Localized Concentration Reversal of Lithium During Intercalation into Nanoparticles

Overview

Journal Sci Adv

Specialties Biology
Science

Date 2018 Jan 18

PMID 29340302

Citations 6

Authors

Wei Zhang

Hui-Chia Yu

Lijun Wu

Hao Liu

Aziz Abdellahi

Bao Qiu

Jianming Bai

Bernardo Orvananos

Fiona C Strobridge

Xufeng Zhou

Zhaoping Liu

Gerbrand Ceder

Yimei Zhu

Katsuyo Thornton

Clare P Grey

Feng Wang

Affiliations

Soon will be listed here.

Abstract

Nanoparticulate electrodes, such as Li FePO, have unique advantages over their microparticulate counterparts for the applications in Li-ion batteries because of the shortened diffusion path and access to nonequilibrium routes for fast Li incorporation, thus radically boosting power density of the electrodes. However, how Li intercalation occurs locally in a single nanoparticle of such materials remains unresolved because real-time observation at such a fine scale is still lacking. We report visualization of local Li intercalation via solid-solution transformation in individual Li FePO nanoparticles, enabled by probing sub-angstrom changes in the lattice spacing in situ. The real-time observation reveals inhomogeneous intercalation, accompanied with an unexpected reversal of Li concentration at the nanometer scale. The origin of the reversal phenomenon is elucidated through phase-field simulations, and it is attributed to the presence of structurally different regions that have distinct chemical potential functions. The findings from this study provide a new perspective on the local intercalation dynamics in battery electrodes.

Citing Articles

Stepwise Structural Relaxation in Battery Active Materials.

Skurtveit A, North E, Park H, Chernyshov D, Wragg D, Koposov A ACS Mater Lett. 2025; 7(1):343-349.

PMID: 39790737 PMC: 11707793. DOI: 10.1021/acsmaterialslett.4c02058.

Inorganic-organic competitive coating strategy derived uniform hollow gradient-structured ferroferric oxide-carbon nanospheres for ultra-fast and long-term lithium-ion battery.

Xia Y, Zhao T, Zhu X, Zhao Y, He H, Hung C Nat Commun. 2021; 12(1):2973.

PMID: 34016965 PMC: 8137936. DOI: 10.1038/s41467-021-23150-8.

Phase evolution and structural modulation during in situ lithiation of MoS, WS and graphite in TEM.

Ghosh C, Singh M, Parida S, Janish M, Dobley A, Dongare A Sci Rep. 2021; 11(1):9014.

PMID: 33907244 PMC: 8079398. DOI: 10.1038/s41598-021-88395-1.

Insights into interfacial effect and local lithium-ion transport in polycrystalline cathodes of solid-state batteries.

Lou S, Liu Q, Zhang F, Liu Q, Yu Z, Mu T Nat Commun. 2020; 11(1):5700.

PMID: 33177510 PMC: 7658997. DOI: 10.1038/s41467-020-19528-9.

Controllable two-dimensional movement and redistribution of lithium ions in metal oxides.

Tang X, Chen G, Mo Z, Ma D, Wang S, Wen J Nat Commun. 2019; 10(1):2888.

PMID: 31253847 PMC: 6599050. DOI: 10.1038/s41467-019-10875-w.

References

Yamada A, Koizumi H, Nishimura S, Sonoyama N, Kanno R, Yonemura M . Room-temperature miscibility gap in LixFePO4. Nat Mater. 2006; 5(5):357-60. DOI: 10.1038/nmat1634. View

Sharma N, Guo X, Du G, Guo Z, Wang J, Wang Z . Direct evidence of concurrent solid-solution and two-phase reactions and the nonequilibrium structural evolution of LiFePO4. J Am Chem Soc. 2012; 134(18):7867-73. DOI: 10.1021/ja301187u. View

Whittingham M . Ultimate limits to intercalation reactions for lithium batteries. Chem Rev. 2014; 114(23):11414-43. DOI: 10.1021/cr5003003. View

Gibot P, Casas-Cabanas M, Laffont L, Levasseur S, Carlach P, Hamelet S . Room-temperature single-phase Li insertion/extraction in nanoscale Li(x)FePO4. Nat Mater. 2008; 7(9):741-7. DOI: 10.1038/nmat2245. View

Nie A, Gan L, Cheng Y, Asayesh-Ardakani H, Li Q, Dong C . Atomic-scale observation of lithiation reaction front in nanoscale SnO2 materials. ACS Nano. 2013; 7(7):6203-11. DOI: 10.1021/nn402125e. View

Gu L, Zhu C, Li H, Yu Y, Li C, Tsukimoto S . Direct observation of lithium staging in partially delithiated LiFePO4 at atomic resolution. J Am Chem Soc. 2011; 133(13):4661-3. DOI: 10.1021/ja109412x. View

Niu J, Kushima A, Qian X, Qi L, Xiang K, Chiang Y . In situ observation of random solid solution zone in LiFePO₄ electrode. Nano Lett. 2014; 14(7):4005-10. DOI: 10.1021/nl501415b. View

Zhang X, van Hulzen M, Singh D, Brownrigg A, Wright J, van Dijk N . Rate-induced solubility and suppression of the first-order phase transition in olivine LiFePO4. Nano Lett. 2014; 14(5):2279-85. DOI: 10.1021/nl404285y. View

Hytch M, Putaux J, Penisson J . Measurement of the displacement field of dislocations to 0.03 A by electron microscopy. Nature. 2003; 423(6937):270-3. DOI: 10.1038/nature01638. View

10.

Arico A, Bruce P, Scrosati B, Tarascon J, van Schalkwijk W . Nanostructured materials for advanced energy conversion and storage devices. Nat Mater. 2005; 4(5):366-77. DOI: 10.1038/nmat1368. View

11.

Singer A, Ulvestad A, Cho H, Kim J, Maser J, Harder R . Nonequilibrium structural dynamics of nanoparticles in LiNi(1/2)Mn(3/2)O4 cathode under operando conditions. Nano Lett. 2014; 14(9):5295-300. DOI: 10.1021/nl502332b. View

12.

Tarascon J, Armand M . Issues and challenges facing rechargeable lithium batteries. Nature. 2001; 414(6861):359-67. DOI: 10.1038/35104644. View

13.

Zhu Y, Wang J, Liu Y, Liu X, Kushima A, Liu Y . In situ atomic-scale imaging of phase boundary migration in FePO(4) microparticles during electrochemical lithiation. Adv Mater. 2013; 25(38):5461-6. DOI: 10.1002/adma.201301374. View

14.

Chu M, Szafraniak I, Scholz R, Harnagea C, Hesse D, Alexe M . Impact of misfit dislocations on the polarization instability of epitaxial nanostructured ferroelectric perovskites. Nat Mater. 2004; 3(2):87-90. DOI: 10.1038/nmat1057. View

15.

Malik R, Burch D, Bazant M, Ceder G . Particle size dependence of the ionic diffusivity. Nano Lett. 2010; 10(10):4123-7. DOI: 10.1021/nl1023595. View

16.

Whittingham M . Lithium batteries and cathode materials. Chem Rev. 2005; 104(10):4271-301. DOI: 10.1021/cr020731c. View

17.

Bai P, Cogswell D, Bazant M . Suppression of phase separation in LiFePO₄ nanoparticles during battery discharge. Nano Lett. 2011; 11(11):4890-6. DOI: 10.1021/nl202764f. View

18.

Ravnsbaek D, Xiang K, Xing W, Borkiewicz O, Wiaderek K, Gionet P . Extended solid solutions and coherent transformations in nanoscale olivine cathodes. Nano Lett. 2014; 14(3):1484-91. DOI: 10.1021/nl404679t. View

19.

Hess M, Sasaki T, Villevieille C, Novak P . Combined operando X-ray diffraction-electrochemical impedance spectroscopy detecting solid solution reactions of LiFePO4 in batteries. Nat Commun. 2015; 6:8169. PMC: 4569719. DOI: 10.1038/ncomms9169. View

20.

Zhang X, van Hulzen M, Singh D, Brownrigg A, Wright J, van Dijk N . Direct view on the phase evolution in individual LiFePO4 nanoparticles during Li-ion battery cycling. Nat Commun. 2015; 6:8333. PMC: 4597332. DOI: 10.1038/ncomms9333. View