WO2021012708A1 - 硅氧修饰的高镍金属氧化物材料及其制备方法 - Google Patents

硅氧修饰的高镍金属氧化物材料及其制备方法 Download PDF

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WO2021012708A1
WO2021012708A1 PCT/CN2020/082647 CN2020082647W WO2021012708A1 WO 2021012708 A1 WO2021012708 A1 WO 2021012708A1 CN 2020082647 W CN2020082647 W CN 2020082647W WO 2021012708 A1 WO2021012708 A1 WO 2021012708A1
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metal oxide
nickel metal
high nickel
alkylsiloxane
preparation
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PCT/CN2020/082647
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English (en)
French (fr)
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郑军伟
曹海尚
戴惠
杜芳惠
周群
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苏州大学
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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/052—Li-accumulators
    • H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/362—Composites
    • H01M4/366—Composites as layered products
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
    • 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
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • 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
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
    • 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
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
    • 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
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/10—Energy storage using batteries

Definitions

  • the invention relates to the technical field of lithium ion cathode material preparation, in particular to a silicon-oxygen modified high nickel metal oxide cathode material and a preparation method thereof.
  • the present invention also relates to a lithium ion battery formed from the high nickel metal oxide material.
  • Lithium-ion batteries have become an important carrier for new energy storage due to their high energy density and long cycle life.
  • the rapid development of new energy sources based on wind and solar energy and electric vehicles driven by electricity in the world have put forward new requirements on the performance of lithium-ion batteries, especially these applications urgently require lithium-ion batteries to have higher The energy density.
  • the energy density of lithium-ion batteries is largely dependent on their cathode materials, so it has become a top priority for the lithium-ion battery industry to promote the large-scale industrialization of large-capacity cathode materials.
  • Lithium ion battery cathode materials are generally lithium-containing transition metal oxides or polyanionic transition metal compounds. At present, cathode materials are mainly concentrated on the structural basis of materials such as lithium cobaltate, lithium nickelate, lithium manganate and lithium iron phosphate, and various related derivative materials are formed through structural modification or surface modification.
  • the layered nickel-based oxide material is a derivative material of lithium nickelate. Through ion doping, other transition metals such as cobalt, aluminum and manganese are introduced into the structure of lithium nickelate.
  • the synergistic effect between the framework metal ions gives high nickel Metal oxides have relatively high specific capacity, excellent cycle performance, high safety and low cost.
  • high nickel metal oxides are usually prepared by co-precipitation, and their capacity increases as their nickel content increases.
  • the high nickel ternary material prepared by the co-precipitation method usually has a strong alkaline surface, which makes it easy to absorb moisture in the environment, and can combine with carbon dioxide in the air on the surface of the electrode material to form lithium carbonate, thereby reducing material performance.
  • battery pole pieces made of high-nickel metal oxide are also very sensitive to environmental humidity. Often, extra moisture is introduced into the battery during the manufacturing process of the battery, which intensifies the side reaction of the electrolyte. This requires an extremely low humidity production environment during the preparation of electrode material slurry and cell preparation, and the corresponding control conditions are extremely harsh, which will undoubtedly greatly increase cell manufacturing costs. Therefore, the stringent requirements of high-nickel ternary materials for environmental humidity are the key bottleneck for their large-scale industrial application.
  • the high surface reaction activity of the high nickel metal oxide makes it easy to cause side reactions at the electrode/electrolyte interface during battery storage and charge-discharge cycles once it comes into contact with the electrolyte, which improves the performance of the battery, especially
  • the rapid deterioration of cycle performance is also a major obstacle to the large-scale application of lithium-ion batteries with high nickel metal oxide as the positive electrode.
  • a large number of studies have so far explored the degradation mechanism and solutions of high nickel metal oxides.
  • the existing technology mainly uses surface coating technology to coat the surface of the material with inert substances, and isolate the material from the environment or the direct contact between the material and the electrolyte through the coating layer on the surface of the high nickel metal oxide material.
  • oxides, metal phosphates, fluorides or other positive electrode materials are used as physical shielding layers to slow down side reactions that occur in contact between high nickel metal oxides and electrolytes and improve the cycle performance of nickel metal oxides.
  • this type of coating technology has the advantages of simple process and low cost, the reported surface coating technology is difficult to obtain a uniform and dense coating layer, and the thickness of the coating layer cannot be accurately controlled, which will seriously affect the charge transfer , Unable to meet the requirements of large-scale production of materials and battery applications.
  • ALD atomic vapor deposition
  • high nickel metal oxide materials still have problems that need to be solved urgently in terms of material production, pole piece production, and battery cell performance.
  • people are eager to increase the charge and discharge capacity of the material and the battery's capacity by increasing the nickel content in the material.
  • Energy density but with the increase of nickel content in the material, the problems of high nickel metal oxide materials have become particularly prominent. Therefore, a new feasible technology has been explored to solve the problem of high nickel metal oxide materials as cathode materials for lithium-ion batteries. Problems are an important prerequisite and guarantee for the industrialization of nickel metal oxide lithium-ion batteries with high energy density and high nickel metal oxide.
  • the purpose of the present invention is to provide a silicon-oxygen modified high nickel metal oxide material and a preparation method thereof.
  • the preparation method of the present invention has simple process, low cost, low environmental humidity requirement, and is suitable for large Large-scale industrialization, the thickness of the modified layer on the surface of the prepared electrode material is extremely thin and controllable, low sensitivity to humidity, stable interface, and excellent electrochemical performance.
  • the invention provides a method for preparing a silicon-oxygen modified high nickel metal oxide material, which comprises the following steps:
  • the alkyl siloxane solution includes the alkyl siloxane, and then react at 40 to 90 °C to obtain the surface modified alkyl High nickel metal oxide of siloxane;
  • the solute of the alkylsiloxane solution is alkylsiloxane
  • the alkylsiloxane includes but is not limited to monooctyltrimethoxysilane and 3-ureapropyltrimethoxysilane.
  • Alkylsiloxane contains a longer carbon chain, has a large steric hindrance, and does not form a large amount of polycondensation products, thereby forming a thick coating on the surface of the particles.
  • the alkyl siloxane is hydrolyzed and condensed with the surface groups of the material to form a very thin alkyl siloxane modified layer.
  • the solvent of the alkylsiloxane solution is an organic solvent
  • the organic solvent includes, but is not limited to, methanol, isopropanol, tert-butanol, ethanol, acetone, n-hexane, benzene and toluene. One or more.
  • the content of alkylsiloxane is 0.1 to 5% of the mass of the high nickel metal oxide.
  • the alkylsiloxane is 0.5 to 1.5% of the mass of the high nickel metal oxide.
  • step (1) the high nickel metal oxide is dispersed in the alkylsiloxane solution for 5 to 120 minutes.
  • the dispersion time is 10-30 minutes.
  • the dispersion method is one or more of ultrasonic, stirring and ball milling.
  • step (1) the reaction is carried out under stirring conditions, and the stirring speed is 200-1000 r/min.
  • the stirring speed is 300 to 500 r/min, and the reaction time is 0.5 to 6 h.
  • the reaction method is a stirring method or a stirring condensation reflux method.
  • step (1) it also includes the step of removing the organic solvent and drying the product.
  • the method of removing the organic solvent is one or more of heat drying, vacuum drying, spray drying and freeze drying.
  • step (2) the calcination time of the high nickel metal oxide in an oxygen-containing atmosphere is 0.5-10 h.
  • the calcination temperature is 500-750°C, and the calcination time is 1 to 3 hours.
  • step (2) during calcination, the temperature is raised from room temperature to 450°C to 800°C for treatment, and the temperature rise rate is 1 to 20°C/min, preferably 5 to 10°C/min.
  • the oxygen-containing atmosphere is one of pure oxygen, a mixed gas of oxygen and nitrogen, and a mixed gas of air and oxygen.
  • the high nickel metal oxide is lithium nickel cobalt aluminate (molecular formula: LiNi 0.8 Co 0.15 Al 0.05 ) or lithium nickel cobalt manganate (molecular formula: LiNi 0.8 Co 0.1 Mn 0.1 ).
  • the other metal element is a rare earth element; more preferably, the other metal element is magnesium, iron, zirconium, molybdenum, titanium or lanthanum.
  • alkyl siloxane is used as a synthetic raw material, which will be initially hydrolyzed when dispersed in an organic solvent, and the R-Si-OH bond (R represents an alkyl chain) and the hydroxyl group on the surface of the high nickel metal oxide undergo condensation reaction , Thereby connecting to the high nickel metal oxide surface.
  • R-Si-OH bond R represents an alkyl chain
  • Changing the mass ratio of high nickel metal oxide to alkylsiloxane can appropriately change the thickness of the silicon-oxygen modified layer on the surface of the electrode material that is finally prepared.
  • the R is oxidized so that the high nickel metal oxide surface groups become Si-O (silicon oxygen ) Group.
  • the present invention uses alkylsiloxane to modify the high nickel metal oxide, and then performs high temperature oxidation to oxidize the modified alkylsiloxane group to siloxy group, so that the modified layer is extremely thin and free of R groups. interference.
  • the second object of the present invention is to provide a silicon-oxygen modified high-nickel metal oxide material prepared by the above preparation method, which includes high-nickel metal oxide particles and several siloxy groups connected to the surface of the particles.
  • the third object of the present invention is to protect the application of the above-mentioned high nickel metal oxide material as an electrode material.
  • the siloxy group is connected to the surface of the high nickel metal oxide particles through a chemical bond, which improves the hydrophobicity of the electrode material, improves the sensitivity of the electrode material to humidity, and does not affect the compatibility of the electrode material surface with the electrolyte.
  • the high nickel metal oxide material modified with siloxy groups are uniform and densely modified on the surface of the material, which can realize the effect of physical shielding, reduce the side reactions caused by the contact between the electrode and the electrolyte, and modify the silicon oxide
  • the layer is extremely thin and does not affect the charge transfer, so the cycle performance is greatly improved compared with the original material, and the storage is more stable at high temperatures.
  • the present invention has at least the following advantages:
  • the preparation method of the present invention adopts a simple process, and the reaction and post-processing equipment used are relatively common. It overcomes the defects of the existing preparation of electrode materials that require strict control of environmental humidity and reaction conditions. It can be realized in a conventional environment without strict The environmental humidity is controlled, the process is easy to realize, the cost is low, the thickness of the modification is controllable, and it is suitable for large-scale industrial production.
  • the surface of high nickel metal oxide particles is first modified with alkylsiloxane, which is an extremely thin, uniform and dense modified layer, and after calcination, a silicon-oxygen modified high nickel metal oxide material is obtained.
  • the modification of the siloxy group not only improves the sensitivity of the material to humidity, but also improves the interface stability of the electrode material. It can protect the electrode and improve the charge transfer during the cycle, thereby improving the battery cycle and rate performance.
  • Figure 1 is a test diagram of the contact angle between different particles and water in Example 1 of the present invention.
  • Figure 2 is a cycle discharge curve at 55°C for batteries made of different materials in Example 1 of the present invention.
  • Figure 3 is a cyclic discharge curve of batteries made of different materials in Example 1 of the present invention when 200 ppm water is added to the electrolyte;
  • Example 4 is a diagram of rate discharge of batteries prepared from different materials in Example 1 of the present invention under different currents;
  • Figure 5 is a scanning electron micrograph of electrodes of different materials in Example 1 of the present invention after high temperature cycling;
  • Fig. 6 is a voltage curve of different materials placed at a high temperature after being charged to 4.3V in Example 1 of the present invention
  • Figure 7 is a test diagram of the contact angle between different particles and water in Example 2 of the present invention.
  • Figure 8 is a cyclic discharge curve at 25°C for batteries made of different materials in Example 2 of the present invention.
  • Fig. 9 is a cycle discharge curve at 55°C of batteries made of different materials in Example 2 of the present invention.
  • Fig. 10 is a scanning electron microscope photograph of the electrode after 500 cycles of different materials in Example 2 of the present invention.
  • This embodiment provides a silicon-oxygen modified high nickel metal oxide material for a lithium ion battery and a preparation method thereof.
  • the lithium nickel cobalt aluminate material (molecular formula: LiNi 0.8 Co 0.15 Al 0.05 ) is used as the original cathode material, which specifically includes the following step:
  • the dried sample is subjected to high-temperature oxidation treatment in an oxygen atmosphere, the temperature is raised from room temperature, the heating rate is 5°C/min, and the temperature is maintained at 500°C for 1h to obtain a silicon-oxygen-modified nickel cobalt lithium aluminum oxide ternary Cathode material.
  • NCA@Si-O silicon-oxygen modified lithium nickel cobalt aluminate ternary cathode material
  • NCA-P nickel cobalt lithium aluminate material
  • the lithium ion battery prepared by the material of the present invention was charged and discharged at 55°C and a current of 1C at 194mAh/g for the first time. After 200 cycles of charge and discharge, the specific capacity was maintained at 133mAh/g Compared with the original cathode material electrode of 196.4mAh/g for the first time, it maintains at 92.8mAh/g after 200 times, and its cycle performance is greatly improved.
  • Figure 3 shows that the battery prepared by the material of the present invention has a smaller reduction in specific capacity after being cycled for 200 cycles, indicating that the electrode material of the present invention has better cycle stability in the presence of a trace amount of water, thus greatly improving Sensitivity to environmental humidity during the preparation of pole pieces and batteries.
  • Figure 4 is the rate discharge diagram of the above two groups of batteries under different currents. It can be seen from the figure that the discharge capacity of the battery prepared by the material of the present invention is basically the same as that of the original material under different current levels, indicating that the discharge capacity of the battery is basically the same as that of the original material.
  • the thin silicon-oxygen modified layer does not affect the charge transfer during charging and discharging.
  • Figure 5 shows that after cycling the lithium nickel cobalt aluminate material in the control group, a large amount of solid electrolyte was formed on the surface of the material.
  • the membrane (SEI membrane) ( Figure 5a) is caused by the side reaction between the electrode material and the electrolyte. A large number of SEI membranes will affect the charge transfer at the interface, thereby affecting the electrochemical performance of the electrode material.
  • the electrode material of the present invention After the electrode material of the present invention is cycled, there are fewer solid electrolyte membranes on the surface of the material, indicating that side reactions between the material and the electrolyte are suppressed, and the interface stability of the material is higher, thereby ensuring the stability of the electrochemical performance of the electrode material.
  • Figure 6 is the voltage curve of the original nickel cobalt lithium aluminate material and the nickel cobalt lithium aluminate ternary cathode material prepared in this example after being charged to 4.3V and standing at 55°C, compared with the original nickel cobalt lithium aluminate material
  • the voltage decay of the silicon-oxygen modified nickel-cobalt-lithium aluminate material is extremely slow during high-temperature standing, which shows that under high temperature and high voltage, the dense ultra-thin silicon-oxygen modified layer can well isolate the contact between the electrode material and the electrolyte. Reduce the chemical reaction activity of the interface, inhibit a large number of side reactions, improve the stability of the interface, so as to obtain excellent electrochemical performance.
  • This embodiment provides a silicon-oxygen modified high nickel metal oxide material for a lithium ion battery and a preparation method thereof.
  • the lithium nickel cobalt manganate material (molecular formula: LiNi 0.8 Co 0.1 Mn 0.1 ) is used as the original cathode material, which specifically includes The following steps:
  • the dried sample is subjected to high-temperature oxidation treatment in an oxygen atmosphere, the temperature is raised from room temperature, the heating rate is 5°C/min, and the temperature is maintained at 500°C for 1h to obtain a silicon-oxygen modified nickel cobalt manganese lithium ternary Cathode material.
  • the lithium nickel cobalt manganese oxide ternary cathode material (NCM@Si-O) prepared in this embodiment is made into a button type lithium ion battery, and the button type lithium ion battery is made of the original nickel cobalt manganese oxide material (NCM-P). Lithium-ion batteries served as a control group. Perform cyclic discharge test on it. The results are shown in Figure 8.
  • NCM@Si-O represents a coin-type lithium ion battery made of the nickel cobalt manganese lithium ternary cathode material prepared in this example, and NCM-P represents a control battery.
  • the first discharge capacity of the lithium-ion battery prepared by the material at 25°C and 1C current is 173.5mAh/g, and the discharge capacity after 300 cycles of charge and discharge is 152mAh/g; the first discharge capacity of the original cathode material electrode is 174mAh/g, 300
  • the discharge capacity after one time was 109mAh/g. It can be seen that the silicon-oxygen modification of the material surface greatly improves the electrochemical performance of the material. At the same time, at 55°C, the cycle charge and discharge performance of the battery prepared by the material of the present invention is also significantly better than that of the control group ( Figure 9).
  • Figure 10 shows that after the electrode material of the present invention is cycled, the surface of the material still has granular morphology (10a, b), indicating that there are few side reactions between the material and the electrolyte, and the electrode morphology is basically not affected. However, the solid electrolyte film formed on the surface of the lithium nickel cobalt manganate material of the control group was very thick after the cycle ( Figure 10c, d).
  • the silicon-oxygen modified high nickel metal oxide material was prepared according to the method of Example 1, except that: in step (1), the alkylsiloxane used was vinyl tris(2-methoxyethoxy Base) silane whose mass is 0.5% of lithium nickel cobalt aluminate, and the stirring speed is 300 r/min.
  • the alkylsiloxane used was vinyl tris(2-methoxyethoxy Base) silane whose mass is 0.5% of lithium nickel cobalt aluminate, and the stirring speed is 300 r/min.
  • the silicon-oxygen modified high nickel metal oxide material was prepared according to the method of Example 1, except that: in step (1), the alkylsiloxane used was vinyl tris(2-methoxyethoxy Base) silane whose mass is 2% of lithium nickel cobalt aluminate and the stirring speed is 400 r/min.
  • the silicon-oxygen-modified high-nickel metal oxide material was prepared according to the method of Example 1, except that: in step (1), the mass of monooctyltrimethoxysilane used was 5 times that of lithium nickel cobalt aluminate. %, the stirring speed is 600r/min.
  • the silicon-oxygen modified high nickel metal oxide material was prepared according to the method of Example 1, except that: in step (2), the heating temperature of the dispersion was 50° C., and the reaction time was 10 hours.
  • the silicon-oxygen modified high-nickel metal oxide material was prepared according to the method of Example 1, except that: in step (2), the heating temperature of the dispersion was 70° C., and the reaction time was 3 h.
  • the silicon-oxygen modified high nickel metal oxide material was prepared according to the method of Example 1, except that: in step (2), the heating temperature of the dispersion was 100° C., and the reaction time was 0.5 h.
  • the silicon-oxygen modified high nickel metal oxide material was prepared according to the method of Example 1, except that: in step (3), the heating rate was 1° C./min, and the temperature was maintained at 400° C. for 10 hours.
  • the silicon-oxygen modified high nickel metal oxide material was prepared according to the method of Example 1, except that: in step (3), the heating rate was 8° C./min, and the temperature was maintained at 600° C. for 6 hours.
  • the silicon-oxygen modified high nickel metal oxide material was prepared according to the method of Example 1, except that: in step (3), the heating rate was 10° C./min, and the temperature was maintained at 700° C. for 3 hours.
  • the silicon-oxygen modified high nickel metal oxide material was prepared according to the method of Example 1, except that: in step (3), the heating rate was 20° C./min, and the temperature was maintained at 800° C. for 0.5 h.

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Abstract

一种硅氧修饰的高镍金属氧化物材料及制备方法，所述的制备方法包括以下步骤：a、制备烷基硅氧烷溶液；b、将高镍金属氧化物加入烷基硅氧烷溶液中分散，对高镍金属氧化物表面进行烷基硅氧烷修饰；c、通过高温处理制备硅氧修饰的高镍金属氧化物材料。由上述方法所制备的电极材料，所制备电极材料表面的修饰层厚度极薄且可控，对湿度敏感性低，所得高镍金属氧化物正极材料界面稳定，能够极大改善相应的锂离子电池的循环和储存性能。

Description

硅氧修饰的高镍金属氧化物材料及其制备方法 技术领域
本发明涉及锂离子正极材料制备技术领域，尤其涉及一种硅氧修饰的高镍金属氧化物正极材料及其制备方法。本发明还涉及由所述高镍金属氧化物材料形成的锂离子电池。
背景技术
能源危机和环境污染问题日渐突出，开发绿色可持续新能源成为社会焦点问题。锂离子电池因其能量密度大、循环寿命长而成为新能源储能的重要载体。目前，国际上迅速发展的以风能、太阳能为主的新能源以及以电力为驱动能的电动汽车，都对锂离子电池性能提出了新的要求，尤其是这些应用迫切需要锂离子电池具有更高的能量密度。而锂离子电池的能量密度很大程度上依赖其正极材料，因而促进大容量正极材料的规模产业化已成为锂离子电池产业的当务之急。
锂离子电池正极材料一般为含锂的过渡金属氧化物或聚阴离子过渡金属化合物。目前，正极材料主要集中于钴酸锂、镍酸锂、锰酸锂和磷酸铁锂等材料的结构基础上，通过结构修饰或表面改性形成相关的各类衍生材料。
层状镍基氧化物材料属于镍酸锂的衍生材料，通过离子掺杂，将其他过渡金属如钴、铝锰等引入到镍酸锂结构中，通过骨架金属离子间的协同效应，赋予高镍金属氧化物相对高比容量、优循环性能、高安全性及低成本。目前，高镍金属氧化物通常采用共沉淀法制备，其容量随着其镍含量的提高而增加。但共沉淀法制备所得高镍三元材料通常表面呈强碱性，使其易吸收环境中水分，并可与空气中二氧化碳在电极材料表面结合形成碳酸锂，从而降低材料性能。同样的，以高镍金属氧化物制备的电池极片对环境湿度也十分敏感，往往在电芯制造过程中，会带入电芯额外水分，从而加剧电解液的副反应。这就要求在电极材料浆料制备和电芯制备过程中，需具备极低湿度的生产环境，其相应的控制条件极端苛刻，无疑会极大地提高了电芯制造成本。因而，高镍三元材料对环境湿度的严苛要求是其规模产业化应用的关键瓶颈问题。另一方面，高镍金属氧化物的高表面反应活性，使其一旦与电解液接触，在电池储存和充放电循环中，易发生电极/电解液界面副反应，从而使电池的性能，尤其是循环性能迅速恶化，这也是以高镍金属氧化物为正极的锂离子电池实现规模化应用的主要障碍。针对这些问题，至今已有大量的研究探索高镍金属氧化物的劣化机理和解决途径。目前，已有的技术主要采用表面包覆技术，对材料表面进行惰性物质包覆，通过高镍金属氧化物材料 表面的包覆层隔离材料与环境或材料与电解液的直接接触。通常选用氧化物、金属磷酸盐、氟化物或其他正极材料作为物理屏蔽层，以此减缓高镍金属氧化物与电解质之间接触发生的副反应，提高镍金属氧化物循环性能。这类包覆技术尽管具有工艺简单，成本低等优点，但是已报道的表面包覆技术很难获得均匀且致密的包覆层，并且包覆层的厚度无法精确调控，从而会严重影响电荷传输，无法满足材料规模化生产及其电池应用需求。为解决材料包覆层均匀性问题，近年发展出原子气相沉积(ALD)材料表面修饰技术，通过对材料表面修饰层生长的原子尺度的精确控制，可以在材料表面形成极薄和致密的包覆层，从而极大改善材料的性能，但是原子气相沉积的设备复杂，操作技术要求高，导致应用该技术成本极高而难以实现规模工业化生产。
总之，高镍金属氧化物材料在材料生产、极片制作和电芯性能等方面尚存在亟待解决的问题，尤其是目前人们迫切期望通过提高材料中镍含量来提升材料的充放电容量和电池的能量密度，但随着材料中镍含量的提高，高镍金属氧化物材料存在的问题变得尤为突出，因而探索一种新的可行技术解决高镍金属氧化物材料作为锂离子电池正极材料的已有问题，是实现高能量密度高镍金属氧化物锂离子电池产业化的重要前提和保障。
发明内容
为解决上述技术问题，本发明的目的是提供一种硅氧修饰的高镍金属氧化物材料及其制备方法，本发明的制备方法工艺简单，成本低，对环境湿度要求较低，适用于大规模工业化，所制备的电极材料表面的修饰层厚度极薄且可控，对湿度敏感性低，界面稳定，具有优异的电化学性能。
本发明提供了一种硅氧修饰的高镍金属氧化物材料的制备方法，包括以下步骤：
(1)将高镍金属氧化物在烷基硅氧烷溶液中分散均匀，所述烷基硅氧烷溶液中包括烷基硅氧烷，然后在40～90℃下反应，得到表面修饰烷基硅氧烷的高镍金属氧化物；
(2)将表面修饰烷基硅氧烷的高镍金属氧化物在含氧气氛中于450℃～800℃下进行煅烧，制得硅氧修饰的高镍金属氧化物材料。
进一步地，在步骤(1)中，烷基硅氧烷溶液的溶质为烷基硅氧烷，烷基硅氧烷包括且不限于一辛基三甲氧基硅烷、3-脲丙基三甲氧基硅烷、乙烯基三(2-甲氧基乙氧基)硅烷、3-缩水甘油醚氧基丙基三甲氧基硅烷和三甲氧基硅烷中的一种或几种。烷基硅氧烷含有较长碳链，空间位阻较大，不会形成大量缩聚产物，从而在粒子表面形成厚包覆层。烷基硅氧烷通过水解并与材料表面基团缩合键连，形成极薄的烷基硅氧烷修饰层。
进一步地，在步骤(1)中，烷基硅氧烷溶液的溶剂为有机溶剂，有机溶剂包括且不限于 甲醇、异丙醇、叔丁醇、乙醇、丙酮、正己烷、苯和甲苯中的一种或几种。
进一步地，在步骤(1)中，表面修饰硅氧烷的高镍金属氧化物中，烷基硅氧烷的含量为高镍金属氧化物质量的0.1～5％。优选地，烷基硅氧烷为高镍金属氧化物质量的0.5～1.5％。
进一步地，在步骤(1)中，高镍金属氧化物在烷基硅氧烷溶液中分散5～120分钟。优选地，分散时间为10～30分钟。
进一步地，在步骤(1)中，分散方法为超声、搅拌和球磨中的一种或几种。
进一步地，在步骤(1)中，反应在搅拌条件下进行，搅拌速度为200～1000r/min。优选地，在步骤(1)中，搅拌速度为300～500r/min，反应时间为0.5～6h。
进一步地，在步骤(1)中，反应方法为搅拌法或搅拌冷凝回流法。
进一步地，在步骤(1)之后，还包括去除有机溶剂并干燥产物的步骤。去除有机溶剂的方法为加热干燥、真空干燥、喷雾干燥和冷冻干燥中的一种或几种。
进一步地，在步骤(2)中，高镍金属氧化物在含氧气氛中的煅烧时间为0.5～10h。
优选地，在步骤(2)中，煅烧温度为500～750℃，煅烧时间为1～3h。
进一步地，在步骤(2)中，煅烧时，从室温升温至450℃～800℃进行处理，升温速率为1～20℃/min，优选为5～10℃/min。
进一步地，在步骤(2)中，含氧气氛为纯氧、氧气和氮气混合气、空气和氧气混合气中的一种。
进一步地，高镍金属氧化物的分子式为LiNi xCo yM1 zM2 αO 2，其中，0.6≤x≤1，0≤y≤0.4，0≤z≤0.4,0≤α≤0.4，其中：x+y+z+α＝1，M1为铝元素或锰元素，M2为其他金属元素。优选地，高镍金属氧化物为镍钴铝酸锂(分子式：LiNi 0.8Co 0.15Al 0.05)或镍钴锰酸锂(分子式：LiNi 0.8Co 0.1Mn 0.1)。
优选地，其他金属元素为稀土元素；更优选地，其他金属元素为镁，铁，锆，钼，钛或镧。
本发明选用烷基硅氧烷作为合成原料，其在有机溶剂中分散时会初步水解，其中的R-Si-OH键(R代表烷基链)与高镍金属氧化物表面的羟基发生缩合反应，从而连接到高镍金属氧化物表面。改变高镍金属氧化物与烷基硅氧烷的质量比，即可以适度改变最终所制备的电极材料表面硅氧修饰层的厚度。
当表面含有若干R-Si-O-基团的高镍金属氧化物在450℃～800℃下煅烧时，其中R被氧化从而使得高镍金属氧化物表面基团变为Si-O(硅氧)基团。本发明使用烷基硅氧烷修饰高镍金属氧化物后，再进行高温氧化，可以将修饰的烷基硅氧烷基团氧化为硅氧基团，使修饰层极薄且不受R基团干扰。
本发明的第二个目的是提供一种采用上述制备方法所制备的硅氧修饰的高镍金属氧化物材料，其包括高镍金属氧化物颗粒以及连接在颗粒表面的若干硅氧基团。
本发明的第三个目的是要求保护上述高镍金属氧化物材料作为电极材料的应用。
硅氧基团通过化学键连接到高镍金属氧化物颗粒的表面，提高电极材料的疏水性能，提高电极材料对湿度的敏感性，并且不影响电极材料表面与电解液的相容性。
修饰了硅氧基团的高镍金属氧化物材料，硅氧基团均匀且致密得修饰在材料表面，可以实现物理屏蔽的作用，减少电极与电解液接触而导致的副反应，并且硅氧修饰层极薄，并不影响电荷传输，因此循环性能较原始材料有了较大改善，高温下存储也更稳定。
借由上述方案，本发明至少具有以下优点：
本发明的制备方法采用的工艺过程简易，所用反应和后处理设备都比较常见，克服了现有制备电极材料需要严格控制环境湿度和反应条件的缺陷，在常规环境下即可实现，不需严格控制环境湿度，工艺易实现，成本低，修饰物厚度可控，且适用于大规模工业生产。
本发明在高镍金属氧化物颗粒表面首先修饰烷基硅氧烷，其为极薄均匀且致密的修饰层，煅烧后得到硅氧修饰的高镍金属氧化物材料。硅氧基团的修饰，不仅改善了材料对湿度的敏感性，且提高了电极材料的界面稳定性，在循环过程中可以极好地保护电极并改善电荷转移，从而改善电池循环与倍率性能。
上述说明仅是本发明技术方案的概述，为了能够更清楚了解本发明的技术手段，并可依照说明书的内容予以实施，以下以本发明的较佳实施例并配合附图详细说明如后。
附图说明
图1是本发明实施例1中不同粒子与水的接触角测试图；
图2是本发明实施例1中不同材料制备的电池在55℃下的循环放电曲线；
图3是本发明实施例1中不同材料制备的电池在电解液中添加200ppm水的循环放电曲线；
图4是本发明实施例1中不同材料的制备的电池在不同电流下的倍率放电图；
图5是本发明实施例1中不同材料在高温循环后电极的扫描电镜照片；
图6是本发明实施例1中不同材料在充电至4.3V后高温放置的电压曲线；
图7是本发明实施例2中不同粒子与水的接触角测试图；
图8是本发明实施例2中不同材料制备的电池在25℃下的循环放电曲线；
图9是本发明实施例2中不同材料制备的电池在55℃下的循环放电曲线；
图10是本发明实施例2中不同材料在500圈循环后电极的扫描电镜照片。
具体实施方式
下面结合附图和实施例，对本发明的具体实施方式作进一步详细描述。以下实施例用于说明本发明，但不用来限制本发明的范围。
实施例1
本实施例提供了一种锂离子电池硅氧修饰的高镍金属氧化物材料及其制备方法，以镍钴铝酸锂材料(分子式：LiNi 0.8Co 0.15Al 0.05)作为原始正极材料，具体包括以下步骤：
(1)将5μL的一辛基三甲氧基硅烷加入到容器中，加入40mL丙酮，在室温下搅拌10分钟，搅拌速度为500r/min；然后向其中加入0.5g镍钴铝酸锂材料，在同样的速度下搅拌10分钟，使二者在丙酮中分散均匀，得到分散液。
(2)将分散液在90℃下加热，采用搅拌冷凝回流法反应6h后停止加热。然后将样品抽滤，洗涤三次后放入鼓风干燥箱中干燥2h，以除去其中的丙酮。
(3)将干燥好的样品在氧气氛围下进行高温氧化处理，从室温进行升温，升温速率为5℃/min，在500℃下维持1h，得到修饰了硅氧的镍钴铝酸锂三元正极材料。
对原始镍钴铝酸锂材料(图1a)与步骤(2)得到的修饰了烷基硅氧烷的镍钴铝酸锂粒子(图1b)进行水接触角测试，结果如图1所示，图1表明，修饰前后，粒子的接触角分别为12.50°和35.00°，静态水接触角的增大，说明烷基硅氧烷已经成功修饰至镍钴铝酸锂粒子表面。
将本实施例制得的硅氧修饰的镍钴铝酸锂三元正极材料(NCA@Si-O)制成纽扣式锂离子电池，同时以原始镍钴铝酸锂材料(NCA-P)制成的纽扣式锂离子电池作为对照组。对其进行循环放电测试。结果如图2所示，图中NCA@Si-O表示以本实施例制得的硅氧修饰镍钴铝酸锂三元正极材料制成的纽扣式锂离子电池，NCA-P表示原始镍钴铝酸锂材料制成的对照组电池，本发明的材料所制备的锂离子电池在55℃，1C电流下首次充放电为194mAh/g，充放循环200次后，比容量维持在133mAh/g，比起原始正极材料电极首次196.4mAh/g，200次后维持在92.8mAh/g，其循环性能有较大改善。
同时在以上两组电池制备过程中，在电解液中添加200ppm水，比较二者的循环放电性能，结果如图3所示。图3表明，本发明的材料制备的电池在循环200圈后，其比容量降低的程度更小，说明本发明的电极材料在微量水存在下，具有更好的循环稳定性，因此极大地提升制备极片及电芯的过程中对环境湿度的敏感性。
图4是以上两组电池在不同电流下的倍率放电图，从图中可看出，本发明的材料所制备的电池在不同的电流大小下，其与原始材料的放电容量基本一致，说明超薄的硅氧修饰层并 未影响充放电过程中的电荷传输。
将电池在55℃下循环后，测试极片的表面形貌，结果如图5a、b所示，图5表明，对照组的镍钴铝酸锂材料在循环后，材料表面形成大量的固体电解质膜(SEI膜)(图5a)，这是由于电极材料与电解液之间的副反应造成的，大量的SEI膜会影响电荷在界面处的传输，从而影响电极材料的电化学性能。而本发明的电极材料在循环后，材料表面的固体电解质膜较少，说明材料与电解液之间副反应得到抑制，材料的界面稳定性更高，从而保证电极材料电化学性能的稳定。
图6是原始镍钴铝酸锂材料与本实施例制得的镍钴铝酸锂三元正极材料在充电至4.3V后在55℃静置的电压曲线，比起原始镍钴铝酸锂材料，硅氧修饰的镍钴铝酸锂材料在高温静置过程中电压衰落极其缓慢，说明在高温高电压下，致密的超薄硅氧修饰层可以很好的隔离电极材料与电解液的接触，降低界面的化学反应活性，抑制大量副反应，提高界面稳定性，从而获得优异的电化学性能。
实施例2
本实施例提供了一种锂离子电池的硅氧修饰的高镍金属氧化物材料及其制备方法，以镍钴锰酸锂材料(分子式：LiNi 0.8Co 0.1Mn 0.1)作为原始正极材料，具体包括以下步骤：
(1)将10μL的3-脲丙基三甲氧基硅烷加入到容器中，加入40mL乙醇，在室温下搅拌10分钟，搅拌速度为500r/min；然后向其中加入0.5g镍钴锰酸锂材料，在同样的速度下搅拌10分钟，使二者在乙醇中分散均匀，得到分散液。
(2)将分散液在70℃下加热，采用搅拌冷凝回流法反应6h后停止加热。然后将样品抽滤，洗涤三次后放入鼓风干燥箱中干燥2h，以除去其中的乙醇。
(3)将干燥好的样品在氧气氛围下进行高温氧化处理，从室温进行升温，升温速率为5℃/min，在500℃下维持1h，得到修饰了硅氧的镍钴锰酸锂三元正极材料。
对原始镍钴锰酸锂材料(图7b)与步骤(2)得到的修饰了烷基硅氧烷的镍钴锰酸锂粒子(图7a)进行水接触角测试，结果如图1所示，图1表明，修饰前后，粒子的接触角分别为15.00°和53.50°，修饰了烷基硅氧烷后，镍钴锰酸锂粒子的水接触角变大，说明烷基硅氧烷已经成功修饰至镍钴锰酸锂粒子表面。
将本实施例制得的镍钴锰酸锂三元正极材料(NCM@Si-O)制成纽扣式锂离子电池，同时以原始镍钴锰酸锂材料(NCM-P)制成的纽扣式锂离子电池作为对照组。对其进行循环放电测试。结果如图8所示，图中NCM@Si-O表示以本实施例制得的镍钴锰酸锂三元正极材料制成的纽扣式锂离子电池，NCM-P表示对照组电池，本发明的材料所制备的锂离子电池在25℃,1C电流下首次放电容量为173.5mAh/g，充放循环300次后放电容量为152mAh/g；原 始正极材料电极首次放电容量为174mAh/g，300次后放电容量为109mAh/g。由此可见，材料表面的硅氧修饰使材料的电化学性能得到较大提高。同时，在55℃下，本发明的材料所制备的电池的循环充放电性能也明显优于对照组(图9)。
将电池在55℃下循环500次后，测试电极材料的形貌，结果如图10所示，图10表明，本发明的电极材料在循环后，材料表面依然存在颗粒状形貌特征(10a、b)，说明材料与电解液之间副反应很少，电极形貌基本不受影响。而对照组的镍钴锰酸锂材料在循环后，材料表面形成的固体电解质膜非常厚(图10c、d)。
实施例3
按照实施例1的方法制备硅氧修饰的高镍金属氧化物材料，不同之处在于：在步骤(1)中，所使用的烷基硅氧烷为乙烯基三(2-甲氧基乙氧基)硅烷，其质量为镍钴铝酸锂的0.5％，搅拌速度为300r/min。
实施例4
按照实施例1的方法制备硅氧修饰的高镍金属氧化物材料，不同之处在于：在步骤(1)中，所使用的烷基硅氧烷为乙烯基三(2-甲氧基乙氧基)硅烷，其质量为镍钴铝酸锂的2％，搅拌速度为400r/min。
实施例5
按照实施例1的方法制备硅氧修饰的高镍金属氧化物材料，不同之处在于：在步骤(1)中，所使用的一辛基三甲氧基硅烷的质量为镍钴铝酸锂的5％，搅拌速度为600r/min。
实施例6
按照实施例1的方法制备硅氧修饰的高镍金属氧化物材料，不同之处在于：在步骤(2)中，分散液的加热温度为50℃，反应时间为10h。
实施例7
按照实施例1的方法制备硅氧修饰的高镍金属氧化物材料，不同之处在于：在步骤(2)中，分散液的加热温度为70℃，反应时间为3h。
实施例8
按照实施例1的方法制备硅氧修饰的高镍金属氧化物材料，不同之处在于：在步骤(2)中，分散液的加热温度为100℃，反应时间为0.5h。
实施例9
按照实施例1的方法制备硅氧修饰的高镍金属氧化物材料，不同之处在于：在步骤(3)中，升温速率为1℃/min，在400℃下维持10h。
实施例10
按照实施例1的方法制备硅氧修饰的高镍金属氧化物材料，不同之处在于：在步骤(3)中，升温速率为8℃/min，在600℃下维持6h。
实施例11
按照实施例1的方法制备硅氧修饰的高镍金属氧化物材料，不同之处在于：在步骤(3)中，升温速率为10℃/min，在700℃下维持3h。
实施例12
按照实施例1的方法制备硅氧修饰的高镍金属氧化物材料，不同之处在于：在步骤(3)中，升温速率为20℃/min，在800℃下维持0.5h。
以上仅是本发明的优选实施方式，并不用于限制本发明，应当指出，对于本技术领域的普通技术人员来说，在不脱离本发明技术原理的前提下，还可以做出若干改进和变型，这些改进和变型也应视为本发明的保护范围。

Claims (10)

  1. 一种硅氧修饰的高镍金属氧化物材料的制备方法，其特征在于，包括以下步骤：
    (1)将高镍金属氧化物在烷基硅氧烷溶液中分散均匀，然后在40～90℃下反应，得到表面修饰烷基硅氧烷的高镍金属氧化物；
    (2)将表面修饰烷基硅氧烷的高镍金属氧化物在含氧气氛中于450℃～800℃下进行煅烧，制得所述硅氧修饰的高镍金属氧化物材料。
  2. 根据权利要求1所述的制备方法，其特征在于：在步骤(1)中，所述烷基硅氧烷溶液的溶质为烷基硅氧烷，所述烷基硅氧烷为一辛基三甲氧基硅烷、3-脲丙基三甲氧基硅烷、乙烯基三(2-甲氧基乙氧基)硅烷、3-缩水甘油醚氧基丙基三甲氧基硅烷和三甲氧基硅烷中的一种或几种。
  3. 根据权利要求1所述的制备方法，其特征在于：在步骤(1)中，所述烷基硅氧烷溶液的溶剂为有机溶剂，所述有机溶剂为甲醇、异丙醇、叔丁醇、乙醇、丙酮、正己烷、苯和甲苯中的一种或几种。
  4. 根据权利要求1所述的制备方法，其特征在于：在步骤(1)中，表面修饰烷基硅氧烷的高镍金属氧化物中，烷基硅氧烷的含量为高镍金属氧化物质量的0.1～5％。
  5. 根据权利要求1所述的制备方法，其特征在于：在步骤(1)中，所述高镍金属氧化物在烷基硅氧烷溶液中分散5～120分钟。
  6. 根据权利要求1所述的制备方法，其特征在于：在步骤(1)中，反应在搅拌条件下进行，搅拌速度为200～1000r/min。
  7. 根据权利要求1所述的制备方法，其特征在于：在步骤(2)中，所述高镍金属氧化物在含氧气氛中的煅烧时间为0.5～10h。
  8. 根据权利要求1所述的制备方法，其特征在于：所述高镍金属氧化物的分子式为LiNi xCo yM1 zM2 αO 2，其中，0.6≤x≤1，0≤y≤0.4，0≤z≤0.4,0≤α≤0.4，其中：x+y+z+α＝1，M1为铝元素或锰元素，M2为其他金属元素。
  9. 一种权利要求1-8中任一项所述的制备方法所制备的硅氧修饰的高镍金属氧化物材料，其特征在于：包括高镍金属氧化物颗粒以及连接在颗粒表面的若干硅氧基团。
  10. 权利要求9所述的高镍金属氧化物材料作为锂离子电池电极材料的应用。
PCT/CN2020/082647 2019-07-25 2020-04-01 硅氧修饰的高镍金属氧化物材料及其制备方法 WO2021012708A1 (zh)

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