Sodium Ion Secondary Batteries Research Articles

Na3Zr2Si2PO12 Solid Electrolyte Separator for Aqueous Sodium-Ion Batteries: Synthesis via the One-Step Sintering of Glass-Ceramics

A dense Na₃Zr₂Si₂PO₁₂ (NZSP) solid electrolyte suitable for aqueous sodium-ion secondary batteries was synthesized using a glass-ceramic composite. The sintering process at temperatures ranging from 1050 to 1150 °C achieved a higher density at lower temperatures than sintering NZSP alone. This temperature range also allowed for greater density consistency. The ionic conductivity of the solid electrolyte was measured to be in the order of 1 mS/cm. Upon testing for water leakage, the electrolyte demonstrated sufficient density. Moreover, batteries employing this solid electrolyte achieved a stable voltage of 2 V and exhibited robust cycle performance, enduring over 100 cycles with good stability.

Manipulating the microstructure of Na2TiV(PO4)3 for aqueous Na ion storage

Polyanionic materials are among the most promising candidates as electrochemically active materials in sodium-ion secondary batteries, yet designing structures facilitating ion diffusion and electron transfer for electrodes that operate on multi-electron redox reactions proves both intriguing and challenging. In this study, we examine the electrochemical properties of mixed-polyanion Na2VTi(PO4)3/NaVP2O7, pure Na2VTi(PO4)3, and disordered Na2VTi(PO4)3 in an aqueous electrolyte. The former two polyanionic phosphates achieve an ultrahigh capacity (195.68 mAh g−1 at 0.2 A g−1) through three-sodium storage, whereas the disordered phosphate stores charge via a capacitive mechanism. Experimental tests and first-principle calculations demonstrate that enhancing the occupancy of asymmetric Na in the lattice establishes a new pathway for Na+ ions transport and narrows the band gap for electron transfer. Our work gives an insight into the local chemical environment of polyanionic phosphates composed of complex microstructures and provides a feasible strategy for obtaining electrode materials with exceptional performance.

Tin antimony alloy based reduced graphene oxide composite for fast charging sodium-ion batteries

Tin antimony alloy anchored reduced graphene oxide (rGO-SnxSby (x ∼ y = 1)) composite, prepared in bulk via a facile chemical route, is shown for its applicability in high current density (500 mAg−1) charging/discharging sodium battery application. The composite electrode delivered ∼320 mAhg 1 capacity in>300 cycles with Sodium as the other electrode. This electrode material retains∼300 mAhg−1 specific capacity at a 500 mAg−1 specific current density even after 2.5 Ag−1charge-discharge rates, indicating its potential in fast charge-discharge energy storage applications. The systematic study conducted here indicates that synergistic effects from the alloy particles and the rGO conductive matrix are leading to this observed phenomenon. The development of such viable anode materials can play a pivotal role in the commercialisation of sodium ion secondary batteries, one of the potential systems for future energy storage applications.

Quasi-Solid State Polymer Electrolytes Based on PVdF-HFP Host Polymer for Sodium-Ion Secondary Batteries

Prices of lithium raw materials keep on increasing exponentially due to their heavy consumption for lithium batteries used in portable electronic devices as well as automobiles. Also, the global lithium deposits are very limited. Hence, sodium-ion batteries (SIBs) have been heavily investigated as cheaper alternatives to expensive lithium-ion batteries, mainly due to the abundance of sodium raw materials. However, one of the major bottlenecks faced by the material research community to commercialize SIBs is the poor ionic conductivity of sodium-ion conducting electrolytes at ambient temperature, especially in the solid-state. Very recently, quasi-solid state polymer electrolytes (QSSPEs) have been proposed to overcome this challenge. In this work, a set of QSSPEs have been synthesized by using poly (vinylidene fluoride-co-hexafluoropropylene) (PVdF-HFP) host polymer and NaBF4 ionic salt dissolved in EC/PC plasticizer/solvent mixture. The highest conducting composition; 6 PVdF-HFP: 14 NaBF4: 40 EC: 40 PC (wt.%); showed an ambient temperature ionic conductivity of 4.1x10-3 S cm-1. The activation energy is almost same for all the sample compositions studied in this work suggesting that the activation process is mainly controlled by EC/PC. DC polarization test on highest conducting electrolyte composition with a configuration of SS/QSSPE/SS revealed that the electrolyte is predominantly ionic conductor with negligible electronic conductivity; a much desired property for a good electrolyte. Linear sweep voltammetric studies confirmed that the electrochemical stability window of the highest conducting electrolyte is about 3.6 V. This highest conducting electrolyte composition is found to be highly suitable for practical applications in sodium batteries.

(Keynote, Digital Presentation) Prussian Blue Analogues as Electrode Material of Batteries

Prussian blue analogues (PBA), which composed of cyano-bridged jungle-gym type framework and alkali metal ions, are promising material for electrode of batteries, because its framework is robust against electrochemical intercalation/deintercalation of alkali metal ions. In addition, the material consists of ubiquitous elements and is easily synthesized from aqueous solution. Thus, PBAs are promising electrode material for sodium ion secondary battery (SIB). We will introduce the overall features of PBAs as SIB electrode. Furthermore, PBAs are promising material for energy harvesting. We proposed a new type of battery (tertiary battery) that can be charged by the environmental heat using the difference in the thermal coefficient (α= dV/dT) of the redox potential (V) between the anode (αanode) and cathode (αcathode) materials. The tertiary battery can convert the environmental heat energy into electric energy during the thermal cycle, i.e., (i) heating to TH, (ii) discharge at TH, (iii) cooling to TL, and (iv) discharge at TL. In the (i) heating process, the V values of the anode and cathode change by αanodeΔTand αcathodeΔT, respectively. We expect a thermally induced change in the cell voltage (V cell) as large as (αcathode - αanode)ΔT. The stored electric energy can be extracted by the (ii) discharge process at TH. We fabricated several tertiary batteries made of PBA electrodes with different a and evaluated the thermal voltage (Vcell) and discharge capacity (Qcell). For example, NaxCo[Fe(CN)6]0.87/NaxNi[Fe(CN)6]0.94 tertiary battery exhibits Vcell = 24 mV and Qcell = 2.4 mAh/g per unit weight of total active material contains in the cathode and anode. We will correlate the observed Qcell values with the electrode parameters of the tertiary batteries. Y. Shimaura, T. Shibata, and Y. Moritomo, "Interrelation between discharge capacity and charge coefficient of redox potential in tertiary batteries made of transition metal hexacyanoferrate", Jpn. J. Appl. Phys. 61, 044004 (2022)I. Nagai, Y. Shimaura, T. Shibata, and Y. Moritomo, "Performance of tertiary battery made of Prussian blue analogues", Appl, Phys. Express. 14, 094004 (2021).Y. Moritomo, Y. Yoshida, D. Inoue, H. Iwaizumi, S. Kobayashi, S. Kawaguchi, and T. Shibata "Origin of the material dependence of the temperature coefficient of the redox potential in coordination polymers", J. Phys. Soc. Jpn. 90, 063801 (2021).T. Shibata, H. Iwaizumi, Y. Fukuzumi, and Y. Moritomo, "Energy harvesting thermocell with use of phase transition” Sci. Res., 10 1813 (2020)I. Takahara, T. Shibata, Y. Fukuzumi, and Y. Moritomo, " Improved thermal cyclability of tertiary battery made of Prussian blue analogues ", Chem. Select 4, 8558-8563 (2019)Y. Fukuzumi, K. Amaha, W. Kobayashi, H. Niwa, and Y. Moritomo, “Prussian blue analogues as promising thermal power generation materials”, Energy Technology, 6 (2018) 1 – 7.T. Shibata, Y. Fukuzumi, W. Kobayashi, and Y. Moritomo, “Thermal efficiency of a thermocell made of Prussian blue analogues”, Sci. Reps. Appl. Phys. Express. 8 (2018) 14784.T. Shibata, Y. Fukuzumi, W. Kobayashi, and Y. Moritomo, Thermal power generation during heat cycle near room temperature, Appl. Phys. Express. 11, 018101 (2018).M. Takachi, T. Matsuda, and Y. Moritomo, “Cobalt hexacyanoferrate as cathode material of Na+ secondary battery”, Appl. Phys. Express 6, 025802 (2013).M. Takachi, T. Matsuda, and Y. Moritomo, “Redox reaction in Prussian blue analogues with fast Na+ intercalation”, Jpn. J. Appl. Phys. 52, 092202 (2013).

Novel Gel-Polymer Electrolytes for Sodium-Ion Secondary Batteries - An Electrochemical Impedance Spectroscopic Studies

Global lithium deposits have been consumed a lot because of the heavy usage of lithium-ion batteries (LIBs) in almost all portable electronic devices and in automobiles. Due to the very limited global lithium resources, the so-called ‘batteries beyond lithium-ion’ such as sodium-ion batteries (SIBs) are becoming popular, particularly in the R&D level. One of the common problems in the commercial level production of SIBs is the synthesis of suitable electrolytes with sufficient ambient temperature ionic conductivities. In this work, a set of novel gel-polymer electrolytes (GPEs) based on poly (methyl methacrylate) (PMMA) host polymer have been synthesized and characterized by electrochemical impedance spectroscopic (EIS), DC polarization and cyclic voltammetric (CV) techniques. The optimized PMMA-NaClO4-EC-DMC GPE composition (10:14:38:38 wt.%) showed an ambient temperature ionic conductivity of 8.4 mS cm-1. Ionic conductivity vs inverse temperature showed Arrhenius behavior with almost same activation energies of 0.16 eV for all the compositions studied. DC polarization test on SS/GPE/SS configuration showed that the best conducting composition is dominantly an ionic conductor (tion ~ 0.998) with negligible electronic conductivity, which is highly desirable to avoid short circuits within the cell. The CV test on best conducting composition revealed that the electrochemical stability window (ESW) of these GPEs is about 4 volts (- 2 to + 2 volts). This optimized composition with highest ambient temperature ionic conductivity and negligible electronic conductivity seems to be a promising candidate for practical applications in sodium-ion secondary batteries.

Synthesis, electrochemical and optical studies of poly(ethylene oxide) based gel-polymer electrolytes for sodium-ion secondary batteries

Sodium-ion batteries are being heavily investigated as cheaper alternatives to expensive lithium-ion batteries. However, synthesizing suitable electrolytes with sufficient ambient temperature ionic conductivities is a major bottleneck. In this work, gel-polymer electrolytes (GPEs) based on poly(ethylene oxide) (PEO) host polymer and NaClO4 ionic salt are developed by using ethylene carbonate (EC) and propylene carbonate (PC) plasticizer/solvent mixture. The optimized PEO:NaClO4:EC:PC composition (7:13:40:40 wt%) exhibits an ambient temperature ionic conductivity of 9.5 mS cm−1 and the variation of ionic conductivity with inverse temperature showed Arrhenius behavior with almost same activation energies for all the compositions. DC polarization studies on optimized composition reveals that the electrolyte is dominantly an ionic conductor (ti = 0.99) with negligible electronic conductivity (te = 0.01), which is highly desirable for an effective electrolyte. Cyclic voltammetric and linear sweep voltammetric studies confirm that the optimized composition is electrochemically stable for a voltage window of −1.85 to +1.85 V. Absence of any crystalline peaks in the X-ray diffractograms of the GPEs is a clear evidence for the amorphous nature of these GPEs. Broadening of the FTIR vibrational bands at 1000–1300 and 1700–1850 cm−1 is ascribed to the lowering of crystallinity resulting from the formation of PEO/Na+ complex through Na+ ion solvation by the polymer host. The GPE with optimized composition and highest ionic conductivity at ambient temperature is a suitable electrolyte for practical applications in sodium-ion batteries.

A Biodegradable Secondary Battery and its Biodegradation Mechanism for Eco-Friendly Energy-Storage Systems.

The production of rechargeable batteries is rapidly expanding, and there are going to be new challenges in the near future about how the potential environmental impact caused by the disposal of the large volume of the used batteries can be minimized. Herein, a novel strategy is proposed to address these concerns by applying biodegradable device technology. An eco-friendly and biodegradable sodium-ion secondary battery (SIB) is developed through extensive material screening followed by the synthesis of biodegradable electrodes and their seamless assembly with an unconventional biodegradable separator, electrolyte, and package. Each battery component decomposes in nature into non-toxic compounds or elements via hydrolysis and/or fungal degradation, with all of the biodegradation products naturally abundant and eco-friendly. Detailed biodegradation mechanisms and toxicity influence of each component on living organisms are determined. In addition, this new SIB delivers performance comparable to that of conventional non-degradable SIBs. The strategy and findings suggest a novel eco-friendly biodegradable paradigm for large-scale rechargeable battery systems.

Electrochemical Studies on Na0.44MnO2 as Cathode Material for Na-Ion Battery Synthesized Through Sol–Gel Auto Combustion Process

Abstract For the development of sodium ion secondary batteries, performance improvement in the positive electrode is the main area of research in recent times. Enhancement in electrochemical performance of Na0.44MnO2(NMO) material as a positive electrode material for sodium ion secondary batteries plays a vital role. In this work, the NMO orthorhombic compound was prepared through sol–gel auto combustion process and characterized. Its electrochemical properties are investigated and discussed. The material displays a discharge capacity of about 102.5 mAh/g at a low current rate (C/20), which decreases to 36.75 mAh/g at a relatively higher rate (2C). The capacity retention at C/10 after 50 cycles is 85.7%. The evaluation of Na-ion diffusion coefficients (DNa+) in NMO is accomplished by potentiostatic intermittent titration technique (PITT) test and galvanostatic intermittent titration technique (GITT) test. The obtained values for the Na-ion diffusivity are ranging between 10−14 and 10−15 cm2 s−1.

Sintering temperature, excess sodium, and phosphorous dependencies on morphology and ionic conductivity of NASICON Na3Zr2Si2PO12

The phase pure NASICON Na3Zr2Si2PO12 materials were synthesized through solid-state synthesis method at different temperatures ranging from 1100 to 1280 °C to understand the effect of final sintering temperature on the material properties. The structural and morphological characterizations were carried out using powder X-ray diffraction and scanning electron microscopy. The electrical characterizations were performed using AC impedance spectroscopy. The highest ionic conductivity of 1.13 mS cm−1 at 20 °C was observed for the NASICON sample, which was sintered at 1100 °C for 12 h using 10 wt% excess sodium precursor NaNO3. The density of the samples appeared to be similar irrespective of the final sintering temperatures. The decrease in conductivity with increase in sintering temperature might be due to the loss of volatile components at high temperature. It is shown by our systematic studies that adding excess Na content alone, rather than adding excess Na and P contents to compensate for the volatile loss, is ideal in synthesizing dense NASICON materials, while keeping the sintering temperature at 1100 °C for 12 h via the solid-state synthesis method. A promising electrochemical stability was observed during the galvanostatic stripping-platting experiment for one of the compositions. This class of materials forms the basis for a sodium-ion electrolyte for all-solid-state sodium-ion secondary battery.

Investigation of electrochemical reaction mechanism for antimony selenide nanocomposite for sodium-ion battery electrodes

Antimony selenide and its carbon composite were synthesized through a mechanochemical process and investigated as anode materials for sodium-ion secondary batteries. X-ray diffraction (XRD) with rietveld refinement and transmission electron microscopy (TEM) analyses confirm that Sb2Se3 were composed of agglomerated highly crystalline nanocrystallites and the Sb2Se3/C composite consisted of nanocrystalline Sb2Se3 dispersed homogeneously throughout an amorphized carbon matrix. The initial Coulombic efficiency, rate capability, and cycle performance of the Sb2Se3/C composite were superior to those of Sb, or Sb2Se3. The Sb2Se3/C composite, in particular, showed excellent cycle stability, with 98.2% of initial capacity at 200 mA g−1 after 200 cycles. Based on the reaction potentials, ex situ XRD patterns and ex situ HR-TEM analysis of the Sb2Se3/C composite electrode revealed the structural changes which occurred reversibly within the Sb2Se3/C composite by conversion and recombination reaction during sodiation and desodiation process. Furthermore, XPS analysis study was carried out for identifying the surface films formed on both the electrodes and their effects on the performances.

(Invited) Polymer Simulations Under External Fields

In order to design next generation functional polymers, not only the structure but the dynamics under external field should be understood. In this paper we report our simulation approach to investigate the structure and dynamics. Polymer brush is used for the model system of very low friction such as synovial joints. Recently, polymer brush is focused as a functional binder of sodium ion secondary battery. Since sodium ions are hard to make passive film, or SEI (solid electrolyte interphase) layer on the negative electrode, functional polymer binder help to stabilize the atmosphere around the electrode. We simulate the ionic conductivity of polyelectrolyte binder system under external electric field. The conductivity depend on the polymer structure, such as hardness and linear charge density of the polymer chain. The other important function of polymers are the fluid dynamics effect of polymers under external fluid field. As a model system of VII (viscosity index improver) polymers, we simulate the dynamics under shear filed. The dynamics of polymers are studied for bulk system and the confined system. We made simulation algorithm. The Brownian motion of polymer segments are treated by Langevin Dynamics, and the solvent flow is treated by Lattice Boltzmann Method, in order to obtain both high computational efficiency and precise dynamics. We succeed to reproduce the flow dynamics of polymers under shear. Moreover, the model is extended to include long-range interactions of functional groups. In low dielectric constant medium such as lubricant oils, the functional groups interact as ionic groups in high dielectric constant medium such as waters. The specific results shows that the colloidal science in oils have many problems to be solved.

Electronic states in oxidized NaxCoO2 as revealed by X-ray absorption spectroscopy coupled with ab initio calculation

Layered cobalt oxides are promising cathode materials for sodium ion secondary batteries (SIBs). By combined study of the X-ray absorption spectroscopy (XAS) around the O K-edge and ab initio calculation, we investigated the electronic state of the NaxCoO2 with different oxidization state, i.e, in O3-Na0.91CoO2 (CoO2−0.91) and P2-Na0.66CoO2 (CoO2−0.66). The O K-edge spectra in the pre-edge (529–536 eV) region shows significant change with oxidization of NaxCoO2. In O3-Na0.91CoO2, the spectra shows an intense band (B band) at 531 eV. In P2-Na0.66CoO2, the spectral weight of the B band increases and a new band (A band) appears at 530 eV. These spectral changes are qualitatively reproduced by the calculated partial density of states (pDOSs) of O3-NaCoO2 and P2-Na1/2CoO2. These results indicate that the electrons are partially removed from the O 2p state with oxidization of NaxCoO2.

Thermal Expansion in Layered NaxMO2

Layered oxide NaxMO2 (M: transition metal) is a promising cathode material for sodium-ion secondary battery. Crystal structure of O3- and P2-type NaxMO2 with various M against temperature (T) was systematically investigated by synchrotron x-ray diffraction mainly focusing on the T-dependences of a- and c-axis lattice constants (a and c) and z coordinate (z) of oxygen. Using a hard-sphere model with minimum Madelung energy, we confirmed that c/a and z values in O3-type NaxMO2 were reproduced. We further evaluated the thermal expansion coefficients (αa and αc) along a- and c-axis at 300 K. The anisotropy of the thermal expansion was quantitatively reproduced without adjustable parameters for O3-type NaxMO2. Deviations of z from the model for P2-type NaxMO2 are ascribed to Na vacancies characteristic to the structure.

Thermal power generation during heat cycle near room temperature

We demonstrate that a sodium-ion secondary battery (SIB)-type thermocell consisting of two types of Prussian blue analogue (PBA) with different electrochemical thermoelectric coefficients (SEC ≡ ∂V/∂T; V and T are the redox potential and temperature, respectively) produces electrical energy during heat cycles. The device produces an electrical energy of 2.3 meV/PBA per heat cycle between 295 K (= TL) and 323 K (= TH). The ideal thermal efficiency (η = 1.0%), which is evaluated using the heat capacity (C = 4.16 meV/K) of ideal Na2Co[Fe(CN)6], reaches 11% of the Carnot efficiency (ηth = 8.7%). Our SIB-type thermocell is a promising thermoelectric device that harvests waste heat near room temperature.

Low Voltage Charge/Discharge Behavior of Manganese Hexacyanoferrate

Recently, Prussian blue analogues (PBAs) have been reported to exhibit a low voltage charge/discharge behavior with high capacity (300–545 mAh/g) in lithium-ion secondary batteries (LIBs) [...]

Domain Size of Phase-Separated NaxCoO2 as Investigated by X-Ray Microdiffraction

O3-NaCoO 2 is a promising cathode material for sodium ion secondary batteries (SIBs). Na x CoO 2 shows phase separation (PS) into the O3 and O ′ 3 phases in the Na concentration range of 0.89 ⩽ x ⩽ 0.99. In order to estimate the domain size (r) in the two-phase region, we performed X-ray microdiffraction (XRMD) of thin films of Na x CoO 2 at x = 0.97 and ∼1. We found that r (≈400 nm) of the O ′ 3 domain is comparable to the particle size d (=331 ± 87 nm) in the as-grown O3-NaCoO 2 film. This observation suggests that individual particles of Na x CoO 2 are single phase to minimize the strain at the O3–O ′ 3 phase boundary.

Sn Negative Electrode Consists of Flexible 3D Structures for Sodium Ion Secondary Batteries

Tin(Sn) and its alloys have been attracting attentions as a negative electrode material for lithium-ion and sodium-ion secondary batteries with high theoretical capacity (Li22Sn5, ca. 990 mAh･g−1) and high electromotiveforce. There still remains the issue as regards the discharge capacity decrease with increasing the number of cycles. In order to improve cycle performance, Sn film which has nano-sized or amorphous grain to alleviation volume expansion with using electrodeposition was developed. In addition, 3D-nano flexible structure was used with collector for creating space to alleviate volume expansion.The effect of additives on the surface morphology and microstructure of Sn film was investigated. Furthermore, we evaluated the effect of 3D-nano flexible structure into the Sn film on cycle performance of the Sn negative electrode.

Interrelation between inhomogeneity and cyclability in O3‐NaFe1/2Co1/2O2

O3‐NaFe1/2Co1/2O2 shows initial capacity of 160 mAh/g and an average operating voltage of 3.1 V (vs. Na) with good cyclability, and is a promising candidate of the cathode materials for sodium‐ion secondary batteries (SIBs). Here, we found that the cyclability of the slowly‐cooled sample is much worse than that of quenched one, even though the former sample keeps the O3‐type structure. The energy dispersive X‐ray spectroscopy (EDX) images suggest that the slow‐cooled sample (Nax Fe1–yCoy O2) is inhomogeneous in the Fe concentration (1 – y), perhaps triggered by the Na deficiency (1 – x). We ascribed the poor cyclability in the slowly‐cooled sample to the concentration inhomogeneity (Δy). The Δy is further responsible for the fluctuation of the lattice constants (a and c), as revealed by the Williamson–Hall plot. (© 2016 WILEY‐VCH Verlag GmbH &Co. KGaA, Weinheim)

Sn Negative Electrode Consists of Flexible 3D Structures for Sodium Ion Secondary Batteries

Tin(Sn) and its alloys have been attracting attentions as a negative electrode material for lithium-ion and sodium-ion secondary batteries with high theoretical capacity (Li22Sn5, ca. 990 mAh･g − 1) and high electromotiveforce. There still remains the issue as regards the discharge capacity decrease with increasing the number of cycles. In order to improve cycle performance, there are many studies such as using Sn-Ni alloy, macroporous patterns and enhancing adhesiveness of active materials. However, most of these studies are using Sn based alloy as negative electrode materials and it suffer from the disadvantage of lowering of discharge capacity. In this study, Sn film which has nano-sized or amorphous grain to alleviation volume expansion with using electrodeposition was developed. In addition, 3D-nano flexible structure was used with collector for creating space to alleviate volume expansion. The effect of additives on the surface morphology and microstructure of Sn film was investigated. Furthermore, we evaluated the effect of 3D-nano flexible structure into the Sn film on cycle performance of the Sn negative electrode. The Sn film was formed by electrodeposition using aqueous bath at low temperature. Cu foil with a thickness of 35 μm was used for the substrates We used 5 types of Sn deposition bath. Tin sulfate (SnSO4) and tin chloride (SnCl2) were used as metal resource reagents. Phosphinic acid (H2PO2), boric acid (H3BO3) and potassium sulfate (K2SO4) were used as additives. In addition, conventional Sn deposition bath, which consists of 30 g L− 1 (0.14 M) tin sulfate (SnSO4), 96 g L− 1 sulfuric acid (H2SO4) and 100 ppm polyethylene glycol (PEG, Mw: 4000), was used for comparison. The electrochemical properties of Sn electrodes were investigated using double pole cell (tomcell) consist of Sn circle film (φ16 mm) as working electrode and Na metal film as counter electrode. The electrolyte consist of a solution of 1M NaPF6 in a 1:2 (vol.%) mixture of ethylene carbonate (EC), dimethyl carbonate (DMC) (Kishida). The whole assemble was processed in an argon-filled glove box. The Charge-Discharge test was galvanostatically examined with a current density of 200 μm. Potential range of the Charge-Discharge test was set between 0.01 to 1.0 V (vs. Na/Na+). The cyclic voltammetry (CV) was performed in the potential range of 0.01-1.0 V (vs. Na/Na+) at a scan rate 0.2 mV/s. The surface morphologies of the electrodes were examined by scanning electron microscope (SEM, JEOL JSM-6700F), and phase identification was investigated by X-ray diffraction (Rigaku, Smart Lab). Both amorphous and crystalline structure was observed in the deposited Sn film. In contrast to conventional Sn electrodeposited film, this unique Sn film has a good cycle characteristic (over 50 cycles) and discharge capacity (over 400 mAh･g-1). Furthermore, in the case of using the bath which includes phosphinic acid (H2PO2) in composition discharge capacity after first cycle approached over 700 mAh g-1 and that of after twenties cycle was over 400 mAh g-1. Amorphous structure in the Sn film showed a microscopic effect on the volume change by lithiation and delithiation. Sn particles became smaller and formed amorphous structure by using pulse current. Sn electrode deposited on 3D-nano flexible structure showed good cycle characteristic (over 50 cycles) and discharge capacity (840 mAh/g (the C-rate of 2)). The Charge-Discharge curves indicated Na-Sn alloy process as follows: β-Sn, NaSn5, NaSn, Na9Sn4.