WO2022032749A1 - 一种三维棒状钛酸钾材料的制备方法 - Google Patents

一种三维棒状钛酸钾材料的制备方法 Download PDF

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WO2022032749A1
WO2022032749A1 PCT/CN2020/112570 CN2020112570W WO2022032749A1 WO 2022032749 A1 WO2022032749 A1 WO 2022032749A1 CN 2020112570 W CN2020112570 W CN 2020112570W WO 2022032749 A1 WO2022032749 A1 WO 2022032749A1
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potassium titanate
titanate material
dimensional rod
potassium
preparing
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French (fr)
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张业龙
孙宏阳
周健文
徐晓丹
陈俞程
曾庆光
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五邑大学
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    • HELECTRICITY
    • H01ELECTRIC ELEMENTS
    • H01MPROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00Electrodes
    • H01M4/02Electrodes composed of, or comprising, active material
    • H01M4/36Selection of substances as active materials, active masses, active liquids
    • H01M4/362Composites
    • HELECTRICITY
    • H01ELECTRIC ELEMENTS
    • H01MPROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00Secondary cells; Manufacture thereof
    • H01M10/05Accumulators with non-aqueous electrolyte
    • H01M10/054Accumulators with insertion or intercalation of metals other than lithium, e.g. with magnesium or aluminium
    • HELECTRICITY
    • H01ELECTRIC ELEMENTS
    • H01MPROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00Electrodes
    • H01M4/02Electrodes composed of, or comprising, active material
    • H01M4/13Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
    • H01M4/131Electrodes based on mixed oxides or hydroxides, or on mixtures of oxides or hydroxides, e.g. LiCoOx
    • HELECTRICITY
    • H01ELECTRIC ELEMENTS
    • H01MPROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00Electrodes
    • H01M4/02Electrodes composed of, or comprising, active material
    • H01M4/13Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
    • H01M4/136Electrodes based on inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy
    • HELECTRICITY
    • H01ELECTRIC ELEMENTS
    • H01MPROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00Electrodes
    • H01M4/02Electrodes composed of, or comprising, active material
    • H01M4/36Selection of substances as active materials, active masses, active liquids
    • H01M4/48Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
    • H01M4/485Selection 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
    • HELECTRICITY
    • H01ELECTRIC ELEMENTS
    • H01MPROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00Electrodes
    • H01M4/02Electrodes composed of, or comprising, active material
    • H01M4/36Selection of substances as active materials, active masses, active liquids
    • H01M4/58Selection of substances as active materials, active masses, active liquids of inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy; of polyanionic structures, e.g. phosphates, silicates or borates
    • YGENERAL 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
    • Y02TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02EREDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/10Energy storage using batteries

Definitions

  • the invention belongs to the field of new energy materials, in particular to a preparation method of a three-dimensional rod-shaped potassium titanate material.
  • lithium-ion batteries As a mature energy storage device, lithium-ion batteries have been widely used in various electronic products and new energy vehicles due to their advantages of high energy density, wide operating temperature, and long cycle life.
  • the prices of upstream materials due to the small reserves and uneven distribution of lithium ore resources in the earth's crust, with the increasing consumption of lithium-ion batteries, the prices of upstream materials (lithium carbonate, cobalt hydroxide, etc.)
  • the high cost of ion batteries makes it difficult for further large-scale applications.
  • the energy storage market urgently needs new energy storage devices with lower cost.
  • Lithium (Li), sodium (Na) and potassium (K) are in the same main group, and their physical and chemical properties are relatively close.
  • the reduction potential of potassium (-2.93V) is closer to that of lithium (-2.93V) than that of sodium (-2.71V). 3.04V), which means that the energy density of potassium-ion batteries (KIBs) is higher than that of sodium-ion batteries (SIBs), and the potassium ore resources have large reserves, low cost (potassium carbonate price is only 7000 yuan / ton), wide distribution, etc.
  • K-ion batteries In the long run, relatively cheap potassium-ion batteries are one of the development directions for large-scale energy storage. Although potassium ion batteries have great prospects for development, there are still some problems in potassium ion batteries.
  • the potassium ion radius is large, although commercial graphite can be embedded, but it is easy to cause huge volume changes during the intercalation and deintercalation, which leads to Performance degrades rapidly. Therefore, it is necessary to develop potassium ion anode materials with good cycling stability.
  • MXenes such as Ti 3 C 2 T x
  • Ti 3 C 2 T x are a new type of two-dimensional transition metal carbon/nitride or carbonitride with high specific surface area and high conductivity, which is conducive to ion and electron transport.
  • the interlayer spacing is small, and the surface functional groups have a certain adsorption, so the ideal fast ion migration effect cannot be achieved.
  • potassium titanate (K 2 Ti 4 O 9 ), which is a layered titanium-based material with a zigzag skeleton, and its large octahedral gap can accommodate potassium ions well, thereby relieving potassium ions in the The volume change during charging and discharging; in addition, the low operating voltage and good environmental friendliness make potassium titanate (K 2 Ti 4 O 9 ) an ideal anode material for potassium-ion batteries.
  • the existing potassium titanate (K 2 Ti 4 O 9 ) is mostly synthesized by the method of hydrothermal treatment. However, the hydrothermal treatment needs to add a strong oxidant H 2 O 2 , so the obtained potassium titanate has poor uniformity and is prone to agglomeration. , and the electrical conductivity is poor, which is not conducive to the full performance of the potassium ion battery.
  • one of the objectives of the present invention is to provide a three-dimensional rod-shaped potassium titanate material.
  • Another object of the present invention is to provide a method for preparing the above three-dimensional rod-shaped potassium titanate material.
  • the present invention provides an application of a three-dimensional rod-shaped potassium titanate material, and the three-dimensional rod-shaped potassium titanate material is used as a negative electrode of a potassium ion battery.
  • the present invention adopts following technical scheme:
  • a preparation method of a three-dimensional rod-shaped potassium titanate material comprising the following steps:
  • potassium hydroxide is added in solvent, be configured as the potassium hydroxide solution that concentration is 1-5mol/L, preferably 2-4mol/L, for example 2mol/L, 3mol/L, 4mol/L, 5mol/L L;
  • step (2) adding Ti 3 C 2 T x to the potassium hydroxide aqueous solution prepared in step (1), then stirring for 5-48 hours, preferably 12-40 hours, such as 5 hours, 16 hours, 20 hours, 24 hours, 36 hours hours, 48 hours to obtain a dispersion;
  • step (3) centrifuging the dispersion obtained in step (2), cleaning with a cleaning agent, and vacuum drying to obtain a precursor
  • step (3) After putting the precursor obtained in step (3) into a corundum crucible, transfer it to a heating furnace, and in an air atmosphere, heat it to 800-1100°C at a heating rate of 3-6°C/min, and keep the temperature for 1- Cool to room temperature after 5 hours;
  • the stirring speed in step (2) is 300-1500r/min, preferably 600-1000r/min, such as 450r/min, 650r/min, 700r/min, 850r/min.
  • the cleaning agent is at least one of water and ethanol.
  • cleaning the product obtained in step (2) with ultrapure water and absolute ethanol can be alternately cleaned with ultrapure water and absolute ethanol 3-6 times, preferably 3 times.
  • the centrifugal rotation speed is 3000-8000r/min, preferably 6500r/min, and the centrifugation time is 2-10min, preferably 3min.
  • the temperature of vacuum drying in step (3) is 60-80°C, preferably 70°C, and the drying time is 4-16 hours, preferably 8 hours, such as 6 hours, 9 hours, 10 hours, 11 hours, 12 hours; vacuum
  • the degree does not exceed 150Pa, preferably 120Pa, such as 133Pa, 130Pa, 120Pa, 110Pa, 100Pa, 90Pa.
  • the heating furnace in step (4) is a high-temperature heating furnace, preferably a tube furnace, and optionally a box-type heating furnace.
  • the heating rate in step (4) is 3-6°C/min, such as 3°C, 4°C, 5°C; the heating temperature is 800-1100°C, such as 1000°C, 800°C, 900°C, 1100°C;
  • the holding time is 1-5 hours, such as 1.5 hours, 3 hours, 4 hours, 5 hours.
  • a negative electrode of a potassium ion battery comprising a three-dimensional rod-shaped potassium titanate material prepared by the preparation method.
  • a potassium ion battery comprising the above-mentioned battery negative electrode.
  • the rod-shaped potassium titanate prepared by using Ti 3 C 2 T x as a precursor in the present invention has a three-dimensional structure, which is conducive to the full contact of the electrolyte and avoids material agglomeration.
  • the intrinsic carbon layer of Ti3C2Tx can significantly enhance the electrical conductivity of potassium titanate, thereby enhancing the rate capability.
  • the preparation method of the material of the present invention is simple, the obtained material has good potassium storage performance, and is suitable for large-scale application.
  • Fig. 1 is the scanning electron microscope image of MXene material in Comparative Example 1;
  • Fig. 2 is the scanning electron microscope picture of the potassium titanate material prepared by hydrothermal method in Comparative Example 2;
  • Fig. 3 is the scanning electron microscope picture of three-dimensional rod-shaped potassium titanate material in embodiment 1;
  • Fig. 4 is the cycle performance graph measured by MXene in Comparative Example 1;
  • Fig. 5 is the cycle performance figure measured by the potassium titanate material prepared by hydrothermal method in Comparative Example 2;
  • Example 6 is a graph of the cycle performance measured by the three-dimensional rod-shaped potassium titanate material in Example 1.
  • the Ti 3 C 2 T x particles were purchased from Beijing Beike New Material Technology Co., Ltd., number BK2020011814, lamellar stacking thickness: 1-5 ⁇ m, purity: 99%, product application fields: energy storage, catalysis, analytical chemistry, etc.
  • Battery performance test Mix the prepared negative electrode material with conductive carbon black and polyvinylidene fluoride binder in a mass ratio of 8:1:1, add an appropriate amount of N-methylpyrrolidone, stir evenly and then coat On the copper foil, vacuum-dried at 80° C. and sliced to obtain a potassium-ion battery negative electrode sheet.
  • the negative electrode, potassium metal foil, and separator (Whatman, GF/F) were assembled into a 2032 button battery in a glove box, and the battery performance was tested by using the Wuhan Blue Electric Battery Test System.
  • a preparation method of a three-dimensional rod-shaped potassium titanate material comprising the following steps:
  • potassium hydroxide is added in solvent, be configured as the potassium hydroxide solution that concentration is 1mol/L;
  • step (3) the product obtained in step (2) is centrifuged at a rotating speed of 6500 r/min, and then alternately washed 3 times with ethanol and ultrapure water;
  • step (3) drying the centrifuged product obtained in step (3) in a vacuum drying oven at a temperature of 70° C. for 12 hours to obtain a precursor;
  • step (4) after the precursor obtained in step (4) is put into the corundum crucible, it is transferred to the tube furnace;
  • the three-dimensional rod-shaped potassium titanate material of this embodiment has a reversible capacity of 182 mAh/g after 150 cycles at a current density of 100 mA/g, and the three-dimensional rod-shaped potassium titanate material of this embodiment has very stable charge-discharge cycle performance.
  • the specific capacity decay rate per turn is only 0.034%.
  • a preparation method of a three-dimensional rod-shaped potassium titanate material comprising the following steps:
  • potassium hydroxide is added in solvent, be configured as the potassium hydroxide solution that concentration is 3mol/L;
  • step (3) the product obtained in step (2) is centrifuged at a rotating speed of 5000 r/min, and then alternately washed 3 times with ethanol and ultrapure water;
  • step (3) drying the centrifuged product obtained in step (3) in a vacuum drying oven at a temperature of 80° C. for 10 hours to obtain a precursor;
  • step (4) after the precursor obtained in step (4) is put into the corundum crucible, it is transferred to the tube furnace;
  • the three-dimensional rod-shaped potassium titanate material of this embodiment has a reversible capacity of 176 mAh/g after 150 cycles at a current density of 100 mA/g, and the three-dimensional rod-shaped potassium titanate material of this embodiment has very stable charge-discharge cycle performance.
  • the specific capacity decay rate per turn is only 0.042%.
  • a preparation method of a three-dimensional rod-shaped potassium titanate material comprising the following steps:
  • potassium hydroxide is added in solvent, be configured as the potassium hydroxide solution that concentration is 5mol/L;
  • step (3) the product obtained in step (2) is centrifuged at a rotating speed of 7000 r/min, and then alternately washed 5 times with ethanol and ultrapure water;
  • step (3) the centrifugation product obtained in step (3) is vacuum-dried at a temperature of 60° C. for 14 hours to obtain a precursor;
  • step (4) after the precursor obtained in step (4) is put into the corundum crucible, it is transferred to the tube furnace;
  • the three-dimensional rod-shaped potassium titanate material of this embodiment has a reversible capacity of 146 mAh/g after 150 cycles at a current density of 100 mA/g, and the three-dimensional rod-shaped potassium titanate material of this embodiment has very stable charge-discharge cycle performance.
  • the specific capacity decay rate per turn is only 0.038%.
  • the potassium titanate material prepared by hydrothermal method comprises the following steps:
  • potassium hydroxide is added in solvent, be configured as the potassium hydroxide solution that concentration is 1mol/L;
  • step (3) transfer the product of step (2) gained in the stainless steel reaction kettle of 50ml to seal, and keep at 150 °C for 12 hours;
  • step (3) the product obtained in step (3) is centrifuged at a rotating speed of 7000 r/min, and then alternately washed 5 times with ethanol and ultrapure water;
  • step (4) vacuum drying the centrifuged product obtained in step (4) at 60° C. for 8 hours to obtain a hydrothermal potassium titanate material.
  • the hydrothermal potassium titanate material of this embodiment has a reversible capacity of 103 mAh/g after 150 cycles at a current density of 100 mA/g, and the three-dimensional rod-shaped potassium titanate material of this embodiment has very stable charge-discharge cycle performance.
  • the specific capacity decay rate per turn is only 0.052%.
  • the layer spacing of the pure Ti3C2Tx material is very small; the hydrothermal potassium titanate has poor uniformity and is prone to agglomeration; the potassium titanate obtained by the present invention has an enlarged layer spacing, uniform material distribution and no agglomeration phenomenon, It has a three-dimensional structure, which is conducive to the full contact of the electrolyte, thereby reducing the diffusion resistance.
  • the intrinsic carbon layer of Ti3C2Tx can significantly enhance the electrical conductivity of potassium titanate, thereby enhancing the rate capability.

Abstract

一种三维棒状钛酸钾材料的制备方法,包括以下步骤:(1)将氢氧化钾溶于水,配置成浓度为1-5mol/L的氢氧化钾溶液;(2)将Ti 3C 2T x加入步骤(1)所制的氢氧化钾溶液中,混匀,充分反应得到前驱体分散液;(3)将步骤(2)所得的分散液离心,洗涤,干燥,得到前驱体;(4)将步骤(3)得到的前驱体在空气气氛中,800-1100℃下,保温1-5小时,冷却,收集固体,得到三维棒状钛酸钾材料。与水热处理方法制备的钛酸钾相比,以Ti 3C 2T x为原料制备的棒状钛酸钾具有三维立体结构,有利于电解液充分接触,从而降低扩散阻力。此外,Ti 3C 2T x的本征碳层可以显著提高钛酸钾的导电性,从而提高倍率性能。

Description

一种三维棒状钛酸钾材料的制备方法 技术领域
本发明属于新能源材料领域,具体涉及一种三维棒状钛酸钾材料的制备方法。
背景技术
锂离子电池作为成熟的储能器件,因其能量密度大、工作温度宽、循环寿命长等优点,已被广泛应用于各种电子产品及新能源汽车。然而,由于锂矿资源在地壳中的储量较少且分布不均,随着锂离子电池用量不断增加,锂离子电池上游材料(碳酸锂、氢氧化钴等)的价格也节节攀升,使得锂离子电池成本居高不下,难以进一步大规模应用。储能市场迫切需要成本更低的新型储能器件。
锂(Li)、钠(Na)和钾(K)处在同一主族,物理化学性质比较接近,钾的还原电势(-2.93V)相较于钠(-2.71V)更接近于锂(-3.04V),这意味着钾离子电池(KIBs)的能量密度高于钠离子电池(SIBs),并且钾矿资源具有储量多、成本低(碳酸钾价格仅为7000元/吨)、分布广等优势。从长远考虑,相对廉价的钾离子电池是大规模储能的发展方向之一。虽然钾离子电池具有极大的发展前景,然而钾离子电池目前也存在一些问题,比如,钾离子半径较大,虽然可以嵌入商用石墨,但在嵌入与脱出期间易造成巨大的体积变化,从而导致性能快速衰减。因此,开发具有良好的循环稳定性的钾离子负极材料是必要的。
目前比较多的是MXene,比如Ti 3C 2T x,作为一种新型的二维过渡金属碳/氮化物或碳氮化物,其具有较高的比表面积和高导电性,有利于离子电子传输,但是其层间距较小,并且表面官能团具有一定的吸附性,因此并不能取得理想的离子快速迁移效果。还有一种就是钛酸钾(K 2Ti 4O 9),其属于层状钛基材料,具有锯齿状的骨架,其较大的八面体间隙可以很好的容纳钾离子,从而缓解钾离子在充放电过程的体积变化;此外,低的工作电压以及良好的环境友好性使得钛酸钾(K 2Ti 4O 9)成为钾离子电池的理想负极材料。现有的钛酸钾(K 2Ti 4O 9)多是通过水热处理的方法合成,然而,水热处理需要加入强氧化剂H 2O 2,因而得到的钛酸钾均匀性较差,容易发生团聚,且导电性能较差,不利于钾离子电池性能的充分发挥。
发明内容
针对现有技术存在的问题,本发明的目的之一在于提供一种三维棒状钛酸钾材料。本发明的另一目的在于提供上述三维棒状钛酸钾材料的制备方法。进一步的,本发明提供一种三 维棒状钛酸钾材料的应用,将所述三维棒状钛酸钾材料用作钾离子电池负极。
本发明采用以下技术方案:
一种三维棒状钛酸钾材料的制备方法,包括以下步骤:
(1)将氢氧化钾加入溶剂中,配置为浓度为1-5mol/L的氢氧化钾溶液,优选的为2-4mol/L,例如2mol/L,3mol/L,4mol/L,5mol/L;
(2)将Ti 3C 2T x加入步骤(1)所制的氢氧化钾水溶液,然后搅拌5-48小时,优选12-40小时,例如5小时,16小时,20小时,24小时,36小时,48小时,得到分散液;
(3)将步骤(2)所得的分散液离心,用清洗剂进行清洗,真空干燥,得到前驱体;
(4)将步骤(3)得到的前驱体放入刚玉坩埚后,转移至加热炉中,在空气气氛中,以3-6℃/min的升温速度加热至800-1100℃,并保温1-5小时后冷却至室温;
(5)收集刚玉坩埚中的固体,即得到三维棒状钛酸钾材料。
进一步地,步骤(2)所述搅拌速度为300-1500r/min,优选600-1000r/min,例如450r/min,650r/min,700r/min,850r/min。
进一步地,所述清洗剂为水和乙醇中的至少一种。
进一步地,用超纯水和无水乙醇清洗步骤(2)所得的产物,可以用超纯水和无水乙醇交替清洗3-6次,优选3次。
进一步地,步骤(2)中所述离心转速为3000-8000r/min,优选6500r/min,离心时间为2-10min,优选3min。
进一步地,步骤(3)中真空干燥的温度为60-80℃,优选70℃,干燥时间4-16小时,优选8小时,例如6小时、9小时、10小时、11小时、12小时;真空度不超过150Pa,优选120Pa,例如133Pa、130Pa、120Pa、110Pa、100Pa、90Pa。
进一步地,步骤(4)所述加热炉为高温加热炉,优选管式炉,可选箱式加热炉。
进一步地,步骤(4)所述升温速度为3-6℃/min,例如3℃,4℃,5℃;加热温度为800-1100℃,例如1000℃,800℃,900℃,1100℃;保温时间为1-5小时,例如1.5小时,3小时,4小时,5小时。
一种钾离子电池负极,其包括所述的制备方法制备得到的三维棒状钛酸钾材料。
一种钾离子电池,其包括上述电池负极。
本发明的有益效果:
(1)与水热处理工艺所得的钛酸钾相比,本发明以Ti 3C 2T x为前驱体制备棒状钛酸钾具有三维立体结构,有利于电解液充分接触,避免材料团聚。此外,Ti 3C 2T x的本征碳层可以显著提高钛酸钾的导电性,从而提高倍率性能。
(2)本发明的材料制备方法简单,所得材料具有良好储钾性能,适合大规模应用。
附图说明
图1是对比例1中MXene材料的扫描电镜图;
图2是对比例2中水热法制备的钛酸钾材料的扫描电镜图;
图3是实施例1中三维棒状钛酸钾材料的扫描电镜图;
图4是对比例1中MXene所测的循环性能图;
图5是对比例2中水热法制备的钛酸钾材料所测的循环性能图;
图6是实施例1中三维棒状钛酸钾材料所测的循环性能图。
具体实施方式
为了更好的解释本发明,现结合以下具体实施例作进一步说明,但是本发明不限于具体实施例。
其中,所述材料如无特别说明均可以在商业途径可得;
所述Ti 3C 2T x颗粒购自北京北科新材科技有限公司,编号BK2020011814,片层堆积厚度:1-5μm,纯度:99%,产品应用领域:储能,催化,分析化学等。
所述方法如无特别说明均为常规方法。
比表面积测试:通过ASAP2460analyzer分析仪器对所获样品进行N2吸附脱附测试,并基于BET理论计算出比表面积。
电池性能测试:将制备的负极材料与导电碳黑、聚偏氟乙烯粘结剂,按质量比为8:1:1的比例进行混合,并加入适量N-甲基吡咯烷酮,搅拌均匀后涂覆在铜箔上,经80℃真空干燥后切片,得到钾离子电池负极片。将该负极极片,金属钾箔,隔膜(Whatman,GF/F)在手套箱中组装成2032型纽扣电池,并利用武汉蓝电电池测试***进行电池性能测试。
实施例1
一种三维棒状钛酸钾材料的制备方法,包括以下步骤:
(1)将氢氧化钾加入溶剂中,配置为浓度为1mol/L的氢氧化钾溶液;
(2)将100mg Ti 3C 2T x加入50ml步骤(1)所制的氢氧化钾水溶液,然后以650r/min 的搅拌速度搅拌12小时;
(3)将步骤(2)所得的产物以6500r/min的转速进行离心,然后用乙醇和超纯水进行交替清洗3次;
(4)将步骤(3)得到的离心产物在真空干燥箱中在70℃的温度下干燥12小时后得到前驱体;
(5)将步骤(4)得到的前驱体放入刚玉坩埚后,转移至管式炉中;
(6)将管式炉在空气气氛中,以3℃/min的升温速度加热至1000℃,并保温1.5小时后冷却至室温;
(7)收集刚玉坩埚中固体,即得到三维棒状钛酸钾材料。
本实施例的三维棒状钛酸钾材料在100mA/g的电流密度下,循环150圈后的可逆容量为182mAh/g,且本实施例三维棒状钛酸钾材料具有非常稳定的充放电循环性能,每圈比容量衰减率仅为0.034%。
实施例2
一种三维棒状钛酸钾材料的制备方法,包括以下步骤:
(1)将氢氧化钾加入溶剂中,配置为浓度为3mol/L的氢氧化钾溶液;
(2)将300mg Ti 3C 2T x加入50ml步骤(1)所制的氢氧化钾水溶液,然后以800r/min的搅拌速度搅拌8小时;
(3)将步骤(2)所得的产物以5000r/min的转速进行离心,然后用乙醇和超纯水进行交替清洗3次;
(4)将步骤(3)得到的离心产物在真空干燥箱中在80℃的温度下干燥10小时后得到前驱体;
(5)将步骤(4)得到的前驱体放入刚玉坩埚后,转移至管式炉中;
(6)将管式炉在空气气氛中,以4℃/min的升温速度加热至800℃,并保温3小时后冷却至室温;
(7)收集刚玉坩埚中固体,即得到三维棒状钛酸钾材料。
本实施例的三维棒状钛酸钾材料在100mA/g的电流密度下,循环150圈后的可逆容量为176mAh/g,且本实施例三维棒状钛酸钾材料具有非常稳定的充放电循环性能,每圈比容量衰减率仅为0.042%。
实施例3
一种三维棒状钛酸钾材料的制备方法,包括以下步骤:
(1)将氢氧化钾加入溶剂中,配置为浓度为5mol/L的氢氧化钾溶液;
(2)将1000mg Ti 3C 2T x加入80ml步骤(1)所制的氢氧化钾水溶液,然后以800r/min的搅拌速度搅拌8小时;
(3)将步骤(2)所得的产物以7000r/min的转速进行离心,然后用乙醇和超纯水进行交替清洗5次;
(4)将步骤(3)得到的离心产物在在60℃的温度下真空干燥14小时后得到前驱体;
(5)将步骤(4)得到的前驱体放入刚玉坩埚后,转移至管式炉中;
(6)将管式炉在空气气氛中,以5℃/min的升温速度加热至900℃,并保温4小时后冷却至室温;
(7)收集刚玉坩埚中固体,即得到三维棒状钛酸钾材料。
本实施例的三维棒状钛酸钾材料在100mA/g的电流密度下,循环150圈后的可逆容量为146mAh/g,且本实施例三维棒状钛酸钾材料具有非常稳定的充放电循环性能,每圈比容量衰减率仅为0.038%。
对比例1:
将单纯的Ti 3C 2T x材料装在100mA/g的电流密度下,循环150圈后的可逆容量为45mAh/g。
对比例2:
水热法制备而得的钛酸钾材料,其制备步骤包括以下步骤:
(1)将氢氧化钾加入溶剂中,配置为浓度为1mol/L的氢氧化钾溶液;
(2)将100mg Ti 3C 2T x加入40ml步骤(1)所制的氢氧化钾水溶液,搅拌10min后再向该混合溶液中加入体积浓度为30%的5ml H 2O 2溶液;
(3)将步骤(2)所得的产物转移至50ml的不锈钢反应釜中密封,并在150℃下保温12小时;
(4)将步骤(3)所得的产物以7000r/min的转速进行离心,然后用乙醇和超纯水进行交替清洗5次;
(5)将步骤(4)得到的离心产物在60℃下真空干燥8小时,即得到水热钛酸钾材料。
本实施例的水热钛酸钾材料在100mA/g的电流密度下,循环150圈后的可逆容量为103mAh/g,且本实施例三维棒状钛酸钾材料具有非常稳定的充放电循环性能,每圈比容量衰减率仅为0.052%。
表1:性能测试
Figure PCTCN2020112570-appb-000001
由表1可知,单纯的Ti 3C 2T x材料的比表面积极低,比容量很小;水热钛酸钾的比表面积、循环稳定性和容量损失率有了一定的改善,但仍然无法满足钾离子电池对负极材料的要求;本发明实施例1-3制备得到的钛酸钾的比表面积、循环稳定性和容量损失率都较水热钛酸钾有了很大的提升,完全满足钾离子电池对负极材料的要求。
由图1-3可知,单纯的Ti3C2Tx材料的层间距很小;水热钛酸钾均匀性较差,容易发生团聚;本发明得到的钛酸钾层间距扩大,材料分布均匀,没有团聚现象,具有三维立体结构,有利于电解液充分接触,从而降低扩散阻力。此外,Ti 3C 2T x的本征碳层可以显著提高钛酸钾的导电性,从而提高倍率性能。
由图4-6可知,单纯的Ti3C2Tx材料比容量很小,这可能由于比表面积低所致;水热钛酸钾的比容量有所提高,但仍然较小;本发明实施例制备得到的钛酸钾比容量很高,并且具有较好的循环稳定性,可以大大改善钾离子电池性能。
以上所述仅为本发明的具体实施例,并非因此限制本发明的专利范围,凡是利用本发明作的等效变换,或直接或间接运用在其它相关的技术领域,均同理包括在本发明的专利保护范围之中。

Claims (10)

  1. 一种三维棒状钛酸钾材料的制备方法,其特征在于,包括以下步骤:
    (1)将氢氧化钾溶于水,配置成浓度为1-5mol/L的氢氧化钾溶液;
    (2)将Ti 3C 2T x加入步骤(1)所制的氢氧化钾溶液中,混匀,充分反应得到前驱体分散液;
    (3)将步骤(2)所得的分散液离心,洗涤,干燥,得到前驱体;
    (4)将步骤(3)得到的前驱体在空气气氛中,800-1100℃下,保温1-5小时,冷却,收集固体,得到三维棒状钛酸钾材料。
  2. 根据权利要求1所述的三维棒状钛酸钾材料的制备方法,其特征在于,步骤(2)中通过搅拌进行混匀,其中搅拌速度为300-1500r/min,搅拌时间为5-48小时。
  3. 根据权利要求1所述的三维棒状钛酸钾材料的制备方法,其特征在于,步骤(3)用清洗剂进行洗涤,所述清洗剂为水和乙醇中的一种或两种。
  4. 根据权利要求1所述的三维棒状钛酸钾材料的制备方法,其特征在于,步骤(3)中所述离心转速为3000-12000r/min,离心时间为2-5min。
  5. 根据权利要求1所述的三维棒状钛酸钾材料的制备方法,其特征在于,步骤(4)中的干燥为真空干燥。
  6. 根据权利要求1所述的三维棒状钛酸钾材料的制备方法,其特征在于,步骤(4)中的干燥温度为50-100℃,干燥时间为5-10小时。
  7. 根据权利要求1所述的三维棒状钛酸钾材料的制备方法,其特征在于,步骤(4)中的真空度低于200Pa。
  8. 根据权利要求1所述的三维棒状钛酸钾材料的制备方法,其特征在于,所述的三维棒状钛酸钾材料的三维结构为类手风琴状结构,其尺寸为1-5μm。
  9. 一种钾离子电池负极,其特征在于,其包括权利要求1-6中任一项所述的制备方法制备得到的三维棒状钛酸钾材料。
  10. 一种钾离子电池,其特征在于,其包括权利要求7所述的电池负极。
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