不同杂原子掺杂钛酸钠对储钠性能的影响.pdf
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1、第 12 卷 第 9 期2023 年 9 月Vol.12 No.9Sept.2023储能科学与技术Energy Storage Science and TechnologyThe effect of different heteroatoms-doped Na2Ti3O7 on sodium ion storageGE Jinyu 4,MENG Xianghui1,QI Yongjun1,SUN Hao2,LI Jianjun2,ZHOU Bing3,GUI Tingting 2,XING Qingwei2,HUANG Man4(1Hebei Aoguan Power Supply Co.,L
2、td.,Hengshui 253800,Hebei,China;2Shandong Allgrand New Energy Technology Co.,Ltd.,Dezhou 25300,Hebei,China;3Hebei Guona New Energy Technology Co.Ltd.,Hengshui 253800,Hebei,China;4Institute for Advanced Interdisciplinary Research(iAIR),School of Chemistry and Chemical Engineering,University of Jinan,
3、Jinan 250022,Shandong,China)Abstract:Sodium-ion batteries(SIBs)are promising energy storage devices because of their low cost and high safety compared with traditional lithium-ion batteries(LIBs).The electrochemical performance of the electrode material determines the whole batterys function.As sodi
4、um ions radius is larger than lithium ions,the ion embedding/removal is relatively slow,and the electrode material is prone to structural damage after multiple cycles,resulting in capacity decay.Therefore,high energy density and long-life electrode materials are the breakthroughs to achieve high-per
5、formance SIBs.Meanwhile,the battery energy storage mechanism and electrode reaction dynamics still need to be further explored.Given the above problems,designing advanced cathode materials to achieve a good match with the existing positive electrodes is one of the urgent problems to be solved in dev
6、eloping high-performance SIBs to improve the energy density and cyclic life of the battery.The TiO6 octahedrons were connected to each other by corners or edges to form tunnel-and layer-structured sodium titanates(NTO).This open structure made NTO promising anode materials for SIBs.In this work,we c
7、ompared the electrochemical behavior difference of P-and S-doped NTO as anode materials for SIBs.We found that phosphorus-doped NTO(P-NTO)had excellent electrochemical performance compared with sulfur-doped NTO(S-NTO);when it was used as an electrode for SIBs,it exhibited outstanding long-term cycli
8、ng stability and rate performance.When the current density was high,up to 2000 mA/g,the P-NTO delivered a reversible capacity of 111 mAh/g.Even after 1300 cycles(500 mA/g),the electrode retained a capacity of 150 mAh/g.These excellent performances are mainly attributed to the open structure of NTO,a
9、nd doping P drastically boosted the electron movement within the nanosheets.Keywords:heteroatoms;doping;Na2Ti3O7 nanosheets;sodium ion storage储能材料与器件收稿日期:2023-04-28;修改稿日期:2023-05-07。基金项目:氧缺陷诱导Bi/TiO2-x异质结构界面键合及内电场联合调控储钠性能研究(52202239)。第一作者:葛金雨(2000),女,硕士研究生,研究方向为能源材料,E-mail:;通讯作者:黄曼,讲师,研究方向为能源材料,E-ma
10、il:huangman_。引用本文:葛金雨,孟祥辉,祁永军,等.不同杂原子掺杂钛酸钠对储钠性能的影响J.储能科学与技术,2023,12(9):2715-2726.Citation:GE Jinyu,MENG Xianghui,QI Yongjun,et al.The effect of different heteroatoms-doped Na2Ti3O7 on sodium ion storageJ.Energy Storage Science and Technology,2023,12(9):2715-2726.2023 年第 12 卷储能科学与技术不同杂原子掺杂钛酸钠对储钠性能的影响
11、葛金雨4,孟祥辉1,祁永军1,孙浩2,李健君2,周冰3,桂亭亭2,邢庆伟2,黄曼4(1河北奥冠电源有限责任公司,河北 衡水 253800;2山东奥冠新能源科技有限公司,山东 德州 253000;3河北国钠新能源科技有限公司,河北 衡水 253800;4济南大学前沿交叉科学研究院 山东 济南 250022)摘要:相比于传统的锂离子电池,钠离子电池具有低成本、高安全性的优点,因此被赋予厚望。电极材料的电化学性能决定着整个电池的功能,由于钠离子半径比锂离子大,使得离子嵌入/脱出比较慢,且多次循环后电极材料容易出现结构破坏,从而引起容量的衰减。因此,高能量密度、长寿命电极材料是实现高性能钠离子电池的突
12、破口。钛酸钠(NTO)中TiO6八面体通过角或边相互连接,形成隧道状和层状结构,这种开放式结构使NTO成为极具潜力的钠离子电池负极材料。在这项工作中,借助扫描电子显微技术(SEM)、透射电镜(TEM)能谱分析技术(EDS)和电化学技术等表征测试手段,对比P和S掺杂NTO作为钠离子电池负极材料的电化学行为差异。我们发现磷掺杂的NTO(P-NTO)与硫掺杂的NTO(S-NTO)相比表现出优异的电化学性能,当它用作钠离子电池电极时,表现出出色的长循环稳定性和倍率性能。当电流密度高达2000 mA/g时,P-NTO提供111 mAh/g的可逆容量。即使经过1300次循环(500 mA/g),该电极仍保
13、持150 mAh/g的可逆容量。这些优异的性能主要归功于NTO的开放结构和P的掺杂大大促进了纳米片的电子传输。关键词:杂原子;掺杂;钛酸钠;储钠性能doi:10.19799/ki.2095-4239.2023.0273 中图分类号:O 469;TB 34 文献标志码:A 文章编号:2095-4239(2023)09-2715-12In recent years,with huge demand for renewable energy and pollution to the environment problem is attracting more and more attention,t
14、he secondary batteries(rechargeable battery or battery),this energy storage technology,which can convert other forms of energy into electrical energy and store it in the form of chemical energy in advance,has ushered in a new development opportunity in the new round of energy reform1-4.With the deep
15、ening of the study,the researchers found that SIBs not only have abundant resources,widely distributed,low cost,no development bottleneck,environment friendly and compatible with lithium-ion battery the advantage of existing production equipment,also have good adaptability power characteristics,wide
16、 temperature range,the safety performance and the advantages of the problem without discharge.At the same time,by virtue of the characteristic that both positive and negative electrodes can use aluminum foil to collect fluid to construct bipolar battery,the energy density of sodium ion battery can b
17、e further improved,so that the sodium ion battery will move towards the direction of low cost,long life,high specific energy and high safety5.The challenges for the SIBs include finding suitable materials and construction of advanced electrodes.Due to the different properties of sodium and lithium(p
18、olarity,ion radius,interaction with the lattice of host,and so on),many complexes that work well in lithium-ion battery(LIB)may not adapt to SIBs at all,with graphite as a good example6.Meanwhile,the electrode materials storing Na ion through alloying or conversion reaction mechanism,such as bismuth
19、(Bi),antimony(Sb)and molybdenum sulfide(MoS2),etc.,have suffered severe volume changes during Na ion insertion and extraction.This phenomenon will cause the active material to crush and fall off in the collector,and eventually lead to a serious decline in battery capacity7.Therefore,it is essential
20、to alleviate the volume expansion or search for materials with stable structure during cycling to achieve long-term cycling performance for SIBs.In this regard,the intercalation-based materials are considered to be the most promising negative materials for sodium ion batteries,because these 2716第 9
21、期葛金雨等:不同杂原子掺杂钛酸钠对储钠性能的影响materials can reversibly insert and exact foreign sodium ions while maintaining structural integrity8.The typical intercalation-based anode materials mainly include carbon based material,titanium oxide and niobium pentoxide and so on.Since 2011,when titanium oxide materials w
22、ere first used as cathode materials for SIBs,researchers have made great efforts to design different strategies for preparing polycrystalline TiO2 structures.However,the capacity,rate performance and cyclic stability of titanium dioxide anode materials,especially the high-rate performance,need to be
23、 further improved to meet the needs of high-energy equipment such as electric vehicles.In addition,for the intercalation-based materials,we should fully balance the dependence between electrochemical properties and structural stability9.With A2TinO2n+1 as the molecular formula,alkali titanate is com
24、posed of titanium oxide layer and interlayer cation,and has a unique layered and tunnel-like crystal structure10.Due to its stability,non-toxicity,low cost and abundance,as well as interesting ion exchange/interlayer characteristics,it has attracted more and more attention.Particularly,the larger la
25、yer spacing of titanate is beneficial to the diffusion of electrolyte and the storage of charge.Notwithstanding,there are still several disadvantages of titanate for SIBs:The nature of low conductivity for titanate due to the large band gap results in low charge transport efficiency,which limits the
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