Single particle nanomechanics in operando batteries via lensless strain mapping.

We reveal three-dimensional strain evolution in situ of a single LiNi0.5Mn1.5O4 nanoparticle in a coin cell battery under operando conditions during charge/discharge cycles with coherent X-ray diffractive imaging. We report direct observation of both stripe morphologies and coherency strain at the nanoscale. Our results suggest the critical size for stripe formation is 50 nm. Surprisingly, the single nanoparticle elastic energy landscape, which we map with femtojoule precision, depends on charge versus discharge, indicating hysteresis at the single particle level. This approach opens a powerful new avenue for studying battery nanomechanics, phase transformations, and capacity fade under operando conditions at the single particle level that will enable profound insight into the nanoscale mechanisms that govern electrochemical energy storage systems.

[1]  Jesse N. Clark,et al.  Coherent diffraction imaging of nanoscale strain evolution in a single crystal under high pressure , 2013, Nature Communications.

[2]  Li Lu,et al.  Nanoscale mapping of lithium-ion diffusion in a cathode within an all-solid-state lithium-ion battery by advanced scanning probe microscopy techniques. , 2013, ACS nano.

[3]  Niitaka Seiji,et al.  有効電子相関がある六方晶C14 Laves型Ru系超伝導体ARu2(A=Lu,Y,Sc)の包括的な巨視的研究 , 2013 .

[4]  A. Sastry,et al.  Molecular Dynamics Simulations of SOC-Dependent Elasticity of LixMn2O4 Spinels in Li-Ion Batteries , 2013 .

[5]  Y. Meng,et al.  Effect of Ni/Mn Ordering on Elementary Polarizations of LiNi0.5Mn1.5O4 Spinel and Its Nanostructured Electrode , 2013 .

[6]  Chong Seung Yoon,et al.  Nanostructured high-energy cathode materials for advanced lithium batteries. , 2012, Nature materials.

[7]  R Harder,et al.  High-resolution three-dimensional partially coherent diffraction imaging , 2012, Nature Communications.

[8]  Fei Gao,et al.  In situ TEM investigation of congruent phase transition and structural evolution of nanostructured silicon/carbon anode for lithium ion batteries. , 2012, Nano letters.

[9]  A. Ulvestad,et al.  Creating universes with thick walls , 2012, 1202.5936.

[10]  Daniel A. Cogswell,et al.  Coherency strain and the kinetics of phase separation in LiFePO4 nanoparticles. , 2011, ACS nano.

[11]  B. Dunn,et al.  Electrical Energy Storage for the Grid: A Battery of Choices , 2011, Science.

[12]  Sergei V. Kalinin,et al.  Nanoscale mapping of ion diffusion in a lithium-ion battery cathode. , 2010, Nature nanotechnology.

[13]  Y. Meng,et al.  Electronic, Structural, and Electrochemical Properties of LiNixCuyMn2–x–yO4 (0 < x < 0.5, 0 < y < 0.5) High-Voltage Spinel Materials , 2010 .

[14]  K. Amine,et al.  Nanostructured Lithium Nickel Manganese Oxides for Lithium-Ion Batteries , 2010 .

[15]  Krishna Garikipati,et al.  The Role of Coherency Strains on Phase Stability in LixFePO4: Needle Crystallites Minimize Coherency Strain and Overpotential , 2009 .

[16]  R. Harder,et al.  Coherent X-ray diffraction imaging of strain at the nanoscale. , 2009, Nature materials.

[17]  R. Huggins Advanced Batteries: Materials Science Aspects , 2008 .

[18]  Martin Z. Bazant,et al.  Intercalation dynamics in rechargeable battery materials : General theory and phase-transformation waves in LiFePO4 , 2008 .

[19]  C. Delmas,et al.  Lithium deintercalation in LiFePO4 nanoparticles via a domino-cascade model. , 2008, Nature materials.

[20]  M. Armand,et al.  Building better batteries , 2008, Nature.

[21]  G. Aeppli,et al.  Direct measurement of antiferromagnetic domain fluctuations , 2007, Nature.

[22]  Garth J. Williams,et al.  Three-dimensional mapping of a deformation field inside a nanocrystal , 2006, Nature.

[23]  J. Newman,et al.  A mathematical model of stress generation and fracture in lithium manganese oxide , 2006 .

[24]  P. Bruce,et al.  Nanostructured materials for advanced energy conversion and storage devices , 2005, Nature materials.

[25]  C. Yoon,et al.  Comparative Study of LiNi0.5Mn1.5O4-δ and LiNi0.5Mn1.5O4 Cathodes Having Two Crystallographic Structures: Fd3̄m and P4332 , 2004 .

[26]  M. Armand,et al.  Issues and challenges facing rechargeable lithium batteries , 2001, Nature.

[27]  H. Frauenfelder,et al.  The energy landscape in non-biological and biological molecules , 1998, Nature Structural Biology.

[28]  A. Khachaturyan Elastic Strains during Decomposition of Homogeneous Solid Solutions — Periodic Distribution of Decomposition Products , 1969 .

[29]  J. Cahn On Spinodal Decomposition , 1961 .