WO2021143373A1 - 无钴层状正极材料及其制备方法、锂离子电池 - Google Patents

无钴层状正极材料及其制备方法、锂离子电池 Download PDF

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WO2021143373A1
WO2021143373A1 PCT/CN2020/132904 CN2020132904W WO2021143373A1 WO 2021143373 A1 WO2021143373 A1 WO 2021143373A1 CN 2020132904 W CN2020132904 W CN 2020132904W WO 2021143373 A1 WO2021143373 A1 WO 2021143373A1
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cobalt
core
positive electrode
free layered
free
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French (fr)
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乔齐齐
江卫军
许鑫培
施泽涛
马加力
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Svolt Energy Technology Co Ltd
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Priority to US17/763,220 priority patent/US20220359866A1/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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    • H01M4/52—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron
    • 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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    • H01M4/628—Inhibitors, e.g. gassing inhibitors, corrosion inhibitors
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    • H01M2004/028—Positive electrodes
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
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    • Y02E60/10—Energy storage using batteries

Definitions

  • the present invention relates to the technical field of lithium ion battery cathode materials. Specifically, the present invention relates to a cobalt-free layered cathode material, a preparation method thereof, and a lithium ion battery.
  • ternary cathode materials are more and more widely used in lithium-ion power batteries.
  • Traditional ternary cathode materials generally contain cobalt, and the price of cobalt is the highest among the three elements, which will cause the price of ternary cathode materials to be significantly higher than other cathode materials such as LiFePO 4 and LiMn 2 O 4 . Therefore, ternary cathode materials are developing towards low-cobalt or even cobalt-free.
  • the non-cobaltization will reduce the conductivity of the cathode material, which in turn affects the rate performance of the material.
  • the inventor of the present invention provides a cathode material coated with highly conductive titanium nitride on the surface, which can not only improve the surface conductivity of cobalt-free materials At the same time, it can also reduce the surface resistance of cobalt-free materials, thereby improving the electrical properties of cobalt-free materials such as cycling and rate.
  • the present invention proposes a cobalt-free layered cathode material.
  • the cobalt-free layered cathode material has a core-shell structure, and the material forming the outer shell of the core-shell structure includes titanium nitride, and the material forming the core of the core-shell structure does not include cobalt and It is a single crystal structure.
  • the cobalt-free layered positive electrode material of the embodiment of the present invention is coated with high-conductivity titanium nitride on the surface of the cobalt-free core, which reduces the price and cost of the positive electrode material, and can also improve the rate performance of the positive electrode material, thereby making The rate performance of the cobalt-free cathode material is better.
  • cobalt-free layered cathode material may also have the following additional technical features:
  • the material forming the core is LiNi x Mn y O 2 , where 0.55 ⁇ x ⁇ 0.95 and 0.05 ⁇ y ⁇ 0.45.
  • the particle size of the material particles forming the core is 1 to 5 microns.
  • the thickness of the shell is 50-500 nm.
  • the content of the titanium nitride is 0.13-0.39% (wt).
  • the present invention proposes a method for preparing a cobalt-free layered cathode material.
  • the method includes: providing a core material, and the core material does not include cobalt; coating a surface of the core material with a titanium compound, wherein the titanium compound is tetravalent titanium
  • the coated core material is subjected to ammonia gas treatment to obtain the cobalt-free layered cathode material coated with titanium nitride.
  • the surface of the core material is coated with a compound of tetravalent titanium, and then processed into a titanium nitride shell in ammonia gas, so that the surface of the cobalt-free core material is coated with high conductivity
  • the titanium nitride shell can make the prepared cobalt-free layered positive electrode material have better electrical properties, and the preparation method has simple steps and has the potential for mass production.
  • the step of providing a core material includes: calcining a precursor mixture to obtain the core material, wherein the precursor mixture includes a precursor of lithium and a precursor of nickel and manganese, and The calcination treatment is 10-15 hours at 800-1000 degrees Celsius.
  • the titanium compound includes at least one of titanium dioxide and tetrabutyl titanate.
  • the high-temperature treatment of the coating is 4-8 hours at 400-700 degrees Celsius.
  • the ammonia gas treatment is 3 to 5 hours at 400-700 degrees Celsius.
  • the present invention proposes a lithium ion battery.
  • the lithium ion battery includes a positive electrode, an electrolyte, and a negative electrode, wherein the positive electrode is formed of the aforementioned cobalt-free layered positive electrode material.
  • the positive electrode is formed of a cobalt-free layered positive electrode material with lower cost and better rate performance, so that the price of the lithium ion battery is lowered and the electrochemical performance is better.
  • FIG. 1 is a schematic cross-sectional structure diagram of a cobalt-free layered cathode material with a core-shell structure according to an embodiment of the present invention
  • FIG. 3 is a first week charge and discharge curve before and after coating of a cobalt-free layered cathode material according to an embodiment of the present invention
  • FIG. 5 is a comparison of discharge specific capacity at different rates before and after coating of a cobalt-free layered cathode material according to an embodiment of the present invention.
  • the present invention proposes a cobalt-free layered cathode material.
  • the cobalt-free layered cathode material has a core-shell structure, and the material forming the outer shell 200 of the core-shell structure includes titanium nitride, and the material forming the core 100 of the core-shell structure does not include cobalt and It is a single crystal structure.
  • the inventor of the present invention discovered during the research process that the cost of the ternary cathode material of lithium ion power battery has been reduced with the development of low cobalt, but the lower the content of cobalt, the conductivity of the cathode material will also change. It is reduced, and the rate performance deteriorates.
  • the inventor coats a layer of titanium nitride (TiN) shell 200 on the surface of the cobalt-free core 100, which can significantly increase the conductivity of the cobalt-free layered cathode material, thereby making the rate performance of the cobalt-free cathode material better .
  • TiN titanium nitride
  • the material forming the core 100 may be LiNi x Mn y O 2 , where 0.55 ⁇ x ⁇ 0.95, 0.05 ⁇ y ⁇ 0.45, specifically, for example, LiNi 0.75 Mn 0.25 O 2 , so that it does not contain
  • the cobalt (Co) core material can make the cobalt-free layered cathode material higher in capacity and lower in cost, which is more conducive to commercial applications.
  • the choice of LiNi x Mn y O 2 (0.55 ⁇ x ⁇ 0.95, 0.05 ⁇ y ⁇ 0.45) as the core material is also obtained by the inventors through a large number of experiments. Compared with other core materials, this core material
  • the positive electrode material formed together with the titanium nitride coating layer can further improve its battery performance, with better rate performance, and higher capacity and capacity retention.
  • the particle size of the material forming the core 100 may be 1 to 5 microns.
  • the shrinkage and expansion during the later cycle of charging and discharging will not be as polycrystalline.
  • the particles produce new grain boundary interfaces or side reactions, so that the cycle stability of the cobalt-free layered cathode material is better.
  • Figure 2 (a) and (b) the surface of the core material before coating is relatively smooth, and the particle size is between 1 to 5 microns; refer to Figure 2 (c) and (d), There is obviously a coating on the surface of the coated positive electrode material.
  • the particle size of the titanium nitride material forming the shell 200 may be 50-500 nm, specifically, for example, 100 nm or less. In this way, the outer surface of the core 100 can be more uniformly coated with high-conductivity Titanium nitride makes the cycle stability of the cobalt-free layered cathode material better.
  • the content of titanium nitride (TiN) is 0.13 to 0.39% (wt), that is, the addition amount of titanium can be 0.10 to 0.30% (wt), so that only
  • the surface of the cobalt-free layered cathode material needs to be coated with a titanium nitride shell of 1/1000 to 4/1000, which can increase the specific capacity of charge and discharge in the first week by 3%, and the capacity retention rate after 50 weeks of 1C rate cycling It is higher than 99%, and the discharge specific capacity under 2C and 4C rate is increased by more than 10%.
  • the first charge and discharge curve can be referred to Figure 3.
  • the first week charge and discharge specific capacities of 0.1C of the cathode material before coating are 200.5 and 173.3, respectively. mAh/g, its first efficiency is 86.4%, and the first week charge and discharge specific capacity of the coated material at 0.1C are 207.5 and 185.0mAh/g, and its first efficiency is 89.2%, indicating that the coated titanium nitride
  • the coating is beneficial to improve the capacity and first-time efficiency of the cobalt-free layered cathode material.
  • the cycle performance comparison before and after coating can refer to Figure 4.
  • the capacity retention of the material before coating after 50 weeks of cycling at a rate of 1C The rate is 96.9%, and the capacity retention rate of the coated material after 50 weeks of cycling at a rate of 1C is 99.3%, indicating that the coating layer of titanium nitride avoids the contact between the cobalt-free layered cathode material and the electrolyte. Reduce the side reaction between it and the electrolyte, thereby increasing the cycle performance by 2.4%.
  • the rate performance before and after coating can refer to Figure 5.
  • the discharge specific capacity of the positive electrode material before coating is only 143mAh/g, and the discharge specific capacity of the material after coating reaches 157mAh/g, while for the 4C rate
  • the specific discharge capacity of the material before coating is only 132mAh/g, and the specific discharge capacity of the material after coating reaches 146mAh/g, indicating that titanium nitride has good conductivity and can improve the electrochemical activity of the cobalt-free layered cathode.
  • the present invention proposes a cobalt-free layered cathode material, which is coated with high-conductivity titanium nitride on the surface of a cobalt-free core, which reduces the price and cost of the cathode material. , Can also improve the rate performance of the cathode material, so that the rate performance of the cobalt-free cathode material is better.
  • the present invention provides a method for preparing a cobalt-free layered cathode material.
  • the preparation method includes:
  • step S100 may be: calcining the precursor mixture to obtain a core material, where the precursor mixture includes a precursor of lithium (Li) and a precursor of nickel (Ni) manganese (Mn), and the calcining treatment may It is 10-15 hours at 800-1000 degrees Celsius.
  • the precursor of lithium can be selected from lithium hydroxide (LiOH) or lithium carbonate (Li 2 CO 3 ) and other lithium salts
  • the precursor of nickel manganese can be selected from Ni x Mn y (OH) 2 , Where 0.55 ⁇ x ⁇ 0.95, 0.05 ⁇ y ⁇ 0.45, in this way, a cobalt-free core material LiNi x Mn y O 2 is formed , specifically, for example, LiNi 0.75 Mn 0.25 O 2 , so that the cobalt-free layered cathode material While the capacity is higher, the preparation cost and price are lower.
  • LiOH or Li 2 CO 3 and Ni x Mn y (OH) 2 (0.55 ⁇ x ⁇ 0.95, 0.05 ⁇ y ⁇ 0.45) can be mixed with high-speed mixing equipment, where the rotation speed is 800-900rpm, and the mixing time In 5-20 minutes; roast the above mixture in a kiln at a temperature of 800-1000°C for 10-15 hours, with an atmosphere of O 2 and an O 2 concentration greater than 90%; crush the sintered material through a pair of rollers With mechanical crushing, the crushed material is passed through a 300-400 mesh sieve to obtain the core material.
  • S200 A compound in which titanium is coated on the surface of the core material.
  • the surface of the core material is coated with a titanium compound, wherein the titanium compound is tetravalent titanium (Ti 4+ ).
  • the titanium compound may include at least one of titanium dioxide and tetrabutyl titanate.
  • titanium dioxide (TiO 2 ) can be selected for the titanium compound. In this way, choosing titanium oxide with a wide range of sources and lower cost as the coating material can make the preparation cost of the cobalt-free layered cathode material lower and include The overlying shell layer is more uniform.
  • the crushed and sieved material in step S100 can be mixed with TiO 2 first , wherein the coating content of Ti is 0.10 to 0.30% (wt), the rotation speed is 800 to 950 rpm, and the mixing time is 5 to 50 minutes. Then the mixture is treated at a high temperature of 400-700 degrees for 4-8 hours to obtain a coated product.
  • S300 Perform ammonia gas treatment on the coated core material to obtain a cobalt-free layered cathode material coated with titanium nitride.
  • the coated core material is treated with ammonia gas to obtain a cobalt-free layered cathode material coated with titanium nitride.
  • ammonia gas can reduce the unstable Ni 3+ of the positive electrode material to stable Ni 2+ , and improve the stability of the material structure.
  • NH 3 can also nitridize the surface of the positive electrode material under high temperature conditions. After the surface conductivity of the material is improved, the heat resistance and corrosion resistance are significantly improved.
  • the product coated in step S200 can be processed in ammonia gas, where the temperature is 400-700 degrees, the time is 3-5 hours, and the natural cooling is performed; finally, the titanium nitride-coated material is processed for 300- The final product is obtained by sieving with 400 mesh.
  • the specific surface area of the cobalt-free layered cathode material coated with titanium nitride may be 0.1-0.8 m 2 /g, the residual alkali content is less than or equal to 0.5%, and the pH is not greater than 12.
  • the present invention proposes a preparation method.
  • the surface of the core material is coated with a compound of tetravalent titanium, and then processed into a titanium nitride shell in ammonia gas.
  • the surface of the cobalt-free core material is coated with a high-conductivity titanium nitride shell, so that the prepared cobalt-free layered cathode material has better electrical properties, and the preparation method has simple steps and has the potential for mass production .
  • a lithium ion battery in another aspect of the present invention, provides a lithium ion battery.
  • a lithium ion battery includes a positive electrode, an electrolyte, and a negative electrode, wherein the positive electrode is formed of the aforementioned cobalt-free layered positive electrode material.
  • a lithium-ion battery in addition to the positive electrode, electrolyte, and negative electrode, a lithium-ion battery also includes other necessary compositions and structures, such as a housing, electrode terminal, etc. Those skilled in the art can perform according to the specific design requirements of the lithium-ion battery. Choose the supplement accordingly, so I won't repeat it here.
  • the positive electrode is formed of a cobalt-free layered positive electrode material with lower cost and better rate performance, so that the price of the lithium ion battery is lowered and the electrochemical performance is better.
  • first and second are only used for description purposes, and cannot be understood as indicating or implying relative importance or implicitly indicating the number of indicated technical features. Therefore, the features defined with “first” and “second” may explicitly or implicitly include at least one of the features.
  • “plurality” means at least two, such as two, three, etc., unless otherwise specifically defined.
  • the lithium salt lithium hydroxide (LiOH) and the precursor of nickel manganese, Ni 0.75 Mn 0.25 (OH) 2 are mixed with high-speed mixing equipment, where the rotating speed is 900 rpm and the mixing time is 20 minutes; the above mixture is roasted in a kiln , The temperature is at 950°C, the time is 10 hours, the atmosphere is O 2 and the O 2 concentration is greater than 90%; the sintered material is crushed by rollers and mechanically crushed, and the crushed material is passed through a 300-mesh sieve to obtain the inner core
  • the material is LiNi 0.75 Mn 0.25 O 2 .
  • S200 A compound in which titanium is coated on the surface of the core material.
  • step S100 The crushed and sieved material of step S100 is mixed with TiO 2 first , where the coating content of Ti is 0.30% (wt), the rotating speed is 950 rpm, and the mixing time is 30 minutes, and then the mixture is treated at a high temperature of 600 degrees 8 Within hours, the coated product can be obtained.
  • S300 Perform ammonia gas treatment on the coated core material to obtain a cobalt-free layered cathode material coated with titanium nitride.
  • the coated product in step S200 can be processed in ammonia gas, where the temperature is 600 degrees, the time is 5 hours, and the natural cooling is performed; finally, the titanium nitride coated material is sieved with 400 mesh to obtain the final product.
  • the specific surface area of the cobalt-free layered cathode material coated with titanium nitride may be 0.6 m 2 /g, the residual alkali content is 0.2%, and the pH is 11.60.
  • the cobalt-free layered cathode material coated with titanium nitride prepared above has an average core size of 3 ⁇ m and an average thickness of the coating layer of 500 nm.
  • the lithium salt lithium hydroxide (LiOH) and the precursor of nickel manganese, Ni 0.95 Mn 0.05 (OH) 2 are mixed with high-speed mixing equipment, where the rotating speed is 900 rpm, and the mixing time is 20 minutes; the above mixture is roasted in a kiln , The temperature is 750°C, the time is 10 hours, the atmosphere is O 2 and the O 2 concentration is greater than 90%; the sintered material is crushed by rollers and mechanically crushed, and the crushed material is passed through a 300-mesh sieve to obtain the inner core
  • the material is LiNi 0.95 Mn 0.05 O 2 .
  • the lithium salt lithium hydroxide (LiOH) and the precursor of nickel manganese, Ni 0.55 Mn 0.45 (OH) 2 are mixed with high-speed mixing equipment, where the rotating speed is 900 rpm, and the mixing time is 20 minutes; the above mixture is roasted in a kiln , The temperature is 1000°C, the time is 10 hours, the atmosphere is O 2 and the O 2 concentration is greater than 90%; the sintered material is crushed by a pair of rollers and mechanically crushed, and the crushed material is passed through a 300-mesh sieve to obtain the inner core
  • the material is LiNi 0.55 Mn 0.45 O 2 .
  • the lithium salt lithium hydroxide (LiOH) and the precursor of nickel manganese, Ni 0.45 Mn 0.55 (OH) 2 are mixed with high-speed mixing equipment, where the rotation speed is 900 rpm and the mixing time is 20 minutes; the above mixture is roasted in a kiln , The temperature is 1050°C, the time is 10 hours, the atmosphere is O 2 and the O 2 concentration is greater than 90%; the sintered material is crushed by rollers and mechanically crushed, and the crushed material is passed through a 300-mesh sieve to obtain the inner core
  • the material is LiNi 0.45 Mn 0.55 O 2 .
  • the method is the same as in Example 1, except that the high temperature temperature is 970°C;
  • S200 A compound in which titanium is coated on the surface of the core material.
  • step S100 The crushed and sieved material of step S100 is mixed with TiO 2 first , where the coating content of Ti is 0.10% (wt), the rotation speed is 950 rpm, and the mixing time is 30 minutes, and then the mixture is treated at a high temperature of 600 degrees 8 Within hours, the coated product can be obtained.
  • S300 Perform ammonia gas treatment on the coated core material to obtain a cobalt-free layered cathode material coated with titanium nitride.
  • the coated product in step S200 can be processed in ammonia gas, where the temperature is 600 degrees, the time is 5 hours, and the natural cooling is performed; finally, the titanium nitride coated material is sieved with 400 mesh to obtain the final product.
  • the cobalt-free layered cathode material coated with titanium nitride prepared above has a core size of 5 ⁇ m and a coating layer thickness of 50 nm.
  • the method is the same as in Example 1, except that the high temperature temperature is 990°C;
  • S200 A compound in which titanium is coated on the surface of the core material.
  • the crushed and sieved material in step S100 is mixed with TiO 2 where the coating content of Ti is 0.40% (wt), the rotation speed is 950 rpm, and the mixing time is 30 minutes, and then the mixture is treated at a high temperature of 600 degrees 8 Within hours, the coated product can be obtained.
  • S300 Perform ammonia gas treatment on the coated core material to obtain a cobalt-free layered cathode material coated with titanium nitride.
  • the coated product in step S200 can be processed in ammonia gas, where the temperature is 600 degrees, the time is 5 hours, and the natural cooling is performed; finally, the titanium nitride coated material is sieved with 400 mesh to obtain the final product.
  • the cobalt-free layered cathode material coated with titanium nitride prepared above has a core size of 6 ⁇ m and a coating layer thickness of 700 nm.
  • the method is the same as in Example 1, except that the precursor is Ni 0.75 Mn 0.20 Co 0.05 (OH) 2 , and the core material is LiNi 0.75 Mn 0.20 Co 0.05 O 2 .
  • Performance characterization The performance characterization of the positive electrode materials prepared in the foregoing examples and comparative examples is as follows: the positive electrode material is homogenized and coated to make a positive electrode sheet, and then assembled into a lithium ion battery, and a metal lithium sheet is used for the negative electrode ;
  • the battery separator uses Celgard2400 microporous polypropylene membrane;
  • the electrolyte uses LiPF 6 (lithium hexafluorophosphate)/EC (ethylene carbonate)-DMC (dimethyl carbonate), and the battery model is R2032. Test the cycle performance, capacity, etc. of the battery, and the results are shown in Table 1:

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Abstract

一种无钴层状正极材料及其制备方法、锂离子电池。该无钴层状正极材料为核壳结构，且形成核壳结构的外壳（200）的材料包括氮化钛，形成核壳结构的内核（100）的材料不包括钴且为单晶结构。所述的无钴层状正极材料，在不含钴的内核（100）表面包覆高导电性的氮化钛，降低正极材料的价格成本的同时，还可使正极材料的倍率性能提升，从而使无钴正极材料的倍率性能更好。

Description

无钴层状正极材料及其制备方法、锂离子电池 技术领域
本发明涉及锂离子电池正极材料技术领域，具体的，本发明涉及无钴层状正极材料及其制备方法、锂离子电池。
背景技术
目前，三元正极材料在锂离子动力电池的应用越来越广泛。传统的三元正极材料中一般都含钴，而钴元素在三种元素中的价格是最高的，会导致三元正极材料的价格相对于LiFePO 4、LiMn 2O 4等其他正极材料明显高很多。所以，三元正极材料向着低钴化甚至无钴化方向发展。
虽然，无钴层状正极材料具有较高的容量和较低的成本，但是，无钴化反而使正极材料的导电性下降，进而影响到材料的倍率性能。
发明内容
本发明是基于发明人的下列发现而完成的：
本发明的发明人针对无钴正极材料存在导电性差、倍率性能差的技术问题，而提供了一种表面包覆有高导电性氮化钛的正极材料，不仅能提高无钴材料的表面导电性，同时还能降低无钴材料的表面阻抗，从而提高无钴材料的循环和倍率等电性能。
在本发明的第一方面，本发明提出了一种无钴层状正极材料。
根据本发明的实施例，所述无钴层状正极材料为核壳结构，且形成所述核壳结构的外壳的材料包括氮化钛，形成所述核壳结构的内核的材料不包括钴且为单晶结构。
本发明实施例的无钴层状正极材料，在不含钴的内核表面包覆高导电性的氮化钛，降低正极材料的价格成本的同时，还可使正极材料的倍率性能提升，从而使无钴正极材料的倍率性能更好。
另外，根据本发明上述实施例的无钴层状正极材料，还可以具有如下附加的技术特征：
根据本发明的实施例，形成所述内核的材料为LiNi xMn yO 2，其中，0.55≤x≤0.95，0.05≤y≤0.45。
根据本发明的实施例，形成所述内核的材料颗粒粒径为1～5微米。
根据本发明的实施例，所述外壳的厚度为50～500nm。
根据本发明的实施例，所述核壳结构中，所述氮化钛的含量为0.13～0.39％(wt)。
在本发明的第二方面，本发明提出了一种制备无钴层状正极材料的方法。
根据本发明的实施例，所述方法包括：提供内核材料，且所述内核材料不包括钴；在所述内核材料的表面包覆钛的化合物，其中，所述钛的化合物中为四价钛；将所述包覆后的所述内核材料进行氨气处理，以获得包覆有氮化钛的所述无钴层状正极材料。
采用本发明实施例的制备方法，先在内核材料表面包覆四价钛的化合物，再在氨气中处理成氮化钛的外壳，如此，在无钴内核材料的表面包覆上高导电性的氮化钛外壳，从而可使制备出的无钴层状正极材料的电性能更好，并且，该制备方法步骤简单且具有批量化生产的潜力。
另外，根据本发明上述实施例的方法，还可以具有如下附加的技术特征：
根据本发明的实施例，所述提供内核材料的步骤包括：对前驱体混合物进行煅烧处理，以获得所述内核材料，其中，前驱体混合物包括锂的前驱体和镍锰的前驱体，且所述煅烧处理为800～1000摄氏度下10～15小时。
根据本发明的实施例，所述钛的化合物包括二氧化钛和钛酸四丁酯中的至少一种。
根据本发明的实施例，所述包覆的高温处理为400～700摄氏度下4～8小时。
根据本发明的实施例，所述氨气处理为400～700摄氏度下3～5小时。
在本发明的第三方面，本发明提出了一种锂离子电池。
根据本发明的实施例，所述锂离子电池包括正极、电解质和负极，其中，所述正极由上述的无钴层状正极材料形成。
本发明实施例的锂离子电池，其正极由成本更低且倍率性能更好的无钴层状正极材料形成，从而使该锂离子电池的价格降低而电化学性能更好。本领域技术人员能够理解的是，前面针对无钴层状正极材料所描述的特征和优点，仍适用于该锂离子电池，在此不再赘述。
本发明的附加方面和优点将在下面的描述中部分给出，部分将从下面的描述中变得明显，或通过本发明的实践了解到。
附图说明
构成本申请的一部分的说明书附图用来提供对本发明的进一步理解，本发明的示意性实施例及其说明用于解释本发明，并不构成对本发明的不当限定。在附图中：
图1是本发明一个实施例的具有核壳结构的无钴层状正极材料的截面结构示意图；
图2是本发明一个实施例的无钴层状正极材料包覆前(a)(b)和包覆后(c)(d)的电镜照片；
图3是本发明一个实施例的无钴层状正极材料包覆前后的首周充放电曲线；
图4是本发明一个实施例的无钴层状正极材料包覆前后的循环保持率对比；
图5是本发明一个实施例的无钴层状正极材料包覆前后的不同倍率的放电比容量对比。
具体实施方式
下面详细描述本发明的实施例，本技术领域人员会理解，下面实施例旨在用于解释本发明，而不应视为对本发明的限制。除非特别说明，在下面实施例中没有明确描述具体技术或条件的，本领域技术人员可以按照本领域内的常用的技术或条件或按照产品说明书进行。
在本发明的一个方面，本发明提出了一种无钴层状正极材料。
根据本发明的实施例，参考图1，无钴层状正极材料为核壳结构，且形成核壳结构的外壳200的材料包括氮化钛，形成核壳结构的内核100的材料不包括钴且为单晶结构。本发明的发明人在研究过程中发现，锂离子动力电池的三元正极材料，随着低钴化的发展虽然成本有所降低，但是，钴的含量越低则正极材料的导电性也会随之下降，而导致倍率性能变差。所以，发明人在无钴的内核100表面包覆一层氮化钛(TiN)的外壳200，可显著地增加无钴层状正极材料的导电性，从而使无钴正极材料的倍率性能更好。
在本发明的一些实施例中，形成内核100的材料可以为LiNi xMn yO 2，其中，0.55≤x≤0.95，0.05≤y≤0.45，具体例如LiNi 0.75Mn 0.25O 2，如此，不含钴(Co)的内核材料，可使无钴层状正极材料的容量更高且成本价格更低，从而更利于商业化的应用。同时，需要说明的是，选择LiNi xMn yO 2(0.55≤x≤0.95，0.05≤y≤0.45)作为内核材料，也是本发明发明人经过大量实验所得，相比其他内核材料，该内核材料与氮化钛包覆层共同形成的正极材料，能够进一步提高其电池性能，倍率性能更好、容量及容量保持率更高。
在本发明的一些实施例中，形成内核100的材料颗粒尺寸可以为1～5微米，如此，采用上述尺寸的单晶结构，可在后期循环充放电过程中的收缩和膨胀不会像多晶颗粒那样产生新晶界界面或发生副反应，从而使无钴层状正极材料的循环稳定性更好。具体的，可以参考图2的(a)和(b)，包覆前的内核材料表面比较光滑，且颗粒尺寸在1～5微米之间；参考图2的(c)和(d)，包覆后的正极材料表面明显存在包覆物。
在本发明的一些实施例中，形成外壳200的氮化钛材料的颗粒尺寸可以为50～500nm，具体例如100nm以下，如此，可在内核100的外表面更均匀地包覆上高导电性的氮化钛，从而使无钴层状正极材料的循环稳定性更好。
在本发明的一些实施例中，在核壳结构中，氮化钛(TiN)的含量为0.13～0.39％(wt)，即钛的添加量可以为0.10～0.30％(wt)，如此，只需在无钴层状正极材料的表面包覆千分之一到千分之四的氮化钛外壳，即可使首周充放电比容量都提高3％、1C倍率循环50周后容量保持率高于99％，且2C和4C倍率下的放电比容量提升10％以上。
具体的，以LiNi 0.75Mn 0.25O 2作为无钴单晶正极材料，其首次充放电曲线可以参考图3，包覆前的正极材料0.1C的首周充电和放电的比容量分别为200.5和173.3mAh/g，其首次效率为86.4％，而包覆后的材料0.1C的首周充电和放电的比容量分别为207.5和185.0mAh/g，其首次效率为89.2％，说明包覆氮化钛的包覆有利于提高无钴层状正极材料的容量和首次效率。
此外，在25℃下以0.5C或1C的倍率且电压为3.0-4.3V，包覆前后的循环性能对比可以参考图4，包覆前的材料在1C的倍率下循环50周后的容量保持率为96.9％，而包覆后的材料在1C的倍率下循环50周后的容量保持率为99.3％，说明氮化钛的包覆层避免了无钴层状正极材料与电解液的接触，减少其与电解液之间的副反应，从而使循环性能提高了2.4％。
而且，包覆前后的倍率性能可以参考图5，对于2C的倍率，包覆前的正极材料放电比容量仅为143mAh/g，包覆后的材料放电比容量达到157mAh/g，而对于4C的倍率，包覆前的材料放电比容量仅为132mAh/g，包覆后的材料放电比容量达到146mAh/g，说明氮化钛导电性良好，可以提高无钴层状正极的电化学活性，从而使材料的倍率性能提升10％以上。
综上所述，根据本发明的实施例，本发明提出了一种无钴层状正极材料，在不含钴的内核表面包覆高导电性的氮化钛，降低正极材料的价格成本的同时，还可使正极材料的倍率性能提升，从而使无钴正极材料的倍率性能更好。
在本发明的另一个方面，本发明提出了一种制备无钴层状正极材料的方法。根据本发明的实施例，该制备方法包括：
S100：提供内核材料。
在该步骤中，提供内核材料，且内核材料不包括钴(Co)。其中，步骤S100可以为，对前驱体混合物进行煅烧处理，以获得内核材料，其中，前驱体混合物包括锂(Li)的前驱体和镍(Ni)锰(Mn)的前驱体，且煅烧处理可以是在800～1000摄氏度下10～15小时。
在本发明的一些实施例中，锂的前驱体可以选择氢氧化锂(LiOH)或碳酸锂(Li 2CO 3)等锂盐，而镍锰的前驱体可以选择Ni xMn y(OH) 2，其中，0.55≤x≤0.95，0.05≤y≤0.45，如此，形成不含钴的内核材料LiNi xMn yO 2，具体例如LiNi 0.75Mn 0.25O 2，从而可使无钴层状正极材料的容量更高的同时，制备成本和价格都更低。
具体的，可以将LiOH或Li 2CO 3和Ni xMn y(OH) 2(0.55≤x≤0.95，0.05≤y≤0.45)采用高速混合设备进行混合，其中，转速在800～900rpm，混合时间在5～20分钟；将上述混合物在窑炉中焙烧，温度在800～1000℃，时间10-15小时，气氛为O 2且O 2浓度大于90％；并将烧结后的物料通过对辊破碎和机械粉碎，将粉碎后的物料过300～400目筛，即可获得内核材料。
S200：在内核材料的表面包覆钛的化合物。
在该步骤中，在内核材料的表面包覆钛的化合物，其中，钛的化合物中为四价钛(Ti 4+)。在本发明的一些实施例中，钛的化合物可以包括二氧化钛和钛酸四丁酯中的至少一种。在一些具体事例中，钛的化合物可以选择二氧化钛(TiO 2)，如此，选择来源广泛且成本较低的氧化钛作为包覆材料，可使无钴层状正极材料的制备成本更低，且包覆的外壳层更均匀。
具体的，可以先将步骤S100的粉碎过筛后的物料与TiO 2混合，其中，Ti的包覆含量为0.10～0.30％(wt)，转速在800～950rpm，混合时间在5～50分钟，然后将混合料在400～700度高温处理4-8小时，即可获得包覆后的产品。
S300：将包覆后的内核材料进行氨气处理，以获得包覆有氮化钛的无钴层状正极材料。
在该步骤中，将包覆后的内核材料进行氨气处理，以获得包覆有氮化钛的无钴层状正极材料。氨气作为还原性气体，可以将正极材料不稳定的Ni 3+还原成稳定的Ni 2+，提高材料结构稳定性，同时在高温条件下NH 3还可以将正极材料表面进行氮化，氮化后材料表面导电性提高，耐热性和耐腐蚀性显著提高。
具体的，可以将步骤S200包覆后的产品在氨气中处理，其中，温度为400～700度，时间为3～5小时，自然冷却；最后，将包覆氮化钛的材料进行300～400目筛分得到最终产品。在本发明的一些实施例中，包覆有氮化钛的无钴层状正极材料的比表面积可以在0.1～0.8m 2/g，残碱含量小于等于0.5％，且pH不大于12。
综上所述，根据本发明的实施例，本发明提出了一种制备方法，先在内核材料表面包覆四价钛的化合物，再在氨气中处理成氮化钛的外壳，如此，在无钴内核材料的表面包覆上高导电性的氮化钛外壳，从而可使制备出的无钴层状正极材料的电性能更好，并且，该制备方法步骤简单且具有批量化生产的潜力。
在本发明的另一个方面，本发明提出了一种锂离子电池。根据本发明的实施例，锂离子电池包括正极、电解质和负极，其中，正极由上述的无钴层状正极材料形成。需要说明的是，锂离子电池除了包括正极、电解质和负极以外，还包括其他必要的组成和结构，具体例如外壳、电极引出端等，本领域技术人员可根据该锂离子电池的具体设计要求进行相应地选择补充，在此不再赘述。
本发明实施例的锂离子电池，其正极由成本更低且倍率性能更好的无钴层状正极材料形成，从而使该锂离子电池的价格降低而电化学性能更好。本领域技术人员能够理解的是，前面针对无钴层状正极材料所描述的特征和优点，仍适用于该锂离子电池，在此不再赘述。
在本发明的描述中，需要理解的是，术语“第一”、“第二”仅用于描述目的，而不能理解为指示或暗示相对重要性或者隐含指明所指示的技术特征的数量。由此，限定有“第一”、“第二” 的特征可以明示或者隐含地包括至少一个该特征。在本发明的描述中，“多个”的含义是至少两个，例如两个，三个等，除非另有明确具体的限定。
在本说明书的描述中，参考术语“一个实施例”、“一些实施例”、“示例”、“具体示例”、或“一些示例”等的描述意指结合该实施例或示例描述的具体特征、结构、材料或者特点包含于本发明的至少一个实施例或示例中。在本说明书中，对上述术语的示意性表述不必须针对的是相同的实施例或示例。而且，描述的具体特征、结构、材料或者特点可以在任一个或多个实施例或示例中以合适的方式结合。此外，在不相互矛盾的情况下，本领域的技术人员可以将本说明书中描述的不同实施例或示例以及不同实施例或示例的特征进行结合和组合。
以下通过实施例进一步说明本发明的有益效果：
实施例1
S100：提供内核材料。
将锂盐氢氧化锂(LiOH)、镍锰的前驱体Ni 0.75Mn 0.25(OH) 2采用高速混合设备进行混合，其中，转速在900rpm，混合时间在20分钟；将上述混合物在窑炉中焙烧，温度在950℃，时间10小时，气氛为O 2且O 2浓度大于90％；并将烧结后的物料通过对辊破碎和机械粉碎，将粉碎后的物料过300目筛，即可获得内核材料LiNi 0.75Mn 0.25O 2。
S200：在内核材料的表面包覆钛的化合物。
先将步骤S100的粉碎过筛后的物料与TiO 2混合，其中，Ti的包覆含量为0.30％(wt)，转速在950rpm，混合时间在30分钟，然后将混合料在600度高温处理8小时，即可获得包覆后的产品。
S300：将包覆后的内核材料进行氨气处理，以获得包覆有氮化钛的无钴层状正极材料。
可以将步骤S200包覆后的产品在氨气中处理，其中，温度为600度，时间为5小时，自然冷却；最后，将包覆氮化钛的材料进行400目筛分得到最终产品。在本发明的一些实施例中，包覆有氮化钛的无钴层状正极材料的比表面积可以在0.6m 2/g，残碱含量0.2％，且pH＝11.60。
上述制备的包覆有氮化钛的无钴层状正极材料，内核平均尺寸为3μm，包覆层平均厚度为500nm。
实施例2
S100：提供内核材料。
将锂盐氢氧化锂(LiOH)、镍锰的前驱体Ni 0.95Mn 0.05(OH) 2采用高速混合设备进行混合，其中，转速在900rpm，混合时间在20分钟；将上述混合物在窑炉中焙烧，温度在750℃，时 间10小时，气氛为O 2且O 2浓度大于90％；并将烧结后的物料通过对辊破碎和机械粉碎，将粉碎后的物料过300目筛，即可获得内核材料LiNi 0.95Mn 0.05O 2。
S200：和实施例1相同；。
S300：和实施例1相同。
实施例3
S100：提供内核材料。
将锂盐氢氧化锂(LiOH)、镍锰的前驱体Ni 0.55Mn 0.45(OH) 2采用高速混合设备进行混合，其中，转速在900rpm，混合时间在20分钟；将上述混合物在窑炉中焙烧，温度在1000℃，时间10小时，气氛为O 2且O 2浓度大于90％；并将烧结后的物料通过对辊破碎和机械粉碎，将粉碎后的物料过300目筛，即可获得内核材料LiNi 0.55Mn 0.45O 2。
S200：和实施例1相同。
S300：和实施例1相同。
实施例4
S100：提供内核材料。
将锂盐氢氧化锂(LiOH)、镍锰的前驱体Ni 0.45Mn 0.55(OH) 2采用高速混合设备进行混合，其中，转速在900rpm，混合时间在20分钟；将上述混合物在窑炉中焙烧，温度在1050℃，时间10小时，气氛为O 2且O 2浓度大于90％；并将烧结后的物料通过对辊破碎和机械粉碎，将粉碎后的物料过300目筛，即可获得内核材料LiNi 0.45Mn 0.55O 2。
S200：和实施例1相同；。
S300：和实施例1相同。
实施例5
S100：提供内核材料。
和实施例1方法相同，区别在于高温温度970℃；
S200：在内核材料的表面包覆钛的化合物。
先将步骤S100的粉碎过筛后的物料与TiO 2混合，其中，Ti的包覆含量为0.10％(wt)，转速在950rpm，混合时间在30分钟，然后将混合料在600度高温处理8小时，即可获得包覆后的产品。
S300：将包覆后的内核材料进行氨气处理，以获得包覆有氮化钛的无钴层状正极材料。
可以将步骤S200包覆后的产品在氨气中处理，其中，温度为600度，时间为5小时，自然冷却；最后，将包覆氮化钛的材料进行400目筛分得到最终产品。
上述制备的包覆有氮化钛的无钴层状正极材料，内核尺寸为5μm，包覆层厚度为50nm。
实施例6
S100：提供内核材料。
和实施例1方法相同，区别在于高温温度990℃；
S200：在内核材料的表面包覆钛的化合物。
先将步骤S100的粉碎过筛后的物料与TiO 2混合，其中，Ti的包覆含量为0.40％(wt)，转速在950rpm，混合时间在30分钟，然后将混合料在600度高温处理8小时，即可获得包覆后的产品。
S300：将包覆后的内核材料进行氨气处理，以获得包覆有氮化钛的无钴层状正极材料。
可以将步骤S200包覆后的产品在氨气中处理，其中，温度为600度，时间为5小时，自然冷却；最后，将包覆氮化钛的材料进行400目筛分得到最终产品。
上述制备的包覆有氮化钛的无钴层状正极材料，内核尺寸为6μm，包覆层厚度为700nm。
对比例1
其他同实施例3，不同之处在于：未进行步骤S200和S300，正极材料仅为LiNi 0.55Mn 0.45O 2。
对比例2
和实施例1方法相同，区别在于其前驱体为Ni 0.75Mn 0.20Co 0.05(OH) 2，内核材料为LiNi 0.75Mn 0.20Co 0.05O 2。
S200：和实施例1相同。
S300：和实施例1相同。
性能表征：对上述各实施例和对比例中制备的正极材料进行性能表征，具体如下：将正极材料材料经过匀浆、涂布制作成正极片，然后组装成锂离子电池，负极选用金属锂片；电池隔膜选用Celgard2400微孔聚丙烯膜；电解液选用LiPF 6(六氟磷酸锂)/EC(碳酸乙烯酯)-DMC(碳酸二甲酯)，电池型号R2032。测试电池的循环性能、容量等，结果见表1：
表1
Figure PCTCN2020132904-appb-000001
尽管上面已经示出和描述了本发明的实施例，可以理解的是，上述实施例是示例性的，不能理解为对本发明的限制，本领域的普通技术人员在本发明的范围内可以对上述实施例进行变化、修改、替换和变型。

Claims (10)

  1. 一种无钴层状正极材料，其特征在于，所述无钴层状正极材料为核壳结构，且形成所述核壳结构的外壳的材料包括氮化钛，形成所述核壳结构的内核的材料不包括钴且为单晶结构。
  2. 根据权利要求1所述的无钴层状正极材料，其特征在于，形成所述内核的材料为LiNi xMn yO 2，其中，0.55≤x≤0.95，0.05≤y≤0.45。
  3. 根据权利要求2所述的无钴层状正极材料，其特征在于，形成所述内核的材料颗粒粒径尺寸为1～5微米。
  4. 根据权利要求1所述的无钴层状正极材料，其特征在于，所述外壳的厚度为50～500nm。
  5. 根据权利要求1所述的无钴层状正极材料，其特征在于，在所述核壳结构中，所述氮化钛的含量为0.13～0.39％(wt)。
  6. 一种制备无钴层状正极材料的方法，其特征在于，包括：
    提供内核材料，其中，所述内核材料不包括钴且为单晶结构；
    在所述内核材料的表面包覆钛的化合物，其中，所述钛的化合物中为四价钛；
    将所述包覆后的所述内核材料进行氨气处理，以获得包覆有氮化钛的所述无钴层状正极材料。
  7. 根据权利要求6所述的方法，其特征在于，所述提供内核材料的步骤包括：
    对前驱体混合物进行煅烧处理，以获得所述内核材料，其中，前驱体混合物包括锂的前驱体和镍锰的前驱体，且所述煅烧处理为800～1000摄氏度下10～15小时。
  8. 根据权利要求6所述的方法，其特征在于，所述钛的化合物包括二氧化钛和钛酸四丁酯中的至少一种。
  9. 根据权利要求6所述的方法，其特征在于，所述包覆的高温处理为400～700摄氏度下4～8小时；所述氨气处理为400～700摄氏度下3～5小时。
  10. 一种锂离子电池，其特征在于，包括正极、电解质和负极，其中，所述正极由权利要求1～5中任一项所述的无钴层状正极材料形成。
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