具有{010}和[111]晶面的锐钛矿型TiO_2纳米晶体的储锂性能（英文）
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摘要
作为锂离子电池的负极材料,具有{001}晶面的锐钛矿型TiO_2纳米晶体通常展现出良好的储锂性能,这是由于该晶面具有更多的接触位点,同时锂离子沿着该晶格方向的扩散速度较快。然而,由于缺乏有效的控制TiO_2晶面的合成方法,对具有其它高能晶面TiO_2晶体的储锂性能的研究较少。本文以剥离的钛酸盐纳米带为前驱体,通过水热法合成了具有{010}和[111]晶面的锐钛矿型TiO_2纳米晶体。通过对该TiO_2纳米晶体的电化学性能进行研究,并与商业用的TiO_2纳米颗粒(P25)的性能进行比较,发现通过减小TiO_2纳米晶的粒径,可以大幅度提高TiO_2纳米晶体的循环和倍率性能。此外,尽管P25具有更小的粒径,相比没有特定晶面的P25,具有{010}和[111]晶面的TiO_2纳米晶体仍展现出更好的储锂能力。这表明TiO_2纳米晶体的暴露晶面对其储锂性能同样具有重要影响。因此,在设计合成具有高性能的TiO_2电极材料时,要同时考虑纳米晶体的粒径和暴露晶面等因素。
As a popular anode material for lithium-ion batteries, anatase TiO_2 nanoparticles with exposed {001} facets usually exhibit exceptional lithium storage performance owing to more accessible sites and fast migration of lithium ions along the good crystalline channels. However, there are few researches on the lithium storage capability of TiO_2 nanocrystals with other high-energy facets owing to lack of effective synthesis method for controlling crystal facets. Herein, anatase TiO_2 nanocrystals with exposed {010}-and [111]-facets are successfully prepared by using the delaminated tetratitanate nanoribbons as precursors. The electrochemical properties of these TiO_2 nanocrystals with high-energy surfaces and the comparison with commercial TiO_2 nanoparticles(P25) are studied. It is found that the cycle and rate performance of TiO_2 nanocrystals is highly improved by reducing the particle size of nanocrystals. Moreover, TiO_2 nanocrystals with exposed {010}-and [111]-facets exhibit better lithium storage capacities in comparison with P25 without a specific facet though P25 has smaller particle size than these TiO_2 nanocrystals, indicating that the exposed facets of TiO_2 nanocrystals have an important impact on their lithium storage capacity. Therefore, the synthesis design of high-performance TiO_2 materials applied in the next-generation secondary batteries should both consider the particle size and the exposed facets of nanocrystals.
As a popular anode material for lithium-ion batteries, anatase TiO_2 nanoparticles with exposed {001} facets usually exhibit exceptional lithium storage performance owing to more accessible sites and fast migration of lithium ions along the good crystalline channels. However, there are few researches on the lithium storage capability of TiO_2 nanocrystals with other high-energy facets owing to lack of effective synthesis method for controlling crystal facets. Herein, anatase TiO_2 nanocrystals with exposed {010}-and [111]-facets are successfully prepared by using the delaminated tetratitanate nanoribbons as precursors. The electrochemical properties of these TiO_2 nanocrystals with high-energy surfaces and the comparison with commercial TiO_2 nanoparticles(P25) are studied. It is found that the cycle and rate performance of TiO_2 nanocrystals is highly improved by reducing the particle size of nanocrystals. Moreover, TiO_2 nanocrystals with exposed {010}-and [111]-facets exhibit better lithium storage capacities in comparison with P25 without a specific facet though P25 has smaller particle size than these TiO_2 nanocrystals, indicating that the exposed facets of TiO_2 nanocrystals have an important impact on their lithium storage capacity. Therefore, the synthesis design of high-performance TiO_2 materials applied in the next-generation secondary batteries should both consider the particle size and the exposed facets of nanocrystals.
引文
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[11]YU Yan-long,WANG Xiao-liang,SUN Hong-yu,AHMADM.3D anatase Ti O2 hollow microspheres assembled with high-energy{001}facets for lithium-ion batteries[J].RSCAdvances,2012,2(20):7901-7905.DOI:10.1039/C2RA20718D.
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[14]XU Hua,REUNCHAN P,OUYANG Shu-xin,TONG Hua,UMEZAWA N,KAKO T,YE Jin-hua.Anatase TiO2 single crystals exposed with high-reactive{111}facets toward efficient H2 evolution[J].Chemistry of Materials,2013,25(3):405-411.DOI:10.1021/cm303502b.
[15]HAN Xi-guang,HAN Xiao,SUN Lin-qiang,WANG Po,JINMing-shang,WANG Xiao-jun.Facile preparation of hybrid anatase/rutile TiO2 nanorods with exposed(010)facets for lithium ion batteries[J].Materials Chemistry and Physics,2016,171:11-15.DOI:10.1016/j.matchemphys.2015.11.048.
[16]DU Yi-en,FENG Qi,CHEN Chang-dong,TANAKA Y,YANG Xiao-jing.Photocatalytic and dye-sensitized solar cell performances of{010}-faceted and[111]-faceted anatase Ti O2 nanocrystals synthesized from tetratitanate nanoribbons[J].ACS Applied Materials&Interfaces,2014,6(18):16007-16019.DOI:10.1021/am503914q.
[17]DU Yi-en,DU De-jian,FENG Qi,YANG Xiao-jing.Delithation,exfoliation,and transformation of rock-saltstructured Li2Ti O3 to highly exposed{010}-faceted anatase[J].ACS Applied Materials&Interfaces,2015,7(15):7995-8004.DOI:10.1021/acsami.5b00227.
[18]PFANZELT M,KUBIAK P,FLEISCHHAMMER M,WOHLFAHRT-MEHRENS M.Ti O2 rutile-An alternative anode material for safe lithium-ion batteries[J].Journal of Power Sources,2011,196(16):6815-6821.DOI:10.1016/j.jpowsour.2010.09.109.
[19]ZHANG Qi,HE Han-na,HUANG Xiao-bing,YAN Jun,TANG You-gen,WANG Hai-yan.TiO2@C nanosheets with highly exposed(001)facets as a high-capacity anode for Na-ion batteries[J].Chemical Engineering Journal,2018,332:57-65.DOI:10.1016/j.cej.2017.09.044.
[20]ZHAO Peng,YUE Wen-bo,YUAN Xu,BAO Hua-ying.Exceptional lithium anodic performance of Pd-doped graphene-based SnO2 nanocomposite[J].Electrochimica Acta,2017,225:322-329.DOI:10.1016/j.electacta.2016.12.124.
[21]ZHANG Si-qi,LIN Rong,YUE Wen-bo,NIU Fang-zhou,MA Jie,YANG Xiao-jing.Novel synthesis of metal sulfides-loaded porous carbon as anode materials for lithium-ion batteries[J].Chemical Engineering Journal,2017,314:19-26.DOI:10.1016/j.cej.2016.12.123.
[22]ABBASI A,MIRHABIBI A,ARABI H,GOLMOHAMMAD M,BRYDSON R.Synthesis,characterization and electrochemical performances ofγ-Fe2O3 cathode material for Li-ion batteries[J].Journal of Materials Science:Materials in Electronics,2016,27(8):7953-7961.DOI:10.1007/s10854-016-4788-7.
[23]XUE Xia,SUN Dan,ZENG Xian-guang,HUANGXiao-bing,ZHANG He-he,TANG You-gen,WANG Hai-yan.Two-step carbon modification of NaTi2(PO4)3 with improved sodium storage performance for Na-ion batteries[J].Journal of Central South University,2018,25(10):2320-2331.DOI:10.1007/s11771-018-3916-3.
[24]CHEN Chang-dong,XU Lin-feng,SEWVANDI G A,KUSUNOSE T,TANAKA Y,NAKANISHI S,FENG Qi.Microwave-assisted topochemical conversion of layered titanate nanosheets to{010}-faceted anatase nanocrystals for high performance photocatalysts and dye-sensitized solar cells[J].Crystal Growth&Design,2014,14(11):5801-5811.DOI:10.1021/cg501062r.
[25]YANG Xu-ming,WANG Chao,YANG Ying-chang,ZHANGYan,JIA Xin-nan,CHEN Jun,JI Xiao-bo.Anatase Ti O2nanocubes for fast and durable sodium ion battery anodes[J].Journal of Materials Chemistry A,2015,3(16):8800-8807.DOI:10.1039/C5TA00614G.
[2]HE Han-na,WANG Hai-yan,SUN Dan,SHAO Min-hua,HUANG Xiao-bing,TANG You-gen.N-doped rutile TiO2/Cwith significantly enhanced Na storage capacity for Na-ion batteries[J].Electrochimica Acta,2017,236:43-52.DOI:10.1016/j.electacta.2017.03.104.
[3]HE Han-na,SUN Dan,ZHANG Qi,FANG Fu,TANGYou-gen,GUO Jun,SHAO Min-hua,WANG Hai-yan.Iron doped cauliflower-like rutile TiO2 with superior sodium storage properties[J].ACS Applied Materials&Interfaces,2017,9(7):6093-6103.DOI:10.1021/acsami.6b15516.
[4]DENG Da,KIM M G,LEE J Y,CHO J.Green energy storage materials:Nanostructured TiO2 and Sn-based anodes for lithium-ion batteries[J].Energy&Environmental Science,2009,2(8):818-837.DOI:10.1039/B823474D.
[5]KAVAN L.Lithium insertion into Ti O2(anatase):electrochemistry,Raman spectroscopy,and isotope labeling[J].Journal of Solid State Electrochemistry,2014,18(8):2297-2306.DOI:10.1007/s10008-014-2435-x.
[6]ARMSTRONG A R,ARMSTRONG G,CANALES J,BRUCE P G.Ti O2-B nanowires as negative electrodes for rechargeable lithium batteries[J].Journal of Power Sources,2005,146(1,2):501-506.DOI:10.1016/j.jpowsour.2005.03.057.
[7]ARMSTRONG G,ARMSTRONG A R,BRUCE P G,REALE P,SCROSATI B.TiO2(B)nanowires as an improved anode material for lithium-ion batteries containing LiFePO4or LiNi0.5Mn1.5O4 cathodes and a polymer electrolyte[J].Advanced Materials,2006,18(19):2597-2600.DOI:10.1002/adma.200601232.
[8]SHI Si-qi,GAO Jian,LIU Yue,ZHAO Yan,WU Qu,JUWang-wei,OUYANG Chu-ying,XIAO Rui-juan.Multi-scale computation methods:Their applications in lithium-ion battery research and development[J].Chinese Physics B,2016,25(1):018212.DOI:10.1088/1674-1056/25/1/018212.
[9]CHEN Jun-song,TAN Yi-liang,LI Chang-ming,CHEAH YL,LUAN De-yan,MADHAVI S,BOEY F Y C,ARCHER LA,LOU Xiong-wen,Constructing hierarchical spheres from large ultrathin anatase Ti O2 nanosheets with nearly 100%exposed(001)facets for fast reversible lithium storage[J].Journal of the American Chemical Society,2010,132(17):6124-6130.DOI:10.1021/ja100102y.
[10]SUN Cheng-hua,YANG Xiao-hua,CHEN Jun-song,LIZhen,LOU Xiong-wen,LI Chun-zhong,SMITH S C,LUGao-qing,Yang Hua-gui.Higher charge/discharge rates of lithium-ions across engineered Ti O2 surfaces leads to enhanced battery performance[J].Chemical Communications,2010,46(33):6129-6131.DOI:10.1039/C0CC00832J.
[11]YU Yan-long,WANG Xiao-liang,SUN Hong-yu,AHMADM.3D anatase Ti O2 hollow microspheres assembled with high-energy{001}facets for lithium-ion batteries[J].RSCAdvances,2012,2(20):7901-7905.DOI:10.1039/C2RA20718D.
[12]CHENG Xun-liang,HU Ming,HUANG R,JIANG Ji-sen,HF-free synthesis of anatase Ti O2 nanosheets with largely exposed and clean{001}facets and their enhanced rate performance as anodes of lithium-ion battery[J].ACSApplied Materials&Interfaces,2014,6(21):19176-19183.DOI:10.1021/am504971h.
[13]MING Hai,KUMAR P,YANG Wen-jing,FU Yu,MING Jun,KWAK W J,LI L J,SUN Y K,ZHENG Jun-wei,Green strategy to single crystalline anatase Ti O2 nanosheets with dominant(001)facets and its lithiation study toward sustainable cobalt-free lithium ion full battery[J].ACSSustainable Chemistry&Engineering,2015,3(12):3086-3095.DOI:10.1021/acssuschemeng.5b00553.
[14]XU Hua,REUNCHAN P,OUYANG Shu-xin,TONG Hua,UMEZAWA N,KAKO T,YE Jin-hua.Anatase TiO2 single crystals exposed with high-reactive{111}facets toward efficient H2 evolution[J].Chemistry of Materials,2013,25(3):405-411.DOI:10.1021/cm303502b.
[15]HAN Xi-guang,HAN Xiao,SUN Lin-qiang,WANG Po,JINMing-shang,WANG Xiao-jun.Facile preparation of hybrid anatase/rutile TiO2 nanorods with exposed(010)facets for lithium ion batteries[J].Materials Chemistry and Physics,2016,171:11-15.DOI:10.1016/j.matchemphys.2015.11.048.
[16]DU Yi-en,FENG Qi,CHEN Chang-dong,TANAKA Y,YANG Xiao-jing.Photocatalytic and dye-sensitized solar cell performances of{010}-faceted and[111]-faceted anatase Ti O2 nanocrystals synthesized from tetratitanate nanoribbons[J].ACS Applied Materials&Interfaces,2014,6(18):16007-16019.DOI:10.1021/am503914q.
[17]DU Yi-en,DU De-jian,FENG Qi,YANG Xiao-jing.Delithation,exfoliation,and transformation of rock-saltstructured Li2Ti O3 to highly exposed{010}-faceted anatase[J].ACS Applied Materials&Interfaces,2015,7(15):7995-8004.DOI:10.1021/acsami.5b00227.
[18]PFANZELT M,KUBIAK P,FLEISCHHAMMER M,WOHLFAHRT-MEHRENS M.Ti O2 rutile-An alternative anode material for safe lithium-ion batteries[J].Journal of Power Sources,2011,196(16):6815-6821.DOI:10.1016/j.jpowsour.2010.09.109.
[19]ZHANG Qi,HE Han-na,HUANG Xiao-bing,YAN Jun,TANG You-gen,WANG Hai-yan.TiO2@C nanosheets with highly exposed(001)facets as a high-capacity anode for Na-ion batteries[J].Chemical Engineering Journal,2018,332:57-65.DOI:10.1016/j.cej.2017.09.044.
[20]ZHAO Peng,YUE Wen-bo,YUAN Xu,BAO Hua-ying.Exceptional lithium anodic performance of Pd-doped graphene-based SnO2 nanocomposite[J].Electrochimica Acta,2017,225:322-329.DOI:10.1016/j.electacta.2016.12.124.
[21]ZHANG Si-qi,LIN Rong,YUE Wen-bo,NIU Fang-zhou,MA Jie,YANG Xiao-jing.Novel synthesis of metal sulfides-loaded porous carbon as anode materials for lithium-ion batteries[J].Chemical Engineering Journal,2017,314:19-26.DOI:10.1016/j.cej.2016.12.123.
[22]ABBASI A,MIRHABIBI A,ARABI H,GOLMOHAMMAD M,BRYDSON R.Synthesis,characterization and electrochemical performances ofγ-Fe2O3 cathode material for Li-ion batteries[J].Journal of Materials Science:Materials in Electronics,2016,27(8):7953-7961.DOI:10.1007/s10854-016-4788-7.
[23]XUE Xia,SUN Dan,ZENG Xian-guang,HUANGXiao-bing,ZHANG He-he,TANG You-gen,WANG Hai-yan.Two-step carbon modification of NaTi2(PO4)3 with improved sodium storage performance for Na-ion batteries[J].Journal of Central South University,2018,25(10):2320-2331.DOI:10.1007/s11771-018-3916-3.
[24]CHEN Chang-dong,XU Lin-feng,SEWVANDI G A,KUSUNOSE T,TANAKA Y,NAKANISHI S,FENG Qi.Microwave-assisted topochemical conversion of layered titanate nanosheets to{010}-faceted anatase nanocrystals for high performance photocatalysts and dye-sensitized solar cells[J].Crystal Growth&Design,2014,14(11):5801-5811.DOI:10.1021/cg501062r.
[25]YANG Xu-ming,WANG Chao,YANG Ying-chang,ZHANGYan,JIA Xin-nan,CHEN Jun,JI Xiao-bo.Anatase Ti O2nanocubes for fast and durable sodium ion battery anodes[J].Journal of Materials Chemistry A,2015,3(16):8800-8807.DOI:10.1039/C5TA00614G.