WO2020098275A1 - 一种SiO 2包覆三元正极材料及其制备方法 - Google Patents

一种SiO 2包覆三元正极材料及其制备方法 Download PDF

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WO2020098275A1
WO2020098275A1 PCT/CN2019/092209 CN2019092209W WO2020098275A1 WO 2020098275 A1 WO2020098275 A1 WO 2020098275A1 CN 2019092209 W CN2019092209 W CN 2019092209W WO 2020098275 A1 WO2020098275 A1 WO 2020098275A1
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cathode material
positive electrode
ternary cathode
preparation
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French (fr)
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王忆
郑泽纯
周勤勤
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五邑大学
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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
    • 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
    • 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
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/058—Construction or manufacture
    • 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
    • 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
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P70/00—Climate change mitigation technologies in the production process for final industrial or consumer products
    • Y02P70/50—Manufacturing or production processes characterised by the final manufactured product

Definitions

  • the invention belongs to the field of lithium ion batteries, and particularly relates to a SiO 2 coated ternary cathode material and a preparation method thereof.
  • the basic structure of a lithium-ion battery includes a positive electrode, a separator, a negative electrode, an organic electrolyte, and a battery case.
  • the lithium ions originally embedded in the micropores of the negative electrode material are extracted and moved to the positive electrode through the electrolyte.
  • the negative electrode material has many micropores, which provide "residence" for lithium ions. The more lithium ions are inserted, the higher the charging capacity.
  • the electrolyte is usually PC (propylene carbonate), DMC (dimethyl carbonate), etc.
  • the anode material is commonly graphite
  • the cathode material is lithium cobalt oxide (LiCoO 2 ), lithium manganate (LiMnO 2 ), lithium iron phosphate (LiFePO 4 ), Etc., but the electrochemical performance of the lithium ion battery prepared by using these cathode materials is not satisfactory, so people have developed better performance ternary cathode materials.
  • lithium-ion batteries made of nickel-cobalt-manganese ternary cathode materials have the advantages of high discharge capacity and stable electrical properties, and have become the focus of research.
  • the ternary cathode material has many advantages, it also has shortcomings, such as poor cycling performance under high voltage, mixed discharge between metal elements, and low conductivity.
  • packaging has become an effective means.
  • the prior art CN108134073A uses aluminum oxide, zinc oxide and other metal oxides to coat modified nickel cobalt manganese, nickel cobalt aluminum ternary cathode materials, but the dry method
  • the mixed coating method not only prepares products with low electrical performance, but also has high energy consumption in the process.
  • CN104882589A uses carbon-coated nickel-cobalt-manganese ternary cathode material, and the prepared product has poor electrochemical performance, such as poor rate charge and discharge performance.
  • the present invention prepares high-performance ternary cathode materials and corresponding button batteries by coating modified ternary cathode materials with SiO 2 .
  • the present invention coats the ternary cathode material with SiO 2 to improve the stability of the material, and prepares a high-performance ternary cathode material and a corresponding button battery.
  • the present invention provides a method for preparing a ternary cathode material coated with SiO 2 .
  • a preparation method of SiO 2 coated ternary cathode material includes the following steps:
  • step (3) Anneal the powder prepared in step (2), and then cool to room temperature to prepare the ternary positive electrode material.
  • Li (Ni 0.5 Co 0.2 Mn 0.3 ) O 2 is configured with water (further preferably, the water is deionized water) as a Li (Ni 0.5 Co 0.2 Mn 0.3 ) O 2 solution, in which Li ( Ni 0.5 Co 0.2 Mn 0.3 ) O 2 : water mass ratio is 1 : 5-10.
  • Li (Ni 0.5 Co 0.2 Mn 0.3 ) O 2 : ethyl orthosilicate is 10-11 g: 0.2-0.5 ml.
  • the heating in step (1) is water bath heating, and the temperature of the water bath heating is 40-85 ° C. More preferably, the temperature of the water bath heating is 70-80 ° C.
  • the stirring time in step (1) is 15-25 min. More preferably, the stirring time is 18-22 min.
  • the lower suspension is dried at 110-130 ° C for 1.5-2.5h.
  • the powder prepared in step (2) is annealed at 700-900 ° C for 2-3h. More preferably, the powder prepared in step (2) is annealed at 700-800 ° C for 2-3h.
  • a method for preparing SiO 2 coated ternary cathode material includes the following steps:
  • step (1) Remove the upper aqueous solution of the beaker in step (1), take the lower suspension and dry it in an electric thermostatic blast drying oven, the drying time is 1.5-2.5h, the drying temperature is 110-130 °C, and finally it is dried Powder, set aside;
  • step (3) Put the powder produced in step (2) into a box-type resistance furnace for annealing at an annealing temperature of 700-900 ° C and an annealing time of 2-3h, and then cool to room temperature to prepare the ternary cathode material.
  • the Li (Ni 0.5 Co 0.2 Mn 0.3 ) O 2 was provided by Jiangmen Keheng Industrial Co., Ltd., the ethyl orthosilicate solution was provided by Tianjin Damao Chemical Reagent Factory, and the model of the water bath heating box was DFD7000, by Jintan Provided by Hengfeng Instrument Manufacturing Co., Ltd., the electric constant temperature blast drying oven model is DHG-9030A, provided by Shanghai Hongdu Electronic Technology Company, and the box resistance furnace model is SX2-S-12, provided by Shenyang Energy Saving Electric Furnace Factory.
  • a button battery includes a positive electrode, and the positive electrode includes a ternary positive electrode material coated with SiO 2 prepared by the preparation method.
  • a method for preparing a button battery includes the following steps:
  • step (2) The aluminum foil prepared in step (1) is vacuum-dried at 120 ° C for more than 24h, and the punching machine punches into a working electrode with a diameter of 14mm, using the working electrode as the positive electrode, the lithium sheet as the negative electrode, and 1mol / L LiPF6 / ( EC + DMC + DEC) (the volume ratio of EC (ethylene carbonate), DMC (dimethyl carbonate), DEC (diethyl carbonate) is 2: 2: 1)
  • the organic solution is electrolyte, polypropylene micropores
  • the membrane (provided by Celgard Corporation of the United States, model number Celgard 2400) is a separator, and the coin cell is assembled in a glove box filled with high-purity argon gas.
  • the preparation method of SiO 2 coated ternary cathode material is simple, no dry grinding is needed, energy consumption is reduced, and the stability is good.
  • the coin battery made of SiO 2 coated ternary cathode material has a high capacity retention rate, and the electrical performance is still stable and good after repeated cycles.
  • FIG. 1 is an SEM image of SiO 2 -coated ternary cathode material prepared in Example 2 of the present invention.
  • FIG. 2 is a graph showing the charging and discharging performance curves of the button batteries prepared in Example 6 and Comparative Example 1 of the present invention.
  • a preparation method of SiO 2 coated ternary cathode material includes the following steps:
  • step (2) Remove the upper layer solution of the beaker in step (1), take the lower layer suspension and dry it in an electric thermostatic blast drying oven, the drying time is 1.5h, the drying temperature is 110 ° C, and finally the dried powder is obtained, ready for use ;
  • step (3) Put the powder produced in step (2) into a box-type resistance furnace for annealing at an annealing temperature of 700 ° C and an annealing time of 2h, and then cool to room temperature to prepare the ternary cathode material.
  • a preparation method of SiO 2 coated ternary cathode material includes the following steps:
  • step (2) Remove the upper layer solution of the beaker in step (1), take the lower layer suspension and dry it in an electric thermostatic blast drying oven, the drying time is 2h, the drying temperature is 120 ° C, and finally the dried powder is obtained and used;
  • step (3) Put the powder produced in step (2) into a box-type resistance furnace for annealing at an annealing temperature of 700 ° C and an annealing time of 2.5h, and then cool to room temperature to prepare the ternary cathode material.
  • Figure 1 is a SEM picture of ternary material prepared in Example 2, the particle surface can be seen from FIG wrapped some dents, there are some small groups attached to the surface of the ternary positive electrode material, SiO 2 is visible up the parcel (SiO 2 A kind of amorphous structure material with good insulation, SiO 2 can cover the ternary cathode material by this method, and does not change the structure of the internal ternary cathode material).
  • a preparation method of SiO 2 coated ternary cathode material includes the following steps:
  • Li (Ni 0.5 Co 0.2 Mn 0.3 ) O 2 solution Li (Ni 0.5 Co 0.2 Mn 0.3 ) O 2 solution
  • step (2) Remove the upper layer solution of the beaker in step (1), take the lower layer suspension and dry it in an electric thermostatic blast drying oven, the drying time is 1.5h, the drying temperature is 115 ° C, and finally the dried powder is obtained for use ;
  • step (3) Put the powder prepared in step (2) into a box-type resistance furnace for annealing at an annealing temperature of 800 ° C and an annealing time of 3 hours to prepare the ternary cathode material.
  • a preparation method of SiO 2 coated ternary cathode material includes the following steps:
  • step (2) Remove the upper layer solution of the beaker in step (1), take the lower layer suspension, and dry it in an electric thermostatic blast drying oven, the drying time is 2h, the drying temperature is 120 ° C, and finally the dried powder is obtained, ready for use ;
  • step (3) Put the powder produced in step (2) into a box-type resistance furnace for annealing at an annealing temperature of 900 ° C and an annealing time of 2h, and then cool to room temperature to prepare the ternary cathode material.
  • a preparation method of SiO2 coated ternary cathode material includes the following steps:
  • Li (Ni 0.5 Co 0.2 Mn 0.3 ) O 2 solution Li (Ni 0.5 Co 0.2 Mn 0.3 ) O 2 solution
  • step (2) Remove the upper layer solution of the beaker in step (1), take the lower layer suspension and dry it in an electric thermostatic blast drying oven, the drying time is 2.5h, the drying temperature is 130 ° C, and finally the dried powder is obtained, ready for use ;
  • step (3) Put the powder produced in step (2) into a box-type resistance furnace for annealing at an annealing temperature of 900 ° C and an annealing time of 2h, and then cool to room temperature to prepare the ternary cathode material.
  • a method for preparing a button battery includes the following steps:
  • step (2) The aluminum foil prepared in step (1) is vacuum-dried at 120 ° C for more than 24h, and the punching machine punches into a working electrode with a diameter of 14mm, using the working electrode as the positive electrode, the lithium sheet as the negative electrode, and 1mol / L LiPF6 EC + DMC + DEC) (the volume ratio of EC, DMC and DEC is 2: 2: 1)
  • the organic solution is electrolyte, polypropylene microporous membrane (model Celgard 2400) is the diaphragm, in a glove box filled with high purity argon Assemble the button battery.
  • a method for preparing a button battery includes the following steps:
  • Uncoated Li (Ni 0.5 Co 0.2 Mn 0.3 ) O 2 is accurately weighed with acetylene black and polyvinylidene fluoride at a mass ratio of 70:20:10, and mixed with an appropriate amount of N-methylpyrrolidone Grind to make slurry and coat it evenly on aluminum foil for future use;
  • step (2) The aluminum foil prepared in step (1) is vacuum-dried at 120 ° C for more than 24h, and the punching machine punches into a working electrode with a diameter of 14mm, using the working electrode as the positive electrode, the lithium sheet as the negative electrode, and 1mol / L LiPF6 / ( EC + DMC + DEC) (the volume ratio of EC, DMC and DEC is 2: 2: 1)
  • the organic solution is electrolyte, polypropylene microporous membrane (model Celgard 2400) is the diaphragm, in a glove box filled with high purity argon Assemble the button battery.
  • FIG. 2 is a cycle curve diagram of a button battery prepared in Comparative Example 1 and Example 6.
  • the battery test temperature is room temperature
  • the voltage window is 2.75-4.3V
  • a charge and discharge cycle is performed at a current of 1C. It can be seen from the figure that the specific capacity of the button battery prepared in Example 6 containing SiO 2 -coated ternary positive electrode material as the positive electrode of the button battery at 100 charge-discharge cycles is 324 mAh / g, which is much higher than the 161 mAh of Comparative Example 1.
  • a high-precision battery performance test system (BST-5V-5mA) produced by Shenzhen New Weir Electronics Co., Ltd. was used to test the charge and discharge capacity of the button battery at room temperature.
  • Table 1 shows that the discharge capacity of Example 6 is better than that of Comparative Example 1 at 0.5C and 1C rate.
  • SiO 2 is wrapped on the ternary positive electrode material to protect the material from corrosion and improve the stability of the material, thereby improving battery performance .

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Abstract

本发明主要公开了一种SiO 2包覆三元正极材料的制备方法，包括以下步骤：按Li(N 0.5Co 0.2Mn 0.3)O 2∶正硅酸乙酯为8-15g∶0.1-1.1ml的比例在40-85℃下水浴加热，搅拌，然后静置，取出悬浊液在110-130℃干燥1.5-2.5h，然后在700-900℃下退火2-3h，制得所述SiO 2包覆三元正极材料。以本发明所述的SiO 2包覆三元正极材料制成的纽扣电池具有制备方法简单，电池容量保持率高，多次循环使用电性能依然稳定良好等优点，具有很好的市场应用价值。

Description

一种SiO 2包覆三元正极材料及其制备方法 技术领域
本发明属于锂离子电池领域，特别涉及一种SiO 2包覆三元正极材料及其制备方法。
背景技术
随着人类的发展，人类对石油、煤、天然气的需求量在迅速增加，由于这些燃料属于不可再生资源，为了实现人类的可持续发展，新能源的开发和应用显得尤为重要。太阳能、地热能、风能、核能等新能源的广泛应用极大地缓解能源危机，促进了社会的极大发展，而电能作为最具绿色的能源得到了最为广泛的应用。电池作为一种将其它能量转化为化学能的储能设备，由于其组合移动方便、高容量等优点使其在电子设备、电动汽车等领域得以广泛的应用，随着科技的进步和发展，对电池的性能要求越来越高。目前市场最受欢迎的是锂离子电池，具有比能量大、比容量大、开路电压高、寿命长、自放电率低等许多优点。锂离子电池的基本结构包括正极，隔膜，负极，有机电解液，电池外壳。当对电池进行放电时，原先嵌在负极材料微孔中的锂离子脱出，经过电解液运动到正极。负极材料有很多微孔，这些微孔为锂离子提供“住所”，嵌入的锂离子越多，充电容量越高。运动到正极的锂离子越多表明放电容量越高；当电池进行充电时，正极上生成锂离子，生成的锂离子经过电解液运动到负极，嵌入的锂离子越多表明充电容量越高。电解质常用PC(丙稀碳酸酯)、DMC(二甲基碳酸酯)等，负极材料常用石墨，正极材料有钴酸锂(LiCoO 2)、锰酸锂(LiMnO 2)、磷酸铁锂(LiFePO 4)等，但利用这些正极材料制备所得的锂离子电池电化学性能不尽如人意，于是人们研发出性能更好的三元正极材料。由于镍(Ni)、钴(Co)、锰(Mn)三种离子半径差不多，它们之间可以相互取代其位置而不改变锂离子电池正极材料的晶格结构，而且三者协同作用，从而增强锂离子电池正极材料的稳定性和电化学性能，因而镍钴锰三元正极材料所制备的锂离子电池同时拥有高放电容量、稳定的电性性能等优点而成为研究的热点。
三元正极材料虽然具备很多优点，但也有不足，比如当在高电压情况下循环性能不好，金属元素之间会产生混排，导电率低等问题。为了改善三元正极材料的性能，包裹成为了有效手段，如现有技术CN108134073A用氧化铝、氧化锌等金属氧化物包覆改性镍钴锰、镍钴铝三元正极材料，但采用干法混包覆的方法制备，不仅制备的产品电性能低，而且过程能耗高。CN104882589A用碳包覆镍钴锰三元正极材料，所制备的产品电化学性能不佳，如倍率充放电性能差等缺点。为了克服现有技术的不足，本发明通过SiO 2包覆改性三元正极材料，制备出高性能的三元正极材料以及相应的纽扣电池。
发明内容
针对现有技术的不足，本发明通过SiO 2包覆三元正极材料，提高材料的稳定性，制备出高性能的三元正极材料以及相应的纽扣电池。
为了达到以上目的，本发明通过提供一种SiO 2包覆三元正极材料的制备方法。
另外，还提供了一种应用上述方法制备的SiO 2包覆三元正极材料的纽扣电池。
一种SiO 2包覆三元正极材料的制备方法，包括以下步骤：
(1)按Li(Ni 0.5Co 0.2Mn 0.3)O 2∶正硅酸乙酯为8-15g∶0.1-1.1ml的比例称取各组份，混合，加热，搅拌，然后静置，备用；
(2)将步骤(1)所得备用物上层溶液除去，取下层悬浊液进行干燥，得到干燥的粉末；
(3)将步骤(2)制得的粉末退火，然后冷却至室温，制得所述三元正极材料。
优选的，混合前，将Li(Ni 0.5Co 0.2Mn 0.3)O 2用水(进一步优选的，所述水为去离子水)配置为Li(Ni 0.5Co 0.2Mn 0.3)O 2溶液，其中Li(Ni 0.5Co 0.2Mn 0.3)O 2∶水的质量比为1∶5-10。
优选的，步骤(1)中Li(Ni 0.5Co 0.2Mn 0.3)O 2∶正硅酸乙酯为10-11g∶0.2-0.5ml。
优选的，步骤(1)中的加热为水浴加热，水浴加热的温度为40-85℃。更优选的，水浴加热的温度为70-80℃。
优选的，步骤(1)中搅拌的时间为15-25min。更优选的，搅拌的时间为18-22min。
优选的，步骤(2)中将下层悬浊液在110-130℃下进行干燥1.5-2.5h。
优选的，步骤(3)中将步骤(2)制得的粉末在700-900℃下退火2-3h。更优选的，将步骤(2)制得的粉末在700-800℃下退火2-3h。
更具体的，一种SiO 2包覆三元正极材料的制备方法，包括以下步骤：
(1)按Li(Ni 0.5Co 0.2Mn 0.3)O 2∶正硅酸乙酯为8-15g∶0.1-1.1ml的比例称取各组份，将Li(Ni 0.5Co 0.2Mn 0.3)O 2倒入三口烧瓶，再倒入水(Li(Ni 0.5Co 0.2Mn 0.3)O 2∶水的质量比为1∶5-10)并置于水浴加热箱中以40-85℃的水浴温度加热搅拌，制得Li(Ni 0.5Co 0.2Mn 0.3)O 2溶液，然后继续以40-85℃的水浴温度加热搅拌，在搅拌过程中用移液管取正硅酸乙酯滴加到Li(Ni 0.5Co 0.2Mn 0.3)O 2溶液中，搅拌15-25min，搅拌完成后将溶液从三口烧瓶倒入烧杯，静置20-30h，备用；
(2)将步骤(1)中烧杯的上层水溶液除去，取下层悬浊液置于电热恒温鼓风干燥箱中干燥，干燥时间为1.5-2.5h，干燥温度为110-130℃，最后得到干燥的粉末，备用；
(3)将步骤(2)制得的粉末置于箱式电阻炉进行退火，退火温度为700-900℃，退火时间为2-3h，然后冷却至室温，制得所述三元正极材料。
所述Li(Ni 0.5Co 0.2Mn 0.3)O 2由江门市科恒实业股份有限公司提供，正硅酸乙酯溶液由天津市大茂化学试剂厂提供，水浴加热箱型号为DFD7000，由金坛市恒丰仪器制造有限公司提供， 电热恒温鼓风干燥箱型号为DHG-9030A，由上海鸿都电子科技公司提供，箱式电阻炉型号为SX2-S-12，由沈阳节能电炉厂提供。
一种纽扣电池，包括正极，该正极包括上述制备方法制备的SiO 2包覆的三元正极材料。
一种纽扣电池的制备方法，包括以下步骤：
(1)将上述方法制备的三元正极材料与乙炔黑和聚偏氟乙烯按质量比为70∶20∶10准确称量，加入适量的N-甲基吡咯烷酮混合研磨制成浆料并均匀地涂覆在铝箔上，备用；
(2)将步骤(1)制备的铝箔在120℃下真空干燥24h以上，冲片机冲成直径为14mm的工作电极，以工作电极为正极、锂片为负极、1mol/L的LiPF6/(EC+DMC+DEC)(EC(碳酸乙烯酯)、DMC(二甲基碳酸酯)、DEC(碳酸二乙酯)的体积比为2∶2∶1)有机溶液为电解液、聚丙烯微孔膜(由美国Celgard公司提供，型号为Celgard2400)为隔膜，在充满高纯氩气的手套箱中组装成所述纽扣电池。
本发明所述技术方案的有益效果：SiO 2包覆三元正极材料的制备方法简单，不需进行干磨，降低能耗，且稳定性好。由SiO 2包覆三元正极材料制备的纽扣电池容量保持率高，多次循环使用电性能依然稳定良好。
附图说明
图1为本发明实施例2制备的SiO 2包覆三元正极材料的SEM图片。
图2为本发明实施例6和对比例1制备的纽扣电池充放电性能曲线。
具体实施方式
为了让本领域技术人员更清楚、明白本发明所述技术方案，以下列举一些实施例。
实施例1
一种SiO 2包覆三元正极材料的制备方法，包括以下步骤：
(1)按Li(Ni 0.5Co 0.2Mn 0.3)O 2∶正硅酸乙酯为10g∶0.1ml的比例称取各组份，将Li(Ni 0.5Co 0.2Mn 0.3)O 2倒入三口烧瓶，再倒入水(Li(Ni 0.5Co 0.2Mn 0.3)O 2∶水的质量比为1∶5)并置于水浴加热箱中以40℃的水浴温度加热搅拌，制得Li(Ni 0.5Co 0.2Mn 0.3)O 2溶液，然后继续以40℃的水浴温度加热，搅拌，并用移液管取正硅酸乙酯滴加到Li(Ni 0.5Co 0.2Mn 0.3)O 2溶液中，搅拌15min，搅拌完成后将溶液从三口烧瓶倒入烧杯，静止20h，备用；
(2)将步骤(1)中烧杯的上层溶液除去，取下层悬浊液置于电热恒温鼓风干燥箱中干燥，干燥时间为1.5h，干燥温度为110℃，最后得到干燥的粉末，备用；
(3)将步骤(2)制得的粉末置于箱式电阻炉进行退火，退火温度为700℃，退火时间为2h，然后冷却至室温，制得所述三元正极材料。
实施例2
一种SiO 2包覆三元正极材料的制备方法，包括以下步骤：
(1)按Li(Ni 0.5Co 0.2Mn 0.3)O 2∶正硅酸乙酯为10g∶0.27ml的比例称取各组份，将Li(Ni 0.5Co 0.2Mn 0.3)O 2倒入三口烧瓶，再倒入去离子水(Li(Ni 0.5Co 0.2Mn 0.3)O 2∶去离子水的质量比为1∶8)并置于水浴加热箱中以80℃的水浴温度加热搅拌，制得Li(Ni 0.5Co 0.2Mn 0.3)O 2溶液，然后继续以80℃的水浴温度加热，搅拌，并用移液管取正硅酸乙酯滴加到Li(Ni 0.5Co 0.2Mn 0.3)O 2溶液中，搅拌20min，搅拌完成后将溶液从三口烧瓶倒入烧杯，静止24h，备用；
(2)将步骤(1)中烧杯的上层溶液除去，取下层悬浊液置于电热恒温鼓风干燥箱中干燥，干燥时间为2h，干燥温度为120℃，最后得到干燥的粉末，备用；
(3)将步骤(2)制得的粉末置于箱式电阻炉进行退火，退火温度为700℃，退火时间为2.5h，然后冷却至室温，制得所述三元正极材料。
图1是实施例2制备的三元材料的SEM图片，由图可见包裹后的颗粒表面出现一些凹痕，也有一些小团附着在三元正极材料表面，可见SiO 2是包裹上去了(SiO 2一种无定型组织的具有较好绝缘性的材料，通过本方法SiO 2能够包覆三元正极材料，并不改变内部三元正极材料的结构)。
实施例3
一种SiO 2包覆三元正极材料的制备方法，包括以下步骤：
(1)按Li(Ni 0.5Co 0.2Mn 0.3)O 2∶正硅酸乙酯溶液为10g∶0.27ml的比例称取各组份，将Li(Ni 0.5Co 0.2Mn 0.3)O 2倒入三口烧瓶，再倒入水(Li(Ni 0.5Co 0.2Mn 0.3)O 2∶水的质量比为1∶10)并置于水浴加热箱中以60℃的水浴温度加热搅拌，制得Li(Ni 0.5Co 0.2Mn 0.3)O 2溶液，然后继续以60℃的水浴温度加热搅拌，并用移液管取正硅酸乙酯滴加到Li(Ni 0.5Co 0.2Mn 0.3)O 2溶液中，搅拌20min，搅拌完成后将溶液从三口烧瓶倒入烧杯，静止24h，备用；
(2)将步骤(1)中烧杯的上层溶液除去，取下层悬浊液置于电热恒温鼓风干燥箱中干燥，干燥时间为1.5h，干燥温度为115℃，最后得到干燥的粉末，备用；
(3)将步骤(2)制得的粉末置于箱式电阻炉进行退火，退火温度为800℃，退火时间为3h，制得所述三元正极材料。
实施例4
一种SiO 2包覆三元正极材料的制备方法，包括以下步骤：
(1)按Li(Ni 0.5Co 0.2Mn 0.3)O 2∶正硅酸乙酯溶液为12g∶0.6ml的比例称取各组份，将Li(Ni 0.5Co 0.2Mn 0.3)O 2倒入三口烧瓶，再倒入水(Li(Ni 0.5Co 0.2Mn 0.3)O 2∶水的质量比为1∶8)并置于水浴加热箱中以70℃的水浴温度加热搅拌，制得Li(Ni 0.5Co 0.2Mn 0.3)O 2溶液，然后继续以70℃的水浴温度加热，搅拌，并用移液管取正硅酸乙酯滴加到Li(Ni 0.5Co 0.2Mn 0.3)O 2溶液中，搅拌 20min，搅拌完成后将溶液从三口烧瓶倒入烧杯，静止20h，备用；
(2)将步骤(1)中烧杯的上层溶液除去，取下层悬浊液，置于电热恒温鼓风干燥箱中干燥，干燥时间为2h，干燥温度为120℃，最后得到干燥的粉末，备用；
(3)将步骤(2)制得的粉末置于箱式电阻炉进行退火，退火温度为900℃，退火时间为2h，然后冷却至室温，制得所述三元正极材料。
实施例5
一种SiO2包覆三元正极材料的制备方法，包括以下步骤：
(1)按Li(Ni 0.5Co 0.2Mn 0.3)O 2∶正硅酸乙酯溶液为15g∶1.1ml的比例称取各组份，将Li(Ni 0.5Co 0.2Mn 0.3)O 2倒入三口烧瓶，再倒入水(Li(Ni 0.5Co 0.2Mn 0.3)O 2∶水的质量比为1∶5)并置于水浴加热箱中以85℃的水浴温度加热搅拌，制得Li(Ni 0.5Co 0.2Mn 0.3)O 2溶液，然后继续以85℃的水浴温度加热搅拌，并用移液管取正硅酸乙酯滴加到Li(Ni 0.5Co 0.2Mn 0.3)O 2溶液中，搅拌25min，搅拌完成后将溶液从三口烧瓶倒入烧杯，静止30h，备用；
(2)将步骤(1)中烧杯的上层溶液除去，取下层悬浊液置于电热恒温鼓风干燥箱中干燥，干燥时间为2.5h，干燥温度为130℃，最后得到干燥的粉末，备用；
(3)将步骤(2)制得的粉末置于箱式电阻炉进行退火，退火温度为900℃，退火时间为2h，然后冷却至室温，制得所述三元正极材料。
实施例6
一种纽扣电池的制备方法，包括以下步骤：
(1)将实施例2制备的三元正极材料与乙炔黑和聚偏氟乙烯按质量比为70∶20∶10的比例准确称量，加入适量的N-甲基吡咯烷酮混合研磨制成浆料并均匀地涂覆在铝箔上，备用；
(2)将步骤(1)制备的铝箔在120℃下真空干燥24h以上，冲片机冲成直径为14mm的工作电极，以工作电极为正极、锂片为负极、1mol/L的LiPF6/(EC+DMC+DEC)(EC、DMC、DEC的体积比为2∶2∶1)有机溶液为电解液、聚丙烯微孔膜(型号为Celgard2400)为隔膜，在充满高纯氩气的手套箱中组装成所述纽扣电池。
对比例1
一种纽扣电池的制备方法，包括以下步骤：
(1)未经包覆处理的Li(Ni 0.5Co 0.2Mn 0.3)O 2与乙炔黑和聚偏氟乙烯按质量比为70∶20∶10准确称量，加入适量的N-甲基吡咯烷酮混合研磨制成浆料并均匀地涂覆在铝箔上，备用；
(2)将步骤(1)制备的铝箔在120℃下真空干燥24h以上，冲片机冲成直径为14mm的工作电极，以工作电极为正极、锂片为负极、1mol/L的LiPF6/(EC+DMC+DEC)(EC、DMC、DEC的体积比为2∶2∶1)有机溶液为电解液、聚丙烯微孔膜(型号为Celgard2400)为 隔膜，在充满高纯氩气的手套箱中组装成所述纽扣电池。
图2为对比例1和实施例6制备的纽扣电池循环曲线图，电池测试温度为室温，电压窗口为2.75-4.3V，在1C的电流进行充放电循环。由图可见，由实施例6制备的包含SiO 2包覆的三元正极材料作纽扣电池的正极的纽扣电池在充放电循环100次的比容量为324mAh/g，远高于对比例1的161mAh/g，且比现有技术CN104882589A用碳包覆三元正极材料作电池正极的比容量131mAh/g高，说明本发明值得的SiO 2包覆的三元正极材料的倍率性能较佳。
产品性能测试
采用深圳新威尔电子有限公司生产的高精度电池性能测试系统(BST-5V-5mA)在室温下测试纽扣电池的充放电容量。
表1：纽扣电池倍率性能测试
  0.5C首次放电容量(mAh/g) 1C首次放电容量(mAh/g)
对比例1 267.1 213.7
实施例6 437.7 348.06
表1可以看出在0.5C，1C倍率下放电容量实施例6明显优于对比例1，SiO 2包裹在三元正极材料上可保护材料免于腐蚀，提高材料的稳定性，从而提高电池性能。
循环实验条件：电池测试温度为室温，电压窗口为2.75-4.3V，在1C的电流进行充放电循环。本发明所述产品的容量保持率的测试结果如表2所示。
表2：
Figure PCTCN2019092209-appb-000001
由表2可以看出在循环100次后，包覆SiO 2的三元正极材料实施例6的容量保持率为93.1％，远高于对比例1，可见包覆SiO 2的三元正极材料比未包覆SiO 2的三元正极材料作为正极制备的纽扣电池的电性能要好。

Claims (9)

  1. 一种SiO 2包覆三元正极材料的制备方法，其特征在于，包括以下步骤：
    (1)按Li(Ni 0.5Co 0.2Mn 0.3)O 2∶正硅酸乙酯为8-15g∶0.1-1.1ml的比例称取各组份，混合，加热，搅拌，然后静置，备用；
    (2)将步骤(1)所得备用物上层溶液除去，取下层悬浊液进行干燥，得到干燥的粉末；
    (3)将步骤(2)制得的粉末退火，然后冷却至室温，制得所述三元正极材料。
  2. 根据权利要求1所述的一种SiO 2包覆三元正极材料的制备方法，其特征在于，步骤(1)中按Li(Ni 0.5Co 0.2Mn 0.3)O 2∶正硅酸乙酯为10-11g∶0.2-0.5ml的比例称取各组份。
  3. 根据权利要求1所述的一种SiO 2包覆三元正极材料的制备方法，其特征在于，步骤(1)中混合前，Li(Ni 0.5Co 0.2Mn 0.3)O 2按照Li(Ni 0.5Co 0.2Mn 0.3)O 2∶水的质量比为1∶5-10的比例配置成Li(Ni 0.5Co 0.2Mn 0.3)O 2溶液。
  4. 根据权利要求1所述的一种SiO 2包覆三元正极材料的制备方法，其特征在于，步骤(1)中的加热为水浴加热，加热温度为40-85℃。
  5. 根据权利要求1所述的一种SiO 2包覆三元正极材料的制备方法，其特征在于，步骤(1)中搅拌的时间为15-25min。
  6. 根据权利要求1所述的一种SiO 2包覆三元正极材料的制备方法，其特征在于，步骤(2)中将下层悬浊液在110-130℃下进行干燥1.5-2.5h。
  7. 根据权利要求1所述的一种SiO 2包覆三元正极材料的制备方法，其特征在于，步骤(3)中，将步骤(2)制得的粉末在700-900℃下退火2-3h。
  8. 一种如权利要求1-7中任意一项所述的制备方法制备的SiO 2包覆三元正极材料。
  9. 一种纽扣电池，包括正极，其特征在于，该正极包括权利要求7所述的SiO 2包覆三元正极材料。
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