现代化工

现代化工 ›› 2025, Vol. 45 ›› Issue (S1) : 326-330. DOI: 10.16606/j.cnki.issn0253-4320.2025.S1.059

科研与开发

N-TiO₂/MXene超结构钾离子电池负极的制备及其性能研究

王重权 ¹ ,
吴邦军 ¹ ,
刘争 ¹^,^* ,
张业龙 ²^,^*

作者信息 +

Preparation and performance study of N-TiO₂/MXene superstructure-based anode for potassium-ion battery

WANG Zhong-quan ¹ ,
WU Bang-jun ¹ ,
LIU Zheng ¹^,^* ,
ZHANG Ye-long ²^,^*

Author information +

文章历史 +

Received		Published
2025-01-20		2025-05-30
Issue Date	Revised Date
2025-05-23	2025-01-20

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摘要

K⁺离子较大的尺寸使得钾离子电池(PIBs)负极在充放电过程中电化学动力学较差,并伴随严重的体积变化。因此,采用原位氧化掺杂法制备了氮掺杂二氧化钛/MXene(N-TiO₂/MXene)超结构PIBs负极材料。结构表征显示,N-TiO₂/MXene超结构具有丰富的氧缺陷、高效的离子扩散通道、良好的电子导电性和较大的比表面积等优点。电池测试结果表明,N-TiO₂/MXene具有优异的储钾性能,在0.2 A/g电流密度下循环150圈后其可逆容量为160.1 mAh/g;即便在10 A/g的大电流密度下,仍能保持58.1 mAh/g的可逆容量。

Abstract

The larger size of K⁺ ions results in poor electrochemical kinetics and serious volume changes during the charge and discharge processes of potassium-ion batteries (PIBs).To address these issues,an N-TiO₂/MXene superstructure anode material for PIBs is prepared via an in-situ oxidation doping method.Structural characterization shows that N-TiO₂/MXene possesses advantages such as abundant oxygen vacancies,efficient ion diffusion channels,good electronic conductivity,and a large specific surface area.Battery testing results reveal that N-TiO₂/MXene anode exhibits excellent potassium storage performance,delivering a reversible capacity of 160.1 mAh·g^-1 after 150 cycles at a current density of 0.2 A·g^-1.Even at a high current density of 10 A·g^-1,it retains a reversible capacity of 58.1 mAh·g^-1.This study provides new insights for the design of novel anode materials for PIBs.

Graphical abstract

关键词

TiO₂ / 钾离子电池 / 负极材料 / MXene

Key words

TiO₂ / potassium ion battery / anode material / MXene

Author summay

王重权(2000-),男,硕士生,研究方向为钾离子电池,wang1278942537@outlook.com。

引用本文

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School of Renewable Energy, Inner Mongolia University of Technology, Ordos 010051, China), AuthorCompanyExt(id=1241415856460100396, tenantId=1226480274814496768, journalId=1226484258170171394, articleId=1240720038237270789, companyId=1241415856443323178, language=CN, country=null, province=null, city=null, postcode=null, companyName=null, departmentName=null, remark=2.内蒙古工业大学新能源学院,内蒙古鄂尔多斯 010051)])])] 王重权,吴邦军,刘争,张业龙. N-TiO₂/MXene超结构钾离子电池负极的制备及其性能研究[J]. 现代化工, 2025, 45(S1): 326-330 DOI:10.16606/j.cnki.issn0253-4320.2025.S1.059

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当今社会,能源紧缺与环境污染问题日益加剧。发展可再生能源可以有效解决这一问题,但是可再生能源的发展需要低成本的大规模储能设备来解决分布不均与间断性问题^[1-2]。锂离子电池在储能领域有着广泛应用,但是由于锂的成本过高,严重限制了锂离子电池的大规模应用^[3]。钾离子电池(PIBs)因其资源丰富、氧化还原电位接近锂和与锂离子电池相似的储能机理等优势,逐渐受到人们的广泛关注^[4-6]。然而,K⁺较大的离子尺寸在充放电过程中会严重影响电池的倍率性能和循环稳定性^[7-8]。因此,开发高性能PIBs负极材料至关重要。

目前,应用于PIBs负极的材料主要包括碳基材料^[9]、过渡金属硫族化物^[10]、过渡金属磷化物^[11]和过渡金属氧化物^[12]。二氧化钛(TiO₂)具有高稳定性、低成本、环保等优点,是潜在的PIBs负极材料^[13]。然而,TiO₂缓慢的K⁺扩散、较低的本征导电性以及在钾化/脱钾化过程中具有较大的体积形变,严重制约了其倍率和循环性能^[14]。与导电基底复合可以有效增强负载物质的导电性,掺杂工程能有效提升本体的反应活性。新型过渡金属碳/氮化物(MXene)具有独特的二维层状结构,拥有优异的机械性能和出色的导电性^[15]。将TiO₂与MXene复合,并引入杂原子,可有效改善其储钾性能。

本文采用原位氧化掺杂法,以水作为氧化剂、稀硝酸作为N源,在高温、高压的水热反应釜中,纯MXene被氧化为N-TiO₂/MXene。N-TiO₂/MXene作为PIBs负极具有以下优势:①MXene与TiO₂之间牢固而紧密的接触增强了TiO₂的导电性,有助于发生快速的电化学反应;②杂原子N的引入,使得TiO₂产生了大量氧缺陷,增加了反应活性位点;③N-TiO₂/MXene具有的三维层级结构和较大的比表面积,有利于电解液渗透,有效缓冲了K⁺离子嵌入/脱出过程产生的体积变化,稳定了电极结构。

1 实验材料与方法

1.1 药品

MAX粉末(Ti₃AlC₂,99.0%)购于先丰纳米公司;氢氟酸(HF,48%)、稀硝酸(HNO₃,65%)、二氧化钛(TiO₂)购于麦克林公司;无水乙醇(C₂H₄O₂)、聚偏氟乙烯(PVDF,99.9%)、N-甲基吡咯烷酮(NMP)购于上海阿拉丁生化科技股份有限公司;电池隔膜(GF/F)购于Whatman公司;电解液:0.8 mol/L的六氟磷钾(KPF₆)溶于乙烯碳酸酯(EC)-碳酸二乙酯(DEC)(体积比1∶1),购于多多试剂。

1.2 分析测试仪器

扫描电子显微镜(SEM,德国ZEISS GEMINISEM 300);投射电子显微镜(TEM,日本JEOLJFM-2100F);X射线衍射仪(XRD,德国Bruker D8 Advance);比表面积测试仪(BET,上海Micromeritics Instrument Corp ASAP 2020 V4.00);X射线光电子能谱仪(XPS,美国Axis Ultra DLD);蓝电测试仪(武汉CT2001A)。

1.3 MXene材料的制备

MXene制备:称取2.0 g Ti₃AlC₂ MAX粉末缓慢加入到30 mL HF溶液中,并在室温下搅拌24 h。将所得产物以3 000 r/min的转速离心10 min,并用去离子水多次洗涤。最后,将产物在60℃的真空烘箱中干燥12 h,得到Ti₃C₂T_x MXene粉末。

1.4 N-TiO₂/MXene的制备

N-TiO₂/MXene的制备:将50 mg MXene加入到35 mL超纯水中,再加入1 mL稀HNO₃,搅拌1 h后转移至50 mL水热反应釜中,并在200℃下反应12 h。随后,将所得产物以3 000 r/min的转速离心10 min,用离子水和乙醇多次洗涤溶液,最后,在70℃的真空环境中干燥8 h。

1.5 电池组装和电化学性能测试

电池组装:按8∶1∶1的质量比将活性物质、碳黑和PVDF混合,然后加入适量NMP,搅拌10 h。将混合物涂布于铜箔表面,随后在真空条件下烘干,得到极片。在手套箱内,使用金属钾片作为对电极、Whatman GF/F玻璃纤维作为隔膜,以0.8 mol/L KPF₆[V(EC)∶V(DEC)=1∶1]的电解液组装CR2032型电池。

电化学测试:在蓝电电池测试仪上进行充放电测试,电压范围为0.01~2.6 V。在电化学工作站(VMP3,Bio-Logic SAS)上进行电化学阻抗谱(EIS)测试,频率范围为100 kHz到0.01 Hz。

2 结果与讨论

2.1 材料的形貌和结构分析

2.1.1 扫描电子显微镜(SEM)、高分辨率透射电镜(HRTEM)和能量色散X射线谱(EDS)表征

从图1(a)和图1(b)可以观察到,经过HF/HNO₃溶液刻蚀处理,MAX转变为具有独特二维手风琴层状结构的MXene。经过水热反应釜高温反应后,MXene原位生成N-TiO₂/MXene超结构,N-TiO₂纳米颗粒牢牢地生长在MXene表面[图1(c)]。图1(d)中可以观察到0.35 nm和0.19 nm的晶格条纹,对应于TiO₂的(101)和(200)晶面^[16]。此外,N-TiO₂/MXene含有大量的缺陷(虚线圆圈),可以为电化学反应提供潜在的活性位点;而层级MXene可以为有效改善N-TiO₂导电性,促进离子的快速传递。EDS分析显示了C、N、Ti和O元素在N-TiO₂/MXene中均匀分布,确认了N-TiO₂/MXene的成功合成[图1(e)]。

2.1.2 X射线衍射(XRD)、X射线光电子能谱(XPS)和N₂物理吸附分析(BET)分析

图2为样品的XRD、BET和XPS测试结果。图2(a)显示了样品的XRD图,N-TiO₂/MXene的衍射峰分别位于25.2、36.9、37.7、38.4°和47.9°,对应于TiO₂(PDF No.21-1272)的(101)、(103)、(004)、(112)和(220)晶面^[17]。此外,MXene的(002)峰明显向低角度移动,表明其沿c轴的层间距增大,有助于离子的迁移^[18]。图2(b)的XPS全谱图,进一步证明了材料中Ti、O、C和N元素的存在。Ti 2p高分辨XPS图谱中[图2(c)]存在Ti—C(455.1 eV和460.8 eV)^[19]、Ti—N(456.6 eV和462.2 eV)^[20]和Ti—O(458.9 eV和464.6 eV)^[21]的特征峰。O 1s高分辨XPS图谱中[图2(d)]位于529.5、530.9 eV和532.2 eV的特征峰,分别归属于O—Ti、Ti—C—O_x和Ti—C—(OH)_x^[22]。值得注意的是,在531.8 eV处存在明显的O缺陷特征峰^[23],和HRTEM的结果相对应。N 1s高分辨XPS图谱[图2(e)]位于401.8、400.1、399.2 eV和397.3 eV的特征峰,分布归属于Graphitic N、Pyrroplic N、Pyridinic N和N-Ti^[24]。BET测试表明[图2(f)],N-TiO₂/MXene的比表面积(92.7 m²/g)远大于TiO₂(64.3 m²/g)和MXene(57.9 m²/g)。这种原位合成的N-TiO₂/MXene超结构具有更多的原子缺陷、较强的化学键连接和丰富的比表面积,从而提供了更多活性位点,有助于电子和离子的迁移^[25]。

2.2 电化学性能分析

图3展示了N-TiO₂/MXene在PIBs负极中的电化学性能测试结果。如图3(a)所示,在第1、20、50圈和100圈循环时,充电比容量分别为289.9、187.4、172.3 mAh/g和165.6 mAh/g。即使循环150圈后[图3(b)],该N-TiO₂/MXene仍能够提供160.1 mAh/g的可逆容量,远大于TiO₂(107.0 mAh/g)和MXene(57.9 mAh/g)。倍率性能测试显示[图3(c)],N-TiO₂/MXene在0.2、0.5、1、2、3、5、8 A/g和10 A/g的电流密度下,可逆容量分别为191.8、148.5、119.6、102.3、87.2、76.7、66.7 mAh/g和58.1 mAh/g,明显大于TiO₂和MXene材料。当电流密度恢复到0.2 A/g时,可逆容量恢复至163.3 mAh/g,表明N-TiO₂/MXene具有优异的倍率性能和电化学稳定性。EIS测试表明[图3(d)],N-TiO₂/MXene电子转移电阻为1 250.7 Ω,明显小于TiO₂(2 921.5 Ω),表明其具有更快的电子转移动力学^[26]。

N-TiO₂/MXene优异的储钾性能来源于以下几个方面(图4):首先,MXene与TiO₂之间的紧密结合显著增强了TiO₂的本征导电性。优异的导电性使得电荷转移更加快速,促进了电化学反应的快速进行。其次,通过引入杂原子N,使TiO₂中产生了大量的氧缺陷,为电化学反应提供了额外的活性位点,提升了钾离子的嵌入/脱出反应动力学。此外,N-TiO₂/MXene展现出独特的三维层级结构和较大的比表面积,有利于容纳更多的电解液,并为离子传输提供了额外路径,而且这种结构能够有效缓冲钾离子嵌入/脱出过程中产生的体积变化,保持电极结构的稳定性。

3 结论

对MXene采用原位氧化掺杂法合成了N-TiO₂/MXene超结构作为PIBs的负极材料。电池测试表明,N-TiO₂/MXene拥有较好的循环稳定性(在0.2 A/g的电流密度下循环150圈后,保持可逆容量为160.1 mAh/g)和优异的倍率性能(当电流密度达到10 A/g时,其可逆容量仍保持58.1 mAh/g)。这种出色的储钾性能来自于N-TiO₂/MXene优异导电性、较大的比表面积、丰富的层级结构、和增加的反应活性位点。本文为构建和设计高性能PIBs负极提供了新的启示。

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