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Electrodeposited Ni-Sn intermetallic alloy electrode for 3D sulfur battery
Available online at www.sciencedirect.com
ScienceDirect Materials Today: Proceedings 4 (2017) 4491–4495
www.materialstoday.com/proceedings
INESS 2016
Electrodeposited Ni-Sn intermetallic alloy electrode for 3D sulfur battery B. Tolegena,b, A. Adia,b, A. Aishovaa,b, Z. Bakenova,b,c,*, A. Nurpeissovab aInstitute of Batteries, Block 13, 53 Kabanbay Batyr Ave., Astana 010000, Kazakhstan Nazarbayev University Research and Innovation System, 53 Kabanbay Batyr Ave., Astana 010000, Kazakhstan cSchool of Engineering, Nazarbayev University, 53 Kabanbay Batyr Ave., Astana 010000, Kazakhstan
b
Abstract 3D architecture appeared to be a promising design to enhance the performance of the Lithium-ion batteries by shortening the lithium ion diffusion path and increasing the energy density per unit area. In this paper, we report preliminary results of facile electrodeposition of intermetallic tin-nickel alloy from electrolyte solution onto 3D structured nickel foam for 3D lithium-sulfur battery. The coated films were characterized for their morphologies, structural and electrochemical properties. Scanning electron microscope images revealed thin and homogenous film while XRD revealed the expected phase of intermetallic alloy Ni3Sn4. The electrochemical activity of the film showed to be a promising start to be used as an anode material and needs further works to be optimized. © 2017 Elsevier Ltd. All rights reserved. Selection and Peer-review under responsibility of 4th International Conference on Nanomaterials and Advanced Energy Storage Systems (INESS 2016). Keywords: 3D structured electrode; 3D nickel foam; tin-nickel alloy; electrodeposition
1. Introduction The development of renewable energy and ecological transport demands high energy density rechargeable batteries. The major concern restricting a wider application of renewable energy is the energy storage systems.
* Corresponding author. Tel.: +7-717-270-6530 E-mail address: [email protected] 2214-7853 © 2017 Elsevier Ltd. All rights reserved. Selection and Peer-review under responsibility of 4th International Conference on Nanomaterials and Advanced Energy Storage Systems (INESS 2016).
4492
B. Tolegen et al./ Materials Today: Proceedings 4 (2017) 4491–4495
Conventional battery technologies suffer from high cost, toxicity and performance limitations such as low capacity and capacity fading. Therefore, development of novel economically feasible high performance batteries is crucial for popularization and expanded application of sustainable energy and electric vehicles. Recently, 3D architecture appeared to be a promising design to overcome the stated disadvantages of the lithium-ion batteries by shortening the lithium ion diffusion path and increasing the energy density per unit area. Mosby and Prieto have already demonstrated an innovative concept of economically feasible three-dimensional (3D) battery manufacturing concept which combines the power density and energy density in a single device [1]. In our laboratory we are developing an innovative 3D all solid-state battery with high energy efficiency and stable cycling by combining the high alloying and de-alloying capacity of tin (730 mAhg-1) [2,3] and the highest energy density of sulfur [4]. This system is promising as a potential electric vehicle battery and the energy storage system for renewable energy sources. In this paper we report on the preliminary results of preparation of 3D structured anode for 3D lithium-sulfur battery. Coating of tin-nickel alloy onto 3D nickel foam was done by electrical deposition as electrochemical deposition from aqueous solutions is one of the simplest and most controllable methods of preparation of coatings on the basis of tin-nickel alloys. Nickel was used as a non-electrochemically active matrix to enhance the poor cycle ability of the tin. In the future 3D anode architecture will be combined with the Li/S battery technology, where sulfur is converted into soluble catholite during charging/discharging and can be impregnated into the 3D architecture more easily than conventional cathode materials.
2. Experimental part All reagents were purchased from Sigma-Aldrich and used as received. Nickel foam was provided by Goodfellow. Three-dimensional (3D) Ni3Sn4 anode was prepared by galvanostatic electrodeposition onto 3D current collector, namely Ni foam with the 1.6 mm thickness and with ≥95% porosity (80-110 Pores per Inch. An average hole diameter is about 0.25mm). Ni3Sn4 films were electrodeposited from an aqueous electrolyte solution consisting of 0.15 molL-1 SnCl2·2H2O, 0.1 molL-1 NiCl2·6H2O, 0.5 molL-1 K4P2O7·3H2O, and 0.125 molL-1 glycine in 2/98 vol. % ethanol/water with 0.1 gL-1 sodium dodecyl sulfate (SDS) used as wetting agent. The pH of the electrolyte was subsequently kept at around 6 using 5 molL-1 NH4OH [5,6]. The film was cathodically electroplated at room temperature with the current density of 28 mAсm-2 for 50 min using potentiostat/galvanostat KP07 (Bank Elektronik, Germany) and a timer QUANTUM2520. A 0.1-mm-thick Ni backing-plate was attached to nickel foam beforehand by using nickel paint adhesive [PELCO® high performance nickel paste (silicate)]. Nickel foam served as a working electrode and platinum (Pt) foil was used as a counter electrode in a two-electrode glass cell. Prior to electrodeposition, the substrate nickel faom was washed with ethanol, with water, and then soaked into a wetting agent solution (2 gL-1 sodium dodecyl sulfate (SDS) in water). The surface and morphology of the electrodeposited foams were assessed by scanning electron microscopy (SEM, JSM-7500F JEOL). The phase of the electroplated sample was identified with X-ray diffraction technique (XRD, Rigaku SmartLab, Japan). The electrochemical activities of the samples were tested in lithium half-cell, CR2032 coin type, which were assembled by sandwiching a Ni3Sn4 electroplated on 3D nickel foam (which acted as current collector), Celgard 2400-0535M-A separator and lithium metal foil as a reference electrode, all soaked in 1M LiPF6 solution in an ethylene carbonate/dimethyl carbonate/ethyl methyl carbonate (EC:DMC:EMC) electrolyte. The electrochemical response of these cells was monitored by a battery tester (Arbin Instruments BT-2000) when cycled between 0.05 V and 1.5 V (vs. Li+/Li) at 0.025 C, 0.05 C rates.
B. Tolegen et al./ Materials Today: Proceedings 4 (2017) 4491–4495
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3. Results and discussion Fig. 1 illustrates the digital pictures and SEM images of pristine 3D nickel foam and 3D nickel foam after electrodeposition process. Comparing Fig. 1a and 1b one can see that the electrodeposition process took place and some changes occurred on the surface of nickel foam. The smooth surface of nickel foam was coated with the thin homogenous film of intermetallic alloy. SEM images also revealed that desirable 3D structure was maintained without blockage of pores present in the structure of 3D nickel foam. These empty spaces will help to accommodate volume expansion during lithium insertion and deinsertion processes and will be utilized in the further works to coat gel electrolyte and the cathode.
Fig. 1. Digital pictures and SEM images of (a,c,e) pristine 3D nickel foam and (b,d,f) electroplated 3D nickel foam.
Fig. 2 illustrates the XRD patterns of the pristine and electroplated 3D nickel foams. The peaks on nickel of foam correspond to (111), (200), (220), (311) and (222) crystallographic planes of transition metal nickel from a smaller angle (JCPDS no. 04-0850). The diffraction pattern of electrolplated nickel foam exhibits obvious signals at 30.6о (102), 44.8о (110), 55.13о (201), 60.11о (103), and 76.58о (211), which are characteristic for tin-nickel alloy with an Ni3Sn4 composition phase (JCPDS no. 04-0845). The high intensity peaks located at 44.8о, 55.13о and 76.58о are the signals of nickel foam substrate which correspond to the (111), (200), (220) crystallographic reflections, respectively. A relatively large diffuse peak is observed at small deflection angles. It gives evidence that an amorphous or incompletely formed crystalline phase is present in the coated intermetallic alloy.
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B. Tolegen et al./ Materials Today: Proceedings 4 (2017) 4491–4495
Fig. 2. XRD patterns of pristine 3D nickel foam (left) and after electrodepostion (right).
Fig. 3 shows the voltage profiles for the 1st, 2nd, and 3rd cycles of half-cells constructed with 3D anode. Large irreversible capacity loss in the first discharge may be the result of the reduction of possible oxide impurities produced during electrodeposition and the formation of SEI on the electrode surface, since the large specific area of the 3D nickel foam can consume much capacity for SEI [7,8]. After the first discharge, the profile of both charge and discharge showed sloping characteristic due to the active/inactive structure of Ni3Sn4 intermetallic as reported before [9]. Increasing the current results in capacity loss in the second cycle reaching up to 150 mAhg-1 capacity with the Sn mass-loading of 15 mgcm-2, thereby delivering an areal capacity of 2.25 mAh cm-2. At the third cycle capacity detereioration occurred with the same tendency delivering less than 100 mAhg-1.
Fig. 3. Voltage profiles for the 1st, 2nd, and 3rd cycles of half-cells with Ni3Sn4 electrodeposited onto 3D nickel foam at different current rates (1st cycle, 0.025 C; 2nd to 3rd cycle, 0.05 C).
These are the typical results, which confirm the possibility of electrodeposititon onto 3D nickel foam. Although alloy was deposited successfully, its performance is not yet fully satisfactory. Therefore, our current works are focused on the optimization of the electrodeposition conditions to achieve a full potential capacity of Sn active material.
B. Tolegen et al./ Materials Today: Proceedings 4 (2017) 4491–4495
4495
4. Conclusion We have successfully electrodeposited intermetallic tin-nickel alloy onto 3D structured nickel foam which served as a current collector and the structure support. The distinct advantage of the electrodeposition was in the direct contact of the alloy material with the conducting substrate without any other additives. The SEM images revealed a thin and homogenous alloy coating while XRD indicated that the deposited alloy was Ni3Sn4 intermetallic phase. In this electrode configuration, 3D nickel foam functioned as a structure support, electron transport paths and interfacial anchors. Electrochemical tests showed a possibility of intercalation/deintercalation of lithium. To further improve the electrochemical activity of the anode, the electrodeposition conditions as time and current density will be optimized in the near future. Also an upgraded 3D anode will be coated with the gel electrolyte and sulfur cathode to be used in all solid 3D lithium-sulfur batteries. Acknowledgements Our group would like to acknowledge the funding by the research grant №317-2016 “Development of economically feasible three-dimensional lithium/sulfur battery” from the Ministry of Education and Science of the Republic of Kazakhstan. References [1] J. Mosby, L. Prieto, J. Am. Chem. Soc., 130 (2008) 10656-10661. [2] M.Wachtler, M.Winter, J.O. Besenhard, J. Power Sources, 105 (2002) 151-160. [3] I.A. Courtney, J.R. Dahn, J. Electrochem. Soc., 144 (1997) 2045-2052. [4] Y. Zhang, Y. Zhao, Z. Bakenov, Nanoscale Res. Lett., 9 (2014) 137. [5] J. Hassoun, S. Panero, B. Scrosati, J. Power Sources, 160 (2006) 1336-1341. [6] Z.Du, S. Zhang, J. Zhao, T. Jiang, Z. Bai, Int. J. Electrochem. Sci., 7 (2012) 1180-1186. [7] N. Tamura, Y. Kato, A. Mikami, M. Kamino, S. Matsuta, and S. Fujitani, J. Electrochem. Soc., 153 (2006) A2227-A1231. [8] A. D. W Todd, R. E. Mar, and J. R. Dahn, J. Electrochem. Soc., 153 (2006) A1998-A2005. [9] Z. Du, S. Zhang, Y. Xing, and X. Wu, J. Power Sources, 196 (2011) 9780-9785
ScienceDirect Materials Today: Proceedings 4 (2017) 4491–4495
www.materialstoday.com/proceedings
INESS 2016
Electrodeposited Ni-Sn intermetallic alloy electrode for 3D sulfur battery B. Tolegena,b, A. Adia,b, A. Aishovaa,b, Z. Bakenova,b,c,*, A. Nurpeissovab aInstitute of Batteries, Block 13, 53 Kabanbay Batyr Ave., Astana 010000, Kazakhstan Nazarbayev University Research and Innovation System, 53 Kabanbay Batyr Ave., Astana 010000, Kazakhstan cSchool of Engineering, Nazarbayev University, 53 Kabanbay Batyr Ave., Astana 010000, Kazakhstan
b
Abstract 3D architecture appeared to be a promising design to enhance the performance of the Lithium-ion batteries by shortening the lithium ion diffusion path and increasing the energy density per unit area. In this paper, we report preliminary results of facile electrodeposition of intermetallic tin-nickel alloy from electrolyte solution onto 3D structured nickel foam for 3D lithium-sulfur battery. The coated films were characterized for their morphologies, structural and electrochemical properties. Scanning electron microscope images revealed thin and homogenous film while XRD revealed the expected phase of intermetallic alloy Ni3Sn4. The electrochemical activity of the film showed to be a promising start to be used as an anode material and needs further works to be optimized. © 2017 Elsevier Ltd. All rights reserved. Selection and Peer-review under responsibility of 4th International Conference on Nanomaterials and Advanced Energy Storage Systems (INESS 2016). Keywords: 3D structured electrode; 3D nickel foam; tin-nickel alloy; electrodeposition
1. Introduction The development of renewable energy and ecological transport demands high energy density rechargeable batteries. The major concern restricting a wider application of renewable energy is the energy storage systems.
* Corresponding author. Tel.: +7-717-270-6530 E-mail address: [email protected] 2214-7853 © 2017 Elsevier Ltd. All rights reserved. Selection and Peer-review under responsibility of 4th International Conference on Nanomaterials and Advanced Energy Storage Systems (INESS 2016).
4492
B. Tolegen et al./ Materials Today: Proceedings 4 (2017) 4491–4495
Conventional battery technologies suffer from high cost, toxicity and performance limitations such as low capacity and capacity fading. Therefore, development of novel economically feasible high performance batteries is crucial for popularization and expanded application of sustainable energy and electric vehicles. Recently, 3D architecture appeared to be a promising design to overcome the stated disadvantages of the lithium-ion batteries by shortening the lithium ion diffusion path and increasing the energy density per unit area. Mosby and Prieto have already demonstrated an innovative concept of economically feasible three-dimensional (3D) battery manufacturing concept which combines the power density and energy density in a single device [1]. In our laboratory we are developing an innovative 3D all solid-state battery with high energy efficiency and stable cycling by combining the high alloying and de-alloying capacity of tin (730 mAhg-1) [2,3] and the highest energy density of sulfur [4]. This system is promising as a potential electric vehicle battery and the energy storage system for renewable energy sources. In this paper we report on the preliminary results of preparation of 3D structured anode for 3D lithium-sulfur battery. Coating of tin-nickel alloy onto 3D nickel foam was done by electrical deposition as electrochemical deposition from aqueous solutions is one of the simplest and most controllable methods of preparation of coatings on the basis of tin-nickel alloys. Nickel was used as a non-electrochemically active matrix to enhance the poor cycle ability of the tin. In the future 3D anode architecture will be combined with the Li/S battery technology, where sulfur is converted into soluble catholite during charging/discharging and can be impregnated into the 3D architecture more easily than conventional cathode materials.
2. Experimental part All reagents were purchased from Sigma-Aldrich and used as received. Nickel foam was provided by Goodfellow. Three-dimensional (3D) Ni3Sn4 anode was prepared by galvanostatic electrodeposition onto 3D current collector, namely Ni foam with the 1.6 mm thickness and with ≥95% porosity (80-110 Pores per Inch. An average hole diameter is about 0.25mm). Ni3Sn4 films were electrodeposited from an aqueous electrolyte solution consisting of 0.15 molL-1 SnCl2·2H2O, 0.1 molL-1 NiCl2·6H2O, 0.5 molL-1 K4P2O7·3H2O, and 0.125 molL-1 glycine in 2/98 vol. % ethanol/water with 0.1 gL-1 sodium dodecyl sulfate (SDS) used as wetting agent. The pH of the electrolyte was subsequently kept at around 6 using 5 molL-1 NH4OH [5,6]. The film was cathodically electroplated at room temperature with the current density of 28 mAсm-2 for 50 min using potentiostat/galvanostat KP07 (Bank Elektronik, Germany) and a timer QUANTUM2520. A 0.1-mm-thick Ni backing-plate was attached to nickel foam beforehand by using nickel paint adhesive [PELCO® high performance nickel paste (silicate)]. Nickel foam served as a working electrode and platinum (Pt) foil was used as a counter electrode in a two-electrode glass cell. Prior to electrodeposition, the substrate nickel faom was washed with ethanol, with water, and then soaked into a wetting agent solution (2 gL-1 sodium dodecyl sulfate (SDS) in water). The surface and morphology of the electrodeposited foams were assessed by scanning electron microscopy (SEM, JSM-7500F JEOL). The phase of the electroplated sample was identified with X-ray diffraction technique (XRD, Rigaku SmartLab, Japan). The electrochemical activities of the samples were tested in lithium half-cell, CR2032 coin type, which were assembled by sandwiching a Ni3Sn4 electroplated on 3D nickel foam (which acted as current collector), Celgard 2400-0535M-A separator and lithium metal foil as a reference electrode, all soaked in 1M LiPF6 solution in an ethylene carbonate/dimethyl carbonate/ethyl methyl carbonate (EC:DMC:EMC) electrolyte. The electrochemical response of these cells was monitored by a battery tester (Arbin Instruments BT-2000) when cycled between 0.05 V and 1.5 V (vs. Li+/Li) at 0.025 C, 0.05 C rates.
B. Tolegen et al./ Materials Today: Proceedings 4 (2017) 4491–4495
4493
3. Results and discussion Fig. 1 illustrates the digital pictures and SEM images of pristine 3D nickel foam and 3D nickel foam after electrodeposition process. Comparing Fig. 1a and 1b one can see that the electrodeposition process took place and some changes occurred on the surface of nickel foam. The smooth surface of nickel foam was coated with the thin homogenous film of intermetallic alloy. SEM images also revealed that desirable 3D structure was maintained without blockage of pores present in the structure of 3D nickel foam. These empty spaces will help to accommodate volume expansion during lithium insertion and deinsertion processes and will be utilized in the further works to coat gel electrolyte and the cathode.
Fig. 1. Digital pictures and SEM images of (a,c,e) pristine 3D nickel foam and (b,d,f) electroplated 3D nickel foam.
Fig. 2 illustrates the XRD patterns of the pristine and electroplated 3D nickel foams. The peaks on nickel of foam correspond to (111), (200), (220), (311) and (222) crystallographic planes of transition metal nickel from a smaller angle (JCPDS no. 04-0850). The diffraction pattern of electrolplated nickel foam exhibits obvious signals at 30.6о (102), 44.8о (110), 55.13о (201), 60.11о (103), and 76.58о (211), which are characteristic for tin-nickel alloy with an Ni3Sn4 composition phase (JCPDS no. 04-0845). The high intensity peaks located at 44.8о, 55.13о and 76.58о are the signals of nickel foam substrate which correspond to the (111), (200), (220) crystallographic reflections, respectively. A relatively large diffuse peak is observed at small deflection angles. It gives evidence that an amorphous or incompletely formed crystalline phase is present in the coated intermetallic alloy.
4494
B. Tolegen et al./ Materials Today: Proceedings 4 (2017) 4491–4495
Fig. 2. XRD patterns of pristine 3D nickel foam (left) and after electrodepostion (right).
Fig. 3 shows the voltage profiles for the 1st, 2nd, and 3rd cycles of half-cells constructed with 3D anode. Large irreversible capacity loss in the first discharge may be the result of the reduction of possible oxide impurities produced during electrodeposition and the formation of SEI on the electrode surface, since the large specific area of the 3D nickel foam can consume much capacity for SEI [7,8]. After the first discharge, the profile of both charge and discharge showed sloping characteristic due to the active/inactive structure of Ni3Sn4 intermetallic as reported before [9]. Increasing the current results in capacity loss in the second cycle reaching up to 150 mAhg-1 capacity with the Sn mass-loading of 15 mgcm-2, thereby delivering an areal capacity of 2.25 mAh cm-2. At the third cycle capacity detereioration occurred with the same tendency delivering less than 100 mAhg-1.
Fig. 3. Voltage profiles for the 1st, 2nd, and 3rd cycles of half-cells with Ni3Sn4 electrodeposited onto 3D nickel foam at different current rates (1st cycle, 0.025 C; 2nd to 3rd cycle, 0.05 C).
These are the typical results, which confirm the possibility of electrodeposititon onto 3D nickel foam. Although alloy was deposited successfully, its performance is not yet fully satisfactory. Therefore, our current works are focused on the optimization of the electrodeposition conditions to achieve a full potential capacity of Sn active material.
B. Tolegen et al./ Materials Today: Proceedings 4 (2017) 4491–4495
4495
4. Conclusion We have successfully electrodeposited intermetallic tin-nickel alloy onto 3D structured nickel foam which served as a current collector and the structure support. The distinct advantage of the electrodeposition was in the direct contact of the alloy material with the conducting substrate without any other additives. The SEM images revealed a thin and homogenous alloy coating while XRD indicated that the deposited alloy was Ni3Sn4 intermetallic phase. In this electrode configuration, 3D nickel foam functioned as a structure support, electron transport paths and interfacial anchors. Electrochemical tests showed a possibility of intercalation/deintercalation of lithium. To further improve the electrochemical activity of the anode, the electrodeposition conditions as time and current density will be optimized in the near future. Also an upgraded 3D anode will be coated with the gel electrolyte and sulfur cathode to be used in all solid 3D lithium-sulfur batteries. Acknowledgements Our group would like to acknowledge the funding by the research grant №317-2016 “Development of economically feasible three-dimensional lithium/sulfur battery” from the Ministry of Education and Science of the Republic of Kazakhstan. References [1] J. Mosby, L. Prieto, J. Am. Chem. Soc., 130 (2008) 10656-10661. [2] M.Wachtler, M.Winter, J.O. Besenhard, J. Power Sources, 105 (2002) 151-160. [3] I.A. Courtney, J.R. Dahn, J. Electrochem. Soc., 144 (1997) 2045-2052. [4] Y. Zhang, Y. Zhao, Z. Bakenov, Nanoscale Res. Lett., 9 (2014) 137. [5] J. Hassoun, S. Panero, B. Scrosati, J. Power Sources, 160 (2006) 1336-1341. [6] Z.Du, S. Zhang, J. Zhao, T. Jiang, Z. Bai, Int. J. Electrochem. Sci., 7 (2012) 1180-1186. [7] N. Tamura, Y. Kato, A. Mikami, M. Kamino, S. Matsuta, and S. Fujitani, J. Electrochem. Soc., 153 (2006) A2227-A1231. [8] A. D. W Todd, R. E. Mar, and J. R. Dahn, J. Electrochem. Soc., 153 (2006) A1998-A2005. [9] Z. Du, S. Zhang, Y. Xing, and X. Wu, J. Power Sources, 196 (2011) 9780-9785