The role of electronic and ionic conductivities in the rate performance of tunnel structured manganese oxides in Li-ion batteries

Byles, B. W.; Palapati, N. K. R.; Subramanian, A.; Pomerantseva, E.

doi:10.1063/1.4948272

Title: The role of electronic and ionic conductivities in the rate performance of tunnel structured manganese oxides in Li-ion batteries

Journal Article · Fri Apr 29 00:00:00 EDT 2016 · APL Materials

DOI:https://doi.org/10.1063/1.4948272· OSTI ID:1262340

Byles, B. W. ^[1]; Palapati, N. K. R. ^[2]; Subramanian, A. ^[2]; Pomerantseva, E. ^[1]

Drexel Univ., Philadelphia, PA (United States)
Virginia Commonwealth Univ., Richmond, VA (United States)

Single nanowires of two manganese oxide polymorphs (α-MnO₂ and todorokite manganese oxide), which display a controlled size variation in terms of their square structural tunnels, were isolated onto nanofabricated platforms using dielectrophoresis. This platform allowed for the measurement of the electronic conductivity of these manganese oxides, which was found to be higher in α-MnO₂ as compared to that of the todorokite phase by a factor of similar to 46. Despite this observation of substantially higher electronic conductivity in α-MnO₂, the todorokite manganese oxide exhibited better electrochemical rate performance as a Li-ion battery cathode. The relationship between this electrochemical performance, the electronic conductivities of the manganese oxides, and their reported ionic conductivities is discussed for the first time, clearly revealing that the rate performance of these materials is limited by their Li⁺ diffusivity, and not by their electronic conductivity. This result reveals important new insights relevant for improving the power density of manganese oxides, which have shown promise as a low-cost, abundant, and safe alternative for next-generation cathode materials. Moreover, the presented experimental approach is suitable for assessing a broader family of one-dimensional electrode active materials (in terms of their electronic and ionic conductivities) for both Li-ion batteries and for electrochemical systems utilizing charge-carrying ions beyond Li⁺.

View Accepted Manuscript (DOE)

Cite

Export

Save

Research Organization:: National Nuclear Security Administration, North Las Vegas, NV (United States)

Sponsoring Organization:: USDOE National Nuclear Security Administration (NNSA); National Science Foundation (NSF); Drexel University

OSTI ID:: 1262340

Journal Information:: APL Materials, Vol. 4, Issue 4; ISSN 2166-532X

Publisher:: American Institute of Physics (AIP)Copyright Statement

Country of Publication:: United States

Language:: English

Citation Metrics:

Cited by: 45 works

Citation information provided by
Web of Science

References (40)

Local coordination of Fe3+ in Li[Co0.98Fe0.02]O2 as cathode material for lithium ion batteries—multi-frequency EPR and Monte-Carlo Newman-superposition model analysis Jakes, Peter; Erdem, Emre; Ozarowski, Andrew Physical Chemistry Chemical Physics, Vol. 13, Issue 20 https://doi.org/10.1039/c0cp02048f	journal	January 2011
Challenges for Rechargeable Li Batteries Goodenough, John B.; Kim, Youngsik Chemistry of Materials, Vol. 22, Issue 3, p. 587-603 https://doi.org/10.1021/cm901452z	journal	February 2010
Direct Measurements of Effective Electronic Transport in Porous Li-Ion Electrodes Peterson, Serena W.; Wheeler, Dean R. Journal of The Electrochemical Society, Vol. 161, Issue 14 https://doi.org/10.1149/2.0661414jes	journal	January 2014
Young’s modulus of [111] germanium nanowires Maksud, M.; Yoo, J.; Harris, C. T. APL Materials, Vol. 3, Issue 11 https://doi.org/10.1063/1.4935060	journal	November 2015
Metal Oxides and Oxysalts as Anode Materials for Li Ion Batteries Reddy, M. V.; Subba Rao, G. V.; Chowdari, B. V. R. Chemical Reviews, Vol. 113, Issue 7 https://doi.org/10.1021/cr3001884	journal	March 2013
Ionic/Electronic Conducting Characteristics of LiFePO[sub 4] Cathode Materials Wang, Chunsheng; Hong, Jian Electrochemical and Solid-State Letters, Vol. 10, Issue 3 https://doi.org/10.1149/1.2409768	journal	January 2007
Simultaneous Deposition of Metallic Bundles of Single-walled Carbon Nanotubes Using Ac-dielectrophoresis Krupke, R.; Hennrich, F.; Weber, H. B. Nano Letters, Vol. 3, Issue 8 https://doi.org/10.1021/nl0342343	journal	August 2003
Batch fabrication of carbon nanotube bearings Subramanian, A.; Dong, L. X.; Tharian, J. Nanotechnology, Vol. 18, Issue 7 https://doi.org/10.1088/0957-4484/18/7/075703	journal	January 2007
Spontaneous formation of inorganic helices Giraldo, Oscar; Brock, Stephanie L.; Marquez, Manuel Nature, Vol. 405, Issue 6782 https://doi.org/10.1038/35011139	journal	May 2000
Electrical Resistivity Measurements on Manganese Oxides with Layer and Tunnel Structures: Birnessites, Todorokites, and Cryptomelanes De Guzman, Roberto N.; Awaluddin, Amir; Shen, Yan-Fei Chemistry of Materials, Vol. 7, Issue 7 https://doi.org/10.1021/cm00055a003	journal	July 1995
Structural and electrochemical properties of the proton / γ-MnO2 system Chabre, Y.; Pannetier, J. Progress in Solid State Chemistry, Vol. 23, Issue 1 https://doi.org/10.1016/0079-6786(94)00005-2	journal	January 1995
Micro-Four-Line Probe to Measure Electronic Conductivity and Contact Resistance of Thin-Film Battery Electrodes Lanterman, Bryson J.; Riet, Adriaan A.; Gates, Nathaniel S. Journal of The Electrochemical Society, Vol. 162, Issue 10 https://doi.org/10.1149/2.0581510jes	journal	January 2015
Carbon Nanotube/Manganese Oxide Ultrathin Film Electrodes for Electrochemical Capacitors Lee, Seung Woo; Kim, Junhyung; Chen, Shuo ACS Nano, Vol. 4, Issue 7 https://doi.org/10.1021/nn100681d	journal	June 2010
Challenges in the development of advanced Li-ion batteries: a review Etacheri, Vinodkumar; Marom, Rotem; Elazari, Ran Energy & Environmental Science, Vol. 4, Issue 9 https://doi.org/10.1039/c1ee01598b	journal	January 2011
Hybrid supercapacitor with nano-TiP2O7 as intercalation electrode Aravindan, V.; Reddy, M. V.; Madhavi, S. Journal of Power Sources, Vol. 196, Issue 20 https://doi.org/10.1016/j.jpowsour.2011.05.074	journal	October 2011
Coaxial MnO ₂ /Carbon Nanotube Array Electrodes for High-Performance Lithium Batteries Reddy, Arava Leela Mohana; Shaijumon, Manikoth M.; Gowda, Sanketh R. Nano Letters, Vol. 9, Issue 3 https://doi.org/10.1021/nl803081j	journal	March 2009
Local control of electric current driven shell etching of multiwalled carbon nanotubes Subramanian, A.; Choi, T. -Y.; Dong, L. X. Applied Physics A, Vol. 89, Issue 1 https://doi.org/10.1007/s00339-007-4128-0	journal	June 2007
Approaching Theoretical Capacity of LiFePO[sub 4] at Room Temperature at High Rates Huang, H.; Yin, S. -C.; Nazar, L. F. Electrochemical and Solid-State Letters, Vol. 4, Issue 10 https://doi.org/10.1149/1.1396695	journal	January 2001
Kinetic characteristics of mixed conductive electrodes for lithium ion batteries Ma, Jianxin; Wang, Chunsheng; Wroblewski, Shannon Journal of Power Sources, Vol. 164, Issue 2 https://doi.org/10.1016/j.jpowsour.2006.11.024	journal	February 2007
Characterization and electrochemical properties of Li+ ion-exchanged products of hollandite-type Ky(Mn1−xCox)O2 for rechargeable lithium battery electrodes Kadoma, Yoshihiro; Oshitari, Satoru; Ui, Koichi Solid State Ionics, Vol. 179, Issue 27-32 https://doi.org/10.1016/j.ssi.2008.03.009	journal	September 2008
Performance and characterization of lithium–manganese-oxide cathode material with large tunnel structure for lithium batteries Yang, Y.; Shu, D.; You, J. K. Journal of Power Sources, Vol. 81-82 https://doi.org/10.1016/s0378-7753(99)00235-9	journal	September 1999
On-chip lithium cells for electrical and structural characterization of single nanowire electrodes Subramanian, A.; Hudak, N. S.; Huang, J. Y. Nanotechnology, Vol. 25, Issue 26 https://doi.org/10.1088/0957-4484/25/26/265402	journal	June 2014
Positive Electrode Materials for Li-Ion and Li-Batteries ^† Ellis, Brian L.; Lee, Kyu Tae; Nazar, Linda F. Chemistry of Materials, Vol. 22, Issue 3 https://doi.org/10.1021/cm902696j	journal	February 2010
Facile one pot synthesis and Li-cycling properties of MnO ₂ Nithyadharseni, P.; Reddy, M. V.; Fanny, Ho RSC Advances, Vol. 5, Issue 74 https://doi.org/10.1039/c5ra09278g	journal	January 2015
Metal ion extraction/insertion reactions with todorokite-type manganese oxide in the aqueous phase Feng, Qi; Kanoh, Hirofumi; Miyai, Yoshitaka Chemistry of Materials, Vol. 7, Issue 9 https://doi.org/10.1021/cm00057a023	journal	September 1995
Mn-substituted spinel Li4Ti5O12 materials studied by multifrequency EPR spectroscopy Kaftelen, Hülya; Tuncer, Mustafa; Tu, Suyan Journal of Materials Chemistry A, Vol. 1, Issue 34 https://doi.org/10.1039/c3ta11590a	journal	January 2013
Electrical Energy Storage for the Grid: A Battery of Choices Dunn, B.; Kamath, H.; Tarascon, J. -M. Science, Vol. 334, Issue 6058 https://doi.org/10.1126/science.1212741	journal	November 2011
Carbon coated nano-LiTi2(PO4)3 electrodes for non-aqueous hybrid supercapacitors Aravindan, V.; Chuiling, W.; Reddy, M. V. Physical Chemistry Chemical Physics, Vol. 14, Issue 16 https://doi.org/10.1039/c2cp40603a	journal	January 2012
Porous Manganese Oxide Octahedral Molecular Sieves and Octahedral Layered Materials Suib, Steven L. Accounts of Chemical Research, Vol. 41, Issue 4 https://doi.org/10.1021/ar7001667	journal	April 2008
A facile route to synthesize uniform single-crystalline -MnO2 nanowires Gao, Yongqian; Wang, Zhenghua; Wan, Junxi Journal of Crystal Growth, Vol. 279, Issue 3-4 https://doi.org/10.1016/j.jcrysgro.2005.02.052	journal	June 2005
A review of conduction phenomena in Li-ion batteries Park, Myounggu; Zhang, Xiangchun; Chung, Myoungdo Journal of Power Sources, Vol. 195, Issue 24 https://doi.org/10.1016/j.jpowsour.2010.06.060	journal	December 2010
Effect of 0.5 M NaNO ₃ : 0.5 M KNO ₃ and 0.88 M LiNO ₃ :0.12 M LiCl Molten Salts, and Heat Treatment on Electrochemical Properties of TiO ₂ Reddy, M. V.; Valerie Teoh, X. W.; Nguyen, T. B. Journal of The Electrochemical Society, Vol. 159, Issue 6 https://doi.org/10.1149/2.077206jes	journal	January 2012
Electrochemical Performance of α-MnO<SUB>2</SUB> Nanorods/Activated Carbon Hybrid Supercapacitor Aravindan, V.; Reddy, M. V.; Madhavi, S. Nanoscience and Nanotechnology Letters, Vol. 4, Issue 7 https://doi.org/10.1166/nnl.2012.1377	journal	July 2012
Issues and challenges facing rechargeable lithium batteries Tarascon, J.-M.; Armand, M. Nature, Vol. 414, Issue 6861, p. 359-367 https://doi.org/10.1038/35104644	journal	November 2001
Dependence of Young's modulus on the sodium content within the structural tunnels of a one-dimensional Na-ion battery cathode Maksud, M.; Palapati, N. K. R.; Byles, B. W. Nanoscale, Vol. 7, Issue 42 https://doi.org/10.1039/C5NR06557G	journal	January 2015
Single nanowire manipulation within dielectrophoretic force fields in the sub-crossover frequency regime Palapati, N. K. R.; Pomerantseva, E.; Subramanian, A. Nanoscale, Vol. 7, Issue 7 https://doi.org/10.1039/C4NR06303A	journal	January 2015
Manganese oxides for lithium batteries Thackeray, Michael M. Progress in Solid State Chemistry, Vol. 25, Issue 1-2 https://doi.org/10.1016/S0079-6786(97)81003-5	journal	January 1997
A new MnO2 tunnel related phase as host lattice for Li intercalation Bach, S. Solid State Ionics, Vol. 80, Issue 1-2 https://doi.org/10.1016/0167-2738(95)00133-Q	journal	August 1995
Revised effective ionic radii and systematic studies of interatomic distances in halides and chalcogenides Shannon, R. D. Acta Crystallographica Section A, Vol. 32, Issue 5, p. 751-767 https://doi.org/10.1107/S0567739476001551	journal	September 1976
Local control of electric current driven shell etching of multiwalled carbon nanotubes Subramanian, A.; Choi, T.; Dong, L. X. ETH Zurich https://doi.org/10.3929/ethz-b-000005960	text	January 2007

Cited By (6)

Structural and Electrical Studies for Birnessite-Type Materials Synthesized by Solid-State Reactions Arias, Nayda P.; Becerra, María E.; Giraldo, Oscar Nanomaterials, Vol. 9, Issue 8 https://doi.org/10.3390/nano9081156	journal	August 2019
Incorporating Ionic Paths into 3D Conducting Scaffolds for High Volumetric and Areal Capacity, High Rate Lithium-Metal Anodes Zhang, Chanyuan; Liu, Shan; Li, Guojie Advanced Materials, Vol. 30, Issue 33 https://doi.org/10.1002/adma.201801328	journal	July 2018
A 3D nanoelectrokinetic model for predictive assembly of nanowire arrays using floating electrode dielectrophoresis Singh, Sachin K.; Aryaan, Nehal; Shikder, Md Ruhul Amin Nanotechnology, Vol. 30, Issue 2 https://doi.org/10.1088/1361-6528/aae9a4	journal	November 2018
Tunable nanomechanical performance regimes in ceramic nanowires Maksud, Mahjabin; Barua, Mathius; Shikder, Md Ruhul Amin Nanotechnology, Vol. 30, Issue 47 https://doi.org/10.1088/1361-6528/ab3dcf	journal	September 2019
Brittle fracture to recoverable plasticity: Polytypism-dependent nanomechanics in todorokite-like nanobelts Shikder, MR Amin; Maksud, M.; Vasudevamurthy, G. University of Illinois at Chicago https://doi.org/10.25417/uic.14910282	text	January 2021
Brittle fracture to recoverable plasticity: Polytypism-dependent nanomechanics in todorokite-like nanobelts Shikder, MR Amin; Maksud, M.; Vasudevamurthy, G. University of Illinois at Chicago https://doi.org/10.25417/uic.14910282.v1	text	January 2021

Similar Records

Tunnel structured manganese oxide nanowires as redox active electrodes for hybrid capacitive deionization

Journal Article · Mon Dec 18 00:00:00 EST 2017 · Nano Energy · OSTI ID:1262340

Byles, Bryan W.; Cullen, David A.; More, Karren Leslie; +1 more

Todorokite-type manganese oxide nanowires as an intercalation cathode for Li-ion and Na-ion batteries

Journal Article · Thu Dec 03 00:00:00 EST 2015 · RSC Advances · OSTI ID:1262340

Byles, B. W.; West, P.; Cullen, D. A.; +2 more

Impact of Stabilizing Cations on Lithium Intercalation in Tunneled Manganese Oxide Cathodes

Journal Article · Fri Oct 15 00:00:00 EDT 2021 · ACS Applied Energy Materials · OSTI ID:1262340

Kempaiah, Ravindra; Chan, Henry; Srinivasan, Srilok; +3 more

Related Subjects

75 CONDENSED MATTER PHYSICS
SUPERCONDUCTIVITY AND SUPERFLUIDITY
25 ENERGY STORAGE
lithium batteries
electrochemical properties
hybrid supercapacitor
carbon nanotubes
challenges
cathode
intercalation
lifepo4
phase
layer
nanowires
manganese
electrodes
ionic conductivity

Title: The role of electronic and ionic conductivities in the rate performance of tunnel structured manganese oxides in Li-ion batteries

Citation Formats

References (40)

Cited By (6)

Similar Records

Related Subjects