WO2021088354A1 - 核壳状铁酸镍及制备方法、铁酸镍@c材料及制备方法与应用 - Google Patents

核壳状铁酸镍及制备方法、铁酸镍@c材料及制备方法与应用 Download PDF

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WO2021088354A1
WO2021088354A1 PCT/CN2020/091872 CN2020091872W WO2021088354A1 WO 2021088354 A1 WO2021088354 A1 WO 2021088354A1 CN 2020091872 W CN2020091872 W CN 2020091872W WO 2021088354 A1 WO2021088354 A1 WO 2021088354A1
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core
shell
nickel ferrite
nickel
ferrite
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PCT/CN2020/091872
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French (fr)
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周国伟
刘田莉
顾少楠
宫庆华
孙彬
王茜
孙学凤
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齐鲁工业大学
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Priority to US17/297,465 priority Critical patent/US20220077456A1/en
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Definitions

  • the present disclosure belongs to the technical field of lithium ion batteries, and relates to lithium ion battery anode materials, in particular to core-shell nickel ferrite and a preparation method, nickel ferrite@C material, and a preparation method and application.
  • lithium-ion batteries have been widely used as an important energy source. It has broad application prospects in the fields of electronic communication and transportation. Lithium-ion batteries have high working voltage, large specific energy, long cycle life, good safety performance, no memory effect, small size, light weight, and lithium-ion batteries do not contain cadmium, lead, mercury and other elements that pollute the environment. Therefore, lithium-ion batteries are an ideal power source for portable electronic devices such as mobile phones and notebook computers, and are expected to become one of the main power sources for electric vehicles and power grids.
  • the transition metal oxide spinel structure has a high theoretical specific capacity, wherein the theoretical nickel ferrite (NiFe 2 O 4) specific capacity was 915mAh g -1, about current commercial graphite anode theoretical specific capacity (375mAh g -1 ) Three times, with good electrochemical performance.
  • the sources of iron and nickel are extensive, the earth reserves are large, and the preparation method is simple and environmentally friendly, it may become an ideal material for the next generation of lithium-ion battery negative electrodes.
  • NiFe 2 O 4 has a high theoretical specific capacity, its large volume expansion effect during charge and discharge leads to serious capacity attenuation, large irreversible capacity, and poor cycle performance.
  • the Chinese patent document with publication number CN 107673752 A discloses a NiFe 2 O 4 conductive material doped with nano-TiN and other additives and a preparation method thereof, by combining NiO powder, Fe 2 O 3 powder, nano TiN powder, and other additives are mixed, a dispersant is added to the mixture and mixed uniformly; calcined under inert gas to obtain doped nano TiN and other additives NiFe 2 O 4 conductive material.
  • the inventors of the present disclosure have discovered that the material has uneven morphology and poor dispersion.
  • the Chinese patent document with the publication number CN 103700842 A discloses a NiFe 2 O 4 /C lithium ion battery negative electrode material and a preparation method thereof.
  • the nickel salt and iron salt are used as the main raw materials, and hydrazine is used as the reducing agent.
  • the precursor NiFe 2 O 4 is obtained through an oxidation-reduction reaction, and the carbohydrate material is coated and calcined in an argon atmosphere to obtain a NiFe 2 O 4 /C composite material.
  • the inventors of the present disclosure found that the agglomeration of the material is relatively serious and the cycle performance is poor.
  • the purpose of the present disclosure is to provide core-shell nickel ferrite, nickel ferrite @C materials, and preparation methods and applications.
  • the core-shell nickel ferrite can be used with a carbon source to prepare ferrite Nickel@C core-shell material, nickel ferrite@C core-shell material as a lithium-ion battery anode has the advantages of uniform morphology, good dispersion, high specific capacity, and stable cycle performance.
  • a core-shell nickel ferrite has a core diameter of 425-450 nm, a shell thickness of 25-30 nm, and a core-shell spacing of 25-30 nm.
  • a method for preparing core-shell nickel ferrite uses nickel salt, iron salt and glycerin as raw materials, and uses a solvothermal method to prepare nickel iron glycerate ball powder. Under air conditions, the nickel iron glycerin The acid ester ball powder is heated at a heating rate of less than 1.5°C/min to not less than 350°C for calcination to obtain core-shell nickel ferrite.
  • the present disclosure has found through experiments that the heating rate during calcination affects the structure of nickel ferrite.
  • the heating rate is higher than 1.5°C/min (especially not lower than 2°C/min)
  • solid spherical nickel ferrite is obtained, and when the temperature is raised
  • the rate is lower than 1.5°C/min (especially not higher than 1°C/min)
  • a core-shell nickel ferrite with a core-shell spacing is obtained.
  • NiFe 2 O 4 core and the NiFe 2 O 4 shell prepared by the present disclosure have obvious hollowness, which can shorten the transmission path of ions and electrons and improve electrochemical performance.
  • a nickel ferrite@C material includes the above-mentioned core-shell nickel ferrite, and the core-shell nickel ferrite is coated with a carbon coating.
  • the present disclosure uses core-shell NiFe 2 O 4 as a support carrier, and a carbon layer as a protective layer, which can alleviate the problem of capacity attenuation caused by volume changes during charging and discharging of lithium-ion batteries.
  • a method for preparing nickel ferrite@C material In the fourth aspect, a method for preparing nickel ferrite@C material.
  • the core-shell nickel ferrite, resorcinol, and formaldehyde are subjected to a phenolic resin condensation reaction to obtain a phenolic resin (RF) coated core-shell nickel ferrite
  • RF phenolic resin
  • the nickel ferrite@RF composite material is calcined and carbonized to obtain the nickel ferrite@C material in an inert atmosphere.
  • the core-shell-shaped NiFe 2 O 4 is coated with a mesoporous carbon layer formed by high-temperature carbonization of a phenolic resin, which can effectively prevent electrochemical wear due to its elastic properties.
  • a negative electrode of a lithium ion battery the active material of which is the above-mentioned nickel ferrite@C material.
  • a lithium ion battery adopts the above-mentioned lithium ion battery negative electrode.
  • a core-shell shape of the present disclosure prepared as NiFe 2 O 4 lithium-ion battery can alleviate the volume brought about dramatic changes during charge and discharge capacity fade, wherein the core NiFe 2 O 4 can be used as solid core, to support the casing layer
  • the huge volume shrinks and guarantees the structural integrity of the electrode during long-term cycling.
  • the hollow between the core and the shell can provide some space to accommodate the volume change of the shell layer and shorten the electron transmission path.
  • the present disclosure is coated with a carbon layer.
  • the carbon layer formed after RF carbonization has a small volume change during charging and discharging, has good cycle stability, and the carbon layer can enhance the conductivity of the material.
  • the core-shell NiFe 2 O 4 @C composite material prepared by the present disclosure has good dispersibility and no obvious adhesion phenomenon.
  • the product performance is good, the synthesis process is simple, the method has low equipment requirements and low cost.
  • Figure 1 is an X-ray diffraction pattern (XRD) of the core-shell NiFe 2 O 4 prepared in Example 1 of the disclosure;
  • Figure 2 is a transmission electron microscopy diagram of the products prepared in Example 1 and Example 2 of the disclosure.
  • (a) is a transmission electron microscopy (TEM) image of the core-shell NiFe 2 O 4 prepared in Example 1 of the disclosure, and
  • (b) is Transmission electron micrograph (TEM) of the NiFe 2 O 4 solid sphere prepared in Example 2 of the present disclosure;
  • Figure 3 is a scanning electron microscope comparison of the products prepared in Example 1 and Example 2 of the disclosure.
  • (a) is a scanning electron microscope image (SEM) of the core-shell NiFe 2 O 4 prepared in Example 1 of the disclosure;
  • (b) is Scanning electron micrograph (SEM) of the core-shell NiFe 2 O 4 @C composite material prepared in Example 1 of the present disclosure;
  • TEM 4 is a transmission electron microscope image (TEM) of the core-shell NiFe 2 O 4 @C composite material prepared in Example 1 of the disclosure;
  • Example 5 is a comparison diagram of the cycle performance of the core-shell NiFe 2 O 4 @C composite material prepared in Example 1 and the solid spherical NiFe 2 O 4 @C composite material prepared in Example 2 of the disclosure.
  • the present disclosure proposes core-shell nickel ferrite and its preparation method, nickel ferrite@C material and its preparation Methods and applications.
  • a typical embodiment of the present disclosure provides a core-shell nickel ferrite, the diameter of the core is 425-450 nm, the thickness of the shell is 25-30 nm, and the core-shell spacing is 25-30 nm.
  • the diameter of the core is 435-445 nm
  • the thickness of the shell is 25-27 nm
  • the core-shell spacing is 25-27 nm.
  • Another embodiment of the present disclosure provides a method for preparing core-shell nickel ferrite, which uses nickel salt, iron salt and glycerin as raw materials, and uses a solvothermal method to prepare nickel iron glycerate ball powder. Under the conditions, the nickel iron glycerate ball powder is heated at a heating rate of less than 1.5° C./min to not less than 350° C. for calcination to obtain core-shell nickel ferrite.
  • the present disclosure has found through experiments that the heating rate during calcination affects the structure of nickel ferrite.
  • the heating rate is higher than 1.5°C/min (especially not lower than 2°C/min)
  • solid spherical nickel ferrite is obtained, and when the temperature is raised
  • the rate is lower than 1.5°C/min (especially not higher than 1°C/min)
  • a core-shell nickel ferrite with a core-shell spacing is obtained.
  • NiFe 2 O 4 core and the NiFe 2 O 4 shell prepared by the present disclosure have obvious hollowness, which can shorten the transmission path of ions and electrons and improve electrochemical performance.
  • the nickel salt mentioned in the present disclosure refers to a compound whose cation is a nickel ion, such as nickel chloride, nickel nitrate, nickel sulfate, and the like.
  • the iron salt described in the present disclosure refers to a compound whose cation is a ferric ion, such as ferric chloride, ferric nitrate, and ferric sulfate.
  • the solvothermal method described in the present disclosure refers to a synthesis method in which an organic substance or a non-aqueous solvent is used as a solvent, and the original mixture is reacted under a certain temperature and autogenous pressure (closed condition) of the solution.
  • the molar ratio of the nickel ion to the iron ion is 1:1.9 to 2.1.
  • the solvent of the solvothermal reaction system is isopropanol.
  • the reaction temperature of the solvothermal method is 150-200°C, and the reaction time is 4-8h.
  • the reaction effect is better.
  • the calcination temperature is 350-450°C
  • the heating rate is 0.9-1.1°C
  • the calcination time is 1.5-2.5 h.
  • the third embodiment of the present disclosure provides a nickel ferrite@C material, which includes the above-mentioned core-shell nickel ferrite, and the core-shell nickel ferrite is coated with a carbon coating.
  • the present disclosure uses core-shell NiFe 2 O 4 as a support carrier, and a carbon layer as a protective layer, which can alleviate the problem of capacity attenuation caused by volume changes during charging and discharging of lithium-ion batteries.
  • the thickness of the carbon coating is 20-25 nm.
  • the fourth embodiment of the present disclosure provides a method for preparing nickel ferrite@C material.
  • the core-shell nickel ferrite, resorcinol, and formaldehyde are subjected to a phenolic resin condensation reaction to obtain a phenolic resin (RF) package.
  • RF phenolic resin
  • the core-shell-shaped NiFe 2 O 4 is coated with a mesoporous carbon layer formed by high-temperature carbonization of a phenolic resin, which can effectively prevent electrochemical wear due to its elastic properties.
  • the inert atmosphere described in the present disclosure refers to a gas atmosphere that does not contain oxygen and can avoid oxidation reactions, such as nitrogen, argon, and the like.
  • the charging ratio of core-shell nickel ferrite, resorcinol, and formaldehyde is 50:0.9 to 1.1:0.11 to 0.13, mg:g:mL.
  • the phenolic resin condensation reaction is carried out under alkaline conditions.
  • ammonia water is added to the phenolic resin condensation reaction system.
  • the feeding ratio of core-shell nickel ferrite to ammonia water is 50:0.9 ⁇ 1.1, mg:mL.
  • the solvent of the phenolic resin condensation reaction system is an aqueous ethanol solution.
  • the volume ratio of ethanol to water is 2:0.9 ⁇ 1.1, the reaction effect is better.
  • the calcination and carbonization temperature is 550-650° C.
  • the calcination time is 1.5-2.5 h.
  • the fifth embodiment of the present disclosure provides an application of the above-mentioned nickel ferrite@C material in a lithium ion battery.
  • the sixth embodiment of the present disclosure provides a lithium ion battery negative electrode, the active material of which is the above-mentioned nickel ferrite@C material.
  • an adhesive and a conductive agent are included.
  • the preparation method is: mixing the active material, the binder, and the conductive agent uniformly, adding a solvent to make a slurry, coating the slurry on the surface of the current collector, and then drying .
  • the seventh embodiment of the present disclosure provides a lithium ion battery, and the negative electrode adopts the above-mentioned lithium ion battery negative electrode.
  • the lithium ion battery is a CR2032 button battery.
  • step (2) Transfer the uniform liquid obtained in step (1) to a 100mL polytetrafluoroethylene lined autoclave, solvothermally react at 180°C for 6 hours, cool to room temperature naturally, and centrifuge, wash, and dry. A yellow nickel-iron glycerate ball powder was obtained; in the air, the temperature was raised to 400°C at 1°C/min and calcined for 2h, and then naturally cooled to room temperature to obtain core-shell NiFe 2 O 4 .
  • step (3) The core-shell NiFe 2 O 4 obtained in step (2) was ultrasonically dispersed in a mixed solution of 10 mL of water and 20 mL of ethanol, and 1 mL of NH 3 ⁇ H 2 O (28 wt%), 1 g of resorcinol and 0.12 mL were added. Formaldehyde, stir for 2h.
  • the core-shell NiFe 2 O 4 @RF composite material is obtained by centrifugation, washing, and drying, and the core- shell NiFe 2 O 4 @C composite material is obtained by calcination at 600° C. for 2 hours in an argon atmosphere.
  • step (2) Transfer the uniform liquid obtained in step (1) to a 100mL polytetrafluoroethylene lined autoclave, solvothermally react at 180°C for 6 hours, cool to room temperature naturally, and centrifuge, wash, and dry. A yellow nickel-iron glycerate ball powder was obtained; in the air, the temperature was increased to 400°C at 2°C/min and calcined for 2h, and then naturally cooled to room temperature to obtain solid spherical NiFe 2 O 4 .
  • step (3) The solid spherical NiFe 2 O 4 obtained in step (2) was ultrasonically dispersed in a mixed solution of 10 mL of water and 20 mL of ethanol, and 1 mL of NH 3 ⁇ H 2 O (28 wt%), 1 g of resorcinol and 0.12 mL of formaldehyde were added. , Stir for 2h.
  • the core-shell NiFe 2 O 4 @RF composite material was obtained by centrifugation, washing, and drying. In an argon atmosphere, the temperature was raised to 600° C. and calcined for 2 hours to obtain solid spherical NiFe 2 O 4 @C.
  • step (2) Transfer the uniform liquid obtained in step (1) to a 100mL polytetrafluoroethylene lined autoclave, after solvothermal reaction at 160°C for 8 hours, after natural cooling to room temperature, centrifugation, washing, and drying A yellow nickel-iron glycerate ball powder was obtained; in the air, the temperature was raised to 400°C at 1°C/min and calcined for 2h, and then naturally cooled to room temperature to obtain core-shell NiFe 2 O 4 .
  • step (3) The solid spherical NiFe 2 O 4 obtained in step (2) was ultrasonically dispersed in a mixed solution of 10 mL of water and 20 mL of ethanol, and 1 mL of NH 3 ⁇ H 2 O (28 wt%), 1 g of resorcinol and 0.12 ml of formaldehyde were added. , Stir for 2h.
  • the core-shell NiFe 2 O 4 @RF composite material is obtained by centrifugation, washing and drying, and the core- shell NiFe 2 O 4 @C composite material is obtained by calcining at 600° C. for 2 hours under an argon atmosphere and in an inert atmosphere.
  • step (2) Transfer the uniform liquid obtained in step (1) to a 100mL polytetrafluoroethylene lined autoclave, solvothermally react at 180°C for 6 hours, cool to room temperature naturally, and centrifuge, wash, and dry. A yellow nickel-iron glycerate ball powder was obtained; in the air, the temperature was raised to 400°C at 1°C/min and calcined for 2h, and then naturally cooled to room temperature to obtain core-shell NiFe 2 O 4 .
  • step (3) The core-shell NiFe 2 O 4 obtained in step (2) was ultrasonically dispersed in a mixed solution of 10 mL of water and 20 mL of ethanol, and 1 mL of NH 3 ⁇ H 2 O (28 wt%), 2 g of resorcinol and 0.24 mL were added. Formaldehyde, stir for 2h.
  • the core-shell NiFe 2 O 4 @RF composite material is obtained by centrifugation, washing, and drying, and the core- shell NiFe 2 O 4 @C composite material is obtained by calcination at 600° C. for 2 hours in an argon atmosphere.
  • step (2) Transfer the uniform liquid obtained in step (1) to a 100mL polytetrafluoroethylene lined autoclave, solvothermally react at 180°C for 6 hours, cool to room temperature naturally, and centrifuge, wash, and dry. A yellow nickel-iron glycerate ball powder was obtained; in the air, the temperature was raised to 400°C at 1°C/min and calcined for 2h, and then naturally cooled to room temperature to obtain core-shell NiFe 2 O 4 .
  • step (3) The core-shell NiFe 2 O 4 obtained in step (2) was ultrasonically dispersed in a mixed solution of 10 mL of water and 20 mL of ethanol, and 1 mL of NH 3 ⁇ H 2 O (28 wt%), 0.5 g of resorcinol and 0.06 were added. ml formaldehyde, stir for 2h.
  • the core-shell NiFe 2 O 4 @RF composite material is obtained by centrifugation, washing, and drying, and the core- shell NiFe 2 O 4 @C composite material is obtained by calcination at 600° C. for 2 hours in an argon atmosphere.
  • the electrochemical performance of the core-shell NiFe 2 O 4 @C composite as a negative electrode material for lithium-ion batteries was evaluated with CR2032 button cells.
  • the battery assembly process is as follows: the active material, the binder, and the conductive agent are mixed uniformly in a mass ratio of 7:2:1, and a certain amount of N-methylpyrrolidone is added to prepare a uniform slurry. Then the slurry was evenly coated on the copper foil and baked at 60°C under vacuum conditions for 24 hours.
  • the battery assembly sequence is: positive case-negative pole piece-electrolyte-diaphragm-electrolyte-lithium sheet-gasket-spring sheet-negative case, the separator is Celgard 2300 membrane, the electrolyte is 1mol/L LiPF6 dissolved in ethylene carbonate The whole process is assembled in a glove box filled with argon in a mixture of esters, dimethyl carbonate and ethyl methyl carbonate. The assembled battery is tested using Xinwei battery test system.
  • Fig. 1 is an X-ray diffraction pattern (XRD) of the core-shell NiFe 2 O 4 prepared in Example 1. There are obvious characteristic diffraction peaks at 30°, 36°, 43°, 57.5°, and 63°, which are consistent with NiFe 2 O 4 (JCPDS No.10-0325) and represent NiFe 2 O 4 (220), (311), (400), (511) and (440) crystal planes.
  • XRD X-ray diffraction pattern
  • FIG. 2 (a) is a transmission electron microscope image of the core-shell NiFe 2 O 4 prepared in Example 1, and (b) is a transmission electron microscope image of the solid spherical NiFe 2 O 4 prepared in Example 2 of the disclosure. As shown in the figure, (a) has an obvious core-shell structure, and there is a certain distance between the core-shell. The figure (b) shows a solid ball.
  • Figure 3 (a) is a scanning electron micrograph of the core-shell NiFe 2 O 4 prepared in Example 1.
  • the NiFe 2 O 4 spheres are composed of fine particles.
  • the core-shell structure can be clearly seen from the damage.
  • (b) The figure is a scanning electron micrograph of the core-shell NiFe 2 O 4 @RF prepared in Example 1 of the present disclosure. As shown in the figure, the sample has a uniform morphology, no adhesion, and good dispersion.
  • Example 4 is a transmission electron microscope image of the core-shell NiFe 2 O 4 @C prepared in Example 1. It can be seen from the figure that the radius of the core-shell NiFe 2 O 4 is 270 nm, the thickness of the shell is 25 nm, the core-shell spacing is 25 nm, and the carbon coating is 20 nm.
  • Example 5 is a comparison diagram of the cycle performance of the core-shell NiFe 2 O 4 @C composite material prepared in Example 1 and the solid spherical NiFe 2 O 4 @C composite material prepared in Example 2 as the negative electrode of a lithium ion battery.
  • the core-shell NiFe 2 O 4 @C composite material prepared in Example 1 has a first discharge charge capacity of 1048 mA h g -1 and 733 mA h g -1 , and a first coulombic efficiency of 70%.
  • the second discharge capacity is 735mA h g -1 , and its irreversible loss of capacity may be attributed to the irreversible reaction of the electrolyte and the formation of solid electrolyte interface membrane (SEI).
  • SEI solid electrolyte interface membrane

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Abstract

本公开提供了核壳状铁酸镍、铁酸镍@C材料及制备方法与应用，采用溶剂热法制备获得镍铁甘油酸酯球粉末，在空气条件下，将镍铁甘油酸酯球粉末以低于1.5℃/min的升温速率升温至不低于350℃进行煅烧，获得核壳状铁酸镍。将上述核壳状铁酸镍、间苯二酚、甲醛进行酚醛树脂缩合反应获得酚醛树脂包覆核壳状铁酸镍的铁酸镍@RF复合材料，在惰性气氛下，将铁酸镍@RF复合材料煅烧碳化获得铁酸镍@C材料。以本公开提供的铁酸镍@C核壳材料作为锂离子电池负极具有形貌均匀、分散性好、比容量高、循环性能稳定等优点。

Description

核壳状铁酸镍及制备方法、铁酸镍@C材料及制备方法与应用 技术领域
本公开属于锂离子电池技术领域，涉及锂离子电池负极材料，具体涉及核壳状铁酸镍及制备方法、铁酸镍@C材料及制备方法与应用。
背景技术
公开该背景技术部分的信息仅仅旨在增加对本公开的总体背景的理解，而不必然被视为承认或以任何形式暗示该信息构成已经成为本领域一般技术人员所公知的现有技术。
能源是人类生存与经济发展的基础，然而随着世界经济的持续、高速发展，能源短缺、环境污染等问题逐渐加深，能源供需矛盾日益突出。新能源技术是公认的高新技术，电池行业作为新能源领域的重要组成部分，已成为全球发展的新热点。目前锂离子电池已经作为一种重要的能源被广泛使用。在电子通讯、交通运输等领域有着广泛的应用前景。锂离子电池工作电压高、比能量大、循环寿命长、安全性能好、无记忆效应、体积小、重量轻，且锂离子电池中不含镉、铅、汞等对环境有污染的元素。因此，锂离子电池是移动电话、笔记本电脑等便携式电子设备的理想电源，并有望成为电动汽车、电网的主要动力来源之一。
尖晶石结构的过渡金属氧化具有较高的理论比容量，其中铁酸镍(NiFe 2O 4)的理论比容量为915mAh g -1，约为目前商用石墨负极理论比容量(375mAh g -1)的三倍，具有良好的电化学性能。此外，铁源和镍源来源广泛、地球储量大，且制备方法简单、对环境友好，有可能成为下一代锂离子电池负极的理想材料。虽然NiFe 2O 4的理论比容量很高，但其充放电过程中体积膨胀效应大而导致容量衰减严重、不可逆容量大、循环性能差。为了改善这种情况，公开号CN 107673752 A(申请号201710861283.2)的中国专利文献公开了一种掺杂纳米TiN和其他添加物的NiFe 2O 4导电材料及其制备方法，通过将NiO粉末、Fe 2O 3粉末、纳米TiN粉末、其他添加物混合，在混合物料中加入分散剂并混合均匀；在惰性气体下煅烧，得到掺杂纳米TiN和其他添加物NiFe 2O 4导电材料。但是，本公开发明人研究发现，该材料形貌不均，分散性较差。公开号CN 103700842 A(申请号201310646625.0)的中国专利文献公开了一种NiFe 2O 4/C锂离子电池负极材料及其制备方法，以镍盐和铁盐为主原料，联氨为还原剂，通过氧化-还原反应得到前驱体NiFe 2O 4，包覆糖类物质后氩气气氛下煅烧得到NiFe 2O 4/C复合材料。但是，经过本公开发明人研究发现，该材料团聚比较严重，且循环性能较差。
发明内容
为了解决现有技术的不足，本公开的目的是提供核壳状铁酸镍、铁酸镍@C材料及制备方法与应用，采用这种核壳状铁酸镍能够与碳源制备出铁酸镍@C核壳材料，铁酸镍@C核壳材料作为锂离子电池负极具有形貌均匀、分散性好、比容量高、循环性能稳定等优点。
为了实现上述目的，本公开的技术方案为：
一方面，一种核壳状铁酸镍，核的直径为425～450nm，壳的厚度为25～30nm，核壳间距为25～30nm。
另一方面，一种核壳状铁酸镍的制备方法，以镍盐、铁盐和甘油作为原料，采用溶剂热法制备获得镍铁甘油酸酯球粉末，在空气条件下，将镍铁甘油酸酯球粉末以低于1.5℃/min的升温速率升温至不低于350℃进行煅烧，获得核壳状铁酸镍。
本公开经过实验发现，煅烧时的升温速率影响铁酸镍的结构，当升温速率高于1.5℃/min(尤其是不低于2℃/min)时，获得实心球状铁酸镍，而当升温速率低于1.5℃/min(尤其是不高于1℃/min)时，获得具有核壳间距的核壳状铁酸镍。
本公开制备的NiFe 2O 4核与NiFe 2O 4壳之间具有明显的空心，可以缩短离子、电子的传输路径，提高电化学性能。
第三方面，一种铁酸镍@C材料，包括上述核壳状铁酸镍，所述核壳状铁酸镍被碳涂层包覆。
本公开利用核壳状的NiFe 2O 4作为支撑载体，碳层作为保护层，可以缓解锂离子电池充放电时体积变化导致的容量衰减问题。
第四方面，一种铁酸镍@C材料的制备方法，将上述核壳状铁酸镍、间苯二酚、甲醛进行酚醛树脂缩合反应获得酚醛树脂(RF)包覆核壳状铁酸镍的铁酸镍@RF复合材料，在惰性气氛下，将铁酸镍@RF复合材料煅烧碳化获得铁酸镍@C材料。
本公开在核壳状的NiFe 2O 4上包覆了由酚醛树脂高温碳化后形成的介孔碳层，因为其弹性性质而能有效地防止电化学磨损。
第五方面，一种上述铁酸镍@C材料在锂离子电池中的应用。
第六方面，一种锂离子电池负极，其活性材料为上述铁酸镍@C材料。
第七方面，一种锂离子电池，负极采用上述锂离子电池负极。
本公开的有益效果为：
(1)本公开制备的核壳状NiFe 2O 4可以缓解锂离子电池在充放电时体积剧烈变化带来的容量衰减，其中NiFe 2O 4的核可以作为坚固的核心，以支持外壳层的巨大体积收缩，并保证长期循环期间电极的结构完整性。核与壳之间的空心可以提供部分空间来适用外壳层的 体积变化并缩短电子传输路径。
(2)本公开采用碳层包覆，RF碳化后形成的碳层在充放电过程中体积变化较小，具有较好的循环稳定性能，且碳层可以增强材料的导电性。
(3)本公开制备的核壳状的NiFe 2O 4@C复合材料分散性较好，没有明显的黏连现象。产物性能好，合成工艺简单，该方法对设备要求低，成本低。
附图说明
构成本公开的一部分的说明书附图用来提供对本公开的进一步理解，本公开的示意性实施例及其说明用于解释本公开，并不构成对本公开的不当限定。
图1为本公开实施例1制备的核壳状NiFe 2O 4的X射线衍射图(XRD)；
图2为本公开实施例1和实施例2制备产品的透射电镜对比图，(a)为本公开实施例1制备的核壳状NiFe 2O 4的透射电镜图(TEM)，(b)为本公开实施例2制备的NiFe 2O 4实心球的透射电镜图(TEM)；
图3为本公开实施例1和实施例2制备产品的扫描电镜对比图，(a)为本公开实施例1制备的核壳状NiFe 2O 4的扫描电镜图(SEM)；(b)为本公开实施例1制备的核壳状NiFe 2O 4@C复合材料的扫描电镜图(SEM)；
图4为本公开实施例1制备的核壳状NiFe 2O 4@C复合材料的透射电镜图(TEM)；
图5为本公开实施例1制备的核壳状NiFe 2O 4@C复合材料和实施例2制备的实心球状NiFe 2O 4@C复合材料的循环性能对比图。
具体实施方式
应该指出，以下详细说明都是示例性的，旨在对本公开提供进一步的说明。除非另有指明，本文使用的所有技术和科学术语具有与本公开所属技术领域的普通技术人员通常理解的相同含义。
需要注意的是，这里所使用的术语仅是为了描述具体实施方式，而非意图限制根据本公开的示例性实施方式。如在这里所使用的，除非上下文另外明确指出，否则单数形式也意图包括复数形式，此外，还应当理解的是，当在本说明书中使用术语“包含”和/或“包括”时，其指明存在特征、步骤、操作、器件、组件和/或它们的组合。
鉴于现有NiFe 2O 4存在体积膨胀效应大导致的容量衰减严重、不可逆容量大、循环性能差的问题，本公开提出了核壳状铁酸镍及制备方法、铁酸镍@C材料及制备方法与应用。
本公开的一种典型实施方式，提供了一种核壳状铁酸镍，核的直径为425～450nm，壳的厚度为25～30nm，核壳间距为25～30nm。
该实施方式的一种或多种实施例中，核的直径为435～445nm，壳的厚度为25～27nm， 核壳间距为25～27nm。
本公开的另一种实施方式，提供了一种核壳状铁酸镍的制备方法，以镍盐、铁盐和甘油作为原料，采用溶剂热法制备获得镍铁甘油酸酯球粉末，在空气条件下，将镍铁甘油酸酯球粉末以低于1.5℃/min的升温速率升温至不低于350℃进行煅烧，获得核壳状铁酸镍。
本公开经过实验发现，煅烧时的升温速率影响铁酸镍的结构，当升温速率高于1.5℃/min(尤其是不低于2℃/min)时，获得实心球状铁酸镍，而当升温速率低于1.5℃/min(尤其是不高于1℃/min)时，获得具有核壳间距的核壳状铁酸镍。
本公开制备的NiFe 2O 4核与NiFe 2O 4壳之间具有明显的空心，可以缩短离子、电子的传输路径，提高电化学性能。
本公开所述的镍盐是指阳离子为镍离子的化合物，例如氯化镍、硝酸镍、硫酸镍等。
本公开所述的铁盐是指阳离子为三价铁离子的化合物，例如三氯化铁、硝酸铁、硫酸铁等。
本公开所述的溶剂热法是指，以有机物或非水溶媒为溶剂，在一定的温度和溶液的自生压力(密闭条件)下，原始混合物进行反应的合成方法。
该实施方式的一种或多种实施例中，镍盐和铁盐中，镍离子与铁离子的摩尔比为1:1.9～2.1。
该实施方式的一种或多种实施例中，溶剂热法反应体系的溶剂为异丙醇。
该实施方式的一种或多种实施例中，溶剂热法的反应温度为150～200℃，反应时间为4～8h。当溶剂热温度为180±2℃、反应时间为5.5～6.5h时，反应效果更好。
该实施方式的一种或多种实施例中，煅烧温度为350～450℃，升温速率为0.9～1.1℃，煅烧时间为1.5～2.5h。
本公开的第三种实施方式，提供了一种铁酸镍@C材料，包括上述核壳状铁酸镍，所述核壳状铁酸镍被碳涂层包覆。
本公开利用核壳状的NiFe 2O 4作为支撑载体，碳层作为保护层，可以缓解锂离子电池充放电时体积变化导致的容量衰减问题。
该实施方式的一种或多种实施例中，碳涂层的厚度为20～25nm。
本公开的第四种实施方式，提供了一种铁酸镍@C材料的制备方法，将上述核壳状铁酸镍、间苯二酚、甲醛进行酚醛树脂缩合反应获得酚醛树脂(RF)包覆核壳状铁酸镍的铁酸镍@RF复合材料，在惰性气氛下，将铁酸镍@RF复合材料煅烧碳化获得铁酸镍@C材料。
本公开在核壳状的NiFe 2O 4上包覆了由酚醛树脂高温碳化后形成的介孔碳层，因为其弹性性质而能有效地防止电化学磨损。
本公开所述的惰性气氛是指不含氧气，且能够避免氧化反应的气体氛围，例如氮气、氩气等。
该实施方式的一种或多种实施例中，核壳状铁酸镍、间苯二酚、甲醛的投料比为50:0.9～1.1:0.11～0.13，mg：g：mL。
该实施方式的一种或多种实施例中，酚醛树脂缩合反应，在碱性条件下进行。
该系列实施例中，酚醛树脂缩合反应体系中添加氨水。核壳状铁酸镍与氨水的投料比为50:0.9～1.1，mg：mL。
该实施方式的一种或多种实施例中，酚醛树脂缩合反应体系的溶剂为乙醇水溶液。当乙醇与水的体积比为2:0.9～1.1时，反应效果更好。
该实施方式的一种或多种实施例中，煅烧碳化的温度为550～650℃，煅烧时间为1.5～2.5h。
本公开的第五种实施方式，提供了一种上述铁酸镍@C材料在锂离子电池中的应用。
本公开的第六种实施方式，提供了一种锂离子电池负极，其活性材料为上述铁酸镍@C材料。
该实施方式的一种或多种实施例中，包括粘结剂、导电剂。
该实施方式的一种或多种实施例中，制备方法为：将活性材料、粘结剂、导电剂混合均匀，加入溶剂制成浆料，将浆料涂覆与集流体表面，然后进行干燥。
本公开的第七种实施方式，提供了一种锂离子电池，负极采用上述锂离子电池负极。
该实施方式的一种或多种实施例中，锂离子电池为CR2032扣式电池。
为了使得本领域技术人员能够更加清楚地了解本公开的技术方案，以下将结合具体的实施例详细说明本公开的技术方案。
实施例1
(1)首先，将8mL的甘油加入到40mL的异丙醇中搅拌均匀，然后依次加入0.0363g Ni(NO 3) 2·6H 2O和0.101g的Fe(NO 3) 3·9H 2O，在室温下搅拌均匀。
(2)将步骤(1)得到均匀液体转移到100mL的聚四氟乙烯内衬的高压反应釜中，于180℃下溶剂热反应6h后，自然冷却至室温后，通过离心、洗涤、干燥后得到黄色的镍铁甘油酸酯球粉末；在空气中，以1℃/min升温至400℃煅烧2h，然后自然冷却至室温得到核壳状的NiFe 2O 4。
(3)将步骤(2)得到的核壳状NiFe 2O 4超声分散在10mL水和20mL乙醇的混合溶液中，加入1mLNH 3·H 2O(28wt％)、1g间苯二酚和0.12mL甲醛，搅拌2h。通过离心、洗涤、干燥得到核壳状NiFe 2O 4@RF复合材料，在氩气气氛下，升温至600℃煅烧2h，得到核壳状NiFe 2O 4@C复合材料。
实施例2
(1)首先，将8mL的甘油加入到40mL的异丙醇中搅拌均匀，然后依次加入0.0363g Ni(NO 3) 2·6H 2O和0.101g的Fe(NO 3) 3·9H 2O，在室温下搅拌均匀。
(2)将步骤(1)得到均匀液体转移到100mL的聚四氟乙烯内衬的高压反应釜中，于180℃下溶剂热反应6h后，自然冷却至室温后，通过离心、洗涤、干燥后得到黄色的镍铁甘油酸酯球粉末；在空气中，以2℃/min升温至400℃煅烧2h，然后自然冷却至室温得到实心球状的NiFe 2O 4。
(3)将步骤(2)得到的实心球状NiFe 2O 4超声分散在10mL水和20mL乙醇的混合溶液中，加入1mLNH 3·H 2O(28wt％)、1g间苯二酚和0.12mL甲醛，搅拌2h。通过离心、洗涤、干燥得到核壳状NiFe 2O 4@RF复合材料，在氩气气氛下，升温至600℃煅烧2h，得到实心球状的NiFe 2O 4@C。
实施例3
(1)首先，将8mL的甘油加入到40mL的异丙醇中搅拌均匀，然后依次加入0.0363g Ni(NO 3) 2·6H 2O和0.101g的Fe(NO 3) 3·9H 2O，在室温下搅拌均匀。
(2)将步骤(1)得到均匀液体转移到100mL的聚四氟乙烯内衬的高压反应釜中，于160℃下溶剂热反应8h后，自然冷却至室温后，通过离心、洗涤、干燥后得到黄色的镍铁甘油酸酯球粉末；在空气中，以1℃/min升温至400℃煅烧2h，然后自然冷却至室温得到核壳状的NiFe 2O 4。
(3)将步骤(2)得到的实心球状NiFe 2O 4超声分散在10mL水和20mL乙醇的混合溶液中，加入1mLNH 3·H 2O(28wt％)、1g间苯二酚和0.12ml甲醛，搅拌2h。通过离心、洗涤、干燥得到核壳状NiFe 2O 4@RF复合材料，在氩气气氛下，在惰性气氛下，升温至600℃煅烧2h，得到核壳状NiFe 2O 4@C复合材料。
实施例4
(1)首先，将8mL的甘油加入到40mL的异丙醇中搅拌均匀，然后依次加入0.0363g Ni(NO 3) 2·6H 2O和0.101g的Fe(NO 3) 3·9H 2O，在室温下搅拌均匀。
(2)将步骤(1)得到均匀液体转移到100mL的聚四氟乙烯内衬的高压反应釜中，于180℃下溶剂热反应6h后，自然冷却至室温后，通过离心、洗涤、干燥后得到黄色的镍铁甘油酸酯球粉末；在空气中，以1℃/min升温至400℃煅烧2h，然后自然冷却至室温得到核壳状的NiFe 2O 4。
(3)将步骤(2)得到的核壳状NiFe 2O 4超声分散在10mL水和20mL乙醇的混合溶液中，加入1mLNH 3·H 2O(28wt％)、2g间苯二酚和0.24mL甲醛，搅拌2h。通过离心、 洗涤、干燥得到核壳状NiFe 2O 4@RF复合材料，在氩气气氛下，升温至600℃煅烧2h，得到核壳状NiFe 2O 4@C复合材料。
实施例5
(1)首先，将8mL的甘油加入到40mL的异丙醇中搅拌均匀，然后依次加入0.0363g Ni(NO 3) 2·6H 2O和0.101g的Fe(NO 3) 3·9H 2O，在室温下搅拌均匀。
(2)将步骤(1)得到均匀液体转移到100mL的聚四氟乙烯内衬的高压反应釜中，于180℃下溶剂热反应6h后，自然冷却至室温后，通过离心、洗涤、干燥后得到黄色的镍铁甘油酸酯球粉末；在空气中，以1℃/min升温至400℃煅烧2h，然后自然冷却至室温得到核壳状的NiFe 2O 4。
(3)将步骤(2)得到的核壳状NiFe 2O 4超声分散在10mL水和20mL乙醇的混合溶液中，加入1mLNH 3·H 2O(28wt％)、0.5g间苯二酚和0.06ml甲醛，搅拌2h。通过离心、洗涤、干燥得到核壳状NiFe 2O 4@RF复合材料，在氩气气氛下，升温至600℃煅烧2h，得到核壳状NiFe 2O 4@C复合材料。
核壳状NiFe 2O 4@C复合材料作为锂离子电池负极材料的电化学性能以CR2032扣式电池评估。电池组装过程如下：将活性物质、粘结剂、导电剂按质量比7:2:1混合均匀，加入一定量的N-甲基吡咯烷酮制得均匀的浆料。然后将浆料均匀涂布于铜箔上并在60℃真空条件下烘24h。电池装配顺序为：正极壳-负极极片-电解液-隔膜-电解液-锂片-垫片-弹簧片-负极壳，隔膜为Celgard 2300膜，电解液为1mol/L的LiPF6溶解在碳酸乙烯酯、碳酸二甲酯和碳酸甲乙酯的混合液中，全程在充满氩气的手套箱中组装。装配好的电池采用新威电池测试系统进行测试。
图1为实施例1制备的核壳状NiFe 2O 4的X射线衍射图(XRD)。在30°、36°、43°、57.5°、63°处具有明显的特征衍射峰，与NiFe 2O 4(JCPDS No.10-0325)相吻合，分别代表了NiFe 2O 4(220)、(311)、(400)、(511)和(440)晶面。
图2(a)为实施例1制备的核壳状NiFe 2O 4的透射电镜图，(b)为公开实施例2制备的实心球状NiFe 2O 4的透射电镜图。如图所示，(a)图有明显的核壳结构，且核壳之间有一定的间距。而(b)图则为实心球。
图3(a)为实施例1制备的核壳状NiFe 2O 4的扫描电镜图，NiFe 2O 4球由细小颗粒组成。从破损处可以清晰地看到核壳结构。(b)图为为本公开实施例1制备核壳状NiFe 2O 4@RF的扫描电镜图，如图所示，样品形貌均匀，没有粘连，分散性较好。
图4为实施例1制备的核壳状NiFe 2O 4@C的透射电镜图。由图可知，核壳状NiFe 2O 4的半径为270nm，壳的厚度为25nm，核壳间距为25nm，碳涂层为20nm。
图5为实施例1制备的核壳状NiFe 2O 4@C复合材料和实施例2制备的实心球状NiFe 2O 4@C复合材料作为锂离子电池负极测得的循环性能对比图。在0.5A g -1的电流密度下，实施例1制备的核壳状NiFe 2O 4@C复合材料首次放充电容量分别为1048mA h g -1和733mA h g -1，首次库伦效率为70％。第2次放电容量为735mA h g -1，其不可逆损失容量可能归因于电解液的不可逆反应和固体电解质界面膜(SEI)的形成。在循环过程，电池容量呈现先下降后上升的趋势，经过165次循环后，放电容量达792.9mA h g -1。与实施例2制备的实心球状NiFe 2O 4@C复合材料相比，循环性能有了较大的提升。
以上所述仅为本公开的优选实施例而已，并不用于限制本公开，对于本领域的技术人员来说，本公开可以有各种更改和变化。凡在本公开的精神和原则之内，所作的任何修改、等同替换、改进等，均应包含在本公开的保护范围之内。

Claims (10)

  1. 一种核壳状铁酸镍，其特征是，核的直径为425～450nm，壳的厚度为25～30nm，核壳间距为25～30nm。
  2. 如权利要求1所述的核壳状铁酸镍，其特征是，核的直径为435～445nm，壳的厚度为25～27nm，核壳间距为25～27nm。
  3. 一种核壳状铁酸镍的制备方法，其特征是，以镍盐、铁盐和甘油作为原料，采用溶剂热法制备获得镍铁甘油酸酯球粉末，在空气条件下，将镍铁甘油酸酯球粉末以低于1.5℃/min的升温速率升温至不低于350℃进行煅烧，获得核壳状铁酸镍。
  4. 如权利要求3所述的核壳状铁酸镍的制备方法，其特征是，镍盐和铁盐中，镍离子与铁离子的摩尔比为1:1.9～2.1；
    或，溶剂热法反应体系的溶剂为异丙醇；
    或，溶剂热法的反应温度为150～200℃，反应时间为4～8h；
    或，煅烧温度为350～450℃，升温速率为0.9～1.1℃，煅烧时间为1.5～2.5h。
  5. 一种铁酸镍@C材料，其特征是，包括权利要求1或2所述的核壳状铁酸镍或权利要求3或4的制备方法获得的核壳状铁酸镍，所述核壳状铁酸镍被碳涂层包覆；
    优选的，碳涂层的厚度为20～25nm。
  6. 一种铁酸镍@C材料的制备方法，其特征是，将权利要求1或2所述的核壳状铁酸镍或权利要求3或4的制备方法获得的核壳状铁酸镍、间苯二酚、甲醛进行酚醛树脂缩合反应获得酚醛树脂包覆核壳状铁酸镍的铁酸镍@RF复合材料，在惰性气氛下，将铁酸镍@RF复合材料煅烧碳化获得铁酸镍@C材料。
  7. 如权利要求6所述的铁酸镍@C材料的制备方法，其特征是，核壳状铁酸镍、间苯二酚、甲醛的投料比为50:0.9～1.1:0.11～0.13，mg：g：mL；
    或，酚醛树脂缩合反应，在碱性条件下进行；优选的，酚醛树脂缩合反应体系中添加氨水；
    或，酚醛树脂缩合反应体系的溶剂为乙醇水溶液；优选的，乙醇与水的体积比为2:0.9～1.1；
    或，煅烧碳化的温度为550～650℃，煅烧时间为1.5～2.5h。
  8. 一种上述铁酸镍@C材料在锂离子电池中的应用。
  9. 一种锂离子电池负极，其特征是，活性材料为权利要求5所述的铁酸镍@C材料或权利要求6或7所述的制备方法获得的铁酸镍@C材料；
    优选的，包括粘结剂、导电剂；
    优选的，制备方法为：将活性材料、粘结剂、导电剂混合均匀，加入溶剂制成浆料，将浆料涂覆与集流体表面，然后进行干燥。
  10. 一种锂离子电池，其特征是，负极采用权利要求9所述的锂离子电池负极。
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CN110790322A (zh) * 2019-11-08 2020-02-14 齐鲁工业大学 核壳状铁酸镍及制备方法、铁酸镍@c材料及制备方法与应用

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