CN110739156A - 一种增强钛酸钾电极电化学性能的处理方法 - Google Patents

一种增强钛酸钾电极电化学性能的处理方法 Download PDF

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CN110739156A
CN110739156A CN201810790431.0A CN201810790431A CN110739156A CN 110739156 A CN110739156 A CN 110739156A CN 201810790431 A CN201810790431 A CN 201810790431A CN 110739156 A CN110739156 A CN 110739156A
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potassium titanate
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夏晖
张薇
徐璟
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Nanjing Tech University
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Abstract

本发明公开了一种增强钛酸钾电极电化学性能的处理方法，对钛酸钾电极进行氩‑氢混合等离子体处理，经本发明提供的氩‑氢混合等离子体处理方法处理后，增加了电极中一维纳米结构表面粗糙度，增大了晶格间距，降低了材料的能隙，提高了其电导率，从而有效增强钛酸钾纳米材料的电化学性能，使之能够更好、更广泛的应用于超级电容、锂离子电池、以及光电催化材料等领域。

Description

一种增强钛酸钾电极电化学性能的处理方法
技术领域
本发明涉及电化学电极材料领域，特别是涉及一种增强钛酸钾电极电化学性能的处理方法。
背景技术
伴随着日益突出的能源匮乏的问题日，寻找廉价的储能材料和清洁能源成为研究的热点。Ti基材料具有成本低、应变小、无毒、化学性质稳定等优势被广泛应用于太阳能电池、光催化、传感器、生物医学等领域。但其较宽的带隙和较差的电导率限制了在储能器件的应用。因此，降低带隙宽度和提高电导率有望使Ti基电极的性能得到很大提升。
钛酸钾是Ti基材料的一种，其工作电位低、化学性质稳定，但是其电导率低，离子扩散动力学缓慢，不适用于储能领域。目前对于钛酸钾的改性方法主要有制备纳米结构的钛酸钾，增大比表面积来增加更多的活性位点，缩短扩散距离，促进离子传输，提高电化学动力学(Zhang,Q.Ultrafine Potassium Titanate Nanowires:a New Ti-Based Anodefor Sodium Ion Batteries.Chem.Commun.2016,52,6229-6232.Jin Han,Exploration ofK2Ti8O17as an anode material for potassium-ion batteries.Chem.Commun.,2016,52,11274)；或者与导电性更高的材料(如石墨烯)进行复合等策略来实现电化学性能的提高。(Cheng Zeng,Confined Transformation Derived Ultrathin Titanate Nanosheets/Graphene Films for Excellent Na/K Ion Storage.Angew.Chem.10.1002/ange.201803511)。
发明内容
鉴于以上所述钛酸钾的缺点,本发明的目的在于提供一种简单高效的增强钛酸钾电极电化学性能的处理方法,用于解决其电导率低，电化学性能差的问题。
为实现上述目的及其他相关目的，本发明提供一种增强钛酸钾电极电化学性能的处理方法，所述的处理方法包括以下步骤：
对制备的电极进行气体等离子体处理，增大其层间距，引入氧空位，从而提高电极材料的导电性和电化学性能。
优选地，采用一步水热法制备钛酸钾电极。
优选地，水热反应在高压反应釜中进行，混合溶液体积为反应釜体积的75％～85％。
优选地，水热反应温度为180℃～220℃，反应时间为5h～12h。
优选地，一维纳米结构为纳米带或纳米线结构。
优选地，等离子体处理采用的气体为氩-氢混合气，气体流量为20-100sccm。
优选地，等离子体处理时，体系气压在20Pa，等离子体气相沉积仪的功率为100-300W，处理时间为30-180min。
如上所述，本发明的增强钛酸钾电极电化学性能的处理方法，具有以下效果：1.通过采用等离子体对制备的一维结构的钛酸钾电极进行处理，可以在较低温度和较短时间内引入氧空位。
2.经过本发明提供的处理方法处理后，由于等离子体的击打作用，电极从一维纳米结构变成二维纳米结构，提高材料的比表面积，并且氧空位的引入降低了材料的能隙，提高材料电导率，从而可有效增强材料的电化学性能，为纳米材料在超级电容器、锂离子电池、钠离子电池、钾离子电池等储能领域的性能提升提供了有效途径。
附图说明
图1是实施例1制备的KTO电极经等离子体处理前后的SEM图
图2为实施例1中制备的KTO电极经等离子体处理后SEM图
图3是实施例1制备的KTO电极经等离子体处理前后的XRD对比图
图4是实施例1制备的KTO电极经等离子体处理前后的XPS对比图
图5为实施例1中制备的KTO电极经等离子体处理前后的循环伏安曲线对比图
图6为实施例1中制备的KTO电极经等离子体处理前后的阻抗曲线对比图
图7为实施例1中制备的KTO电极经等离子体处理前后的恒流充放电曲线对比图
图8为实施例2中制备的KTO电极经等离子体处理前后的循环伏安曲线对比图
具体实施方式
下面结合实施例和附图对本发明做进一步详细的描述。
实施例1
采用一步水热法制备钛酸钾电极。首先，依次用丙酮、乙醇和水将两片Ti箔超声清洗15min，接着，将Ti箔作为钛源，放入盛有1M KOH聚四氟乙烯内衬的高压釜内，将高压釜密封后置于烘箱内，于200℃下恒温5h后，取出Ti箔，用去离子水冲洗，烘干。
将制备的两个KTO电极中的其中一个KTO电极不做等离子体处理，另一个放入等离子体气相沉积仪的反应腔室中，进行等离子体处理，其中，处理所用的气体为氩-氢混合气，气流量为50sccm，等离子体清洗仪的功率为200W，处理时间为60min。
对上述制备的未经等离子体处理和经过等离子体处理的两个KTO电极分别进行了各项测试，测试内容有：
对未经等离子体处理和经过等离子体处理的两个电极进行形貌观察，如图1和图2分别为未经等离子体处理和经等离子体处理后的电极的SEM图。由图看出，初始制备的电极为纳米带结构，经过等离子体处理后，电极材料中有二维纳米片出现，提高了电极接触面积，增加了电极活性位点。此外由于等离子体本身具有较强的刻蚀作用，用等离子体处理过的电极的表面显然更为粗糙，使得电极材料的比表面积增大，这也有利于电极电化学性能的增强。
对未经等离子体处理和经过等离子体处理的两个电极进行XRD测试，如图3为经等离子体处理前后电极的XRD对比图谱。从图中看出，经等离子体处理过的电极(200)晶面主峰向左偏移，表明晶面间距增大，由于所述制备的材料为一种层状钛酸钾材料，由XRD图谱看出经等离子处理后的电极材料的层间距扩大，这有利于离子的嵌入与脱出，促进其电化学性能的增强。
对未经等离子体处理和经过等离子体处理的两个电极进行XPS测试，如图4为经等离子体处理前后电极的XPS对比图谱。从图中看出，经等离子体处理过的电极Ti2p3/2的结合能从458.52eV向左偏移到458.28eV，Ti2p1/2的峰位置从464.34eV左移至464.16Ev，表明经等离子体处理后有Ti3+存在，说明产生了氧空位，提高了导电性，这有利于电子的传输，促进其电化学性能的增强。
对未经等离子体处理和经过等离子体处理的两个电极进行循环伏安曲线测试，以待测试的电极作为工作电极，铂片作为对电极，Ag/AgCl作为参比电极，电解液为0.5MK2SO4。如图5为经等离子体处理前后的电极的循环伏安曲线对比图，测试时扫描速度均为50mv/s。从图中看出，经等离子体处理过的电极曲线电流和包围的面积明显增加，这表明处理过的KTO电极的电化学性能有明显的提高，电容增加。
对未经等离子体处理和经过等离子体处理的两个电极进行阻抗测试，测试体系与循环伏安曲线与相同，如图6为经等离子体处理前后的KTO电极的阻抗曲线对比图。可以看出，处理后的电极阻抗曲线中半圆半径很小，这就意味着处理后的电极具有更小的内阻和更好的导电性，更窄的能隙。这可能是由于等离子体部分还原，形成Ti3+自掺杂和氧空位，降低材料的能隙，提高了导电性能。
对未经等离子体处理和经过等离子体处理的两个电极以1Ag-1电流密度恒电流充放电进行充放电测试。如图7为经等离子体处理前后的KTO电极的恒电流充放电对比图。可以看出，没有经等离子体处理和经过等离子体处理的电极比电容分别能达到78.5F/g和160.8F/g，从数据看出，经过等离子体处理的电极的电化学性能有很大提高。
实施例2
钛酸钾电极制备方法与实施例1相同，采用一步水热法，将Ti箔作为钛源，放入盛有1M KOH聚四氟乙烯内衬的高压釜内，将高压釜密封后置于200℃的烘箱内，恒温5h后，取出Ti箔，用去离子水冲洗，烘干。对其进行等离子体处理。采用氩-氢混合气，功率为100W，处理时间为30min。电极测试过程与实施例1相同，获得的未处理和处理的电极的形貌照片、阻抗测试曲线的对比结果与实施例1相同。以50mv/s扫速进行循环伏安测试，测试结果如图8所示。经计算得出不处理和处理的电极比电容分别为78.5F/g和100.7F/g，从数据看出，经过等离子体处理的电极的电化学性能有了提高。
综上所述，本发明提供一种简单高效的增强钛酸钾电极电化学性能的处理方法，通过采用等离子体处理的方法，对制备的一维结构的电极进行处理，经过本发明提供的处理方法处理后，材料从一维纳米带结构变成二维纳米片结构，使得离子扩散距离缩短，接触面积增大，此外还增加了电极表面粗糙度，提高了比表面积，并且等离子体部分还原Ti4+形成Ti3+自掺杂和氧空位，降低了材料的能隙，提高了其导电性能，从而有效地增强材料的电化学性能，钛酸钾纳米材料能够更好、更广泛的应用于超级电容、锂离子电池以及光电催化材料等领域。

Claims (7)

1.一种增强钛酸钾电极电化学性能的处理方法，其特征在于，所述钛酸钾电极的处理方法，包括以下步骤：
用氩氢混合等离子体对所制备的钛酸钾电极进行处理，增大其层间距，引入氧空位，提高电导率和电化学性能。
2.根据权利要求1所述的增强钛酸钾电极电化学性能的处理方法，其特征在于，采用水热法制备所述的钛酸钾电极。
3.根据权利要求2所述的增强钛酸钾电极电化学性能的处理方法，其特征在于，所述的水热反应在高压反应釜中进行，混合溶液体积为反应釜体积的75％～85％。
4.根据权利要求2或3所述的增强钛酸钾电极电化学性能的处理方法，其特征在于，所述的水热反应温度为160℃～220℃，反应时间为5h～12h。
5.根据权利要求1所述的制备增强钛酸钾电极电化学性能的处理方法，其特征在于，所述电极为层状结构纳米材料。
6.根据权利要求1所述的增强钛酸钾电极电化学性能的处理方法，其特征在于，等离子体处理采用的气体为氩-氢混合气，气体流量为20-100sccm。
7.根据权利要求1所述的增强钛酸钾电极电化学性能的处理方法，其特征在于，等离子体处理时，体系气压在20Pa，等离子体气相沉积仪的功率为100-300W，处理时间为30-180min。
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