Nanostructured flexible Mg-modified LiMnPO4 matrix as high-rate cathode materials for Li-ion batteries

One-dimensional (1D) electrode materials have attracted much attention recently because of their potential application in flexible battery technology. Many 1D anode materials based on carbon and metal oxides have been synthesized for flexible batteries, however only limited studies on the cathode side have been conducted. Here, we report the synthesis of high-rate cathode electrodes based on Mg-modified LiMnPO4 nanofibers. The nanofibers are embedded inside a nanostructured conducting carbon matrix to enhance their electronic conductivity and structural integrity while retaining flexibility. As a result, a 50% increase in capacity is obtained, achieving an outstanding performance of 135 mA h g−1 at a C/10 rate (15 mA g−1). This nanostructured Mg-modified LiMnPO4 matrix also exhibited superior rate capability and much better cycleability compared to its LiMnPO4 counterpart. Even at a high charge/discharge rate of 5C (750 mA g−1), 80% of the capacity (107 mA h g−1) is still retained, representing, to the best of our knowledge, the best rate performance for LiMnPO4-based electrodes. More importantly, such a superior rate capability is achieved with an excellent cycleability (no capacity fading for 200 deep cycles).

[1]  M. Whittingham,et al.  Lithium batteries and cathode materials. , 2004, Chemical reviews.

[2]  Seung M. Oh,et al.  Double-structured LiMn(0.85)Fe(0.15)PO4 coordinated with LiFePO4 for rechargeable lithium batteries. , 2012, Angewandte Chemie.

[3]  Haoshen Zhou,et al.  The design of a LiFePO4/carbon nanocomposite with a core-shell structure and its synthesis by an in situ polymerization restriction method. , 2008, Angewandte Chemie.

[4]  Linda F Nazar,et al.  Proof of intercrystallite ionic transport in LiMPO(4) electrodes (M = Fe, Mn). , 2009, Journal of the American Chemical Society.

[5]  Guangyuan Zheng,et al.  Silicon-conductive nanopaper for Li-ion batteries , 2013 .

[6]  K. Kang,et al.  LiFePO4 with an alluaudite crystal structure for lithium ion batteries , 2013 .

[7]  Bruno Scrosati,et al.  Double Carbon Coating of LiFePO4 as High Rate Electrode for Rechargeable Lithium Batteries , 2010, Advanced materials.

[8]  Wei-Jun Zhang.  Comparison of the Rate Capacities of LiFePO4 Cathode Materials , 2010 .

[9]  Sehee Lee,et al.  Face-centered-cubic lithium crystals formed in mesopores of carbon nanofiber electrodes. , 2013, ACS nano.

[10]  K. S. Nanjundaswamy,et al.  Phospho‐olivines as Positive‐Electrode Materials for Rechargeable Lithium Batteries , 1997 .

[11]  Jim Benson,et al.  Ultra strong silicon-coated carbon nanotube nonwoven fabric as a multifunctional lithium-ion battery anode. , 2012, ACS nano.

[12]  Chongyin Yang,et al.  Low-temperature aluminum reduction of graphene oxide, electrical properties, surface wettability, and energy storage applications. , 2012, ACS nano.

[13]  Guoying Chen,et al.  Improved kinetics and stabilities in Mg-substituted LiMnPO4 , 2010 .

[14]  Byoungwoo Kang,et al.  Battery materials for ultrafast charging and discharging , 2009, Nature.

[15]  Chongwu Zhou,et al.  Hierarchical three-dimensional ZnCo₂O₄ nanowire arrays/carbon cloth anodes for a novel class of high-performance flexible lithium-ion batteries. , 2012, Nano letters.

[16]  P. Bruce,et al.  Nanomaterials for rechargeable lithium batteries. , 2008, Angewandte Chemie.

[17]  Bruno Scrosati,et al.  High‐Performance Carbon‐LiMnPO4 Nanocomposite Cathode for Lithium Batteries , 2010 .

[18]  Yi Cui,et al.  Transparent lithium-ion batteries , 2011, Proceedings of the National Academy of Sciences.

[19]  John A Rogers,et al.  Semiconductor wires and ribbons for high-performance flexible electronics. , 2008, Angewandte Chemie.

[20]  Min Gyu Kim,et al.  Recent Progress in Nanostructured Cathode Materials for Lithium Secondary Batteries , 2010 .

[21]  Zhenguo Yang,et al.  LiMnPO4 nanoplate grown via solid-state reaction in molten hydrocarbon for Li-ion battery cathode. , 2010, Nano letters.

[22]  John A Rogers,et al.  Stretchable, Curvilinear Electronics Based on Inorganic Materials , 2010, Advanced materials.

[23]  E. Yoo,et al.  Enhanced cyclic performance and lithium storage capacity of SnO2/graphene nanoporous electrodes with three-dimensionally delaminated flexible structure. , 2009, Nano letters.

[24]  Yi Cui,et al.  Scalable coating and properties of transparent, flexible, silver nanowire electrodes. , 2010, ACS nano.

[25]  Yan Yu,et al.  Electrospinning of highly electroactive carbon-coated single-crystalline LiFePO4 nanowires. , 2011, Angewandte Chemie.

[26]  H. Dai,et al.  LiMn(1-x)Fe(x)PO4 nanorods grown on graphene sheets for ultrahigh-rate-performance lithium ion batteries. , 2011, Angewandte Chemie.

[27]  H. Hng,et al.  Olivine-type nanosheets for lithium ion battery cathodes. , 2013, ACS nano.

[28]  G. Konstantatos,et al.  Nanostructured materials for photon detection. , 2010, Nature nanotechnology.

[29]  Lain-Jong Li,et al.  Graphene-modified LiFePO4 cathode for lithium ion battery beyond theoretical capacity , 2013, Nature Communications.

[30]  Guoying Chen,et al.  Solid Solution Phases in the Olivine-Type LiMnPO4/MnPO4 System , 2009 .

[31]  Xifei Li,et al.  Engineering nanostructured anodes via electrostatic spray deposition for high performance lithium ion battery application , 2013 .

[32]  Yi Cui,et al.  Thin, flexible secondary Li-ion paper batteries. , 2010, ACS nano.

[33]  J. Goodenough,et al.  Two-phase interface in LiMnPO4 nanoplates , 2012 .

[34]  Guoying Chen,et al.  Improving the Performance of Lithium Manganese Phosphate Through Divalent Cation Substitution , 2008 .

[35]  K. Möller,et al.  Electrospun LiFe1−yMnyPO4/C Nanofiber Composites as Self‐Supporting Cathodes in Li‐Ion Batteries , 2012 .

[36]  J. Goodenough,et al.  The Prepared and Electrochemical Property of Mg Doped LiMnPO4 Nanoplates as Cathode Materials for Lithium-Ion Batteries , 2012 .

[37]  Xifei Li,et al.  Three‐Dimensional Porous Core‐Shell Sn@Carbon Composite Anodes for High‐Performance Lithium‐Ion Battery Applications , 2012 .