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High-Performance Aqueous Symmetric Sodium-Ion Battery Using Nano Research DOI 10.1007/s12274-017-1657-5 High-performance aqueous symmetric sodium-ion battery using NASICON-structured Na2VTi(PO4)3 Hongbo Wang1, Tianran Zhang2, Chao Chen3, Min Ling4, Zhan Lin1,3 (), Shanqing Zhang4, Feng Pan5, and Chengdu Liang1 1 Zhejiang Provincial Key Laboratory of Advanced Chemical Engineering Manufacture Technology, College of Chemical and Biological Engineering, Zhejiang University, Hangzhou 310027, China 2 Department of Mechanical Engineering, National University of Singapore, Singapore 117576, Singapore 3 College of Light Industry and Chemical Engineering, Guangdong University of Technology, Guangzhou 510006, China 4 Centre for Clean Environment and Energy, Environmental Futures Research Institute and Griffith School of Environment, Gold Coast Campus, Griffith University, QLD 4222, Australia 5 School of Advanced Materials, Peking University, Shenzhen Graduate School, Shenzhen 518055, China Received: 26 February 2017 ABSTRACT Revised: 25 April 2017 A high-safety and low-cost route is important in the development of sodium-ion Accepted: 30 April 2017 batteries, especially for large-scale stationary battery systems. An aqueous sodium-ion battery is demonstrated using a single NASICON-structured © Tsinghua University Press 4+ 3+ 4+ 3+ Na2VTi(PO4)3 material with the redox couples of V /V and Ti /Ti working and Springer-Verlag Berlin on the cathode and anode, respectively. The symmetric full cell fabricated based Heidelberg 2017 on the bi-functional electrode material exhibits a well-defined voltage plateau at ~1.2 V and an impressive cycling stability with capacity retention of 70% KEYWORDS exceeding 1,000 cycles at 10C (1C = 62 mA·g–1). This study provides a feasible Na2VTi(PO4)3, strategy for obtaining high-safety and low-cost rechargeable batteries using a aqueous, single active material in aqueous media. symmetric, sodium-ion batteries 1 Introduction Sodium-ion batteries (NIBs) are potential alternatives to LIBs for use in stationary energy storage systems Mobile electronic devices require rechargeable batteries because of the abundance of natural sodium sources exhibiting high energy and power densities, and with a low cost [3, 4]. Furthermore, symmetric NIBs lithium-ion batteries (LIBs) have been widely com- are promising from a commercial standpoint as the mercialized for this purpose [1, 2]. However, the same active material can be used as both the cathode relatively high cost of LIBs has prevented their use and anode. This bi-functional material simplifies the in further applications in stationary power stations. electrode design and reduces the manufacturing cost Address correspondence to [email protected] 2 Nano Res. as a single powder preparation and slurry casting are more important than specific energy [24, 25]. The process can be employed for fabricating the positive resulting symmetric NIB exhibits an energy density of and negative electrodes in NIBs [5–8]. ~30 Wh·kg–1 with a superior long life, i.e., exceeding For developing symmetric NIBs, an electrode material 1,000 cycles with a capacity retention of 70% even at that serves both as a sodium-rich cathode and a high current rate of 10C, making it a promising sodium-deficient anode is required, e.g., layered metal rechargeable battery for stationary power stations. oxides, such as P2-Na0.6Cr0.6Ti0.4O2 and O3-Na0.8Ni0.4Ti0.6O2, that were successfully used in non-aqueous electro- 2 Experimental lytes [9, 10]. However, non-aqueous electrolytes are inflammable; and the cycling performances of currently 2.1 Material preparations developed symmetric NIBs in non-aqueous electrolytes are insufficient for use in long-term operations in Na2VTi(PO4)3 was prepared using CH3COONa, NH4VO3, stationary electrical energy storage requiring high safety. (CH3CH2CH2CH2O)4Ti, and NH4H2PO4 as the raw As compared with non-aqueous electrolytes, the use materials. Citric acid was employed as both a chelating of NIBs exhibiting a much higher safety and lower agent and a carbon source, which reduces V5+ to V3+. cost in aqueous electrolytes is a promising approach Initially, CH3COONa, NH4VO3, NH4H2PO4, and citric for achieving large-scale electrical energy storage acid with stoichiometric ratios were dissolved in distilled for stationary applications [11–13]. However, both the water with magnetic stirring. After using acetic acid positive and negative electrodes in aqueous NIBs to adjust the pH of the above solution to 4.0, a diluted should function within the electrochemical potential solution of (CH3CH2CH2CH2O)4Ti in ethanol was poured windows of water [14, 15]. Thus, it is greatly significant into the solution to achieve the final stoichiometry and challenging to search for a suitable bi-functional under vigorous stirring. The obtained mixture was material to fabricate aqueous symmetric NIBs exhibiting evaporated at 80 °C in a water bath to form a uniform a long cycle life for applications in high-performance sol and further dried in an oven at 120 °C overnight to stationary power stations. obtain a gel precursor. This gel precursor was sintered As well known, the redox potentials of vanadium (V) at 450 °C under argon flow for 3 h followed by 850 °C and titanium (Ti) present in NASICON-structured for 12 h. The resultant material was pulverized and compounds are within the electrochemical potential sieved by ~300 meshes for performing the electro- window of water [16]. NASICON-structured Na3V2(PO4)3 chemical and structural studies. is believed to be a promising cathode material, while 2.2 Material characterizations the isostructural NaTi2(PO4)3 served as a good anode material in aqueous NIBs [17–20]. However, V-based Powder X-ray diffraction (XRD) analysis was per- phosphate cathode materials degrade easily in com- formed on a PANalytical Empyrean200895 with Cu monly used aqueous electrolytes [21–23], which can Kα radiation. The XRD data was refined using the be stabilized by substituting half of the V sites with GSAS Rietveld software, and the electrodes obtained Ti for applications in aqueous media. Herein, we by dissembling batteries cycled at various voltages synthesized NASICON-structured Na2VTi(PO4)3 that were characterized using ex-situ XRD. Transmission served as not only as the cathode but also as the anode electron microscopy (TEM) and scanning electron to construct a symmetric NIB in aqueous electrolyte. microscopy (SEM) measurements were performed The resultant symmetric cell exhibits a voltage of ca. on JEOL JEM2100 and FEI SIRION100 microscopes 1.2 V with an initial discharge capacity of 50 mAh·g–1 equipped with energy dispersive X-ray spectroscopy at a rate of 1C (1C = 62 mA·g–1), corresponding to 80.3% (EDS) for performing elemental analysis, respectively. of the theoretical maximum capacity (62 mAh·g–1). X-ray photoelectron spectroscopy (XPS) measurements The important properties required for stationary were performed on a ThermoFisher Escalab250Xi batteries to be used in large-scale electrical energy equipment. Raman spectra were recorded on a Horiba storage are long life, high safety, and low cost, which LabRAM HR microscope using 532 nm excitation. | www.editorialmanager.com/nare/default.asp Nano Res. 3 Thermal gravimetric analysis (TGA) was carried out on a Mettler TA Q500 instrument at a heating rate of 10 °C·min–1 under air atmosphere. 2.3 Electrochemical measurements The working electrode was prepared by rolling a mixture of 70 wt.% Na2VTi(PO4)3, 20 wt.% carbon black, and 10 wt.% polytetrafluoroethylene (PTFE) into a thin film, followed cutting it into a circular strip of 8 mm in diameter and pressing the strip (ca. 4.5 mg) onto a Ti mesh. The electrode was used in a three- –1 electrode system with 1.0 mol·L Na2SO4 as the aqueous electrolyte, Na2VTi(PO4)3 as the working electrode, activated carbon as the counter electrode, and the Figure 1 XRD pattern of Na2VTi(PO4)3 and Rietveld refinement. Ag/AgCl electrode saturated with KCl (0.197 V vs. The inset schematically represents the crystal structure of NHE) as the reference electrode. The symmetric aqueous Na2VTi(PO4)3. cell fabricated with Na2VTi(PO4)3 as the cathode and the anode was assembled in a 2025-type coin cell schematic illustration of the NASICON unit cell of using glass fiber as the separator. The weight ratio Na2VTi(PO4)3 is represented in the inset of Fig. 1, in of the anode to the cathode in the cell was ~1.10. The which the isolated VO6 or TiO6 octahedra shares all specific capacity of the half-cell in the three-electrode of its corners with PO4 tetrahedra, forming a three- system was calculated using the mass of the active dimensional (3D) framework. Two different types of material of Na2VTi(PO4)3, while the specific capacity sodium ions are located in the interstitial sites of the of the symmetric full-cell was calculated based on the framework with two different oxygen environments: mass of the corresponding active material in the positive A single interstitial site per unit cell with a six-fold electrode. Cyclic voltammetry (CV) and linear sweep coordination (Na1 site) is occupied by a less mobile voltammetry tests were carried out on a CHI760D sodium-ion, while two equivalent sites per unit cell –1 electrochemical workstation at a scan rate of 0.5 mV·s . with an eight-fold coordination (Na2 sites) are occupied Galvanostatic charge and discharge measurements by a mobile sodium-ion. Sodium ions positioned at were conducted on a LAND battery testing system at the Na2 sites can be extracted/inserted for the electro- various rates at room temperature. chemical activity [26]. As a result, one sodium ion per unit cell is extracted from Na2VTi(PO4)3 with the 4+ 3+ 3 Results and discussion formation of NaVTi(PO4)3 through the V /V redox couple, while another sodium ion per unit cell is The crystal structure of Na2VTi(PO4)3 was characterized inserted into Na2VTi(PO4)3 with the formation of 4+ 3+ using XRD, as shown in Fig.
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