Abstract
Porous Na3Fe2(PO4)3 has been synthesized via a sol-gel method using citric acid as a metal ion complexing agent and polyvinyl alcohol as a structure-guiding agent. The obtained porous Na3Fe2(PO4)3 with particle size distribution of 40–60 nm has a typical NASICON structure in a space group of C2/c and the specific surface area is 40.2 m2 g−1. Electrochemical measurement results indicate that the initial discharge-specific capacity of porous Na3Fe2(PO4)3 is up to 92.5 mAh g−1 and maintains at 86 mAh g−1 after 200 cycles at 20 mA g−1 (92% of theoretical capacity) and the corresponding coulombic efficiency is up to 100% as well as high rate capability performance (71.5 mAh g−1 after 1000 cycles under 500 mA g−1). The excellent electrochemical properties are attributed to its particular [Fe2(PO4)3] “lantern units” stacked crystal structure and porous morphology, which significantly improves intercalation/de-intercalation kinetic of sodium ions.
Similar content being viewed by others
References
Nooredn RV (2014) The rechargeable revolution: a better battery, Nature, 507
Larcher D, Tarascon JM (2015) Towards greener and more sustainable batteries for electrical energy storage. Nat Chem 7:19–29
U.M.Y. U.S. Geological Survey (USGS) (2012) volume I. metals and minerals, mineral commodity summaries 2010, January, 2010
Kim S-W, Seo D-H, Ma X, Ceder G, Kang K (2012) Electrode materials for rechargeable sodium-ion batteries: potential alternatives to current lithium-ion batteries. Adv Energy Mater 2:710–721
Yabuuchi N, Kubota K, Dahbi M, Komaba S (2014) Research development on sodium-ion batteries. Chem Rev 114:11636–11682
Palomares V, Serras P, Villaluenga I, Hueso KB, Carretero-Gonzalez J, Rojo T (2012) Na-ion batteries, recent advances and present challenges to become low cost energy storage systems. Energy Environ Sci 5:5884–5901
Nithya C, Gopukumar S (2015) Sodium ion batteries: a newer electrochemical storage. Wires Energy Environ 4:253–278
Padhi AK, Nanjundaswamy KS, Goodenough JB (1997) Phospho-olivines as positive-electrode materials for rechargeable lithium batteries. J Electrochem Soc 144:1188–1194
Zaghib K, Julien CM (2005) Structure and electrochemistry of FePO4·2H2O hydrate. J Power Sources 142:279–284
Karami H, Taala F (2011) Synthesis, characterization and application of Li3Fe2(PO4)3 nanoparticles as cathode of lithium-ion rechargeable batteries. J Power Sources 196:6400–6411
Yin Y, Hu Y, Wu P, Zhang H, Cai C (2012) A graphene-amorphous FePO4 hollow nanosphere hybrid as a cathode material for lithium ion batteries. Chem Commun 48:2137–2139
Guo B, Ruan H, Zheng C, Fei H, Wei M (2013) Hierarchical LiFePO4 with a controllable growth of the (010) facet for lithium-ion batteries. Sci Rep 3:2788–2793
Zhang SM, Zhang JX, Xu SJ, Yuan XJ, Tan T (2013) Synthesis, morphological analysis and electrochemical performance of iron hydroxyl phosphate as a cathode material for lithium ion batteries. J Power Sources 243:274–279
Liu Y, Xu S, Zhang S, Zhang J, Fan J, Zhou Y (2015) Direct growth of FePO4/reduced graphene oxide nanosheet composites for the sodium-ion battery. J Mater Chem A 3:5501–5508
Xu S, Zhang S, Zhang J, Tan T, Liu Y (2014) A maize-like FePO4@MCNT nanowire composite for sodium-ion batteries via a microemulsion technique. J Mater Chem A 2:7221–7228
Liu Y, Zhou Y, Zhang J, Zhang S, Ren P (2015) Amorphous iron phosphate/carbonized polyaniline nanorods composite as cathode material in sodium-ion batteries. J Solid State Electrochem
Liu Y, Zhou Y, Zhang J, Zhang S, Xu S (2015) The transformation from amorphous iron phosphate to sodium iron phosphate in sodium-ion batteries. Phys Chem Chem Phys 3:22144–22151
Liu Y, Zhou Y, Zhang J, Zhang S, Ren P (2016) The relation between the structure and electrochemical performance of sodiated iron phosphate in sodium-ion batteries. J Power Sources 314:1–9
Duan W, Zhu Z, Li H, Hu Z, Zhang K, Cheng F, Chen J (2014) Na3V2(PO4)3@C core–shell nanocomposites for rechargeable sodium-ion batteries. J Mater Chem A 2:8668–8675
Bianchini M, Brisset N, Fauth F, Weill F, Elkaim E, Suard E, Masquelier C, Croguennec L (2014) Na3V2(PO4)2F3 revisited: a high-resolution diffraction study. Chem Mater 26:4238–4247
Shiva K, Singh P, Zhou W, Goodenough JB (2016) NaFe2PO4(SO4)2: a potential cathode for a Na-ion battery. Energy Environ Sci 9:3103–3106
Yanjun C, Youlong X, Sun Xiaofei Z, Baofeng Z, Shengnan H, Long Li L (2018) Preventing structural degradation from Na3V2(PO4)3 to V2(PO4)3: F-doped Na3V2(PO4)3/C cathode composite with stable lifetime for sodium ion batteries. J Power Sources 378:423–432
Zhu Q, Cheng H, Zhang X, He L, Hu L, Yang J (2018) Improvement in electrochemical performance of Na3V2(PO4)3/C cathode material for sodium-ion batteries by K-Ca co-doping. Electrochim Acta, 281
Masquelier CWC, Rodrı guez-Carvajal J, Gaubicher J, Nazar L (2000) A powder neutron diffraction investigation of the two rhombohedral NASICON analogues: γ-Na3Fe2(PO4)3 and Li3Fe2(PO4)3. Chem Mater 12:525–532
Kabbour H, Coillot D, Colmont M, Masquelier C, Mentre O (2011) alpha-Na3M2(PO4)3 (M = Ti, Fe): absolute cationic ordering in NASICON-type phases. J Am Chem Soc 133:11900–11903
Liu Y, Zhou Y, Zhang J, Xia Y, Zhang S (2016) Monoclinic phase Na3Fe2(PO4 )3: synthesis, structure, and electrochemical performance as cathode material in sodium-ion batteries. ACS Sustain Chem Eng 5:1306–1314
Rajagopalan R, Chen B, Zhang Z, Wu XL, Du Y, Huang Y, Li B, Zong Y, Wang J, Nam GH, Sindoro M, Dou SX, Liu HK, Zhang H (2017) Improved reversibility of Fe3+ /Fe4+ redox couple in sodium super ion conductor type Na3Fe2(PO4)3 for sodium-ion batteries. Adv Mater 29:1605694
Kim H, Shakoor RA, Park C, Lim SY, Kim JS, Jo YN, Cho W, Miyasaka K, Kahraman R, Jung Y, Choi JW (2013) Na2FeP2O7 as a promising iron-based pyrophosphate cathode for sodium rechargeable batteries: a combined experimental and theoretical study. Adv Funct Mater 23:1147–1155
Chen X, Du K, Lai Y, Shang G, Li H, Xiao Z, Chen Y, Li J, Zhang Z (2017) In-situ carbon-coated Na2FeP2O7 anchored in three-dimensional reduced graphene oxide framework as a durable and high-rate sodium-ion battery cathode. J Power Sources 357:164–172
Wang X, Zhang Y, Luo W, Elzatahry AA, Cheng X, Alghamdi A, Abdullah AM, Deng Y, Zhao D (2016) Synthesis of ordered mesoporous silica with tunable morphologies and pore sizes via a nonpolar solvent-assisted Stöber method. Chem Mater 28:2356–2362
Fang Y, Lv Y, Che R, Wu H, Zhang X, Gu D, Zheng G, Zhao D (2013) Two-dimensional mesoporous carbon nanosheets and their derived graphene nanosheets: synthesis and efficient lithium ion storage. J Am Chem Soc 135:1524–1530
Rici L, Brost RA, Delany AC, Huebert BJ (1988) Numerical modeling of concentrations and fluxes of HNO3, NH3, and NH4NO3 near the surface. J Geophys Res 93:7137–7152
Liu S, Xiu Z, Liu Ja, Xu F, Yu W, Yu J, Feng G (2008) Combustion synthesis and characterization of perovskite SrTiO3 nanopowders. J Alloys Compd 457:L12–L14
Nagamiga T (1952) On the theory of the dielectric, piezoelectric, and elastic properties of NH4H2PO4. Prog Theor Phys 7:275–284
Jones, Liewellyn H, McLaren, Eugene (1954) Infrared spectra of CH3COONa and CD3COONa and assignments of vibrational frequencies. J Chem Phys 22:1796–1800
Thomas LV, Arun U, Remya S, Nair PD (2009) A biodegradable and biocompatible PVA–citric acid polyester with potential applications as matrix for vascular tissue engineering. J Mater Sci-Mater M 20:259–269
Lertpanyapornchai B, Yokoi T, Ngamcharussrivichai C (2016) Citric acid as complexing agent in synthesis of mesoporous strontium titanate via neutral-templated self-assembly sol–gel combustion method. Microporous Mesoporous Mater 226:505–509
Wang Y, Li H, He P, Hosono E, Zhou H (2010) Nano active materials for lithium-ion batteries. Nanoscale 2:1294–1305
Larson AC (1994) Dreele, General structure analysis system (GSAS), Los Alamos National Laboratory Report LAUR. Los Alamos National Laboratory Report LAUR, 86–748
Sing KS (1985) Reporting physisorption data for gas/solid systems with special reference to the determination of surface area and porosity (recommendations 1984). Pure Appl Chem 57:603–619
Lee J, Orilall MC, Warren SC, Kamperman M, DiSalvo FJ, Wiesner U (2008) Direct access to thermally stable and highly crystalline mesoporous transition-metal oxides with uniform pores. Nat Mater 7:222–228
Funding
This work was financially supported by the financial support of Shanghai Science and Technology Commission (14DZ2261000). This work was supported by the national key research and development Program of China (2016YFB0901500).
Author information
Authors and Affiliations
Corresponding authors
Additional information
Highlights
• Monoclinic Na3Fe2(PO4)3 is synthesized via sol-gel method.
• Na3Fe2(PO4)3 shows open mesoporous structure with diameters ranging from 40 to 60 nm.
• Porous Na3Fe2(PO4)3 displays excellent electrochemical performance in SIBs.
• Porous Na3Fe2(PO4)3 shows the rate performance of 71.5 mAh g−1 at 500 mA g-1 after 1000 cycles.
Electronic supplementary material
ESM 1
(DOC 4881 kb)
Rights and permissions
About this article
Cite this article
Cao, Y., Liu, Y., Chen, T. et al. Sol-gel synthesis of porous Na3Fe2(PO4)3 with enhanced sodium-ion storage capability. Ionics 25, 1083–1090 (2019). https://doi.org/10.1007/s11581-018-2804-z
Received:
Revised:
Accepted:
Published:
Issue Date:
DOI: https://doi.org/10.1007/s11581-018-2804-z