A Facile Surface Reconstruction Mechanism toward Better Electrochemical Performance of Li4Ti5O12 in Lithium‐Ion Battery

Abstract Through a facile sodium sulfide (Na2S)‐assisted hydrothermal treatment, clean and nondefective surfaces are constructed on micrometer‐sized Li4Ti5O12 particles. The remarkable improvement of surface quality shows a higher first cycle Coulombic efficiency (≈95%), a significantly enhanced cycling performance, and a better rate capability in electrochemical measurements. A combined study of Raman spectroscopy and inductive coupled plasma emission spectroscopy reveals that the evolution of Li4Ti5O12 surface in a water‐based hydrothermal environment is a hydrolysis–recrystallization process, which can introduce a new phase of anatase‐TiO2. While, with a small amount of Na2S (0.004 mol L−1 at least), the spinel‐Li4Ti5O12 phase is maintained without a second phase. During this process, the alkaline environment created by Na2S and the surface adsorption of the sulfur‐containing group (HS− or S2−) can suppress the recrystallization of anatase‐TiO2 and renew the particle surfaces. This finding gives a better understanding of the surface–property relationship on Li4Ti5O12 and guidance on preparation and modification of electrode material other than coating or doping.

[1]  Bo Ding,et al.  Improving the Performance of High Capacity Li-Ion Anode Materials by Lithium Titanate Surface Coating , 2012 .

[2]  Byunggwan Lee,et al.  Synthesis of high-performance Li4Ti5O12 and its application to the asymmetric hybrid capacitor , 2013, Electronic Materials Letters.

[3]  Tsutomu Ohzuku,et al.  Zero‐Strain Insertion Material of Li [ Li1 / 3Ti5 / 3 ] O 4 for Rechargeable Lithium Cells , 1995 .

[4]  Robert Kostecki,et al.  Mechanism of Phase Propagation During Lithiation in Carbon‐Free Li4Ti5O12 Battery Electrodes , 2013 .

[5]  Ho-Hwan Chun,et al.  Stabilization of Oxygen-deficient Structure for Conducting Li4Ti5O12-δ by Molybdenum Doping in a Reducing Atmosphere , 2014, Scientific Reports.

[6]  Lin Gu,et al.  New insight into the atomic-scale bulk and surface structure evolution of Li4Ti5O12 anode. , 2015, Journal of the American Chemical Society.

[7]  Bo B. Iversen,et al.  Controlling Size, Crystallinity, and Electrochemical Performance of Li4Ti5O12 Nanocrystals , 2013 .

[8]  Rémi Dedryvère,et al.  Surface film formation on a graphite electrode in Li‐ion batteries: AFM and XPS study , 2005 .

[9]  Michelle Foster,et al.  Spectroscopic Compositional Analysis of Electrolyte during Initial SEI Layer Formation , 2014 .

[10]  Neeraj Sharma,et al.  Br‐Doped Li4Ti5O12 and Composite TiO2 Anodes for Li‐ion Batteries: Synchrotron X‐Ray and in situ Neutron Diffraction Studies , 2011 .

[11]  Yun-Sung Lee,et al.  Research Progress on Negative Electrodes for Practical Li‐Ion Batteries: Beyond Carbonaceous Anodes , 2015 .

[12]  Guozhong Cao,et al.  General strategy for designing core-shell nanostructured materials for high-power lithium ion batteries. , 2012, Nano letters.

[13]  Guozhong Cao,et al.  Hydrogenated Li4Ti5O12 Nanowire Arrays for High Rate Lithium Ion Batteries , 2012, Advanced materials.

[14]  Lin Gu,et al.  Rutile-TiO2 nanocoating for a high-rate Li4Ti5O12 anode of a lithium-ion battery. , 2012, Journal of the American Chemical Society.

[15]  Yingchang Yang,et al.  Lithium Titanate Tailored by Cathodically Induced Graphene for an Ultrafast Lithium Ion Battery , 2014 .

[16]  Yan Shen,et al.  Rutile-TiO2 decorated Li4Ti5O12 nanosheet arrays with 3D interconnected architecture as anodes for high performance hybrid supercapacitors , 2015 .

[17]  Alexander M. Skundin,et al.  High grain boundary density Li4Ti5O12/anatase-TiO2 nanocomposites as anode material for Li-ion batteries , 2016 .

[18]  Karim Zaghib,et al.  In situ studies of SEI formation , 2001 .

[19]  Dejun Li,et al.  Novel understanding of carbothermal reduction enhancing electronic and ionic conductivity of Li4Ti5O12 anode , 2015 .

[20]  Jinwoo Lee,et al.  Highly Improved Rate Capability for a Lithium‐Ion Battery Nano‐Li4Ti5O12 Negative Electrode via Carbon‐Coated Mesoporous Uniform Pores with a Simple Self‐Assembly Method , 2011 .

[21]  Chong Seung Yoon,et al.  Comparison of the structural and electrochemical properties of layered Li[NixCoyMnz]O2 (x = 1/3, 0.5, 0.6, 0.7, 0.8 and 0.85) cathode material for lithium-ion batteries , 2013 .

[22]  Martin Søndergaard,et al.  Solid State Formation Mechanism of Li 4 Ti 5 O 12 from an Anatase TiO 2 Source , 2014 .

[23]  Jeng-Ywan Shih,et al.  Preparation of High-rate Performance Li4Ti5O12/C Anode Material in Li4Ti5O12/LiFe0.5Mn0.5PO4 Batteries , 2014 .

[24]  Volker Hennige,et al.  Small Change—Great Effect: Steep Increase of Li Ion Dynamics in Li4Ti5O12 at the Early Stages of Chemical Li Insertion , 2015 .

[25]  Neeraj Sharma,et al.  Lithium migration in Li4Ti5O12 studied using in-situ neutron powder diffraction , 2014 .

[26]  Yang-Kook Sun,et al.  Nanostructured Anode Material for High‐Power Battery System in Electric Vehicles , 2010, Advanced materials.

[27]  Ming Liu,et al.  A review of gassing behavior in Li4Ti5O12-based lithium ion batteries , 2017 .

[28]  Zhiyu Jiang,et al.  In situ synthesis of carbon incorporated TiO2 with long-term performance as anode for lithium-ion batteries , 2016 .

[29]  Kai Wu,et al.  Study of spinel Li4Ti5O12 electrode reaction mechanism by electrochemical impedance spectroscopy , 2013 .

[30]  Jae Hyun Kim,et al.  Electron beam modification of anode materials for high-rate lithium ion batteries , 2015 .

[31]  Feiyu Kang,et al.  A robust strategy for crafting monodisperse Li4Ti5O12 nanospheres as superior rate anode for lithium ion batteries , 2016 .

[32]  Wei Lv,et al.  Gassing in Li4Ti5O12-based batteries and its remedy , 2012, Scientific Reports.

[33]  Guozhong Cao,et al.  Three-dimensional coherent titania-mesoporous carbon nanocomposite and its lithium-ion storage properties. , 2012, ACS applied materials & interfaces.

[34]  Jun Liu,et al.  Li4Ti5O12 nanosheets as high-rate and long-life anode materials for sodium-ion batteries , 2015 .

[35]  Kazuki Nakanishi,et al.  Hierarchically Porous Li4Ti5O12 Anode Materials for Li‐ and Na‐Ion Batteries: Effects of Nanoarchitectural Design and Temperature Dependence of the Rate Capability , 2015 .

[36]  Seok-Gwang Doo,et al.  Nitridation-driven conductive Li4Ti5O12 for lithium ion batteries. , 2008, Journal of the American Chemical Society.

[37]  Guozhong Cao,et al.  Advanced Energy‐Storage Architectures Composed of Spinel Lithium Metal Oxide Nanocrystal on Carbon Textiles , 2013 .

[38]  Zhiqun Lin,et al.  Hollow titanium dioxide spheres as anode material for lithium ion battery with largely improved rate stability and cycle performance by suppressing the formation of solid electrolyte interface layer , 2015 .