WO2021258662A1 - 一种正极材料、其制备方法和锂离子电池 - Google Patents

一种正极材料、其制备方法和锂离子电池 Download PDF

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Publication number
WO2021258662A1
WO2021258662A1 PCT/CN2020/135523 CN2020135523W WO2021258662A1 WO 2021258662 A1 WO2021258662 A1 WO 2021258662A1 CN 2020135523 W CN2020135523 W CN 2020135523W WO 2021258662 A1 WO2021258662 A1 WO 2021258662A1
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positive electrode
cobalt
active material
single crystal
free single
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English (en)
French (fr)
Inventor
乔齐齐
江卫军
孙明珠
许鑫培
施泽涛
马加力
王鹏飞
陈思贤
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Svolt Energy Technology Co Ltd
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Svolt Energy Technology Co Ltd
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Priority to EP20942284.9A priority Critical patent/EP4024519A4/en
Priority to JP2022521737A priority patent/JP7324946B2/ja
Priority to KR1020227024891A priority patent/KR102834066B1/ko
Priority to US17/787,923 priority patent/US20230335713A1/en
Publication of WO2021258662A1 publication Critical patent/WO2021258662A1/zh
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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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    • H01M4/485—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of mixed oxides or hydroxides for inserting or intercalating light metals, e.g. LiTi2O4 or LiTi2OxFy
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    • H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
    • H01M4/50—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of manganese
    • 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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    • H01M4/525—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron of mixed oxides or hydroxides containing iron, cobalt or nickel for inserting or intercalating light metals, e.g. LiNiO2, LiCoO2 or LiCoOxFy
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    • H01M4/58—Selection of substances as active materials, active masses, active liquids of inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy; of polyanionic structures, e.g. phosphates, silicates or borates
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Definitions

  • the present disclosure relates to the field of battery technology, for example, to a positive electrode material, a preparation method thereof, and a lithium ion battery.
  • the new energy vehicle field has more stringent requirements for lithium-ion power batteries, such as safety performance, cycle performance, and cost.
  • the cost of the cathode material accounts for 30-40% of the total cost of the power battery. If the cost of the power battery is reduced, the cost of the cathode material needs to be reduced.
  • the lithium ion conductivity of pure cobalt-free single crystal materials is poor.
  • the ion conductivity restricts the insertion and migration speed of lithium ions during the charging and discharging process of the battery, which is not conducive to the development of the material capacity, and affects the rate performance of the material.
  • the internal resistance of the battery is increased, and the battery is prone to heat generation, which poses a great safety hazard in use.
  • CN109686970A discloses a cobalt-free lithium-rich ternary cathode material NMA and a preparation method thereof.
  • the chemical formula of the cobalt-free lithium-rich ternary cathode material NMA is Li 1+P Ni 1-xyz Mn x Al y M z O 2 , and its precursor chemical formula is Ni 1-xyz Mn x Al y M z (OH) 2 , Where 0.03 ⁇ P ⁇ 0.3, 0.1 ⁇ X ⁇ 0.6, 0.01 ⁇ Y ⁇ 0.1, 0.01 ⁇ Z ⁇ 0.3, M is one or more of Ce 3+ , Ti 4+ , Zr 4+ , Mg 2+
  • the precursor is a nano-flaky agglomerated particle, and the thickness of the nano-flaky precursor is 30-50 nanometers.
  • the electrochemical performance of the cathode material obtained by the method is poor.
  • CN103943844B discloses a cobalt-free lithium-rich manganese-based positive electrode material and a preparation method and application thereof.
  • the chemical formula of the positive electrode material is Li 1+x Ni y Mn 0.8-y O 2 (0 ⁇ x ⁇ 1/3, 0 ⁇ y ⁇ 0.8).
  • the preparation process of the positive electrode material the precursor is prepared in ethanol or deionized water solvent by the sol-gel method, after low-temperature pre-sintering, ball milling, and then high-temperature solid-phase sintering to obtain the prepared positive electrode material.
  • the electrochemical performance of the cathode material obtained by the method is poor.
  • the present disclosure provides a cathode material, a preparation method thereof, and a lithium ion battery.
  • An embodiment of the present disclosure provides a positive electrode material.
  • the positive electrode material has a core-shell structure, the core layer includes a cobalt-free single crystal positive electrode active material, and the shell layer includes LiAlO 2 and LiFePO 4 .
  • the positive electrode material is coated with LiAlO 2 and LiFePO 4 on the surface of the cobalt-free single crystal positive electrode active material to improve the conductivity of the cobalt-free single crystal layered positive electrode material, thereby increasing the capacity, rate, and capacity of the material. Cycle performance.
  • the shell layer must contain both LiAlO 2 and LiFePO 4 to achieve excellent electrochemical performance. There is only LiAlO 2 in the shell layer, and the material stability cannot be significantly improved; the shell layer only contains LiFePO 4 and the cycle performance of the material cannot be significantly improved.
  • the content of the cobalt-free single crystal positive active material is 98.5 to 99.9% by weight, for example, 98.6% by weight, 98.8% by weight, 99.0% by weight, 99.2% by weight, 99.4% by weight, 99.5% by weight or 99.8. wt% etc.
  • the content of the LiAlO 2 is 0.05 to 0.5 wt%, for example, 0.1 wt%, 0.15 wt%, 0.2 wt%, 0.25 wt%, 0.3 wt%, 0.35 wt%, 0.4 wt%, 0.45 wt % Or 0.48wt% etc.
  • the content of LiAlO 2 in the positive electrode material is 0.05 to 0.5 wt%. If the content of LiAlO 2 is too much, the capacity of the obtained positive electrode material is low; the content of LiAlO 2 is too small, and the shell coating is not Evenly.
  • the content of LiFePO 4 is 0.05 to 1 wt%, such as 0.08 wt%, 0.1 wt%, 0.15 wt%, 0.2 wt%, 0.25 wt%, 0.3 wt%, 0.35 wt%, 0.4 wt% , 0.45wt%, 0.5wt%, 0.55wt%, 0.6wt%, 0.65wt%, 0.7wt%, 0.75wt%, 0.8wt%, 0.85wt%, 0.9wt% or 0.95wt%, etc.
  • the content of the cathode material LiFePO 4 was 0.05 ⁇ 1wt%, the content of LiFePO 4 is excessive, resulting in reduced capacity of the cathode material; LiFePO 4 content is too small, can not be uniformly coated, the positive electrode material remained Some parts are in direct contact with the electrolyte, which affects the electrochemical performance.
  • the cobalt-free single crystal positive active material is LiNi x Mn y O 2 , 0.45 ⁇ x ⁇ 0.95, such as 0.5, 0.55, 0.6, 0.65, 0.68, 0.7, 0.75, 0.8, 0.85, 0.88 or 0.9 etc.; 0.05 ⁇ y ⁇ 0.55, such as 0.1, 0.12, 0.15, 0.18, 0.2, 0.25, 0.3, 0.35, 0.38, 0.4, 0.45, 0.48 or 0.5, etc.
  • a method for preparing a cathode material includes the following steps:
  • the cobalt-free single crystal positive electrode active material, lithium salt, aluminum-containing material, and FePO 4 are mixed and calcined to obtain a positive electrode material.
  • the method for preparing the cobalt-free single crystal positive electrode active material includes: mixing a lithium salt and a cobalt-free positive electrode active material precursor, and sintering to obtain a cobalt-free single crystal positive electrode active material.
  • the chemical formula of the cobalt-free positive active material precursor is Ni x Mn y (OH) 2 , 0.45 ⁇ x ⁇ 0.95, such as 0.5, 0.55, 0.6, 0.65, 0.68, 0.7, 0.75, 0.8, 0.85, 0.88 or 0.9, etc.; 0.05 ⁇ y ⁇ 0.55, such as 0.1, 0.12, 0.15, 0.18, 0.2, 0.25, 0.3, 0.35, 0.38, 0.4, 0.45, 0.48 or 0.5, etc.
  • the lithium salt includes LiOH and/or Li 2 CO 3 .
  • the sintering temperature is 800-1000°C, such as 820°C, 850°C, 880°C, 900°C, 920°C, 950°C, or 980°C.
  • the sintering temperature is 800-1000° C., the sintering temperature is too low, and the material crystal structure is incomplete; the sintering temperature is too high, and the material particle size is too large, resulting in a decrease in capacity.
  • the sintering time is 10-20h, such as 11h, 12h, 13h, 14h, 15h, 16h, 17h, 18h, 19h, etc.
  • the sintering atmosphere is air atmosphere or O 2 atmosphere.
  • after the sintering it further includes crushing the obtained product.
  • the crushed material is passed through a 300-400 mesh sieve, such as 300 mesh, 310 mesh, 320 mesh, 330 mesh, 340 mesh, 350 mesh, 360 mesh, 370 mesh, 380 mesh, 390 mesh or 400 mesh. Wait.
  • a 300-400 mesh sieve such as 300 mesh, 310 mesh, 320 mesh, 330 mesh, 340 mesh, 350 mesh, 360 mesh, 370 mesh, 380 mesh, 390 mesh or 400 mesh. Wait.
  • the residual alkali content of the cobalt-free single crystal positive active material is ⁇ 0.5wt%, for example, 0.05wt%, 0.08wt%, 0.1wt%, 0.12wt%, 0.15wt%, 0.18wt%, 0.2 wt%, 0.22wt%, 0.25wt%, 0.28wt%, 0.3wt%, 0.35wt%, 0.4wt% or 0.45wt%, etc.
  • the pH value of the cobalt-free single crystal positive electrode active material is ⁇ 12, such as 7, 8, 9, 10, 11, or 12, etc.
  • the cobalt-free single crystal surface area of the positive active material ⁇ 2m 2 / g, e.g. 0.5m 2 /g,0.6m 2 /g,0.8m 2 / g , 1m 2 /g,1.2m 2 /g,1.4m 2 /g,1.5m 2 /g,1.6m 2 /g,1.7m 2 / g or 1.8m 2 / g and the like.
  • the aluminum-containing material is Al 2 O 3 and/or Al(OH) 3 .
  • the mixing is stirring and mixing.
  • the stirring rate is 900-1000 rpm, such as 910 rpm, 920 rpm, 930 rpm, 940 rpm, 950 rpm, 960 rpm, 970 rpm, 980 rpm, or 990 rpm.
  • the mixing time is 5-20 min, such as 6 min, 7 min, 8 min, 9 min, 10 min, 11 min, 12 min, 13 min, 14 min, 15 min, 16 min, 17 min, 18 min, 19 min or 20 min, etc.
  • the calcination temperature is 400-700°C, such as 450°C, 500°C, 550°C, 600°C, or 650°C.
  • the calcination temperature is 400-700°C, the calcination temperature is too low, the bonding force between the body material and the coating material is weak, and the coating material is easy to fall off; the calcination temperature is too high , The coating material is easy to enter the body material (cobalt-free single crystal positive electrode active material), and can not play the role of coating.
  • the calcination time is 5-8h, such as 5.2h, 5.5h, 5.8h, 6h, 6.2h, 6.5h, 6.8h, 7h, 7.2h, 7.5h or 7.8h.
  • the calcination further includes a process of screening the product with 300-400 mesh, such as 300 mesh, 310 mesh, 320 mesh, 330 mesh, 340 mesh, 350 mesh, 360 mesh, 370 mesh, 380 mesh, 390 mesh or 400 mesh, etc.
  • 300-400 mesh such as 300 mesh, 310 mesh, 320 mesh, 330 mesh, 340 mesh, 350 mesh, 360 mesh, 370 mesh, 380 mesh, 390 mesh or 400 mesh, etc.
  • the method includes the following steps:
  • step (1) In air or O 2 atmosphere, the product obtained in step (1) is sintered at 800-1000°C for 10-20 hours, and the sintered product is crushed by a pair of rollers and airflow crushed, and the crushed material is passed 300- A 400 mesh sieve is used to obtain a cobalt-free single crystal positive active material;
  • the content of the cobalt-free single crystal positive electrode active material is 98.5 to 99.9 wt%
  • the content of LiAlO 2 is 0.05 to 0.5 wt%
  • the content of LiFePO 4 is 0.05 to 1 wt%.
  • a lithium ion battery is provided, and the lithium ion battery includes the positive electrode material described in an embodiment.
  • Figures 1 to 2 are SEM images of a positive electrode material prepared in an embodiment of the present disclosure
  • 3 to 4 are SEM images of a positive electrode material prepared in a comparative example of the present disclosure.
  • FIG. 5 is a comparison diagram of first charge and discharge curves of positive electrode materials prepared in an embodiment of the present disclosure and a comparative example
  • FIG. 6 is a comparison diagram of the cycle performance of positive electrode materials prepared in an embodiment of the present disclosure and a comparative example
  • FIG. 7 is a comparison diagram of rate performance of positive electrode materials prepared in an embodiment of the present disclosure and a comparative example.
  • a method for preparing a positive electrode material includes the following steps:
  • step (1) In an air atmosphere, the product obtained in step (1) was sintered at 900°C for 15 hours, and the sintered product was crushed by a pair of rollers and airflow crushed, and the crushed material was passed through a 400-mesh sieve to obtain a cobalt-free single crystal Positive active material;
  • the content of the cobalt-free single crystal positive electrode active material is 99.2% by weight, the content of LiAlO 2 is 0.3% by weight, and the content of LiFePO 4 is 0.5% by weight.
  • Figures 1 and 2 are SEM images of the positive electrode material prepared in this embodiment. It can be seen from the figures that the uniformity of the particle size of the positive electrode material prepared in this embodiment is relatively high.
  • a method for preparing a positive electrode material includes the following steps:
  • step (1) In an air atmosphere, the product obtained in step (1) is sintered at 1000°C for 10 hours, and the sintered product is crushed by a pair of rollers and airflow crushed, and the crushed material is passed through a 300-mesh sieve to obtain a cobalt-free single crystal Positive active material;
  • the content of the cobalt-free single crystal positive electrode active material is 98.8% by weight, the content of LiAlO 2 is 0.5% by weight, and the content of LiFePO 4 is 0.7% by weight.
  • a method for preparing a positive electrode material includes the following steps:
  • step (1) In an O 2 atmosphere, the product obtained in step (1) was sintered at 800°C for 20 hours, and the sintered product was crushed by a pair of rollers and airflow crushed, and the crushed material was passed through a 300-mesh sieve to obtain a cobalt-free monolith.
  • Crystal positive active material
  • the content of the cobalt-free single crystal positive electrode active material is 99.6 wt%
  • the content of LiAlO 2 is 0.15 wt%
  • the content of LiFePO 4 is 0.25 wt%.
  • Example 1 The difference from Example 1 is that the addition amount of Al 2 O 3 and FePO 4 in step (3) is changed, so that in the cathode material obtained, the content of the cobalt-free single crystal cathode active material is 99.2 wt%, and the content of LiAlO 2 It is 0.05wt%, and the content of LiFePO 4 is 0.75wt%.
  • Example 1 The difference from Example 1 is that the addition amount of Al 2 O 3 and FePO 4 in step (3) is changed so that the content of the cobalt-free single crystal cathode active material in the cathode material obtained is 99.2 wt%, and the content of LiAlO 2
  • the content of LiFePO 4 is 0.5% by weight, and the content of LiFePO 4 is 0.3% by weight.
  • Example 1 The difference from Example 1 is that the addition amount of Al 2 O 3 and FePO 4 in step (3) is changed so that the content of the cobalt-free single crystal cathode active material in the cathode material obtained is 99.2 wt%, and the content of LiAlO 2 It is 0.02wt%, and the content of LiFePO 4 is 0.78wt%.
  • Example 1 The difference from Example 1 is that the addition amount of Al 2 O 3 and FePO 4 in step (3) is changed, so that in the cathode material obtained, the content of the cobalt-free single crystal cathode active material is 99.2 wt%, and the content of LiAlO 2 It is 0.78wt%, and the content of LiFePO 4 is 0.02wt%.
  • Example 1 The difference from Example 1 is that the addition amount of Al 2 O 3 and FePO 4 in step (3) is changed so that the content of the cobalt-free single crystal positive electrode active material in the positive electrode material obtained is 98.5 wt%, and the content of LiAlO 2
  • the content of LiFePO 4 is 0.2% by weight, and the content of LiFePO 4 is 1.3% by weight.
  • Example 1 The difference from Example 1 is that the calcination temperature in step (3) is 300°C.
  • Example 1 The difference from Example 1 is that the calcination temperature in step (3) is 800°C.
  • the cobalt-free single crystal positive electrode active material obtained in step (2) of Example 1 is used as the positive electrode material, that is, there is no LiAlO 2 and LiFePO 4 coating layer.
  • Figures 3 and 4 are SEM images of the cathode material prepared in this comparative example. It can be seen from Figures 1 and 2 that the morphology and primary particle size before and after coating are basically unchanged; the difference is that the material before coating ( The surface of this comparative example is relatively smooth, and there is obvious coating on the surface of the coated sample (Example 1).
  • Example 5 is a comparison diagram of the first charge and discharge curves of the positive electrode materials prepared in Example 1 of the present disclosure and the comparative example. It can be seen from the figure that the first week charge and discharge of the uncoated positive electrode material (this comparative example) at 0.1C The specific capacities are 219.2mAh/g and 189.2mAh/g, and the initial efficiency is 86.3%. The first week charge and discharge specific capacities of the coated material (Example 1) at 0.1C are 224.3mAh/g and 197.7mAh/g, respectively. The first-time efficiency is 88.1%. Therefore, the coating is beneficial to improve the capacity and first-time efficiency of the cobalt-free single crystal layered cathode material.
  • Figure 6 is a comparison diagram of the cycle performance of the positive electrode materials prepared in Example 1 of the present disclosure and the comparative example. It can be seen from the figure that the capacity retention rate of the uncoated material (the comparative example) after 50 weeks of 1C cycle is 94.0%. The capacity retention rate of the coated material (Example 1) after 50 weeks of 1C cycle was 99.1%, and the cycle performance was improved by 5.1%.
  • Figure 7 is a comparison diagram of the rate performance of the positive electrode materials prepared in Example 1 of the present disclosure and the comparative example (the abscissa in the figure is the discharge rate). It can be seen from the test results that the material has a large rate after coating LiAlO 2 and LiFePO 4 There is a certain improvement in performance.
  • the discharge specific capacity of the uncoated material is only 154.9 mAh/g, and the specific discharge capacity of the coated material (Example 1) reaches 160.7 mAh/g; at a rate of 4C, the discharge capacity is only 154.9 mAh/g;
  • the specific discharge capacity of the coated material is only 140.6 mAh/g, and the specific discharge capacity of the coated material (Example 1) reaches 147.6 mAh/g.
  • the reason for the improvement of the rate performance in Example 1 is that the ion conductivity of LiAlO 2 and LiFePO 4 is better.
  • the electrochemical activity of the cobalt-free single crystal layered cathode material can be improved, thereby improving the rate performance of the material.
  • Example 1 The difference from Example 1 is that the Al 2 O 3 in step (3) is replaced with an equivalent amount of FePO 4 , that is, there is no LiAlO 2 in the product .
  • Example 1 The difference from Example 1 is that the FePO 4 described in step (3) is replaced with the same amount of Al 2 O 3 , that is, there is no LiFePO 4 in the product .
  • Example 3 228.9 87.5 97.9
  • Example 4 225.3 87.2 98.6
  • Example 5 223.4 87.4 98.2
  • Example 6 221.8 87.1 97.2
  • Example 7 220.9 86.9 97.3
  • Example 8 219.8 86.7 97.1
  • Example 9 229.7 88.0 96.8
  • Example 10 218.5 86.5 100.2
  • Comparative example 1 219.2 86.3 94.0
  • Comparative example 3 222.3 87.5 96.2
  • Example 1 From the comparison between Example 1 and Examples 6-8, it can be seen that when the coating amount of LiAlO 2 or LiFePO 4 in Examples 6-7 is too small, the coating layer cannot be uniformly coated on the body material (cobalt-free single crystal positive electrode active material) The surface is poor in cycle performance; when the amount of LiFePO 4 coated in Example 8 is too large, the coating layer is too thick, resulting in low material capacity and poor cycle performance.
  • Example 1 From the comparison between Example 1 and Examples 9-10, it can be seen that when the calcination temperature is too low, the bonding force between the coating layer and the body material is poor, and the cycle performance is poor; when the calcination temperature is too high, the coating layer is easy to enter the body material , Low capacity.
  • Example 1 From the comparison between Example 1 and Comparative Example 1, it can be seen that the material capacity, first effect and cycle performance are improved after coating LiAlO 2 and LiFePO 4. From the comparison between Example 1 and Comparative Examples 2-3, it can be seen that only the LiAlO 2 or LiFePO 4 is coated, and the cycle performance of the material is not as good as that of the co-coated.

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Abstract

一种正极材料、其制备方法和锂离子电池。所述正极材料为核壳结构，核层包括无钴单晶正极活性物质，壳层包括LiAlO 2和LiFePO 4。通过在无钴单晶正极活性物质表面包覆LiAlO 2和LiFePO 4，提高无钴单晶层状正极材料的导电性，从而提高材料的容量、倍率和循环性。

Description

一种正极材料、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，例如涉及一种正极材料、其制备方法和锂离子电池。
背景技术
当前，新能源汽车领域对锂离子动力电池的要求更加严苛，如安全性能、循环性能、成本等。而正极材料成本占动力电池总成本的30～40％，若降低动力电池的成本，需要降低正极材料的成本。
NCM中钴元素价格的波动制约了电池的成本控制，且钴金属价格昂贵，易对环境造成污染，因此需要降低三元正极材料的钴含量，或者使材料中不含钴，进而才能降低生产成本。
然而，单纯的无钴单晶材料的锂离子导电性差，离子导电性制约了电池在充放电过程中锂离子的嵌入迁出速度，不利于材料容量的发挥，影响了材料的倍率性能，且随着循环的进行增加电池内阻，电池易产热，有很大的使用安全隐患。
CN109686970A公开了一种无钴富锂三元正极材料NMA及其制备方法。所述无钴富锂三元正极材料NMA的化学式为Li 1+PNi 1-x-y-zMn xAl yM zO 2，其前驱体化学式为Ni 1-x-y-zMn xAl yM z(OH) 2，其中0.03<P<0.3，0.1<X<0.6，0.01<Y<0.1，0.01<Z<0.3，M为Ce 3+、Ti 4+、Zr 4+、Mg 2+的一种或两种以上；所述前驱体为纳米片状团聚粒子，所述纳米片状前驱体的厚度30～50纳米。但是，所述方法得到的正极材料电化学性能较差。
CN103943844B公开了一种无钴富锂锰基正极材料及其制备方法和应用，所 述正极材料化学式为Li 1+xNi yMn 0.8-yO 2(0<x<1/3，0<y<0.8)。正极材料的制备过程：采用溶胶-凝胶法在乙醇或去离子水溶剂中制备前驱体，经低温预烧、球磨后，再经高温固相烧结得到所制备的正极材料。但是，所述方法得到的正极材料电化学性能较差。
因此，本领域需要开发一种新型无钴材料，所述无钴材料具有优异的电化学性能，且成本较低，制备方法简单，可工业化生产。
公开内容
本公开提供一种正极材料、其制备方法和锂离子电池。
本公开在一实施例中提供一种正极材料，所述正极材料为核壳结构，核层包括无钴单晶正极活性物质，壳层包括LiAlO 2和LiFePO 4。
本公开提供的一实施例中，正极材料通过在无钴单晶正极活性物质表面包覆LiAlO 2和LiFePO 4，提高无钴单晶层状正极材料的导电性，从而提高材料的容量、倍率和循环性能。壳层必须同时含有LiAlO 2和LiFePO 4才能达到优异的电化学性能，壳层只存在LiAlO 2，材料稳定性无法显著提高；壳层只存在LiFePO 4，材料循环性能无法显著提高。
在一实施例中，所述无钴单晶正极活性物质的含量为98.5～99.9wt％，例如98.6wt％、98.8wt％、99.0wt％、99.2wt％、99.4wt％、99.5wt％或99.8wt％等。
在一实施例中，所述LiAlO 2的含量为0.05～0.5wt％，例如0.1wt％、0.15wt％、0.2wt％、0.25wt％、0.3wt％、0.35wt％、0.4wt％、0.45wt％或0.48wt％等。
本公开提供的一实施例中，正极材料中LiAlO 2的含量为0.05～0.5wt％，LiAlO 2的含量过多，得到的正极材料容量较低；LiAlO 2的含量过少，壳层包覆不均匀。
在一实施例中，所述LiFePO 4的含量为0.05～1wt％，例如0.08wt％、0.1wt％、 0.15wt％、0.2wt％、0.25wt％、0.3wt％、0.35wt％、0.4wt％、0.45wt％、0.5wt％、0.55wt％、0.6wt％、0.65wt％、0.7wt％、0.75wt％、0.8wt％、0.85wt％、0.9wt％或0.95wt％等。
本公开提供的一实施例中，正极材料中LiFePO 4的含量为0.05～1wt％，LiFePO 4的含量过多，导致正极材料容量降低；LiFePO 4的含量过少，不能均匀包覆，正极材料仍然有部分和电解液直接接触，影响电化学性能。
在一实施例中，所述无钴单晶正极活性物质为LiNi xMn yO 2，0.45≤x≤0.95，例如0.5、0.55、0.6、0.65、0.68、0.7、0.75、0.8、0.85、0.88或0.9等；0.05≤y≤0.55，例如0.1、0.12、0.15、0.18、0.2、0.25、0.3、0.35、0.38、0.4、0.45、0.48或0.5等。
本公开在一实施例中提供了一种正极材料的制备方法，所述方法包括如下步骤：
将无钴单晶正极活性物质、锂盐、含铝材料和FePO 4混合，煅烧，得到正极材料。
在一实施例中，所述无钴单晶正极活性物质的制备方法包括：将锂盐和无钴正极活性物质前驱体混合，烧结，得到无钴单晶正极活性物质。
在一实施例中，所述无钴正极活性物质前驱体的化学式为Ni xMn y(OH) 2，0.45≤x≤0.95，例如0.5、0.55、0.6、0.65、0.68、0.7、0.75、0.8、0.85、0.88或0.9等；0.05≤y≤0.55，例如0.1、0.12、0.15、0.18、0.2、0.25、0.3、0.35、0.38、0.4、0.45、0.48或0.5等。
在一实施例中，所述锂盐包括LiOH和/或Li 2CO 3。
在一实施例中，所述烧结的温度为800～1000℃，例如820℃、850℃、880℃、 900℃、920℃、950℃或980℃等。
在本公开提供的一实施例中，烧结的温度为800～1000℃，烧结的温度过低，材料晶体结构不完整；烧结的温度过高，材料粒径过大，导致容量降低。
在一实施例中，所述烧结的时间为10～20h，例如11h、12h、13h、14h、15h、16h、17h、18h或19h等。
在一实施例中，所述烧结的气氛为空气气氛或O 2气氛。
在一实施例中，所述烧结之后，还包括将得到的产物进行破碎。
在一实施例中，破碎后的物料过300～400目筛，例如300目、310目、320目、330目、340目、350目、360目、370目、380目、390目或400目等。
在一实施例中，所述无钴单晶正极活性物质的残碱含量≤0.5wt％，例如0.05wt％、0.08wt％、0.1wt％、0.12wt％、0.15wt％、0.18wt％、0.2wt％、0.22wt％、0.25wt％、0.28wt％、0.3wt％、0.35wt％、0.4wt％或0.45wt％等。
在一实施例中，所述无钴单晶正极活性物质的pH值≤12，例如7、8、9、10、11或12等。
在一实施例中，所述无钴单晶正极活性物质的比表面积≤2m 2/g，例如0.5m 2/g、0.6m 2/g、0.8m 2/g、1m 2/g、1.2m 2/g、1.4m 2/g、1.5m 2/g、1.6m 2/g、1.7m 2/g或1.8m 2/g等。
在一实施例中，所述含铝材料为Al 2O 3和/或Al(OH) 3。
在一实施例中，所述混合为搅拌混合。
在一实施例中，搅拌的速率为900～1000rpm，例如910rpm、920rpm、930rpm、940rpm、950rpm、960rpm、970rpm、980rpm或990rpm等。
在一实施例中，所述混合的时间为5～20min，例如6min、7min、8min、9min、 10min、11min、12min、13min、14min、15min、16min、17min、18min、19min或20min等。
在一实施例中，所述煅烧的温度为400～700℃，例如450℃、500℃、550℃、600℃或650℃等。
在本公开提供的一实施例中，煅烧的温度为400～700℃，煅烧的温度过低，本体材料和包覆材料之间的结合力较弱，包覆材料容易脱落；煅烧的温度过高，包覆材料易进入到本体材料(无钴单晶正极活性物质)中，起不到包覆作用。
在一实施例中，所述煅烧的时间为5～8h，例如5.2h、5.5h、5.8h、6h、6.2h、6.5h、6.8h、7h、7.2h、7.5h或7.8h等。
在一实施例中，所述煅烧之后，还包括将产物进行300～400目筛分的过程，例如300目、310目、320目、330目、340目、350目、360目、370目、380目、390目或400目等。
在一实施例中，所述方法包括如下步骤：
(1)将锂盐和无钴正极活性物质前驱体进行搅拌混合5～15min，搅拌的转速为800～900rpm；
(2)在空气或O 2气氛下，将步骤(1)得到的产物在800～1000℃烧结10～20h，将烧结得到的产物通过对辊破碎和气流粉碎，将粉碎后的物料过300～400目筛，得到无钴单晶正极活性物质；
(3)将所述无钴单晶正极活性物质、锂盐、含铝材料和FePO 4进行搅拌混合5～20min，搅拌的速率为900～1000rpm，然后进行400～700℃煅烧5～8h，300～400目筛分，得到正极材料；
所述正极材料中，所述无钴单晶正极活性物质的含量为98.5～99.9wt％，所 述LiAlO 2的含量为0.05～0.5wt％，所述LiFePO 4的含量为0.05～1wt％。
本公开在一实施例中提供了一种锂离子电池，所述锂离子电池包括一实施例所述的正极材料。
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-图2是本公开一个实施例制备得到的正极材料的SEM图；
图3-图4是本公开一个对比例制备得到的正极材料SEM图；
图5是本公开一个实施例和对比例制备得到的正极材料首次充放电曲线对比图；
图6是本公开一个实施例和对比例制备得到的正极材料循环性能对比图；
图7是本公开一个实施例和对比例制备得到的正极材料倍率性能对比图。
具体实施例
下面结合附图并通过具体实施例来进一步说明本公开的技术方案。
实施例1
一种正极材料的制备方法包括如下步骤：
(1)将LiOH和无钴正极活性物质前驱体Ni 0.75Mn 0.25(OH) 2进行搅拌混合10min，搅拌的转速为900rpm，所述LiOH中Li元素的摩尔量与无钴正极活性物质前驱体中金属元素的总摩尔量之比为1.05；
(2)在空气气氛下，将步骤(1)得到的产物在900℃烧结15h，将烧结得到的产物通过对辊破碎和气流粉碎，将粉碎后的物料过400目筛，得到无钴单晶正极活性物质；
(3)将所述无钴单晶正极活性物质、LiOH、Al 2O 3和FePO 4进行搅拌混合10min，搅拌的速率为1000rpm，所述无钴单晶正极活性物质、LiOH、Al 2O 3和FePO 4的质量比为99.2:0.18:0.23:0.48，然后进行600℃煅烧6h，400目筛分，得 到正极材料；
本实施例制备得到的正极材料中，无钴单晶正极活性物质的含量为99.2wt％，LiAlO 2的含量为0.3wt％，LiFePO 4的含量为0.5wt％。
图1和图2是本实施例制备得到的正极材料的SEM图，由图中可以看出，本实施例制备得到的正极材料粒度均匀性较高。
实施例2
一种正极材料的制备方法包括如下步骤：
(1)将LiOH和无钴正极活性物质前驱体Ni 0.75Mn 0.25(OH) 2进行搅拌混合15min，搅拌的转速为800rpm，所述LiOH中Li元素的摩尔量与无钴正极活性物质前驱体中金属元素的总摩尔量之比为1.05；
(2)在空气气氛下，将步骤(1)得到的产物在1000℃烧结10h，将烧结得到的产物通过对辊破碎和气流粉碎，将粉碎后的物料过300目筛，得到无钴单晶正极活性物质；
(3)将所述无钴单晶正极活性物质、LiOH、Al 2O 3和FePO 4进行搅拌混合5min，搅拌的速率为1000rpm，所述无钴单晶正极活性物质、LiOH、Al 2O 3和FePO 4的质量比为98.8:0.27:0.38:0.58，然后进行700℃煅烧5h，300目筛分，得到正极材料；
本实施例制备得到的正极材料中，无钴单晶正极活性物质的含量为98.8wt％，LiAlO 2的含量为0.5wt％，LiFePO 4的含量为0.7wt％。
实施例3
一种正极材料的制备方法包括如下步骤：
(1)将LiOH和无钴正极活性物质前驱体Ni 0.75Mn 0.25(OH) 2进行搅拌混合5min，搅拌的转速为900rpm，所述LiOH中Li元素的摩尔量与无钴正极活性物质前驱体中金属元素的总摩尔量之比为1.05；
(2)在O 2气氛下，将步骤(1)得到的产物在800℃烧结20h，将烧结得到的产物通过对辊破碎和气流粉碎，将粉碎后的物料过300目筛，得到无钴单晶正极活性物质；
(3)将所述无钴单晶正极活性物质、LiOH、Al 2O 3和FePO 4进行搅拌混合20min，搅拌的速率为900rpm，所述无钴单晶正极活性物质、LiOH、Al 2O 3和FePO 4的质量比为99.6:0.09:0.12:0.24，然后进行400℃煅烧8h，300目筛分，得到正极材料；
本实施例制备得到的正极材料中，无钴单晶正极活性物质的含量为99.6wt％，LiAlO 2的含量为0.15wt％，LiFePO 4的含量为0.25wt％。
实施例4
与实施例1的区别在于，改变步骤(3)中Al 2O 3和FePO 4的添加量，使得到的正极材料中，无钴单晶正极活性物质的含量为99.2wt％，LiAlO 2的含量为0.05wt％，LiFePO 4的含量为0.75wt％。
实施例5
与实施例1的区别在于，改变步骤(3)中Al 2O 3和FePO 4的添加量，使得到的正极材料中，无钴单晶正极活性物质的含量为99.2wt％，LiAlO 2的含量为0.5wt％，LiFePO 4的含量为0.3wt％。
实施例6
与实施例1的区别在于，改变步骤(3)中Al 2O 3和FePO 4的添加量，使得到的正极材料中，无钴单晶正极活性物质的含量为99.2wt％，LiAlO 2的含量为0.02wt％，LiFePO 4的含量为0.78wt％。
实施例7
与实施例1的区别在于，改变步骤(3)中Al 2O 3和FePO 4的添加量，使得到的正极材料中，无钴单晶正极活性物质的含量为99.2wt％，LiAlO 2的含量为0.78wt％，LiFePO 4的含量为0.02wt％。
实施例8
与实施例1的区别在于，改变步骤(3)中Al 2O 3和FePO 4的添加量，使得到的正极材料中，无钴单晶正极活性物质的含量为98.5wt％，LiAlO 2的含量为0.2wt％，LiFePO 4的含量为1.3wt％。
实施例9
与实施例1的区别在于，步骤(3)所述煅烧的温度为300℃。
实施例10
与实施例1的区别在于，步骤(3)所述煅烧的温度为800℃。
对比例1
采用实施例1中步骤(2)得到的无钴单晶正极活性物质作为正极材料，即不存在LiAlO 2和LiFePO 4包覆层。
图3和图4是本对比例制备得到的正极材料SEM图，结合图1和图2可以看出，包覆前后形貌和一次颗粒粒径基本不变；不同的是，包覆前材料(本对比例)表面比较光滑，包覆后的样品(实施例1)表面存在明显的包覆物。
图5是本公开实施例1和本对比例制备得到的正极材料首次充放电曲线对比图，从图中可以看出，不包覆的正极材料(本对比例)0.1C的首周充电和放电比容量分别为219.2mAh/g和189.2mAh/g，首次效率86.3％，包覆的材料(实施例1)0.1C的首周充电和放电比容量分别为224.3mAh/g和197.7mAh/g，首次效率为88.1％，因此，包覆有利于改善无钴单晶层状正极材料的容量和首次效率。
图6是本公开实施例1和本对比例制备得到的正极材料循环性能对比图，从图中可以看出，未包覆材料(本对比例)1C循环50周后容量保持率为94.0％，包覆后的材料(实施例1)1C循环50周后容量保持率为99.1％，循环性能提高了5.1％。
图7是本公开实施例1和本对比例制备得到的正极材料倍率性能对比图(图中横坐标为放电倍率)，从测试结果可以看出，包覆LiAlO 2和LiFePO 4后，材料大倍率性能有一定的提升。例如：2C倍率下，未包覆的材料(本对比例)放电比容量仅为154.9mAh/g，包覆后的材料(实施例1)放电比容量达到160.7mAh/g；4C倍率下，未包覆的材料(本对比例)放电比容量仅为140.6mAh/g，包覆后的材料(实施例1)放电比容量达到147.6mAh/g。实施例1中倍率性能提高的原因为LiAlO 2和LiFePO 4离子电导率较好，包覆后可以提高无钴单晶层状正极材料的电化学活性，从而提升材料的倍率性能。
对比例2
与实施例1的区别在于，步骤(3)所述Al 2O 3替换为等量的FePO 4，即产品中不存在LiAlO 2。
对比例3
与实施例1的区别在于，步骤(3)所述FePO 4替换为等量的Al 2O 3，即产品中不存在LiFePO 4。
性能测试：
将本公开提供的实施例与对比例制备得到的正极材料组装成电池：
按照正极材料：导电炭黑：粘结剂PVDF(聚偏氟乙烯)＝90:5:5的质量比混合，以去NMP(N-甲基吡咯烷酮)为溶剂混浆后涂布于铝箔上，经过90℃真空干燥得到正极极片；然后将所述负极极片(锂片)、正极极片、电解液(1mol/L的六氟磷酸锂LiPF 6，碳酸乙烯酯EC：碳酸甲乙酯EMC＝1:1)和隔膜组装成电池。
(1)首周充电比容量和首周效率测试：将得到的电池在25±2℃环境下进行充放电测试，充放电电压为3.0～4.4V，电流密度为0.1C/0.1C(0.1C充电，0.1C放电)，测试结果如表1所示；
(2)50周循环性能测试：将得到的电池在25±2℃环境下进行充放电测试，充放电电压为3.0～4.4V，电流密度为0.5C/1C(0.5C充电，1C放电)，测试结果如表1所示；
(3)倍率性能测试：将实施例1和对比例1得到的电池在25±2℃环境下进行充放电测试，充放电电压为3.0～4.4V，分别在0.3C、0.5C、1C、2C、3C和4C进行放电比容量测试，测试结果如表2所示。
表1
  首周充电比容量(mAh/g) 首周效率(％) 50周循环性能(％)
实施例1 224.3 88.1 99.1
实施例2 222.5 87.9 99.8
实施例3 228.9 87.5 97.9
实施例4 225.3 87.2 98.6
实施例5 223.4 87.4 98.2
实施例6 221.8 87.1 97.2
实施例7 220.9 86.9 97.3
实施例8 219.8 86.7 97.1
实施例9 229.7 88.0 96.8
实施例10 218.5 86.5 100.2
对比例1 219.2 86.3 94.0
对比例2 221.6 87.1 95.4
对比例3 222.3 87.5 96.2
表2
Figure PCTCN2020135523-appb-000001
通过实施例1与实施例6-8对比可知，实施例6-7中LiAlO 2或LiFePO 4包覆量过少时，包覆层不能均匀的包覆在本体材料(无钴单晶正极活性物质)的表面，循环性能差；实施例8中LiFePO 4包覆量过多时，包覆层太厚，导致材料容量低，且循环性能较差。
通过实施例1与实施例9-10对比可知，当煅烧温度过低时，包覆层与本体材料结合力差，循环性能差；当煅烧温度过高时，包覆层易进入到本体材料中，容量低。
通过实施例1与对比例1对比可知，包覆LiAlO 2和LiFePO 4后材料容量、 首效和循环性能均有所提高。通过实施例1与对比例2-3对比可知，只包覆LiAlO 2或LiFePO 4，材料循环性能均不如共包覆的。

Claims (26)

  1. 一种正极材料，所述正极材料为核壳结构，核层包括无钴单晶正极活性物质，壳层包括LiAlO 2和LiFePO 4。
  2. 根据权利要求1所述的正极材料，其中，所述无钴单晶正极活性物质的含量为98.5～99.9wt％。
  3. 根据权利要求1或2所述的正极材料，其中，所述LiAlO 2的含量为0.05～0.5wt％。
  4. 根据权利要求1-3任一项所述的正极材料，其中，所述LiFePO 4的含量为0.05～1wt％。
  5. 如权利要求1-4任一项所述的正极材料，其中，所述无钴单晶正极活性物质为LiNi xMn yO 2，0.45≤x≤0.95，0.05≤y≤0.55。
  6. 一种如权利要求1-5任一项所述正极材料的制备方法，所述方法包括如下步骤：
    将无钴单晶正极活性物质、锂盐、含铝材料和FePO 4混合，煅烧，得到正极材料。
  7. 如权利要求6所述的方法，其中，所述无钴单晶正极活性物质的制备方法包括：将锂盐和无钴正极活性物质前驱体混合，烧结，得到无钴单晶正极活性物质。
  8. 如权利要求7所述的方法，其中，所述无钴正极活性物质前驱体的化学式为Ni xMn y(OH) 2，0.45≤x≤0.95，0.05≤y≤0.55。
  9. 如权利要求6-8任一项所述的方法，其中，所述锂盐包括LiOH和/或Li2CO3。
  10. 如权利要求7-9任一项所述的方法，其中，所述烧结的温度为800～1000℃。
  11. 如权利要求7-10任一项所述的方法，其中，所述烧结的时间为10～20h。
  12. 如权利要求7-11任一项所述的方法，其中，所述烧结的气氛为空气气氛或O2气氛。
  13. 如权利要求7-12任一项所述的方法，其中，所述烧结之后，还包括将得到的产物进行破碎。
  14. 如权利要求13所述的方法，其中，破碎后的物料过300～400目筛。
  15. 如权利要求6-14任一项所述的方法，其中，所述无钴单晶正极活性物 质的残碱含量≤0.5wt％。
  16. 如权利要求6-15任一项所述的方法，其中，所述无钴单晶正极活性物质的pH值≤12。
  17. 如权利要求6-16任一项所述的方法，其中，所述无钴单晶正极活性物质的比表面积≤2m 2/g。
  18. 如权利要求6-17任一项所述的方法，其中，所述含铝材料为Al 2O 3和/或Al(OH) 3。
  19. 如权利要求6-18任一项所述的方法，其中，所述混合为搅拌混合。
  20. 如权利要求19所述的方法，其中，搅拌的速率为900～1000rpm。
  21. 如权利要求6-20任一项所述的方法，其中，所述混合的时间为5～20min。
  22. 如权利要求6-21任一项所述的方法，其中，所述煅烧的温度为400～700℃。
  23. 如权利要求6-22任一项所述的方法，其中，所述煅烧的时间为5～8h。
  24. 如权利要求6-23任一项所述的方法，其中，所述煅烧之后，还包括将产物进行300～400目筛分的过程。
  25. 如权利要求6-24任一项所述的方法，其中，所述方法包括如下步骤：
    (1)将锂盐和无钴正极活性物质前驱体进行搅拌混合5～15min，搅拌的转速为800～900rpm；
    (2)在空气或O 2气氛下，将步骤(1)得到的产物在800～1000℃烧结10～20h，将烧结得到的产物通过对辊破碎和气流粉碎，将粉碎后的物料过300～400目筛，得到无钴单晶正极活性物质；
    (3)将所述无钴单晶正极活性物质、锂盐、含铝材料和FePO 4进行搅拌混合5～20min，搅拌的速率为900～1000rpm，然后进行400～700℃煅烧5～8h，300～400目筛分，得到正极材料；
    所述正极材料中，所述无钴单晶正极活性物质的含量为98.5～99.9wt％，所述LiAlO 2的含量为0.05～0.5wt％，所述LiFePO 4的含量为0.05～1wt％。
  26. 一种锂离子电池，所述锂离子电池包括权利要求1-5任一项所述的正极材料。
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* Cited by examiner, † Cited by third party
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CN114335467A (zh) * 2021-12-28 2022-04-12 北京理工大学 一种包覆改性层状LiMO2正极材料及其制备方法
CN115000396A (zh) * 2022-06-01 2022-09-02 大连理工大学 一种表面多组分改性无钴富锂锰基正极材料及制备方法
CN115050945A (zh) * 2022-07-15 2022-09-13 湖北工业大学 一种生物质氮掺杂碳包覆富锂磷酸铁锂正极材料的制备方法
CN115140782A (zh) * 2022-04-27 2022-10-04 南通金通储能动力新材料有限公司 一种核壳结构的富锂锰基正极材料前驱体及其制备方法
JP2024070794A (ja) * 2022-11-11 2024-05-23 リヴィアン アイピー ホールディングス，エルエルシー 電極コーティング及びその構成要素
CN119361664A (zh) * 2024-12-26 2025-01-24 宁波容百新能源科技股份有限公司 一种正极活性材料及其制备方法、钠离子电池和用电设备

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KR102734799B1 (ko) * 2019-07-03 2024-11-27 유미코아 재충전 가능한 리튬 이온 배터리용 양극 활물질로서의 리튬 니켈 망간 코발트 복합 산화물
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CN112582594B (zh) * 2020-12-14 2022-03-15 格林美(湖北)新能源材料有限公司 一种无钴单晶正极材料及其制备方法和应用
CN114195200B (zh) * 2021-11-03 2023-11-10 荆门市格林美新材料有限公司 镍锰铝核壳结构前驱体和无钴锂离子正极材料的制备方法
CN114122552A (zh) * 2021-11-23 2022-03-01 合肥综合性国家科学中心能源研究院(安徽省能源实验室) 一种回收退役锂离子电池制备LiAlO2包覆单晶正极材料的方法
KR102743444B1 (ko) * 2022-05-30 2024-12-16 삼성에스디아이 주식회사 리튬 이차 전지용 양극 활물질, 리튬 이차 전지용 양극 및 리튬 이차 전지
CN116247173A (zh) * 2022-12-29 2023-06-09 远东电池江苏有限公司 一种无钴锂离子电池
KR20250062877A (ko) * 2023-10-31 2025-05-08 삼성에스디아이 주식회사 양극 활물질과 그 제조 방법, 이를 포함하는 양극, 및 리튬 이차 전지

Citations (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101740752A (zh) * 2009-12-16 2010-06-16 深圳市德方纳米科技有限公司 具有核壳结构的锂离子电池用复合正极材料及其制备方法
CN102903904A (zh) * 2012-10-09 2013-01-30 江苏科捷锂电池有限公司 LiAlO2包覆尖晶石锰酸锂正极材料的制备方法
CN103413932A (zh) * 2013-08-19 2013-11-27 北大先行科技产业有限公司 一种改性单晶型多元正极材料及其制备方法
CN103715409A (zh) * 2012-09-29 2014-04-09 河南科隆集团有限公司 一种包覆型镍锰酸锂锂离子电池正极材料的制备方法
CN103943844A (zh) 2014-04-04 2014-07-23 西安交通大学 一种无钴富锂锰基正极材料及其制备方法和应用
CN104241636A (zh) * 2014-10-20 2014-12-24 上海空间电源研究所 一种表面包覆LiAlO2的锂离子电池锰系正极材料及其制备方法
CN105185954A (zh) * 2015-06-17 2015-12-23 电子科技大学 一种LiAlO2包覆LiNi1-xCoxO2的锂离子电池正极材料及其制备方法
CN109686970A (zh) 2018-12-27 2019-04-26 四川万邦胜辉机械设备有限公司 一种无钴富锂三元正极材料nma及其制备方法
CN111653752A (zh) * 2020-06-24 2020-09-11 蜂巢能源科技有限公司 一种正极材料、其制备方法和锂离子电池

Family Cites Families (16)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP3130813B2 (ja) * 1995-11-24 2001-01-31 富士化学工業株式会社 リチウムニッケル複合酸化物、その製造方法および二次電池用正極活物質
JP5036348B2 (ja) 2007-02-27 2012-09-26 三洋電機株式会社 非水電解質二次電池用正極活物質の製造方法
KR100889622B1 (ko) * 2007-10-29 2009-03-20 대정이엠(주) 안전성이 우수한 리튬 이차전지용 양극 활물질 및 그제조방법과 이를 포함하는 리튬 이차전지
KR101050438B1 (ko) 2008-11-10 2011-07-19 주식회사 코캄 안전성이 우수한 리튬 이차전지용 양극 활물질 및 그 제조방법과 이를 포함하는 리튬 이차전지
JP2010129471A (ja) 2008-11-28 2010-06-10 Sony Corp 正極活物質および非水電解質電池
KR20130143551A (ko) * 2010-09-30 2013-12-31 아사히 가라스 가부시키가이샤 비수계 이차 전지용 정극 합제, 그것을 사용한 비수계 이차 전지용 정극 및 이차 전지
KR101465490B1 (ko) * 2011-11-30 2014-11-26 주식회사 코캄 안전성과 안정성이 향상된 리튬 이차 전지
CN102646826B (zh) * 2012-05-21 2015-02-04 甘肃大象能源科技有限公司 一种核-壳型锰酸锂复合正极材料及其制备方法和应用
CN103715424B (zh) * 2014-01-06 2016-06-08 中国科学院宁波材料技术与工程研究所 一种核壳结构正极材料及其制备方法
EP3238290B1 (en) * 2014-12-23 2024-05-01 QuantumScape Battery, Inc. Lithium rich nickel manganese cobalt oxide (lr-nmc)
US10833321B2 (en) * 2015-03-06 2020-11-10 Uchicago Argonne, Llc Cathode materials for lithium ion batteries
CN105552324A (zh) * 2015-12-15 2016-05-04 天津斯特兰能源科技有限公司 一种磷酸铁锂包覆镍钴锰酸锂复合材料的制备方法
US12315915B2 (en) * 2017-07-14 2025-05-27 Umicore Ni based cathode material for rechargeable lithium-ion batteries
CN108172826A (zh) * 2017-12-30 2018-06-15 国联汽车动力电池研究院有限责任公司 一种磷酸铁锂纳米颗粒包覆高镍三元材料的方法
CN108172813B (zh) * 2018-02-01 2020-12-08 广东工业大学 一种复合正极材料及其制备方法
CN111244459A (zh) * 2020-01-21 2020-06-05 华东理工大学 高镍正极材料、镍钴前驱体材料及制备方法、锂离子电池

Patent Citations (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101740752A (zh) * 2009-12-16 2010-06-16 深圳市德方纳米科技有限公司 具有核壳结构的锂离子电池用复合正极材料及其制备方法
CN103715409A (zh) * 2012-09-29 2014-04-09 河南科隆集团有限公司 一种包覆型镍锰酸锂锂离子电池正极材料的制备方法
CN102903904A (zh) * 2012-10-09 2013-01-30 江苏科捷锂电池有限公司 LiAlO2包覆尖晶石锰酸锂正极材料的制备方法
CN103413932A (zh) * 2013-08-19 2013-11-27 北大先行科技产业有限公司 一种改性单晶型多元正极材料及其制备方法
CN103943844A (zh) 2014-04-04 2014-07-23 西安交通大学 一种无钴富锂锰基正极材料及其制备方法和应用
CN104241636A (zh) * 2014-10-20 2014-12-24 上海空间电源研究所 一种表面包覆LiAlO2的锂离子电池锰系正极材料及其制备方法
CN105185954A (zh) * 2015-06-17 2015-12-23 电子科技大学 一种LiAlO2包覆LiNi1-xCoxO2的锂离子电池正极材料及其制备方法
CN109686970A (zh) 2018-12-27 2019-04-26 四川万邦胜辉机械设备有限公司 一种无钴富锂三元正极材料nma及其制备方法
CN111653752A (zh) * 2020-06-24 2020-09-11 蜂巢能源科技有限公司 一种正极材料、其制备方法和锂离子电池

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
See also references of EP4024519A4

Cited By (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN114335467A (zh) * 2021-12-28 2022-04-12 北京理工大学 一种包覆改性层状LiMO2正极材料及其制备方法
CN115140782A (zh) * 2022-04-27 2022-10-04 南通金通储能动力新材料有限公司 一种核壳结构的富锂锰基正极材料前驱体及其制备方法
CN115140782B (zh) * 2022-04-27 2023-11-14 南通金通储能动力新材料有限公司 一种核壳结构的富锂锰基正极材料前驱体及其制备方法
CN115000396A (zh) * 2022-06-01 2022-09-02 大连理工大学 一种表面多组分改性无钴富锂锰基正极材料及制备方法
CN115000396B (zh) * 2022-06-01 2024-03-26 大连理工大学 一种表面多组分改性无钴富锂锰基正极材料及制备方法
CN115050945A (zh) * 2022-07-15 2022-09-13 湖北工业大学 一种生物质氮掺杂碳包覆富锂磷酸铁锂正极材料的制备方法
CN115050945B (zh) * 2022-07-15 2023-09-22 湖北工业大学 一种生物质氮掺杂碳包覆富锂磷酸铁锂正极材料的制备方法
JP2024070794A (ja) * 2022-11-11 2024-05-23 リヴィアン アイピー ホールディングス，エルエルシー 電極コーティング及びその構成要素
CN119361664A (zh) * 2024-12-26 2025-01-24 宁波容百新能源科技股份有限公司 一种正极活性材料及其制备方法、钠离子电池和用电设备

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