量、以及3-4.5V电压区间内的循环保持率和DCR增幅如表3所示。由该正极材料A1制得的扣式电池的循环保持率、DCR结果分别详见附图2、附图3。
实施例2
S1、配制1.5mol/L的镍钴锰硫酸盐混合溶液(摩尔比Ni:Co:Mn＝50:18:24)，3mol/L的NaOH溶液，2mol/L的氨水，15g/L的PEG1000分散剂水溶液，0.5mol/L的Al 2(SO 4) 3溶液，将上述几种溶液以并流的方式通入反应釜中，其中Al 2(SO 4) 3通入量为[n(Ni)+n(Co)+n(Mn)]:n(Al)＝0.92:0.01，保持反应温度为50℃，反应pH值为11。反应完成后陈化12h，然后经压滤、洗涤、110℃烘干、过筛，继续在空气气氛中400℃条件下热处理10h，得到多元正极材料前驱体。
S2、将所述多元正极材料前驱体、碳酸锂、二硼化钇(YB 2)，按照[n(Ni)+n(Co)+n(Mn)]:n(Li):n(Y)＝0.92:1.20:0.01的比例，在高混机中充分混合，900℃温度下焙烧18h，其中，焙烧过程在600℃以下的升温过程采用的是氧气含量为10vol％的氮气和空气混合气氛，600℃以上切换为氧气含量为21vol％的干燥空气气氛，经自然冷却降温，经破碎、过筛后，得到多元正极材料过程品I。
S3、将该多元正极材料过程品I、硼化钴(CoB)按照[n(Ni)+n(Co)+n(Mn)]:n(Co)＝0.92:0.02的比例，在高混机中充分混合，干燥空气气氛中400℃煅烧10h，自然冷却降温，过400目筛后得到多元正极材料A2，其组成为Li 1.20Ni 0.5Co 0.2Mn 0.24Al 0.01Y 0.01B 0.04O 2。
其中，该正极材料A2的焙烧产率以及过筛、除磁产能如表1所示。
该正极材料A2的组成、粒径D 50、LiOH含量、安息角、I (006)/I (012)以及A (006)/A (012)如表2所示。由该正极材料A2制得的扣式电池在4.45V电压下的克容量、以及3-4.5V电压区间内的循环保持率和DCR增幅如表3所示。
实施例3
S1、配制2.5mol/L的镍钴锰硫酸盐混合溶液(摩尔比Ni:Co:Mn＝50:19.9:29.5)，10mol/L的NaOH溶液，8mol/L的氨水，100g/L的PEG1000分散剂水溶液，0.2mol/L的Al 2(SO 4) 3溶液，将上述几种溶液以并流的方式通入反应釜中，其中Al 2(SO 4) 3通入量为[n(Ni)+n(Co)+n(Mn)]:n(Al)＝0.994:0.001，保持反应温度为70℃，反应pH值为13。反应完成后陈化2h，然后经压滤、洗涤、120℃烘干、过筛，继续在空气气氛中600℃条件下热处理3h，得到多元正极材料前驱体。
S2、将所述多元正极材料前驱体、碳酸锂、二硼化钇(YB 2)，按照[n(Ni)+n(Co)+n(Mn)]:n(Li):n(Y)＝0.994:1.0:0.001的比例，在高混机中充分混合，950℃温度下焙烧4h，其中，焙烧过程在600℃以下的升温过程采用的是氧气含量为5vol％的氮气和空气混合气氛，600℃以上切换为氧气含量为21vol％的干燥空气气氛，经自然冷却降温，经破碎、过筛后，得到多元正极材料过程品I。
S3、将该多元正极材料过程品I、硼化钴(CoB)按照[n(Ni)+n(Co)+n(Mn)]:n(Co)＝0.994:0.001的比例，在高混机中充分混合，干燥空气气氛中900℃煅烧6h，自然冷却降温，过400目筛后得到 多元正极材料A3，其组成为LiNi 0.5Co 0.2Mn 0.295Al 0.001Y 0.001B 0.003O 2。
其中，该正极材料A3的焙烧产率以及过筛、除磁产能如表1所示。
该正极材料A3的组成、粒径D 50、LiOH含量、安息角、I (006)/I (012)以及A (006)/A (012)如表2所示。由该正极材料A3制得的扣式电池在4.45V电压下的克容量、以及3-4.5V电压区间内的循环保持率和DCR增幅如表3所示。
实施例4
按照实施例1的方法制备多元正极材料A4，不同的是：
步骤S1中，反应完成后陈化6h，然后经压滤、洗涤、110℃烘干、过筛后未在空气气氛中500℃条件下热处理；
步骤S2中，采用Y 2O 3和B 2O 3替换二硼化钇(YB 2)，且n(Y 2O 3):n(B 2O 3)＝1:2，其中，Y元素加入量与实施例1相同；
步骤S3中，采用Co(OH) 2和H 3BO 3替换硼化二钴(Co 2B)，且n(Co(OH) 2):n(H 3BO 3)＝2:1，其中，Co元素加入量与实施例1相同。
制得正极材料A4，其组成为Li 1.05Ni 0.5Co 0.2Mn 0.286Al 0.003Y 0.002B 0.009O 2，与正极材料A1的组成相同。该正极材料A4的循环保持率、DCR结果分别详见附图2、附图3。
其中，该正极材料A4的焙烧产率以及过筛、除磁产能如表1所示。
该正极材料A4的组成、粒径D 50、LiOH含量、安息角、I (006)/I (012)以及A (006)/A (012)如表2所示。由该正极材料A4制得的扣式电池在4.45V电压下的克容量、以及3-4.5V电压区间内的循环保持率和DCR增幅如表3所示。
实施例5
按照实施例1的方法制备多元正极材料A5，不同的是：
步骤S1中，反应完成后陈化6h，然后经压滤、洗涤、110℃烘干、过筛后未在空气气氛中500℃条件下热处理；
步骤S2中，不添加二硼化钇(YB 2)；
步骤S3中，采用Y 2O 3、Co(OH) 2和H 3BO 3替代硼化二钴(Co 2B)且n(Y 2O 3)：n(Co(OH) 2):n(H 3BO 3)＝1:10:9，Co元素加入量与实施例1相同。
制得正极材料A5，其组成为Li 1.05Ni 0.5Co 0.2Mn 0.286Al 0.003Y 0.002B 0.009O 2，与正极材料A1的组成相同。该正极材料A5的循环保持率、DCR结果分别详见附图2、附图3。
其中，该正极材料A5的焙烧产率以及过筛、除磁产能如表1所示。
该正极材料A5的组成、粒径D 50、LiOH含量、安息角、I (006)/I (012)以及A (006)/A (012)如表2所示。由该正极材料A5制得的扣式电池在4.45V电压下的克容量、以及3-4.5V电压区间内的循环保持率和DCR增幅如表3所示。
实施例6
S1、配制2mol/L的镍钴锰硫酸盐混合溶液(摩尔比Ni:Co:Mn＝65:15:19)，2.5mol/L的NaOH溶液，3mol/L的氨水，20g/L的PEG1000分散剂水溶液，将上述几种溶液以并流的方式通入反应釜中，保持反应温度为65℃，反应pH值为11.5。反应完成后陈化6h，然后经压滤、洗涤、110℃烘干、过筛，继续在空气气氛中500℃条件下热处理5h，得到多元正极材料前驱体。
S2、将所述多元正极材料前驱体、氢氧化锂、六硼化锶(SrB 6)，按照[n(Ni)+n(Co)+n(Mn)]:n(Li):n(Sr)＝0.99:1.03:0.001的比例，在高混机中充分混合，920℃温度下焙烧12h，其中，焙烧过程在600℃以下的升温过程采用的是氧气含量为0vol％的氮气气氛，600℃以上切换为氧气含量为21vol％的干燥空气气氛，经自然冷却降温，经破碎、过筛后，得到多元正极材料过程品I。
S4、将该多元正极材料过程品I、硼化二钨(W 2B)按照[n(Ni)+n(Co)+n(Mn)]:n(W)＝0.99:0.002 的比例，在高混机中充分混合，干燥空气气氛中700℃煅烧10h，自然冷却降温，过400目筛后得到多元正极材料A6，其组成为Li 1.03Ni 0.65Co 0.15Mn 0.19Sr 0.001W 0.002B 0.007O 2。
其中，该正极材料A6的焙烧产率以及过筛、除磁产能如表1所示。
该正极材料A6的组成、粒径D 50、LiOH含量、安息角、I (006)/I (012)以及A (006)/A (012)如表2所示。由该正极材料A6制得的扣式电池在4.40V电压下的克容量、以及3-4.45V电压区间内的循环保持率和DCR增幅如表3所示。
实施例7
S1、配制2mol/L的镍钴锰硫酸盐混合溶液(摩尔比Ni:Co:Mn＝80:10:9.1)，2.5mol/L的NaOH溶液，3mol/L的氨水，20g/L的PEG1000分散剂水溶液，将上述几种溶液以并流的方式通入反应釜中，保持反应温度为55℃，反应pH值为12.0。反应完成后陈化6h，然后经压滤、洗涤、110℃烘干、过筛，继续在空气气氛中500℃条件下热处理6h，得到多元正极材料前驱体。
S2、将所述多元正极材料前驱体、氢氧化锂、二硼化钡(BaB 2)，按照[n(Ni)+n(Co)+n(Mn)]:n(Li):n(Ba)＝0.991:1.08:0.001的比例，在高混机中充分混合，810℃温度下焙烧10h，其中，焙烧过程在600℃以下的升温过程采用的是氧气含量为15vol％的氮气和空气混合气氛，600℃以上切换为氧气含量为100vol％的干燥氧气气氛，经自然冷却降温，经破碎、过筛后，得到多元正极材料过程品I。
S3、将该多元正极材料过程品I、二硼化锆(ZrB 2)按照[n(Ni)+n(Co)+n(Mn)]:n(Zr)＝0.991:0.002的比例，在高混机中充分混合，干燥空气气氛中600℃煅烧8h，自然冷却降温，过400目筛后得到多元正极材料A7，其组成为Li 1.08Ni 0.8Co 0.1Mn 0.091Ba 0.001Zr 0.002B 0.006O 2。
其中，该正极材料A7的焙烧产率以及过筛、除磁产能如表1所示。
该正极材料A7的组成、粒径D 50、LiOH含量、安息角、I (006)/I (012)以及A (006)/A (012)如表2所示。由该正极材料A7制得的扣式电池在4.40V电压下的克容量、以及3-4.45V电压区间内的循环保持率和DCR增幅如表3所示。
实施例8
按照实施例7的方法制备多元正极材料A8，不同的是：
步骤S1中，第一次反应物除镍钴锰硫酸盐混合溶液、NaOH溶液、氨水、PEG1000分散剂溶液以外，同时以并流的方式向反应釜中通入0.1mol/L的酸性偏硼酸钡(Ba(BO 2) 2)溶液，其中[n(Ni)+n(Co)+n(Mn)]:n(Ba)＝0.991:0.001；
步骤S1中，第一次反应完成经压滤、洗涤、110℃烘干、过筛后未在空气气氛中500℃条件下进行低温热处理；
步骤S2中，不添加二硼化钡(BaB 2)；
步骤S3中，采用ZrO 2和B 2O 3替代二硼化锆(ZrB 2)，且n(Zr):n(B)＝1:2，Zr元素加入量与实施例7相同。
制得正极材料A8，其组成为Li 1.08Ni 0.8Co 0.1Mn 0.091Ba 0.001Zr 0.002B 0.006O 2，与正极材料A7的组成相同。
其中，该正极材料A8的焙烧产率以及过筛、除磁产能如表1所示。
该正极材料A8的组成、粒径D 50、LiOH含量、安息角、I (006)/I (012)以及A (006)/A (012)如表2所示。由该正极材料A8制得的扣式电池在4.40V电压下的克容量、以及3-4.45V电压区间内的循环保持率和DCR增幅如表3所示。
实施例9
按照实施例7的方法制备多元正极材料A9，不同的是：
步骤S1中，混合硫酸盐溶液中镍钴锰摩尔比为Ni:Co:Mn＝80:10:9.5；
步骤S1中，第一次反应完成经压滤、洗涤、110℃烘干、过筛后未在空气气氛中500℃条件 下进行低温热处理；
步骤S3中，第三添加剂使用二氧化锆(ZrO 2)替代二硼化锆(ZrB 2)，且Zr元素加入量与实施例7相同。
制得正极材料A9，其组成为Li 1.08Ni 0.8Co 0.1Mn 0.095Ba 0.001Zr 0.002B 0.002O 2。
其中，该正极材料A9的焙烧产率以及过筛、除磁产能如表1所示。
该正极材料A9的组成、粒径D 50、LiOH含量、安息角、I (006)/I (012)以及A (006)/A (012)如表2所示。由该正极材料A9制得的扣式电池在4.40V电压下的克容量、以及3-4.45V电压区间内的循环保持率和DCR增幅如表3所示。
实施例10
按照实施例7的方法制备多元正极材料A10，不同的是：
步骤S1中，混合硫酸盐溶液中镍钴锰摩尔比为Ni:Co:Mn＝80:9:9.2；
步骤S1中，第一次反应完成经压滤、洗涤、110℃烘干、过筛后未在空气气氛中500℃条件下进行低温热处理；
步骤S2中，第二添加剂使用二硼化钛(TiB 2)替代二硼化钡(BaB 2)，并且[n(Ni)+n(Co)+n(Mn)]:n(Li):n(Ti)＝0.982:1.03:0.001；
步骤S3中，第三添加剂使用硼化二钴(Co 2B)替代二硼化锆(ZrB 2)，且[n(Ni)+n(Co)+n(Mn)]:n(B)＝0.982:0.005。
制得正极材料A10，其组成为Li 1.03Ni 0.8Co 0.1Mn 0.092Ti 0.001B 0.007O 2。
其中，该正极材料A10的焙烧产率以及过筛、除磁产能如表1所示。
该正极材料A10的组成、粒径D 50、LiOH含量、安息角、I (006)/I (012)以及A (006)/A (012)如表2所示。由该正极材料A10制得的扣式电池在4.40V电压下的克容量、以及3-4.45V电压区间内的循环保持率和DCR增幅如表3所示。
实施例11
S1、配制2mol/L的镍钴锰硫酸盐混合溶液(摩尔比Ni:Co:Mn＝15:14:70)，2.5mol/L的NaOH溶液，3mol/L的氨水，20g/L的PEG1000分散剂水溶液，将上述几种溶液以并流的方式通入反应釜中，保持反应温度为65℃，反应pH值为11.5。反应完成后陈化6h，然后经压滤、洗涤、110℃烘干、过筛，继续在空气气氛中500℃条件下热处理5h，得到多元正极材料前驱体。
S2、将所述多元正极材料前驱体、氢氧化锂、六硼化锶(SrB 6)，按照[n(Ni)+n(Co)+n(Mn)]:n(Li):n(Sr)＝0.99:1.23:0.001的比例，在高混机中充分混合，900℃温度下焙烧12h，其中，焙烧过程在600℃以下的升温过程采用的是氧气含量为15vol％的氮气和空气混合气氛，600℃以上切换为氧气含量为21vol％的干燥空气气氛，经自然冷却降温，经破碎、过筛后，得到多元正极材料过程品I。
S4、将该多元正极材料过程品I、硼化二钨(W 2B)按照[n(Ni)+n(Co)+n(Mn)]:n(W)＝0.99:0.002的比例，在高混机中充分混合，干燥空气气氛中600℃煅烧10h，自然冷却降温，过400目筛后得到多元正极材料A11，其组成为Li 1.23Ni 0.15Co 0.14Mn 0.70Sr 0.001W 0.002B 0.007O 2。
其中，该正极材料A11的焙烧产率以及过筛、除磁产能如表1所示。
该正极材料A11的组成、粒径D 50、LiOH含量、安息角、I (006)/I (012)以及A (006)/A (012)如表2所示。由该正极材料A11制得的扣式电池在4.60V电压下的克容量、以及3-4.5V电压区间内的循环保持率和DCR增幅如表3所示。
实施例12
按照实施例7的方法制备多元正极材料A12，不同的是：
步骤S1中，混合硫酸盐溶液中镍钴锰摩尔比为Ni:Co:Mn＝80:9:9.6；
步骤S1中，第一次反应完成经压滤、洗涤、110℃烘干、过筛后未在空气气氛中500℃条件 下进行低温热处理；
步骤S2中，不添加二硼化钡(BaB 2)；
步骤S3中，第三添加剂使用氢氧化亚钴(Co(OH) 2)和磷化镓(GaP)替代二硼化锆(ZrB 2)，且[n(Ni)+n(Co)+n(Mn)]:n(Co(OH) 2):n(GaP)＝0.986:0.01:0.002。
制得正极材料A12，其组成为Li 1.08Ni 0.8Co 0.1Mn 0.096Ga 0.002P 0.002O 2。
其中，该正极材料A12的焙烧产率以及过筛、除磁产能如表1所示。
该正极材料A12的组成、粒径D 50、LiOH含量、安息角、I (006)/I (012)以及A (006)/A (012)如表2所示。由该正极材料A12制得的扣式电池在4.40V电压下的克容量、以及3-4.45V电压区间内的循环保持率和DCR增幅如表3所示。
实施例13
按照实施例7的方法制备多元正极材料A13，不同的是：
步骤S1中，第一次反应完成经压滤、洗涤、110℃烘干、过筛后未在空气气氛中500℃条件下进行低温热处理；
步骤S3中，第三添加剂使用二硅化锆(ZrSi 2)替代二硼化锆(ZrB 2)，且[n(Ni)+n(Co)+n(Mn)]:n(Zr)＝0.991:0.002。
制得正极材料A13，其组成为Li 1.08Ni 0.8Co 0.1Mn 0.096Ba 0.001Zr 0.002B 0.002Si 0.004O 2。
其中，该正极材料A13的焙烧产率以及过筛、除磁产能如表1所示。
该正极材料A13的组成、粒径D 50、LiOH含量、安息角、I (006)/I (012)以及A (006)/A (012)如表2所示。由该正极材料A12制得的扣式电池在4.40V电压下的克容量、以及3-4.45V电压区间内的循环保持率和DCR增幅如表3所示。
实施例14
按照实施例7的方法制备多元正极材料A14，不同的是：
步骤S1中，混合硫酸盐溶液中镍钴锰摩尔比为Ni:Co:Mn＝80:10:9；步骤S2中，第二添加剂使用四硼化镁(MgB 4)替代二硼化钡(BaB 2)，且Mg加入量控制为[n(Ni)+n(Co)+n(Mn)]:n(Mg)＝0.99:0.001；
步骤S3中，第三添加剂使用四硼化钇(YB 4)替代二硼化锆(ZrB 2)，加入量控制为[n(Ni)+n(Co)+n(Mn)]:n(Y)＝0.99:0.001；
制得正极材料A14，其组成为Li 1.08Ni 0.8Co 0.1Mn 0.09Mg 0.001Y 0.001B 0.008O 2。
其中，该正极材料A14的焙烧产率以及过筛、除磁产能如表1所示。
该正极材料A14的组成、粒径D 50、LiOH含量、安息角、I (006)/I (012)以及A (006)/A (012)如表2所示。由该正极材料A14制得的扣式电池在4.40V电压下的克容量、以及3-4.45V电压区间内的循环保持率和DCR增幅如表3所示。
实施例15
按照实施例7的方法制备多元正极材料A15，不同的是：
步骤S1中，混合硫酸盐溶液中镍钴锰摩尔比为Ni:Co:Mn＝80:10:8.6；步骤S2中，第二添加剂使用六硼化钡(BaB 6)替代二硼化钡(BaB 2)，且Ba加入量控制为[n(Ni)+n(Co)+n(Mn)]:n(Ba)＝0.986:0.001；
步骤S3中，第三添加剂使用六硼化镧(LaB 6)替代二硼化锆(ZrB 2)，加入量控制为[n(Ni)+n(Co)+n(Mn)]:n(La)＝0.986:0.001；
制得正极材料A15，其组成为Li 1.08Ni 0.8Co 0.1Mn 0.086Ba 0.001La 0.001B 0.012O 2。
其中，该正极材料A15的焙烧产率以及过筛、除磁产能如表1所示。
该正极材料A15的组成、粒径D 50、LiOH含量、安息角、I (006)/I (012)以及A (006)/A (012)如表2所示。由该正极材料A15制得的扣式电池在4.40V电压下的克容量、以及3-4.45V电压区间内的循环 保持率和DCR增幅如表3所示。
对比例1
S1、配制2mol/L的镍钴锰硫酸盐混合溶液(摩尔比Ni:Co:Mn＝50:20:29.5)，2.5mol/L的NaOH溶液，3mol/L的氨水，20g/L的PEG1000分散剂水溶液，将上述几种溶液以并流的方式通入反应釜中，保持反应温度为60℃，反应pH值为12.0。反应完成后陈化6h，然后经压滤、洗涤、110℃烘干、过筛，得到多元正极材料前驱体。
S2、将所述多元正极材料前驱体、碳酸锂、三氧化二铝(Al 2O 3)，按照[n(Ni)+n(Co)+n(Mn)]:n(Li):n(Al)＝0.995:1.05:0.003的比例，在高混机中充分混合，干燥空气气氛中1000℃焙烧12h，自然冷却降温，经破碎、过筛后，得到多元正极材料过程品I。
S3、将该多元正极材料过程品I、三氧化二钇(Y 2O 3)按照[n(Ni)+n(Co)+n(Mn)]:n(Y)＝0.995:0.002的比例，在高混机中充分混合，干燥空气气氛中800℃煅烧8h，自然冷却降温，过400目筛后得到多元正极材料D1，其组成为Li 1.05Ni 0.5Co 0.2Mn 0.295Al 0.003Y 0.002O 2。该正极材料D1的XRD、循环保持率、DCR结果分别详见附图1、附图2、附图3。
其中，该正极材料D1的焙烧产率以及过筛、除磁产能如表1所示。
该正极材料D1的组成、粒径D 50、LiOH含量、安息角、I (006)/I (012)以及A (006)/A (012)如表2所示。由该正极材料D1制得的扣式电池在4.40V和4.45V电压下的克容量、以及3-4.5V电压区间内的循环保持率和DCR增幅如表3所示。
对比例2
S1、配制1mol/L的镍钴锰硫酸盐混合溶液(摩尔比Ni:Co:Mn＝80:10:9.1)，8mol/L的NaOH溶液，5mol/L的氨水，10g/L的PEG1000分散剂水溶液，将上述几种溶液以并流的方式通入反应釜中，保持反应温度为60℃，反应pH值为12。反应完成后陈化12h，然后经压滤、洗涤、110℃烘干、过筛，得到多元正极材料前驱体。
S2、将所述多元正极材料前驱体、氢氧化锂、氢氧化钡(Ba(OH) 2)，按照[n(Ni)+n(Co)+n(Mn)]:n(Li):n(Ba)＝0.991:1.08:0.001的比例，在高混机中充分混合，干燥氧气气氛中810℃焙烧10h，自然冷却降温，经破碎、过筛后，得到多元正极材料过程品I。
S3、将该多元正极材料过程品I、二氧化锆(ZrO 2)、三氧化二硼(B 2O 3)按照[n(Ni)+n(Co)+n(Mn)]:n(Zr):n(B)＝0.991:0.002:0.006的比例，在高混机中充分混合，过400目筛后得到多元正极材料D2，其组成为Li 1.08Ni 0.8Co 0.1Mn 0.091Ba 0.001Zr 0.002B 0.006O 2。
该正极材料D2中，I (006)/I (012)＝0.42，A (006)/A (012)＝0.39，循环保持率为68％，DCR增幅为233％。
其中，该正极材料D2的焙烧产率以及过筛、除磁产能如表1所示。
该正极材料D2的组成、粒径D 50、LiOH含量、安息角、I (006)/I (012)以及A (006)/A (012)如表2所示。由该正极材料D2制得的扣式电池在4.35V和4.40V电压下的克容量、以及3-4.45V电压区间内的循环保持率和DCR增幅如表3所示。
对比例3
按照实施例7的方法制备多元正极材料D3，不同的是：
步骤S1中，混合硫酸盐溶液中镍钴锰摩尔比为Ni:Co:Mn＝80:10:3；步骤S2中，第二添加剂使用六硼化钡(BaB 6)替代二硼化钡(BaB 2)，且Ba加入量控制为[n(Ni)+n(Co)+n(Mn)]:n(Ba)＝0.93:0.005；
步骤S3中，第三添加剂使用六硼化镧(LaB 6)替代二硼化锆(ZrB 2)，加入量控制为[n(Ni)+n(Co)+n(Mn)]:n(La)＝0.93:0.005；
制得正极材料D3，其组成为Li 1.08Ni 0.8Co 0.1Mn 0.03Ba 0.005Zr 0.005B 0.06O 2。
其中，该正极材料D3的焙烧产率以及过筛、除磁产能如表1所示。
该正极材料D3的组成、粒径D 50、LiOH含量、安息角、I (006)/I (012)以及A (006)/A (012)如表2所示。 由该正极材料D3制得的扣式电池在4.40V电压下的克容量、以及3-4.45V电压区间内的循环保持率和DCR增幅如表3所示。
对比例4
按照实施例7的方法制备多元正极材料D4，不同的是：
步骤S2中，焙烧温度为550℃，焙烧时间为30h；
制得正极材料D4，其组成为Li 1.08Ni 0.8Co 0.1Mn 0.091Ba 0.001Zr 0.002B 0.006O 2。
其中，该正极材料D4的焙烧产率以及过筛、除磁产能如表1所示。
该正极材料D4的组成、粒径D 50、LiOH含量、安息角、I (006)/I (012)以及A (006)/A (012)如表2所示。由该正极材料D4制得的扣式电池在4.40V电压下的克容量、以及3-4.45V电压区间内的循环保持率和DCR增幅如表3所示。
表1
实施例 焙烧产率％ 过筛除磁产能kg/h
实施例1 85.9 300
实施例2 85.0 330
实施例3 85.2 280
实施例4 74.5 310
实施例5 74.0 280
实施例6 83.9 290
实施例7 84.1 305
实施例8 72.3 285
实施例9 72.2 273
实施例10 72.0 297
实施例11 83.5 310
实施例12 72.3 305
实施例13 72.2 287
实施例14 84.3 302
实施例15 84.6 321
对比例1 74.0 190
对比例2 72.0 170
对比例3 70.8 205
对比例4 72.1 158
表2
Figure PCTCN2022092619-appb-000001
Figure PCTCN2022092619-appb-000002
表3
Figure PCTCN2022092619-appb-000003
*表示循环保持率和DCR增幅是在3-4.45V的电压区间内进行测试得到的，其余在3-4.5V的电压区间内进行测试得到的。
通过表1-表3及附图2、附图3的结果可以看出，采用本发明引入B、P、Si元素的实施例1-实施例10制得多元正极材料具有峰强度之比I (006)/I (012)≥0.8、峰面积之比A (006)/A (012)≥0.5的特定结构，较未引入B、P、Si或引入B元素后未进行煅烧的对比例1、对比例2中峰强度之比I (006)/I (012)＜0.8、峰面积之比A (006)/A (012)＜0.5的多元正极材料，能够在更高电压窗口下使用，其中，实施例1、实施例4、实施例5在3.0-4.5V电压窗口下的循环保持率不仅较对比例1在3.0-4.5V下的循环保持率、DCR增幅明显更优，而且还明显优于对比例1在3.0-4.45V电压窗口下的循环保持率及DCR增幅。
具体地，与对比例1相比，采用本发明引入B元素、峰强度之比I (006)/I (012)≥0.8、峰面积之比 A (006)/A (012)≥0.5的实施例1、实施例2、实施例3、实施例4、实施例5具有明显更高的过筛除磁产能，并且制得的多元正极材料具有更小的安息角，更高的LiOH含量，将该多元正极材料用于制备电池时，电池具有更高的克容量，更优的循环保持率，更低的DCR增幅等。
具体地，与对比例2相比，本发明中正极材料S3步骤包括煅烧过程的引入B元素和/或P元素和/或Si元素、峰强度之比I (006)/I (012)≥0.8、峰面积之比A (006)/A (012)≥0.5的实施例7、实施例8、实施例9、实施例10、实施例12、实施例13具有明显更高的过筛除磁产能，并且制得的多元正极材料具有更小的安息角，该多元正极材料用于制备电池时，电池具有更高的克容量，更优的循环保持率，更低的DCR增幅等。
具体地，与对比例3相比，采用本发明限定取值范围内取值的参数0＜a≤0.03、参数0＜b≤0.04、参数0＜b/a≤5、峰强度之比I (006)/I (012)≥0.8、峰面积之比A (006)/A (012)≥0.5的实施例7、实施例8、实施例9、实施例10、实施例12、实施例13具有明显更高的过筛除磁产能，并且制得的多元正极材料具有更小的安息角，该多元正极材料用于制备电池时，电池具有更高的克容量，更优的循环保持率，更低的DCR增幅等。
具体地，与对比例4相比，采用本发明限定焙烧温度范围内、峰强度之比I (006)/I (012)≥0.8、峰面积之比A (006)/A (012)≥0.5的实施例7、实施例8、实施例9、实施例10、实施例12、实施例13具有明显更高的过筛除磁产能，并且制得的多元正极材料具有更小的安息角，该多元正极材料用于制备电池时，电池具有显著更高的克容量，显著更优的循环保持率，显著更低的DCR增幅等。
进一步地，采用本发明包含低温热处理工序的实施例1、实施例2、实施例3较不包含低温热处理工序的实施例4、实施例5、对比例1具有焙烧产率明显提高的效果。
进一步地，采用本发明包含低温热处理工序的实施例7较不包含低温热处理工序的实施例8、实施例9、实施例10、实施例12、实施例13、对比例2、对比例3、对比例4具有焙烧产率明显提高的效果。
进一步地，与实施例9-10相比，采用本发明包含优选的第一添加剂的实施例8的多元正极材料制得的电池具有更高的循环保持率。
进一步地，与实施例8相比，采用本发明包含优选的第二添加剂的实施例7的多元正极材料制得的电池具有更高的循环保持率。
进一步地，与使用非优选第二添加剂的实施例4和不含有第二添加剂的实施例5相比，采用本发明包含优选的第二、第三添加剂的实施例1、实施例2、实施例3的多元正极材料制得的电池具有更高的克容量及循环保持率。
进一步地，与使用非优选第三添加剂的实施例9相比，采用本发明包含优选的第三添加剂的实施例7的多元正极材料制得的电池具有更高的循环保持率。
进一步地，与使用b/a取值较大的实施例10、实施例15相比，采用本发明b/a取值较小的实施例7、实施例8、实施例9的多元正极材料制得的电池具有更高的循环保持率和更低的DCR增幅。
此外，以上详细描述了本发明的优选实施方式，但是，本发明并不限于此。在本发明的技术构思范围内，可以对本发明的技术方案进行多种简单变型，包括各个技术特征以任何其它的合适方式进行组合，这些简单变型和组合同样应当视为本发明所公开的内容，均属于本发明的保护范围。

Claims (10)

  1. 一种多元正极材料，其特征在于，所述多元正极材料通过XRD获得的(006)晶面的峰强度I (006)与(012)晶面的峰强度I (012)之比I (006)/I (012)≥0.8；
    所述多元正极材料通过XRD获得的(006)晶面的峰面积A (006)与(012)晶面的峰面积A (012)之比A (006)/A (012)≥0.5。
  2. 根据权利要求1所述的多元正极材料，其中，I (006)/I (012)≥1；
    优选地，A (006)/A (012)≥0.8。
  3. 根据权利要求1或2所述的多元正极材料，其中，所述多元正极材料具有通式I所示的组成：
    Li nNi xCo yMn 1-x-y-a-bM aQ bO 2式I；
    其中，0.9≤n≤1.3，0≤x＜1，0≤y＜1，0≤a≤0.04，0＜b≤0.05，0＜b/a≤100；
    M为W、Mo、V、Ca、Al、Si、Ni、Mn、Hf、Ta、Y、Sr、Ba、Er、Ga、Mg、Ti、Zr、La、Ce、Co和Nb中的至少一种；
    Q为B、P和Si中的至少一种；
    优选地，式I中，1≤n≤1.2，0≤x＜1，0≤y＜1，0＜a≤0.03，0＜b≤0.04，0＜b/a≤20；
    M为W、Al、Si、Ta、Y、Sr、Ga、Mg、Ti、Zr、Co和Nb中的至少一种；
    Q为B；
    优选地，0＜b/a≤5。
  4. 根据权利要求1-3中任意一项所述的多元正极材料，其中，所述多元正极材料的中值粒径为3-20μm，优选为4-17μm；
    优选地，所述多元正极材料的安息角为≤35°，优选为≤30°；
    优选地，以所述多元正极材料的总重量为基准，LiOH的含量为1000-3000ppm，优选为1200-2500ppm。
  5. 一种多元正极材料的制备方法，其特征在于，所述方法包括以下步骤：
    (1)将镍盐、钴盐、锰盐按照n(Ni)∶n(Co)∶n(Mn)＝x∶y∶(1-x-y-a-b)的摩尔比配制混合盐溶液；将沉淀剂、络合剂、分散剂和可选地第一添加剂，分别配制为沉淀剂溶液、络合剂溶液、分散剂溶液和可选地第一添加剂混合物；
    (2)将所述混合盐溶液、沉淀剂溶液、络合剂溶液、分散剂溶液和可选地第一添加剂混合物同时、分别通入反应釜，进行反应、陈化，得到固液混合物；
    (3)将所述固液混合物进行压滤，得到滤饼，将滤饼进行洗涤、烘干得到多元正极材料前驱体；
    (4)将所述多元正极材料前驱体、锂源和可选地第二添加剂进行混合，得到混合物I；
    (5)将所述混合物I进行焙烧、冷却、破碎、筛分，得到多元正极材料过程品；
    (6)将所述多元正极材料过程品与可选地第三添加剂进行混合，得到混合物II；
    (7)将混合物II进行煅烧、冷却、筛分、除磁，得到所述多元正极材料；
    其中，至少包括所述第一添加剂、所述第二添加剂和所述第三添加剂中的一种；所述第一添加剂、所述第二添加剂和所述第三添加剂中的至少一种为能够提供Q的化合物。
  6. 根据权利要求5所述的制备方法，其中，所述多元正极材料通过XRD获得的(006)晶面的峰强度I (006)与(012)晶面的峰强度I (012)之比I (006)/I (012)≥0.8，优选地，I (006)/I (012)≥1；
    所述正极材料通过XRD获得的(006)晶面的峰面积A (006)与(012)晶面的峰面积A (012)之比 A (006)/A (012)≥0.5，优选地，A (006)/A (012)≥0.8；
    优选地，所述多元正极材料具有通式I所示的组成：
    Li nNi xCo yMn 1-x-y-a-bM aQ bO 2式I；
    其中，0.9≤n≤1.3，0≤x＜1，0≤y＜1，0≤a≤0.04，0＜b≤0.05，0＜b/a≤100；
    M为W、Mo、V、Ca、Al、Si、Ni、Mn、Hf、Ta、Y、Sr、Ba、Er、Ga、Mg、Ti、Zr、La、Ce、Co和Nb中的至少一种；
    Q为B、P和Si中的至少一种；
    优选地，1≤n≤1.2，0≤x＜1，0≤y＜1，0＜a≤0.03，0＜b≤0.04，0＜b/a≤20；
    M为W、Al、Si、Ta、Y、Sr、Ga、Mg、Ti、Zr、Co和Nb中的至少一种；
    Q为B；
    优选地，0＜b/a≤5。
  7. 根据权利要求5或6所述的制备方法，其中，所述第一添加剂、所述第二添加剂和所述第三添加剂各自独立地选自能够提供M和/或Q的化合物中的一种或多种；
    优选地，所述第一添加剂选自能够提供M和/或Q的可溶性化合物中的一种或多种；
    优选地，所述第二添加剂和所述第三添加剂各自独立地选自能够提供M和Q的化合物中的一种或多种；
    优选地，所述反应的条件包括：反应的温度为40-80℃；反应的pH值为10-13；
    优选地，所述陈化的时间为2-8h；
    优选地，所述多元正极材料前驱体、所述锂源和所述第二添加剂的用量使得0.9≤n(Li)/[n(Ni)+n(Co)+n(Mn)+n(M)+n(Q)]≤1.3；
    0≤n(M)/[n(Ni)+n(Co)+n(Mn)+n(M)+n(Q)]≤0.04；
    0≤n(Q)/[n(Ni)+n(Co)+n(Mn)+n(M)+n(Q)]≤0.05；
    优选地，所述焙烧的条件包括：焙烧温度为600-1100℃，优选为700-1000℃，焙烧时间为4-18h，优选为6-15h；
    优选地，所述焙烧过程在600℃以下的升温过程采用的是氧气含量＜20vol％的贫氧或无氧气氛，600℃及以上采用氧气含量≥20vol％的空气和/或氧气气氛；
    优选地，所述多元正极材料过程品与所述第三添加剂的用量使得0≤n(M)/[n(Ni)+n(Co)+n(Mn)+n(M)+n(Q)]≤0.04；
    0≤n(Q)/[n(Ni)+n(Co)+n(Mn)+n(M)+n(Q)]≤0.05；
    优选地，所述煅烧的条件包括：煅烧温度为300-1000℃，优选为400-900℃，煅烧时间为4-12h，优选为6-10h。
  8. 根据权利要求5-7中任意一项所述的制备方法，其中，所述制备方法还包括：对滤饼洗涤、烘干后的产物进行低温热处理，得到所述多元正极材料前驱体；
    优选地，所述低温热处理的条件包括：在空气和/或氧气的存在下，在300-700℃的温度下处理3-12h。
  9. 由权利要求5-8中任意一项所述的制备方法制得的多元正极材料。
  10. 一种权利要求1-4和权利要求9中任意一项所述的多元正极材料在锂离子电池中的应用。
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