The Effect of Antisite Disorder and Particle Size on Li Intercalation Kinetics in Monoclinic LiMnBO3
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- The Effect of Antisite Disorder and Particle Size on Li Intercalation Kinetics in Monoclinic LiMnBO3
- Kim, Jae Chul; Seo, Dong-Hwa; Chen, Hailong; Ceder, Gerbrand
- Issue Date
- WILEY-V C H VERLAG GMBH
- ADVANCED ENERGY MATERIALS, v.5, no.8, pp.1401916
- In materials containing 1D lithium diffusion channels, cation disorder can strongly affect lithium intercalation processes. This work presents a model to explain the unusual transport properties of monoclinic LiMnBO3, a material determined by scanning electron microscopy and synchrotron X-ray diffraction to contain a wide particle size distribution and Mn/Li antisite disorder. First-principles calculations indicate that Mn occupying Li sites obstruct the 1D lithium diffusion channel along the  direction. While channel blockage by the antisites significantly lowers Li mobility in large particles, Li kinetics in small particles and particle surfaces are found to be less sensitive to the presence of antisite disorder. Thus, in an electrode containing a large particle size distribution, smaller particles have higher Li mobility, and the measured Li diffusivity as determined by potentiostatic intermittent titration test varies as a function of particle size. The Li capacity in monoclinic LiMnBO3 is kinetically controlled by the fraction of large particles with antisite disorder, but is not intrinsically limited. These results strongly suggest that particle nanosizing will significantly enhance the electrochemical performance of LiMnBO3
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