WO2022206465A1 - 一种层状无钴正极材料、其制备方法和锂离子电池 - Google Patents

一种层状无钴正极材料、其制备方法和锂离子电池 Download PDF

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WO2022206465A1
WO2022206465A1 PCT/CN2022/082155 CN2022082155W WO2022206465A1 WO 2022206465 A1 WO2022206465 A1 WO 2022206465A1 CN 2022082155 W CN2022082155 W CN 2022082155W WO 2022206465 A1 WO2022206465 A1 WO 2022206465A1
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positive electrode
electrode material
layered
calcination
cobalt
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French (fr)
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潘海龙
李子郯
杨红新
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Svolt Energy Technology Co Ltd
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Svolt Energy Technology Co Ltd
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Definitions

  • the present disclosure relates to the technical field of batteries, and relates to a layered cobalt-free positive electrode material, a preparation method thereof, and a lithium ion battery.
  • Lithium-ion batteries a clean and efficient energy device
  • battery life, and life of lithium-ion batteries are getting higher and higher, the design and optimization of batteries are becoming more and more important.
  • the development of new energy vehicles has an urgent need to increase the specific energy of power batteries and reduce the cost.
  • the specific energy of lithium iron phosphate batteries has tended to the limit, and the synthesis cost of high-capacity layered structure cathode materials is high.
  • the traditional synthesis process of layered cathode materials requires co-precipitation to synthesize the precursor, and then mixed lithium calcination to obtain the target product.
  • the precipitant is obtained by controlling the pH of the solution, the stirring temperature and speed, the reaction time and the concentration of the solution.
  • the disadvantage of this process is that it generates more industrial waste water, has many synthetic process steps, and has high cost.
  • the precursor and lithium salt are mixed and doped, it is not uniform, and many elements cannot be incorporated into the lattice.
  • a method for preparing a layered cobalt-free positive electrode material includes the following steps:
  • the doping element M in the dopant is selected from at least one of Ta, Rb, Sr, Zr, Na, Cs, Y, W, B, Nb, Ba, Mo and P.
  • a may be, for example, 1.0, 1.05, 1.1, 1.05, 1.1, or 1.2, etc.
  • b may be, for example, 0, 0.1, 0.2, 0.3, 0.5 , 0.7, 0.8 or 1.0, etc.
  • c can be, for example, 0, 0.2, 0.3, 0.4, 0.5, 0.6, 0.8, or 1.0, etc.
  • d can be, for example, 0.002, 0.003, 0.004, 0.005, 0.006, 0.008, 0.01, 0.015, 0.017 , 0.02, 0.025, 0.03, 0.035, 0.04, 0.045, 0.05, 0.055, 0.06, 0.065, 0.07, 0.075, 0.08, 0.085, 0.09, or 0.1, etc.
  • d is 0.002 ⁇ 0.01.
  • the amounts of nickel source, manganese source, lithium salt and dopant should meet the formula amount, that is, the molar ratio of the corresponding elements lithium, nickel, manganese and M should meet a:b:c:d.
  • the method provided by an embodiment of the present disclosure directly mixes the raw materials, and prepares a layered positive electrode material by calcination.
  • This process method is less studied at home and abroad. Compared with the traditional co-precipitation method and the sol-gel method, this method has the following advantages : The method is simple, the process produces less waste water, and the cost is low, and the bulk doping of elements can be realized on the premise of omitting cobalt, the doping elements are uniformly entered into the interior of the lattice, and the stability of the material is improved.
  • the doping element M is at least one of Zr, Sr, Ta, W and Y.
  • the doping element M is Zr, or a combination of Zr and Sr, or a combination of Zr and Ta, or a combination of W and Y.
  • Different types of doping elements result in different crystal parameters in the crystal structure, and the layered materials mainly exhibit different c-axis, resulting in different electrical properties.
  • the dopant is M oxide and/or M salt.
  • the dopant is an M oxide.
  • the nickel source in step (1) is selected from at least one of nickel salts or nickel oxides.
  • the nickel source in step (1) is NiO.
  • the manganese source in step (1) is selected from at least one of manganese salts or manganese oxides.
  • the manganese source in step (1) is Mn 3 O 4 .
  • the lithium salt in step (1) includes Li 2 CO 3 and/or LiOH.
  • the nickel source, the manganese source and the lithium salt are selected from NiO, Mn 3 O 4 , Li 2 CO 3 and LiOH. These products are market commodities with stable performance and easy processing.
  • the rotational speed of the wet ball milling in step (1) is 2000r/min ⁇ 3000r/min, such as 2000r/min, 2200r/min, 2300r/min, 2400r/min, 2500r/min, 2600r/min, 2800r /min or 3000r/min, etc.; the time is 1h to 2h, such as 1h, 1.2h, 1.3h, 1.5h, 1.7h, 1.8h or 2h, etc.
  • the volume fraction of oxygen in the oxygen-containing atmosphere in step (3) is greater than 20%, such as 21%, 25%, 30%, 50%, 60%, 70%, 80%, 90% or 100% %.
  • the temperature of the primary calcination in step (3) is 700°C to 1100°C, such as 700°C, 750°C, 800°C, 825°C, 850°C, 880°C, 900°C, 950°C, 1000°C , 1050°C or 1100°C, etc.
  • the temperature of the primary calcination in step (3) is 800°C to 950°C.
  • the time of the primary calcination in step (3) is 6h-20h, for example, 6h, 8h, 9h, 10h, 12h, 15h, 17h, 18h or 20h.
  • the time of the primary calcination in step (3) is 8h-15h.
  • the temperature and time of the primary calcination will affect the formation of the layered structure of the positive electrode material and have a certain influence on the crystallinity. Within the above range, the layered structure is easily formed and the crystallinity is high.
  • the method further includes, after step (3), coating the layered cobalt-free positive electrode material.
  • the coating treatment includes: mixing the layered cobalt-free positive electrode material with a coating agent, and calcining the layered cobalt-free positive electrode material in an oxygen-containing atmosphere for a second time to obtain the coated layered cobalt-free positive electrode material.
  • the capping agent includes at least one of Al 2 O 3 , ZrO 2 and WO 3 .
  • the mass ratio of the layered cobalt-free positive electrode material to the coating agent is 100:(0.12-0.4), for example, 100:0.12, 100:0.15, 100:0.18, 100:0.2, 100 :0.22, 100:0.26, 100:0.28, 100:0.3, 100:0.33, 100:0.35, 100:0.37, or 100:0.4, etc.
  • the temperature of the secondary calcination is 300°C to 900°C, such as 300°C, 350°C, 400°C, 500°C, 550°C, 600°C, 650°C, 700°C, 750°C or 800°C Wait.
  • the temperature of the secondary calcination is 500°C to 800°C.
  • the time of the secondary calcination is 3h to 10h, for example, 3h, 4h, 5h, 6h, 7h, 8h, 9h or 10h.
  • the time of the secondary calcination is 4h-7h.
  • the conductivity of the material can be enhanced and the surface of the positive electrode material can be repaired, preventing strong side reactions between the surface of the positive electrode material and the electrolyte.
  • a better coating effect can be obtained.
  • the layered cobalt-free positive electrode material is subjected to the steps of pulverizing and sieving before the coating treatment.
  • the method includes the steps of:
  • Lithium salt, nickel source, manganese source and dopant MO x (x is the oxygen content that satisfies the valence balance of MOx element) are prepared according to the molar ratio of elements lithium, nickel, manganese and M as a:b:c:d , and then added to deionized water and mixed evenly to form a suspension.
  • the suspension was added to a ceramic grinder and ground for 1 hour at a rotational speed of 2000r/min to obtain a slurry;
  • the layered positive electrode material Li a Ni b Mn c M d O 2 and the coating agent are mixed according to the mass ratio of 100: (0.15-0.4), mixed under a high-speed mixer, and the obtained mixed material is calcined in an air atmosphere, the calcination temperature is 500°C ⁇ 800°C, and the calcination time is 4h ⁇ 7h to obtain the coated layered cobalt-free positive electrode material, which is also a layered positive electrode material;
  • the dopant is selected from at least one of oxides of Zr, Sr, Ta, W and Y;
  • the coating agent is selected from at least one of Al 2 O 3 , ZrO 2 and WO 3 .
  • doping elements especially selecting doping elements with larger ionic radius (such as Zr, Sr, Ta, W, and Y), instead of expensive cobalt elements, Combined with wet ball milling and spray drying process, it can not only realize bulk doping, but also increase the c-axis of the material during crystal formation, and make the layered more obvious, reduce the mixing of lithium and nickel, and improve the stability of the material, so as to obtain excellent results. electrochemical performance.
  • the method provided by an embodiment of the present disclosure directly mixes the raw materials, and prepares layered cathode materials by calcination.
  • the method has the following advantages: the method is simple, the process produces less waste water, The cost is low, and the bulk doping of elements can be realized on the premise of omitting cobalt, and the doping elements uniformly enter the interior of the lattice to improve the stability of the material.
  • a layered cobalt-free positive electrode material prepared by the above method is provided.
  • a lithium-ion battery in an embodiment of the present disclosure, includes the above-mentioned layered cobalt-free positive electrode material.
  • Fig. 1 is a graph comparing the specific capacity of the layered positive electrode material obtained in Example 4 of the present disclosure and the layered positive electrode material obtained in Comparative Example 1.
  • Example 2 is a cycle comparison diagram of the layered positive electrode material obtained in Example 4 of the present disclosure and the layered positive electrode material obtained in Comparative Example 1.
  • Example 3 is a XRD comparison diagram of the layered positive electrode material obtained in Example 4 of the present disclosure and the layered positive electrode material obtained in Comparative Example 1.
  • This embodiment provides a method for preparing a layered positive electrode material, and the method includes the following steps:
  • Lithium salt Li 2 CO 3 , nickel source NiO, manganese source Mn 3 O 4 , dopant ZrO 2 are prepared according to the molar ratio of lithium, nickel, manganese and zirconium contained in 1.05:0.6:0.4:0.003, Then add deionized water in turn and mix evenly to form a suspension. Add the suspension to a ceramic grinder and grind at a speed of 2000r/min for 1 hour to obtain a slurry. The slurry is spray-dried at 180°C to obtain a powder.
  • the calcination temperature is 900°C
  • the calcination time is 12h
  • cooled, pulverized and sieved to obtain a layered positive electrode material.
  • the positive electrode material obtained above and the coating agent WO 3 are prepared according to the mass ratio of 100:0.13, mixed in a high-speed mixer, and the mixed material is calcined in an air atmosphere, the calcination temperature is 500 ° C, and the calcination time is 5 h, and the final product can be obtained.
  • layered cathode material is prepared according to the mass ratio of 100:0.13, mixed in a high-speed mixer, and the mixed material is calcined in an air atmosphere, the calcination temperature is 500 ° C, and the calcination time is 5 h, and the final product can be obtained.
  • layered cathode material is prepared according to the mass ratio of 100:0.13, mixed in a high-speed mixer, and the mixed material is calcined in an air atmosphere, the calcination temperature is
  • This embodiment provides a method for preparing a layered positive electrode material.
  • the method includes the following steps: (1) Lithium salt Li 2 CO 3 , nickel source NiO, manganese source Mn 3 O 4 , and dopant ZrO 2 are prepared according to The molar ratio of lithium, nickel, manganese and zirconium is 1.05: 0.75: 0.25: 0.004, then add deionized water and mix evenly to form a suspension, add the suspension to the ceramic grinder, rotate at 2000r/ min grinding for 1 h to obtain a slurry, which was spray-dried at 180°C to obtain a powder.
  • the calcination temperature is 880°C
  • the calcination time is 10h
  • the layered positive electrode material is obtained by cooling, pulverizing and sieving.
  • the positive electrode material obtained above and the coating agent Al 2 O 3 are prepared according to the mass ratio of 100:0.2, mixed in a high-speed mixer, and the mixed material is calcined in an air atmosphere at a calcination temperature of 600 ° C and a calcination time of 5 hours.
  • the final layered cathode material is obtained.
  • This embodiment provides a method for preparing a layered positive electrode material, and the method includes the following steps:
  • the molar ratio of lithium salt LiOH, nickel source NiCO 3 , manganese source MnCO 3 , and dopants is 1.06:0.3: 0.7: 0.006: 0.004 ingredients, then add deionized water and mix evenly to form a suspension, add the suspension to a ceramic grinder, grind at a speed of 2500r/min for 1.5h to obtain a slurry, and grind the slurry at 180 It spray-dried at °C to obtain a powder.
  • the above powder is calcined in an air atmosphere, the calcination temperature is 860° C., the calcination time is 10h, and the layered positive electrode material is obtained by cooling, pulverizing and sieving.
  • the above-obtained positive electrode material and the coating agent WO 3 are prepared in a mass ratio of 100:0.15, mixed in a high-speed mixer, and the mixed material is calcined in an air atmosphere at a calcination temperature of 500°C and a calcination time of 6h, that is, The final layered cathode material can be obtained.
  • This embodiment provides a method for preparing a layered positive electrode material, and the method includes the following steps:
  • Lithium salt Li 2 CO 3 , nickel source NiO, manganese source Mn 3 O 4 , and dopant ZrO 2 are prepared according to the molar ratio of lithium, nickel, manganese and zirconium contained in 1.06:0.8:0.2:0.002, Then add deionized water in turn and mix evenly to form a suspension. Add the suspension to a ceramic grinder and grind at a speed of 2500r/min for 1.2h to obtain a slurry. The slurry is spray-dried at 180°C to obtain a powder . The above powder is calcined in an air atmosphere, the calcination temperature is 860° C., the calcination time is 10h, and the layered positive electrode material is obtained by cooling, pulverizing and sieving.
  • the positive electrode material obtained above and the coating agent ZrO 2 and Al 2 O 3 are mixed according to the mass ratio of 100: 0.17: 0.2, mixed under a high-speed mixer, and the mixed material is calcined in an air atmosphere, and the calcination temperature is 700 °C °C, the calcination time is 6h, the final layered cathode material can be obtained.
  • This embodiment provides a method for preparing a layered positive electrode material, and the method includes the following steps:
  • the molar ratio of lithium salt Li 2 CO 3 , nickel source NiO, manganese source MnCO 3 , and dopants (WO 3 and Y 2 O 3 ) is 1.07 according to the molar ratio of lithium, nickel, manganese, tungsten and yttrium contained: 0.9: 0.1: 0.003: 0.004 ingredients, then add deionized water and mix evenly to form a suspension, add the suspension to a ceramic grinder, grind at a speed of 2800r/min for 2 hours, and obtain a slurry, and the slurry is It spray-dried at 180 degreeC, and obtained the powder.
  • the above powder is calcined in an air atmosphere, the calcination temperature is 920° C., the calcination time is 10h, and the layered positive electrode material is obtained by cooling, pulverizing and sieving.
  • the above-obtained positive electrode material and the coating agent ZrO 2 are mixed according to the mass ratio of 100:0.17, mixed under a high-speed mixer, and the mixed material is calcined in an air atmosphere, the calcination temperature is 700 ° C, and the calcination time is 6h, that is, The final layered cathode material can be obtained.
  • This embodiment provides a method for preparing a layered positive electrode material, and the method includes the following steps:
  • Lithium salt Li 2 CO 3 , nickel source NiCO 3 , manganese source MnCO 3 , dopant BaCO 3 are prepared according to the molar ratio of lithium, nickel, manganese and barium contained in 1.05:0.5:0.5:0.003, and then Add deionized water in turn and mix evenly to form a suspension. Add the suspension to a ceramic grinder and grind at a speed of 2500r/min for 1.5h to obtain a slurry. The slurry is spray-dried at 180°C to obtain a powder.
  • the calcination temperature is 860° C.
  • the calcination time is 10h
  • the layered positive electrode material is obtained by cooling, pulverizing and sieving.
  • the above-obtained positive electrode material and the coating agent WO 3 are mixed according to the mass ratio of 100: 0.2, mixed in a high-speed mixer, and the mixed material is calcined in an air atmosphere, the calcination temperature is 400 ° C, and the calcination time is 6 h, and the final product can be obtained.
  • layered cathode material is
  • This embodiment provides a method for preparing a layered positive electrode material, and the method includes the following steps:
  • Lithium salt Li 2 CO 3 , nickel source NiO, manganese source MnO 2 , dopant ZrO 2 are prepared according to the molar ratio of lithium, nickel, manganese and zirconium contained in 1.05:0.25:0.75:0.003, and then sequentially Add deionized water and mix evenly to form a suspension. Add the suspension to a ceramic grinder and grind at 3000r/min for 1.5h to obtain a slurry. The slurry is spray-dried at 180°C to obtain a powder.
  • the calcination temperature is 950° C.
  • the calcination time is 10h
  • the layered positive electrode material is obtained by cooling, pulverizing and sieving.
  • the positive electrode material obtained above and the coating agent Al 2 O 3 are prepared according to the mass ratio of 100:0.2, mixed in a high-speed mixer, and the mixed material is calcined in an air atmosphere at a calcination temperature of 600 ° C and a calcination time of 5 hours.
  • the final layered cathode material is obtained.
  • This embodiment provides a method for preparing a layered positive electrode material, and the method includes the following steps:
  • Lithium salt Li 2 CO 3 , nickel source NiO, manganese source Mn 3 O 4 , and dopant BaO are prepared according to the molar ratio of lithium, nickel, manganese and barium contained in 1.06:0.8:0.2:0.002, and then Add deionized water in turn and mix evenly to form a suspension. Add the suspension to a ceramic grinder and grind at a speed of 2500r/min for 1.2 hours to obtain a slurry. The slurry is spray-dried at 180°C to obtain a powder. The above powder is calcined in an air atmosphere, the calcination temperature is 860° C., the calcination time is 10h, and the layered positive electrode material is obtained by cooling, pulverizing and sieving.
  • the positive electrode material obtained above and the coating agent ZrO 2 and Al 2 O 3 are mixed according to the mass ratio of 100: 0.17: 0.2, mixed under a high-speed mixer, and the mixed material is calcined in an air atmosphere, and the calcination temperature is 700 °C °C, the calcination time is 6h, the final layered cathode material can be obtained.
  • This embodiment provides a method for preparing a layered positive electrode material, and the method includes the following steps:
  • the molar ratio of lithium salt Li 2 CO 3 , nickel source NiO, manganese source Mn 3 O 4 , and dopant B 2 O 3 is 1.06:0.8:0.2:0.002 according to the molar ratio of lithium, nickel, manganese and boron contained
  • the slurry is spray-dried at 180°C. Get powder.
  • the above powder is calcined in an air atmosphere, the calcination temperature is 860° C., the calcination time is 10h, and the layered positive electrode material is obtained by cooling, pulverizing and sieving.
  • the positive electrode material obtained above and the coating agent ZrO 2 and Al 2 O 3 are mixed according to the mass ratio of 100: 0.17: 0.2, mixed under a high-speed mixer, and the mixed material is calcined in an air atmosphere, and the calcination temperature is 700 °C °C, the calcination time is 6h, the final layered cathode material can be obtained.
  • This embodiment provides a method for preparing a layered positive electrode material, and the method includes the following steps:
  • Lithium salt Li 2 CO 3 , nickel source NiO, manganese source Mn 3 O 4 , and dopant ZrO 2 are prepared according to the molar ratio of lithium, nickel, manganese and zirconium contained in 1.06:0.8:0.2:0.002, Then add deionized water in turn and mix evenly to form a suspension. Add the suspension to a ceramic grinder and grind at a speed of 2500r/min for 1.2h to obtain a slurry. The slurry is spray-dried at 180°C to obtain a powder . The above powder is calcined in an air atmosphere, the calcination temperature is 700° C., the calcination time is 10h, and the layered positive electrode material is obtained by cooling, pulverizing and sieving.
  • the positive electrode material obtained above and the coating agent ZrO 2 and Al 2 O 3 are mixed according to the mass ratio of 100: 0.17: 0.2, mixed under a high-speed mixer, and the mixed material is calcined in an air atmosphere, and the calcination temperature is 700 °C °C, the calcination time is 6h, the final layered cathode material can be obtained.
  • This embodiment provides a method for preparing a layered positive electrode material, and the method includes the following steps:
  • Lithium salt Li 2 CO 3 , nickel source NiO, manganese source Mn 3 O 4 , and dopant ZrO 2 are prepared according to the molar ratio of lithium, nickel, manganese and zirconium contained in 1.06:0.8:0.2:0.002, Then add deionized water in turn and mix evenly to form a suspension. Add the suspension to a ceramic grinder and grind at a speed of 2500r/min for 1.2h to obtain a slurry. The slurry is spray-dried at 180°C to obtain a powder . The above powder is calcined in an air atmosphere, the calcination temperature is 1100° C., the calcination time is 10h, and the layered positive electrode material is obtained by cooling, pulverizing and sieving.
  • the positive electrode material obtained above and the coating agent ZrO 2 and Al 2 O 3 are mixed according to the mass ratio of 100: 0.17: 0.2, mixed under a high-speed mixer, and the mixed material is calcined in an air atmosphere, and the calcination temperature is 700 °C °C, the calcination time is 6h, the final layered cathode material can be obtained.
  • This embodiment provides a method for preparing a layered positive electrode material, and the method includes the following steps:
  • Lithium salt Li 2 CO 3 , nickel source NiO, manganese source Mn 3 O 4 , dopant ZrO 2 are prepared according to the molar ratio of lithium, nickel, manganese and zirconium contained in 1.06:0.8:0.2:0.1, Then add deionized water and mix evenly to form a suspension. Add the suspension to a ceramic grinder and grind at a speed of 2500r/min for 1.2h to obtain a slurry. The slurry is spray-dried at 180°C to obtain powder . The above powder is calcined in an air atmosphere, the calcination temperature is 860° C., the calcination time is 10h, and the layered positive electrode material is obtained by cooling, pulverizing and sieving.
  • This comparative example provides a method for preparing a layered positive electrode material, the method comprising the following steps:
  • the nickel source NiCl 2 and the manganese source MnCl were prepared into a mixed aqueous solution with a molar ratio of nickel and manganese of 0.8:0.2 and a concentration of 80 g/L.
  • a sodium hydroxide aqueous solution with a concentration of 100 g/L and an ammonia solution with a concentration of 180 g/L were prepared respectively, and the two solutions were uniformly mixed in a volume ratio of 10:1 to prepare a precipitant.
  • the two kinds of solutions prepared above were added to the reactor with stirring through a constant flow pump, the flow rate of the mixed solution of nickel and manganese salts was controlled to be 300ml/h, and the pH value in the reactor was controlled to be 9.0 by adjusting the flow rate of the precipitant, and controlled
  • the reaction temperature was 60°C, and after the reaction time was 40 h, the obtained precipitate was repeatedly filtered and washed with pure water at 80°C.
  • the obtained precipitate was placed in an oven with a temperature set to 80° C. for drying treatment to obtain a positive electrode precursor.
  • This comparative example provides a method for preparing a layered positive electrode material, the method comprising the following steps:
  • the molar ratio of lithium salt Li 2 CO 3 , nickel source NiO, manganese source Mn 3 O 4 , and dopant Al 2 O 3 is 1.06:0.8:0.2:0.002 according to the molar ratio of lithium, nickel, manganese and aluminum contained
  • the slurry is spray-dried at 180°C. Get powder.
  • the above powder is calcined in an air atmosphere, the calcination temperature is 860° C., the calcination time is 10h, and the layered positive electrode material is obtained by cooling, pulverizing and sieving.
  • the positive electrode material obtained above and the coating agent ZrO 2 and Al 2 O 3 are mixed according to the mass ratio of 100: 0.17: 0.2, mixed under a high-speed mixer, and the mixed material is calcined in an air atmosphere, and the calcination temperature is 700 °C °C, the calcination time is 6h, the final layered cathode material can be obtained.
  • the positive electrode materials of each embodiment and comparative example were tested according to the same method.
  • the prepared layered positive electrode materials were added with carbon black (SP) and polyvinylidene fluoride (PVDF) in a mass ratio of 92:4:4. into N-methylpyrrolidone (NMP), mixed evenly, coated on aluminum foil, dried at 100°C for 4 hours, cut into positive plates with a diameter of 12mm, assembled into a button half-cell, left standing for 12 hours, and carried out electrochemical test, test The results are shown in Table 1.
  • Cycling Test This test is the retention rate for 50 weeks of cycling at 1C.
  • Fig. 1 and Fig. 2 show that the layered positive electrode material prepared by the present disclosure has better cycle performance and better stability than the layered positive electrode material prepared by the traditional co-precipitation method under the condition of equivalent capacity.
  • FIG. 3 show that the present disclosure indeed produces a layered positive electrode material, and the peak shape corresponds to that of the layered positive electrode material prepared by the traditional co-precipitation method.
  • zirconium doping has better capacity and retention rate of the cathode material obtained by doping zirconium.
  • Example 4 From the comparison between Example 4 and Examples 10-11, it can be seen that the first firing temperature has an important influence on the performance of the product, the crystal structure is more obvious in the preferred range of 800°C to 950°C, and the electrical properties are better.

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Abstract

提供一种层状无钴正极材料的制备方法，包括步骤：(1)将锂盐、镍源、锰源、掺杂剂与溶剂混合后，进行湿法球磨，得到混合浆料；(2)采用混合浆料进行喷雾干燥，得到前驱体；(3)对前驱体在含氧气氛中进行一次煅烧，得到层状无钴正极材料。还提供该制备方法得到的层状无钴正极材料以及包含层状无钴正极材料的锂离子电池。该制备方法采用特定种类的掺杂元素取代昂贵的钴元素，配合湿法球磨和喷雾干燥工艺，不仅可以实现体相掺杂，使材料在晶体形成时，c轴增大，层状更明显，减少锂镍混排，提高材料稳定性，获得优异的电化学性能。

Description

一种层状无钴正极材料、其制备方法和锂离子电池 技术领域
本公开涉及电池技术领域，涉及一种层状无钴正极材料、其制备方法和锂离子电池。
背景技术
全球能源问题日益严重，环境问题也日渐突出。开发新型高效的能源技术以及新的能源材料成为解决社会能源环境问题的重要方式。锂离子电池这一清洁高效的能源装置受到广泛的关注，锂离子电池由于具有能量密度高、循环性能好等优点被广泛应用于电子产品、汽车、航天等各个领域。随着人们对锂离子电池的环保、续航、寿命等要求越来越高，电池的设计和优化也越来越重要。而新能源汽车的发展对动力电池比能量的提升和成本的下降需求紧迫。
目前磷酸铁锂电池比能量已经趋于极限，高容量层状结构正极材料合成成本高。而传统的层状结构正极材料的合成工艺都要经过共沉淀合成前驱体，然后混锂煅烧得到目标产品，例如，按照下述方式共沉淀合成前驱体：先选用硫酸盐为原料，加入合适的沉淀剂，通过控制溶液的酸碱度、搅拌温度与速度、反应时间以及溶液浓度等得到沉淀物。该工艺的缺点是产生较多的工业废水，合成工艺步骤较多，成本较高，且在前驱体与锂盐混合掺杂时不均匀，很多元素并不能掺进晶格内部。通常，共沉淀阶段会有专业的公司生产前驱体，再将前驱体卖给正极材料厂，中间经过很多步骤、同时也增加了很多运输成本。且大部分正极材料厂家在合成层状正极材料时只能通过界面掺杂来稳定结构，缺点是循环过程中会衰减很快。
公开内容
本公开在一实施例中提供了一种层状无钴正极材料的制备方法，所述方法包括以下步骤：
(1)将锂盐、镍源、锰源、掺杂剂与溶剂混合后，进行湿法球磨，得到混合浆料；
(2)采用所述的混合浆料进行喷雾干燥，得到前驱体；
(3)对所述的前驱体在含氧气氛中进行一次煅烧，得到层状无钴正极材料，所述层状无钴正极材料的化学通式为Li aNi bMn cM dO 2，其中1.0≤a≤1.2，0≤b≤1.0，0≤c≤1.0，b+c＝1，0<d≤0.1；
其中，掺杂剂中的掺杂元素M选自Ta、Rb、Sr、Zr、Na、Cs、Y、W、B、Nb、Ba、Mo和P中的至少一种。
在本公开一实施例提供的方法制备得到的层状无钴正极材料中，a例如可以是1.0、1.05、1.1、1.05、1.1或1.2等，b例如可以是0、0.1、0.2、0.3、0.5、0.7、0.8或1.0等，c例如可以是0、0.2、0.3、0.4、0.5、0.6、0.8或1.0等，d例如可以是0.002、0.003、0.004、0.005、0.006、0.008、0.01、0.015、0.017、0.02、0.025、0.03、0.035、0.04、0.045、0.05、0.055、0.06、0.065、0.07、0.075、0.08、0.085、0.09或0.1等。
在一实施例中，d为0.002～0.01。
本公开中，镍源、锰源、锂盐和掺杂剂的用量应满足配方量，也即相应的元素锂、镍、锰和M的摩尔比满足a:b:c:d。
镍钴锰三元材料中，钴对于稳定结构发挥了非常重要的作用，但是，由于钴的价格昂贵限制了三元材料的发展和应用，无钴材料由于避免了钴的使用，大大降低了成本，有望取代三元材料，但是由于钴的缺失，其结构稳定性大幅 下降，影响了其电化学性能的发挥。本公开一实施例通过采用上述特定种类的掺杂元素尤其是选用较大离子半径的掺杂元素，取代昂贵的钴元素，配合湿法球磨和喷雾干燥工艺，不仅可以实现体相掺杂，还可以使材料在晶体形成时，c轴增大，层状更明显，减少锂镍混排，提高材料稳定性，从而获得优异的电化学性能。
本公开一实施例提供的方法直接将原材料混合，经煅烧制备层状正极材料，该工艺方法在国内外研究较少，该方法相比于传统的共沉淀法和溶胶-凝胶法具有如下优势：方法简单、过程产生废水较少、成本较低，且能够在省略钴的前提下实现元素的体相掺杂，掺杂元素均匀地进入晶格内部，提高材料稳定性。
在一实施例中，所述掺杂元素M为Zr、Sr、Ta、W和Y中的至少一种。
在一实施例中在一实施例中，所述掺杂元素M为Zr，或者Zr和Sr的组合，或者Zr和Ta的组合，或者W和Y的组合。
掺杂元素的种类不同，造成晶体结构中晶体参数不同，层状材料主要表现c轴不同，导致电性能有所差异。
在一实施例中，所述掺杂剂为M的氧化物和/或M的盐类。
在一实施例中，所述掺杂剂为M的氧化物。
在一实施例中，步骤(1)所述镍源选自镍盐或镍的氧化物中的至少一种。
在一实施例中，步骤(1)所述镍源为NiO。
在一实施例中，步骤(1)所述锰源选自锰盐或锰的氧化物中的至少一种。
在一实施例中，步骤(1)所述锰源为Mn 3O 4。
在一实施例中，步骤(1)所述锂盐包括Li 2CO 3和/或LiOH。
在一实施例中，镍源、锰源和锂盐选自NiO、Mn 3O 4、Li 2CO 3和LiOH，这 些产品为市场大宗商品，性能稳定，容易加工。
在一实施例中，步骤(1)湿法球磨的转速为2000r/min～3000r/min，例如2000r/min、2200r/min、2300r/min、2400r/min、2500r/min、2600r/min、2800r/min或3000r/min等；时间为1h～2h，例如1h、1.2h、1.3h、1.5h、1.7h、1.8h或2h等。
在一实施例中，步骤(3)所述含氧气氛中氧气的体积分数大于20％，例如21％、25％、30％、50％、60％、70％、80％、90％或100％。
在一实施例中，步骤(3)所述一次煅烧的温度为700℃～1100℃，例如700℃、750℃、800℃、825℃、850℃、880℃、900℃、950℃、1000℃、1050℃或1100℃等。
在一实施例中，步骤(3)所述一次煅烧的温度为800℃～950℃。
在一实施例中，步骤(3)所述一次煅烧的时间为6h～20h，例如6h、8h、9h、10h、12h、15h、17h、18h或20h等。
在一实施例中，步骤(3)所述一次煅烧的时间为8h～15h。
一次煅烧的温度和时间会影响正极材料层状结构的形成并对结晶性有一定影响，在上述范围内，层状结构容易形成且结晶性高。
在一实施例中，所述方法还包括在步骤(3)之后，对层状无钴正极材料进行包覆处理。
在一实施例中，所述包覆处理包括：将层状无钴正极材料与包覆剂混合，在含氧气氛下二次煅烧，得到包覆后的层状无钴正极材料。
在一实施例中，所述包覆剂包括Al 2O 3、ZrO 2和WO 3中的至少一种。
在一实施例中，所述层状无钴正极材料与所述包覆剂的质量比为 100:(0.12～0.4)，例如100:0.12、100:0.15、100:0.18、100:0.2、100:0.22、100:0.26、100:0.28、100:0.3、100:0.33、100:0.35、100:0.37或100:0.4等。
在一实施例中，所述二次煅烧的温度为300℃～900℃，例如300℃、350℃、400℃、500℃、550℃、600℃、650℃、700℃、750℃或800℃等。
在一实施例中，所述二次煅烧的温度为500℃～800℃。
在一实施例中，所述二次煅烧的时间为3h～10h，例如3h、4h、5h、6h、7h、8h、9h或10h等。
在一实施例中，所述二次煅烧的时间为4h～7h。
通过对层状无钴正极材料进行包覆并二次煅烧，可以增强材料的导电性并修复正极材料表面，防止正极材料表面和电解液发生强的副反应。通过优化二次煅烧的温度和时间，可获得更佳的包覆效果。
在一实施例中，所述层状无钴正极材料在包覆处理前进行粉碎和过筛的步骤。
在一实施例中，所述方法包括以下步骤：
S1：将锂盐、镍源、锰源和掺杂剂MO x(x为满足MOx元素化合价平衡的氧含量)按照元素锂、镍、锰、M的摩尔比为a:b:c:d配料，然后依次加入去离子水中混合均匀，形成悬浊液，将悬浊液加入到陶瓷研磨机中，以转速2000r/min研磨1h，得到浆料；
S2：将所述浆料进行喷雾干燥，得到粉末，将所述粉末在空气气氛下煅烧，煅烧温度800℃～950℃，煅烧时间8h～15h，冷却、粉碎并过筛得到层状正极材料Li aNi bMn cM dO 2，其中1.0≤a≤1.2，0≤b≤1.0，0≤c≤1.0，b+c＝1，0<d≤0.1；
S3：将所述的层状正极材料Li aNi bMn cM dO 2与包覆剂按照质量比为 100:(0.15～0.4)配料，在高速混合机下混合，将得到的混合物料在空气气氛下煅烧，煅烧温度500℃～800℃，煅烧时间4h～7h，得到包覆后的层状无钴正极材料，该正极材料也是一种层状正极材料；
其中，所述掺杂剂选自Zr、Sr、Ta、W和Y的氧化物中的至少一种；
所述包覆剂选自Al 2O 3、ZrO 2和WO 3中的至少一种。
在本公开一实施例提供的方法中，通过采用上述特定种类的掺杂元素尤其是选用较大离子半径的掺杂元素(例如Zr、Sr、Ta、W和Y)，取代昂贵的钴元素，配合湿法球磨和喷雾干燥工艺，不仅可以实现体相掺杂，还可以使材料在晶体形成时，c轴增大，层状更明显，减少锂镍混排，提高材料稳定性，从而获得优异的电化学性能。
本公开一实施例提供的方法直接将原材料混合，经煅烧制备层状正极材料，该方法相比于传统的共沉淀法和溶胶-凝胶法具有如下优势：方法简单、过程产生废水较少、成本较低，且能够在省略钴的前提下实现元素的体相掺杂，掺杂元素均匀地进入晶格内部，提高材料稳定性。
本公开在一实施例中提供一种采用上述的方法制备得到的层状无钴正极材料。
本公开在一实施例中提供一种锂离子电池，所述锂离子电池包括上述的层状无钴正极材料。
附图说明
附图用来提供对本公开技术方案的进一步理解，并且构成说明书的一部分，与本申请的实施例一起用于解释本公开的技术方案，并不构成对本公开技术方案的限制。
图1是本公开实施例4所得层状正极材料与对比例1所得层状正极材料的 比容量对比图。
图2是本公开实施例4所得层状正极材料与对比例1所得层状正极材料的循环对比图。
图3是本公开实施例4所得层状正极材料与对比例1所得层状正极材料的XRD对比图。
具体实施例
下面通过具体实施方式来进一步说明本公开的技术方案。本领域技术人员应该明了，所述实施例仅仅是帮助理解本公开，不应视为对本公开的具体限制。
实施例1
本实施例提供一种层状正极材料的制备方法，所述方法包括以下步骤：
(1)将锂盐Li 2CO 3、镍源NiO、锰源Mn 3O 4、掺杂剂ZrO 2按照所含锂、镍、锰、锆的摩尔比为1.05：0.6：0.4：0.003配料，然后依次加入去离子水中混合均匀，形成悬浊液，将悬浊液加入到陶瓷研磨机中，以转速2000r/min研磨1h，得到浆料，将浆料以180℃进行喷雾干燥，得到粉末。
(2)将上述粉末在空气气氛下煅烧，煅烧温度900℃，煅烧时间12h，冷却、粉碎、过筛得到层状正极材料。将上述得到的正极材料与包覆剂WO 3按照质量比为100：0.13配料，在高速混合机下混合，将混合物料在空气气氛下煅烧，煅烧温度500℃，煅烧时间5h，即可得到最终的层状正极材料。
实施例2
本实施例提供一种层状正极材料的制备方法，所述方法包括以下步骤：(1)将锂盐Li 2CO 3、镍源NiO、锰源Mn 3O 4、掺杂剂ZrO 2按照所含锂、镍、锰、锆的摩尔比为1.05：0.75：0.25：0.004配料，然后依次加入去离子水中混合均匀，形成悬浊液，将悬浊液加入到陶瓷研磨机中，以转速2000r/min研磨1h，得到浆 料，将浆料以180℃进行喷雾干燥，得到粉末。
(2)将上述粉末在空气气氛下煅烧，煅烧温度880℃，煅烧时间10h，冷却、粉碎、过筛得到层状正极材料。将上述得到的正极材料与包覆剂Al 2O 3按照质量比为100：0.2配料，在高速混合机下混合，将混合物料在空气气氛下煅烧，煅烧温度600℃，煅烧时间5h，即可得到最终的层状正极材料。
实施例3
本实施例提供一种层状正极材料的制备方法，所述方法包括以下步骤：
(1)将锂盐LiOH、镍源NiCO 3、锰源MnCO 3、掺杂剂(Ta 2O 5和ZrO 2)按照所含锂、镍、锰、钽、锆的摩尔比为1.06：0.3：0.7：0.006：0.004配料，然后依次加入去离子水中混合均匀，形成悬浊液，将悬浊液加入到陶瓷研磨机中，以转速2500r/min研磨1.5h，得到浆料，将浆料以180℃进行喷雾干燥，得到粉末。将上述粉末在空气气氛下煅烧，煅烧温度860℃，煅烧时间10h，冷却、粉碎、过筛得到层状正极材料。
(2)将上述得到的正极材料与包覆剂WO 3按照质量比为100：0.15配料，在高速混合机下混合，将混合物料在空气气氛下煅烧，煅烧温度500℃，煅烧时间6h，即可得到最终的层状正极材料。
实施例4
本实施例提供一种层状正极材料的制备方法，所述方法包括以下步骤：
(1)将锂盐Li 2CO 3、镍源NiO、锰源Mn 3O 4、掺杂剂ZrO 2按照所含锂、镍、锰、锆的摩尔比为1.06：0.8：0.2：0.002配料，然后依次加入去离子水中混合均匀，形成悬浊液，将悬浊液加入到陶瓷研磨机中，以转速2500r/min研磨1.2h，得到浆料，将浆料以180℃进行喷雾干燥，得到粉末。将上述粉末在空气 气氛下煅烧，煅烧温度860℃，煅烧时间10h，冷却、粉碎、过筛得到层状正极材料。
(2)将上述得到的正极材料与包覆剂ZrO 2和Al 2O 3按照质量比为100：0.17：0.2配料，在高速混合机下混合，将混合物料在空气气氛下煅烧，煅烧温度700℃，煅烧时间6h，即可得到最终的层状正极材料。
实施例5
本实施例提供一种层状正极材料的制备方法，所述方法包括以下步骤：
(1)将锂盐Li 2CO 3、镍源NiO、锰源MnCO 3、掺杂剂(WO 3和Y 2O 3)按照所含锂、镍、锰、钨、钇的摩尔比为1.07：0.9：0.1：0.003：0.004配料，然后依次加入去离子水中混合均匀，形成悬浊液，将悬浊液加入到陶瓷研磨机中，以转速2800r/min研磨2h，得到浆料，将浆料以180℃进行喷雾干燥，得到粉末。将上述粉末在空气气氛下煅烧，煅烧温度920℃，煅烧时间10h，冷却、粉碎、过筛得到层状正极材料。
(2)将上述得到的正极材料与包覆剂ZrO 2按照质量比为100：0.17配料，在高速混合机下混合，将混合物料在空气气氛下煅烧，煅烧温度700℃，煅烧时间6h，即可得到最终的层状正极材料。
实施例6
本实施例提供一种层状正极材料的制备方法，所述方法包括以下步骤：
(1)将锂盐Li 2CO 3、镍源NiCO 3、锰源MnCO 3、掺杂剂BaCO 3按照所含锂、镍、锰、钡的摩尔比为1.05：0.5：0.5：0.003配料，然后依次加入去离子水中混合均匀，形成悬浊液，将悬浊液加入到陶瓷研磨机中，以转速2500r/min研磨1.5h，得到浆料，将浆料以180℃进行喷雾干燥，得到粉末。
(2)将上述粉末在空气气氛下煅烧，煅烧温度860℃，煅烧时间10h，冷却、粉碎、过筛得到层状正极材料。将上述得到的正极材料与包覆剂WO 3按照质量比为100：0.2配料，在高速混合机下混合，将混合物料在空气气氛下煅烧，煅烧温度400℃，煅烧时间6h，即可得到最终的层状正极材料。
实施例7
本实施例提供一种层状正极材料的制备方法，所述方法包括以下步骤：
(1)将锂盐Li 2CO 3、镍源NiO、锰源MnO 2、掺杂剂ZrO 2按照所含锂、镍、锰、锆的摩尔比为1.05：0.25：0.75：0.003配料，然后依次加入去离子水中混合均匀，形成悬浊液，将悬浊液加入到陶瓷研磨机中，以转速3000r/min研磨1.5h，得到浆料，将浆料以180℃进行喷雾干燥，得到粉末。
(2)将上述粉末在空气气氛下煅烧，煅烧温度950℃，煅烧时间10h，冷却、粉碎、过筛得到层状正极材料。将上述得到的正极材料与包覆剂Al 2O 3按照质量比为100：0.2配料，在高速混合机下混合，将混合物料在空气气氛下煅烧，煅烧温度600℃，煅烧时间5h，即可得到最终的层状正极材料。
实施例8
本实施例提供一种层状正极材料的制备方法，所述方法包括以下步骤：
(1)将锂盐Li 2CO 3、镍源NiO、锰源Mn 3O 4、掺杂剂BaO按照所含锂、镍、锰、钡的摩尔比为1.06：0.8：0.2：0.002配料，然后依次加入去离子水中混合均匀，形成悬浊液，将悬浊液加入到陶瓷研磨机中，以转速2500r/min研磨1.2h，得到浆料，将浆料以180℃进行喷雾干燥，得到粉末。将上述粉末在空气气氛下煅烧，煅烧温度860℃，煅烧时间10h，冷却、粉碎、过筛得到层状正极材料。
(2)将上述得到的正极材料与包覆剂ZrO 2和Al 2O 3按照质量比为100：0.17：0.2配料，在高速混合机下混合，将混合物料在空气气氛下煅烧，煅烧温度700℃，煅烧时间6h，即可得到最终的层状正极材料。
实施例9
本实施例提供一种层状正极材料的制备方法，所述方法包括以下步骤：
(1)将锂盐Li 2CO 3、镍源NiO、锰源Mn 3O 4、掺杂剂B 2O 3按照所含锂、镍、锰、硼的摩尔比为1.06：0.8：0.2：0.002配料，然后依次加入去离子水中混合均匀，形成悬浊液，将悬浊液加入到陶瓷研磨机中，以转速2500r/min研磨1.2h，得到浆料，将浆料以180℃进行喷雾干燥，得到粉末。将上述粉末在空气气氛下煅烧，煅烧温度860℃，煅烧时间10h，冷却、粉碎、过筛得到层状正极材料。
(2)将上述得到的正极材料与包覆剂ZrO 2和Al 2O 3按照质量比为100：0.17：0.2配料，在高速混合机下混合，将混合物料在空气气氛下煅烧，煅烧温度700℃，煅烧时间6h，即可得到最终的层状正极材料。
实施例10
本实施例提供一种层状正极材料的制备方法，所述方法包括以下步骤：
(1)将锂盐Li 2CO 3、镍源NiO、锰源Mn 3O 4、掺杂剂ZrO 2按照所含锂、镍、锰、锆的摩尔比为1.06：0.8：0.2：0.002配料，然后依次加入去离子水中混合均匀，形成悬浊液，将悬浊液加入到陶瓷研磨机中，以转速2500r/min研磨1.2h，得到浆料，将浆料以180℃进行喷雾干燥，得到粉末。将上述粉末在空气气氛下煅烧，煅烧温度700℃，煅烧时间10h，冷却、粉碎、过筛得到层状正极材料。
(2)将上述得到的正极材料与包覆剂ZrO 2和Al 2O 3按照质量比为100：0.17：0.2配料，在高速混合机下混合，将混合物料在空气气氛下煅烧，煅烧温度700℃，煅烧时间6h，即可得到最终的层状正极材料。
实施例11
本实施例提供一种层状正极材料的制备方法，所述方法包括以下步骤：
(1)将锂盐Li 2CO 3、镍源NiO、锰源Mn 3O 4、掺杂剂ZrO 2按照所含锂、镍、锰、锆的摩尔比为1.06：0.8：0.2：0.002配料，然后依次加入去离子水中混合均匀，形成悬浊液，将悬浊液加入到陶瓷研磨机中，以转速2500r/min研磨1.2h，得到浆料，将浆料以180℃进行喷雾干燥，得到粉末。将上述粉末在空气气氛下煅烧，煅烧温度1100℃，煅烧时间10h，冷却、粉碎、过筛得到层状正极材料。
(2)将上述得到的正极材料与包覆剂ZrO 2和Al 2O 3按照质量比为100：0.17：0.2配料，在高速混合机下混合，将混合物料在空气气氛下煅烧，煅烧温度700℃，煅烧时间6h，即可得到最终的层状正极材料。
实施例12
本实施例提供一种层状正极材料的制备方法，所述方法包括以下步骤：
(1)将锂盐Li 2CO 3、镍源NiO、锰源Mn 3O 4、掺杂剂ZrO 2按照所含锂、镍、锰、锆的摩尔比为1.06：0.8：0.2：0.1配料，然后依次加入去离子水中混合均匀，形成悬浊液，将悬浊液加入到陶瓷研磨机中，以转速2500r/min研磨1.2h，得到浆料，将浆料以180℃进行喷雾干燥，得到粉末。将上述粉末在空气气氛下煅烧，煅烧温度860℃，煅烧时间10h，冷却、粉碎、过筛得到层状正极材料。
(2)将上述得到的正极材料与包覆剂ZrO 2和Al 2O 3按照质量比为100：0.17： 0.2配料，在高速混合机下混合，将混合物料在空气气氛下煅烧，煅烧温度700℃，煅烧时间6h，即可得到最终的层状正极材料。
对比例1
本对比例提供一种层状正极材料的制备方法，所述方法包括以下步骤：
(1)将镍源NiCl 2、锰源MnCl，配置成镍、锰的摩尔比为0.8：0.2、浓度为80g/L的混合水溶液。分别配制浓度为100g/L的氢氧化钠水溶液，浓度为180g/L的氨水溶液，将两种溶液按体积比10∶1均匀混合，配制成沉淀剂。将上述配制的两种溶液通过恒流泵加入带有搅拌的反应釜中，控制镍、锰盐混合溶液流量为300ml/h，通过调解沉淀剂的流量控制反应釜中的pH值为9.0，控制反应温度为60℃，反应时间40h后，用80℃的纯水反复过滤洗涤所得沉淀物。所得的沉淀物放在温度设定为80℃的烘箱进行干燥处理，得到正极前驱体。
(2)将正极材料前驱体与锂源LiOH、掺杂剂ZrO 2混合(混合后满足锂、镍、锰、锆的摩尔比为1.06：0.8：0.2：0.002)，得到混合后产物；将混合后产物在860℃下煅烧10h，并将煅烧后产物进行破碎和过筛；将一烧产物与包覆剂ZrO 2、Al 2O 3按照质量比100：0.17：0.2混合后在700℃下热处理6h，自然冷却、过筛得到层状正极材料。
对比例2
本对比例提供一种层状正极材料的制备方法，所述方法包括以下步骤：
(1)将锂盐Li 2CO 3、镍源NiO、锰源Mn 3O 4、掺杂剂Al 2O 3按照所含锂、镍、锰、铝的摩尔比为1.06：0.8：0.2：0.002配料，然后依次加入去离子水中混合均匀，形成悬浊液，将悬浊液加入到陶瓷研磨机中，以转速2500r/min研磨1.2h，得到浆料，将浆料以180℃进行喷雾干燥，得到粉末。将上述粉末在空气 气氛下煅烧，煅烧温度860℃，煅烧时间10h，冷却、粉碎、过筛得到层状正极材料。
(2)将上述得到的正极材料与包覆剂ZrO 2和Al 2O 3按照质量比为100：0.17：0.2配料，在高速混合机下混合，将混合物料在空气气氛下煅烧，煅烧温度700℃，煅烧时间6h，即可得到最终的层状正极材料。
测试：
将各个实施例和对比例的正极材料按照相同的方法进行测试，首先将制备的层状正极材料分别与炭黑(SP)、聚偏氟乙烯(PVDF)按92：4：4的质量比加入到N-甲基吡咯烷酮(NMP)中，混合均匀后涂在铝箔上，以100℃干燥4h，裁成直径为12mm的正极片，组装成纽扣半电池，静置12h，进行电化学测试，测试结果见表1。
容量测试：该测试为0.1C下的首次放电容量。
循环测试：该测试为1C下循环50周的保持率。
实施例4和对比例1所得的锂离子电池层状正极材料的容量、循环和XRD对比图分别见图1、图2和图3。
图1、图2结果表明本公开制备的层状正极材料与传统共沉淀法制备的层状正极材料相比，在容量相当的情况下，循环性能更加优异，稳定性好。图3结果表明，本公开确实制备出层状正极材料，峰型与传统共沉淀方法制备的层状正极材料的峰形对应。
表1
Figure PCTCN2022082155-appb-000001
Figure PCTCN2022082155-appb-000002
本公开通过采用特定种类的元素进行体相掺杂，可以在省略钴的前提下获得良好的结构稳定性，在不损失容量的前提下获得了优异的循环性能。
通过实施例4与实施例8-9的对比可知，锆掺杂与钡和硼掺杂相比，掺杂锆所得正极材料的容量和保持率都更加优异。
通过实施例4与实施例10-11的对比可知，一烧温度对产品性能有重要影响，晶体结构在800℃～950℃的优选范围内层状更加明显，电性能更优。
通过实施例4与实施例12的对比可知，锆掺杂量太多，对容量的发挥会起到抑制作用。
通过实施例4与对比例2的对比可知，锆掺杂比铝掺杂在容量发挥上更有优势。

Claims (13)

  1. 一种层状无钴正极材料的制备方法，所述方法包括以下步骤：
    (1)将锂盐、镍源、锰源、掺杂剂与溶剂混合后，进行湿法球磨，得到混合浆料；
    (2)采用所述的混合浆料进行喷雾干燥，得到前驱体；
    (3)对所述的前驱体在含氧气氛中进行一次煅烧，得到层状无钴正极材料，所述层状无钴正极材料的化学通式为Li aNi bMn cM dO 2，其中1.0≤a≤1.2，0≤b≤1.0，0≤c≤1.0，b+c＝1，0<d≤0.1；
    其中，掺杂剂中的掺杂元素M选自Ta、Rb、Sr、Zr、Na、Cs、Y、W、B、Nb、Ba、Mo和P中的至少一种。
  2. 根据权利要求1所述的方法，其中，所述掺杂元素M为Zr、Sr、Ta、W和Y中的至少一种。
  3. 根据权利要求2所述的方法，其中，所述掺杂元素M为Zr，或者Zr和Sr的组合，或者Zr和Ta的组合，或者W和Y的组合。
  4. 根据权利要求1-3任一项所述的方法，其中，所述掺杂剂为M的氧化物和/或M的盐类；
    步骤(1)所述镍源选自镍盐或镍的氧化物中的至少一种；
    步骤(1)所述锰源选自锰盐或锰的氧化物中的至少一种；
    步骤(1)所述锂盐包括Li 2CO 3和/或LiOH。
  5. 根据权利要求1-4任一项所述的方法，其中，步骤(1)湿法球磨的转速为2000r/min～3000r/min，时间为1h～2h。
  6. 根据权利要求1-5任一项所述的方法，其中，步骤(3)所述含氧气氛中氧气的体积分数大于20％；
    步骤(3)所述一次煅烧的温度为700℃～1100℃，
    步骤(3)所述一次煅烧的时间为6h～20h。
  7. 根据权利要求1-6任一项所述的方法，其中，所述方法还包括在步骤(3)之后，对层状无钴正极材料进行包覆处理；
    所述包覆处理包括：将层状无钴正极材料与包覆剂混合，在含氧气氛下二次煅烧，得到包覆后的层状无钴正极材料；所述包覆剂包括Al 2O 3、ZrO 2和WO 3中的至少一种。
  8. 根据权利要求1-7任一项所述的方法，其中，所述层状无钴正极材料与所述包覆剂的质量比为100:(0.12～0.4)。
  9. 根据权利要求1-8任一项所述的方法，其中，所述二次煅烧的温度为300℃～900℃，所述二次煅烧的时间为3h～10h。
  10. 根据权利要求7-9任一项所述的方法，其中，所述层状无钴正极材料在包覆处理前进行粉碎和过筛的步骤。
  11. 根据权利要求1-10任一项所述的方法，其中，所述方法包括以下步骤：
    S1：将锂盐、镍源、锰源和掺杂剂MO x按照元素锂、镍、锰、M的摩尔比为a:b:c:d配料，然后依次加入去离子水中混合均匀，形成悬浊液，将悬浊液加入到陶瓷研磨机中，以转速2000r/min研磨1h，得到浆料；
    S2：将所述浆料进行喷雾干燥，得到粉末，将所述粉末在空气气氛下煅烧，煅烧温度800℃～950℃，煅烧时间8h～15h，冷却、粉碎并过筛得到层状正极材料Li aNi bMn cM dO 2，其中1.0≤a≤1.2，0≤b≤1.0，0≤c≤1.0，b+c＝1，0<d≤0.1；
    S3：将所述的层状正极材料Li aNi bMn cM dO 2与包覆剂按照质量比为100:(0.15～0.4)配料，在高速混合机下混合，将得到的混合物料在空气气氛下煅 烧，煅烧温度500℃～800℃，煅烧时间4h～7h，得到包覆后的层状无钴正极材料；
    其中，所述掺杂剂选自Zr、Sr、Ta、W和Y的氧化物中的至少一种；
    所述包覆剂选自Al 2O 3、ZrO 2和WO 3中的至少一种。
  12. 一种采用权利要求1-11任一项所述的方法制备得到的层状无钴正极材料。
  13. 一种锂离子电池，所述锂离子电池包括权利要求12所述的层状无钴正极材料。
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