A Self‐Forming Composite Electrolyte for Solid‐State Sodium Battery with Ultralong Cycle Life

Replacing organic liquid electrolyte with inorganic solid electrolytes (SE) can potentially address the inherent safety problems in conventional rechargeable batteries. However, solid‐state batteries (SSBs) have been plagued by the relatively low ionic conductivity of SEs and large charge‐transfer resistance between electrode and SE. Here, a new design strategy is reported for improving the ionic conductivity of SE by self‐forming a composite material. An optimized Na+ ion conducting composite electrolyte derived from the Na1+ n Zr2Si n P3− n O12 NASICON (Na Super Ionic Conductor) structure is successfully synthesized, yielding ultrahigh ionic conductivity of 3.4 mS cm−1 at 25 °C and 14 mS cm−1 at 80 °C. On the other hand, in order to enhance the charge‐transfer rate at the electrode/electrolyte interface, an interface modification strategy is demonstrated by utilization of a small amount of nonflammable and nonvolatile ionic liquid (IL) at the cathode side in SSBs. The IL acts as a wetting agent, enabling a favorable interface kinetic in SSBs. The Na3V2(PO4)3/IL/SE/Na SSB exhibits excellent cycle performance and rate capability. A specific capacity of ≈90 mA h g−1 is maintained after 10 000 cycles without capacity decay under 10 C rate at room temperature. This provides a new perspective to design fast ion conductors and fabricate long life SSBs.

[1]  G. G. Stokes.  "J." , 1890, The New Yale Book of Quotations.

[2]  H. Rietveld.  A profile refinement method for nuclear and magnetic structures , 1969 .

[3]  C. Liang.  Conduction Characteristics of the Lithium Iodide‐Aluminum Oxide Solid Electrolytes , 1973 .

[4]  H. Hong,et al.  Crystal structures and crystal chemistry in the system Na1+xZr2SixP3−xO12☆ , 1976 .

[5]  John B. Goodenough,et al.  Fast Na+-ion transport in skeleton structures , 1976 .

[6]  J. Boilot,et al.  Phase transformation in Na1+xSixZr2P3−xO12 compounds , 1979 .

[7]  U. Alpen,et al.  Phase transition in nasicon (Na3Zr2Si2PO12) , 1979 .

[8]  Composition and conduction mechanism of the NASICON structure X-ray diffraction study on two crystals at different temperatures , 1983 .

[9]  W. H. Baur,et al.  Neutron powder diffraction study and ionic conductivity of Na2Zr2SiP2O12 and Na3Zr2Si2PO12 , 1986 .

[10]  J. Boilot,et al.  Crystal structure of the true nasicon: Na3Zr2Si2PO12 , 1987 .

[11]  Joachim Maier,et al.  Ionic conduction in space charge regions , 1995 .

[12]  Daniele Mazza,et al.  Conductivity Measurements on Nasicon and Nasicon-modified materials , 1999 .

[13]  Hajime Matsumoto,et al.  N-Methyl-N-propylpiperidinium bis(trifluoromethanesulfonyl)imide (PP13–TFSI) – novel electrolyte base for Li battery , 2003 .

[14]  H. Sakaebe,et al.  Fast cycling of Li/LiCoO2 cell with low-viscosity ionic liquids based on bis(fluorosulfonyl)imide [FSI]− , 2006 .

[15]  K. Zaghib,et al.  LiFePO4 and graphite electrodes with ionic liquids based on bis(fluorosulfonyl)imide (FSI)-for Li-ion batteries , 2008 .

[16]  P. Kamaraj,et al.  Synthesis of NASICON—A Molecular Precursor-Based Approach , 2008 .

[17]  Binod Kumar,et al.  Composite effect in superionically conducting lithium aluminium germanium phosphate based glass-ceramic , 2008 .

[18]  Hirokazu Kitaura,et al.  Novel technique to form electrode-electrolyte nanointerface in all-solid-state rechargeable lithium batteries , 2008 .

[19]  Binod Kumar,et al.  Space-Charge-Mediated Superionic Transport in Lithium Ion Conducting Glass–Ceramics , 2009 .

[20]  A. Hayashi,et al.  All-solid-state lithium secondary batteries using LiCoO2 particles with pulsed laser deposition coatings of Li2S–P2S5 solid electrolytes , 2011 .

[21]  Gerbrand Ceder,et al.  Electrode Materials for Rechargeable Sodium‐Ion Batteries: Potential Alternatives to Current Lithium‐Ion Batteries , 2012 .

[22]  A. Hayashi,et al.  High-capacity Li2S–nanocarbon composite electrode for all-solid-state rechargeable lithium batteries , 2012 .

[23]  Teófilo Rojo,et al.  Na-ion batteries, recent advances and present challenges to become low cost energy storage systems , 2012 .

[24]  Huilin Pan,et al.  Carbon coated Na3V2(PO4)3 as novel electrode material for sodium ion batteries , 2012 .

[25]  John B. Goodenough,et al.  Rechargeable batteries: challenges old and new , 2012, Journal of Solid State Electrochemistry.

[26]  Soo Yeon Lim,et al.  Electrochemical and Thermal Properties of NASICON Structured Na3V2(PO4)3 as a Sodium Rechargeable Battery Cathode: A Combined Experimental and Theoretical Study , 2012 .

[27]  Shinji Inazawa,et al.  NaFSA–C1C3pyrFSA ionic liquids for sodium secondary battery operating over a wide temperature range , 2013 .

[28]  Teófilo Rojo,et al.  High temperature sodium batteries: status, challenges and future trends , 2013 .

[29]  Li Li,et al.  11 nm hard X-ray focus from a large-aperture multilayer Laue lens , 2013, Scientific Reports.

[30]  Jing Zhou,et al.  Superior Electrochemical Performance and Storage Mechanism of Na3V2(PO4)3 Cathode for Room‐Temperature Sodium‐Ion Batteries , 2013 .

[31]  Kazunori Takada,et al.  Interfacial nanoarchitectonics for solid-state lithium batteries. , 2013, Langmuir : the ACS journal of surfaces and colloids.

[32]  H. Yamasaki,et al.  Dielectric Modification of 5V‐Class Cathodes for High‐Voltage All‐Solid‐State Lithium Batteries , 2014 .

[33]  Young Jin Nam,et al.  Excellent Compatibility of Solvate Ionic Liquids with Sulfide Solid Electrolytes: Toward Favorable Ionic Contacts in Bulk‐Type All‐Solid‐State Lithium‐Ion Batteries , 2015 .

[34]  Chunsheng Wang,et al.  A Battery Made from a Single Material , 2015, Advanced materials.

[35]  Linda F Nazar,et al.  The emerging chemistry of sodium ion batteries for electrochemical energy storage. , 2015, Angewandte Chemie.

[36]  S Kalbfleisch,et al.  Pushing the limits: an instrument for hard X-ray imaging below 20 nm. , 2015, Journal of synchrotron radiation.

[37]  Yong-Sheng Hu,et al.  Batteries: Getting solid , 2016, Nature Energy.