Symposium Organizers
Veronica Augustyn, North Carolina State University
Doron Aurbach, Bar-Ilan University
Y. Shirley Meng, University of California, San Diego
Naoaki Yabuuchi, Tokyo Denki University
Symposium Support
Bio-Logic USA
M. Braun Inc.
Pine Research Instrumentation
WITec Instruments Corp
ES3.1: High-Capacity Li Intercalation
Session Chairs
Valerie Pralong
M Stanley Whittingham
Tuesday PM, April 18, 2017
PCC North, 200 Level, Room 226 A
2:30 PM - *ES3.1.01
Multi-Electron Cathodes—Two Li vs One Mg Intercalation Using Ti and V Model Compounds
M Stanley Whittingham 1
1 , Binghamton University, Binghamton, New York, United States
Show AbstractThere is an increasing demand for higher and higher energy density batteries for portable applications. One way of achieving higher energy densities is to react more than one electron per redox center. We have chosen as a more pragmatic approach to study the intercalation of two lithium ions rather than a multi-valent ion such as magnesium. Our results on model compounds, such as VOPO4 and TiS2/VSe2 will be compared with comparable studies using a magnesium anode. This work is being funded by the US DOE through the NECCES EFRC.
3:00 PM - ES3.1.02
Comparative Ab Initio Study of Li, Na, Mg and Al Insertion in Vanadium Pentoxides and Dioxides
Vadym Kulish 1 , Sergei Manzhos 1
1 , National University of Singapore, Singapore Singapore
Show AbstractVanadium oxides (VOx) are among the most promising electrode materials since they are able to operate in most major types of batteries (Li, Na, Mg and Al-ion). The practical development of VOx electrodes, however, is complicated by the presence of multiple VOx stoichiometries and phases with distinctly different lattice stabilities, electron transport properties and, hence, metal-ion insertion thermodynamics and kinetics. We present a systematic comparative ab initio study of four most stable VOx phases (α-V2O5, β-V2O5, VO2(R) and VO2(B)) and their interaction mechanism with Li, Na, Mg, and Al atoms. Our results show that among the studied phases, VO2 (R) exhibits the largest Al binding energy and a low Al diffusion barrier, which makes it quite promising for Al-ion batteries. At the same time, the β-V2O5 phase exhibits the highest binding energy for Mg insertion and significant reduction of the Mg diffusion barrier compared to conventionally used α-V2O5. Our results highlight the benefits of rational phase engineering and may assist further experimental studies of high performance VOx electrodes for Na, Mg, and Al-ion batteries.
3:15 PM - *ES3.1.03
Design of Materials with Original Structures, Ionic Conducting Properties Materials for Energy Storage
Valerie Pralong 1 , Melanie Freire 1 , Evan Adamczyk 1 , Emmanuel Anger 1 , Antoine Maignan 1 , Oleg Lebedev 1
1 , CNRS CRISMAT, Caen France
Show AbstractRegarding the field of energy storage, the design of new materials that are showing high ionic mobility together with being economic and environmental benign is crucial. Our research is focused on the synthesis by soft chemistry of new frameworks with large tunnels or layered structures in order to favor ionic mobility. We will discuss on our strategies to generate such original frameworks (1). The first approach is based on topotactic reactions starting from existing phases with a compact anionic framework. In this case, we will show that the lithium/sodium insertion leads to rock salt type structure (Li2VO3, Ti2Nb2O9, Li5W2O7, Li4Mn2O5,…). The second approach is related to polyanionic frameworks. In order to favor reactivity, we are using protonic materials, either as precursors or as matrix for intercalation, containing transition elements with adequate redox potential (Fe, Mn, V, Ti). These materials are obtained by precipitation or condensation. Then, structure-properties relationships are studied and the possibility to use these materials as electrode materials for power generation systems is evaluated in Li/Na ions batteries. We will discuss our recent results on iron, manganese and vanadium based materials (LixFeOHSO4, Li2Mn(SO4)2…).
3:45 PM - ES3.1.04
Structure and Electrochemistry of Transition Metal Substituted ε-VOPO4
Carrie Siu 1 , Fredrick Omenya 1 , Natalya Chernova 1 , M Stanley Whittingham 1 , Linda Wangoh 1 , Louis Piper 1 , Yuh-Chieh Lin 2 , Shyue Ping Ong 2
1 NECCES, Binghamton University, Binghamton, New York, United States, 2 NECCES, University of California San Diego, La Jolla, California, United States
Show AbstractTo increase the energy density of current commercialized lithium-ion batteries, the challenge of maintaining structural reversibility of multiple electron transfer cathodes for the intercalation process must be resolved. ε-VOPO4 is a promising cathode material with two redox transitions of V3+/V4+ and V4+/V5+. However, the reversibility is compromised with only ~1.2 lithium inserted. The goal of this work is to investigate whether transition metal substitution can enhance the electrochemical performance of ε-VOPO4. We have substituted ε-VOPO4 with different molar percentages of transition metals into the vanadium positions in attempt to improve the capacity. We have focused on transition metals that are predicted by first-principle calculations to display multiple redox potentials in useful voltage windows and to form relatively stable substituted ε-VOPO4 phases. By combing the analysis of X-ray diffraction, and inductively coupled plasma mass spectrometry (ICP-MS), we have determined the limits of transition metal substitution in the structure. X-ray absorption spectroscopy (XAS) and X-ray photoelectron spectroscopy (XPS) were also used to investigate the oxidation states of the transition metals and the mechanism of charge compensation. The effects of the substitution on the electrochemical performance will also be discussed. This research is supported as part of the NorthEast Center for Chemical Energy Storage (NECCES), an Energy Frontier Research Center funded by the U.S. Department of Energy, Office of Science, Office of Basic Energy Sciences under Award Number DE-SC0012583. CS gratefully acknowledges the financial support from Graduate Assistance in Areas of National Need (GAANN) Fellowship and Binghamton University Provost's Doctoral Summer Fellowship.
ES3.2: High-Capacity Intercalation
Session Chairs
Ismael Saadoune
Naoaki Yabuuchi
Tuesday PM, April 18, 2017
PCC North, 200 Level, Room 226 A
4:30 PM - *ES3.2.01
Na2/3Co1-xMn2x/3Nix/3O2 (x=0, 2/3, 1/2, 1/3, 1) Layered Oxides as Good Cathode Materials for Sodium-Ion Batteries
Siham Doubaji 1 , Kristina Edstrom 2 , Khalil Amine 3 , Tianpin Wu 4 , Jun Lu 3 , Jones Alami 5 , Saadoune Ismael 1
1 LCME, FST Marrakesh, Université Cadi Ayyad, Marrakech Morocco, 2 Department of Chemistry-Angstrom Laboratory, Uppsala University, Uppsala Sweden, 3 Chemical Sciences and Engineering Division, Argonne National Laboratory, Lemont, Illinois, United States, 4 X-Ray Science Division, Argonne National Laboratory, Lemont, Illinois, United States, 5 Materials Science and Nano-Engineering Department, Mohammed VI Polytechnic University, Ben Guerir Morocco
Show AbstractSodium-ion batteries are actually regarded as a promising energy storage technology leading the electrochemical energy storage community to search for suitable high performance sodium-ion insertion electrode materials. A number of potential candidates have been presented as cathode materials. 2D-layered transition metal materials NaxMO2 with M=Co, Fe, Ni, Mn, Ti… are among these cathode materials where the combination of different transition metals in the same sample helped improving the electrochemical properties.
Here we present the solid solution (1-x) Na2/3CoO2 – (x) Na2/3Mn2/3Ni1/3O2 synthesized by a simple sol-gel method with x=0, 1/3, 1/2, 2/3, 1. The synthesis conditions were optimized in order to obtain pure P2-type phase (P63/mmc space group) for all the compositions. The effect of changing the composition on the oxidation state of transition metals in the samples was examined using XAS measurements.
Na2/3Co1-xMn2x/3Nix/3O2 materials were cycled in Na half cells between 2.0 and 4.2V vs. Na+/Na and delivered specific discharge capacities ranging from 132 to 90 mAhg-1, depending on ‘x’. High capacity retention were obtained (50 cycles) ranging between 92% and 97%, for all the compositions. After 100 cycles, the capacity retention of both samples Na2/3CoO2, Na2/3Co2/3Mn2/9Ni1/9O2 were still good (84% and 87% respectively) but exceptionally high values were recorded for Na2/3Co1/2Mn1/3Ni1/6O2, Na2/3Co1/3Mn4/9Ni2/9O2, (more than 97%).
The structural stability of the P2-type materials was checked using operando/in-situ measurements for Na2/3Co2/3Mn2/9Ni1/9O2 cycled between 2.0 and 4.5V vs Na+/Na. In order to follow the chemical composition of the electrode/electrolyte interface and its behavior during cycling, and determine the oxidation states of the transition metals and their evolution, both in-house XPS (hν= 1486eV) and HAXPES (hν = 4000eV) measurements were performed for the pristine material Na2/3Co2/3Mn2/9Ni1/9O2. The evolution of the interface was followed by HAXPES (performed at Helmholtz Zentrum Berlin) measurements at different steps of the charge and discharge of the material.
ACKNOWLEGEMENTS
This work was done under the R&D Phosphates Project (LiNa). The authors are grateful to OCP S.A. for the financial support.
5:00 PM - ES3.2.02
Room-Temperature Na–CuCl2 Rechargeable Battery Using SO2-Based Non-Flammable Inorganic Liquid Electrolyte
Ayoung Kim 1 , Goojin Jeong 2 , Young-Jun Kim 3 , Hansu Kim 1
1 , Hanyang University, Seoul Korea (the Republic of), 2 , Korea Electronics Technology Institute, Seongnam Korea (the Republic of), 3 , Sungkyunkwan University, Suwon Korea (the Republic of)
Show AbstractNa rechargeable batteries have gained much attention as alternative power sources to replace Li rechargeable batteries. However, Na rechargeable batteries need to be further advanced to successfully penetrate rechargeable battery market because of their low energy density and poor reliability. Here, we demonstrate a new type of room temperature Na rechargeable battery that employs CuCl2/C nanocomposite cathode material and SO2-based inorganic liquid electrolyte. The cell delivered a high discharge capacity of 200 mAh g−1, corresponding to a theoretical energy density of 580 Wh kg−1. It also showed a high round-trip energy efficiency (>96%) and remarkable cycle-life over 1000 cycles, which has never been obtained in an organic electrolyte system. These excellent electrochemical performances are mainly attributed to the use of the SO2-based electrolyte, which guarantees a reversible conversion reaction between CuCl2 and CuCl with NaCl. The detailed reaction mechanism of this new battery system will be also discussed in this presentation.
5:15 PM - ES3.2.03
Bimetallic Dodecaborate LiNaB12H12 and Its Application in All-Solid-State Batteries
Liqing He 1 , Hai-Wen Li 2 3 , Hironori Nakajima 4 , Yaroslav Filinchuk 5 , Hans Hagemann 6 , Etsuo Akiba 2 3 4 , Zhouguang Lu 1
1 Department of Materials Science & Engineering, South University of Science and Technology of China, Shenzhen, Guangdong, China, 2 International Research Center for Hydrogen Energy, Kyushu University, Fukuoka Japan, 3 WPI International Institute for Carbon-Neutral Energy Research (WPI-I2CNER), Kyushu University, Fukuoka Japan, 4 Department of Mechanical Engineering, Kyushu University, Fukuoka Japan, 5 Institute of Condensed Matter and Nanosciences, Universite catholique de Louvain, Louvain Belgium, 6 Département de Chimie Physique, Universite de Genève, Geneva Switzerland
Show AbstractMetal dodecaborate M2/n(B12H12) is well-known as unexpected stable dehydrogenation intermediate of metal borohydride M(BH4)n possessing high hydrogen storage density [1-3]. Nevertheless, the high stability of M2/n(B12H12) may be beneficial to its application as electrolytes in all-solid-state batteries due to the super ionic conductivity discovered in M2/n(B12H12) [4,5]. Though its stability, the ionic conductivity of M2/n(B12H12) at room temperature is much lower than that of liquid organic electrolyte which hampers the practical application of M2/n(B12H12) in batteries. With the anticipation to improve the ionic conductivity of M2/n(B12H12) and develop new solid electrolyte compatible with both Li and Na-ion batteries, we firstly design a new compound LiNaB12H12. LiNaB12H12 is successfully synthesized by heat treatment of LiBH4+NaBH4+B10H14 (1:1:1 in mole rate) in stainless steel crucibles using the previously reported method [6]. It exhibits excellent thermal stability below 573K and a reversible order-disorder phase transition at around 488K. The ionic conductivity of LiNaB12H12 reaches 0.79 S/cm at 550 K above its phase transition which is approximately 8 and 11 times higher than those for the monometallic systems such as Na2B12H12 and Li2B12H12 [7]. The all-solid-state Li and Na-ion battery measurements using LiNaB12H12 as solid electrolyte are under way.
Acknowledgements:
This work was partly supported by Grants-in-Aid for Scientific Research No. 25709067, JSPS Invitation Fellowship for Research in Japan (Short-Term), the International Institute for Carbon Neutral Energy Research (WPI-I2CNER), sponsored by the Japanese Ministry of Education, Culture, Sports, Science and Technology of Japan, Fonds Speciaux de Recherche and FNRS as well as SNBL (ESRF) for the beamtime, and the Swiss National Science Foundation. This work was also partly supported by the National Natural Science Foundation of China (No. 21671096 and 21603094) and the Postdoctoral Research Fellowship of SUSTC.
References:
[1] Li H W, Miwa K, Ohba N, et al. Nanotechnology, 2009, 20(20): 204013.
[2] Liu Y, Giri S, Zhou J, et al. The Journal of Physical Chemistry C, 2014, 118(49): 28456-28461.
[3] Hansen B R S, Paskevicius M, Li H W, et al. Coordination Chemistry Reviews, 2015.
[4] Udovic T J, Matsuo M, Unemoto A, et al. Chemical Communications, 2014, 50(28): 3750-3752.
[5] Teprovich J A, Colón-Mercado H, Washington II A L, et al. Journal of Materials Chemistry A, 2015, 3(45): 22853-22859.
[6] He L, Li H W, Hwang S J, et al. The Journal of Physical Chemistry C, 2014, 118(12): 6084-6089.
[7] He L, Li H W, Nakajima H, et al. Chemistry of Materials, 2015, 27(16): 5483-5486.
5:30 PM - ES3.2.04
DFT Study on the Li Mobility in Li-Ion-Based Solid-State Electrolytes
Md Shafiqul Islam 1 , Paul Simanjuntak 1 , Saibal Mitra 1 , Ridwan Sakidja 1
1 , Missouri State University, Springfield, Missouri, United States
Show AbstractSolid state electrolytes has generated a lot of excitement as the next generation electrolytic material for Li-ion batteries because of their superior thermal stability and safety as compared with liquid counterparts. However, our understanding of the basic diffusion mechanism of Li-ions in such electrolyte is limited. In this study, we have investigated the diffusion mechanisms of Li-ion in the model systems for Li-ion compounds like lithium phosphite (LiPO3) and lithium phosphate (Li3PO4) and x Li2SO4 – (1-x) (Li2O-P2O5) amorphous electrolytes. For this purpose, we have performed Density Functional Theory (DFT) calculations on the various diffusion pathways that are available from different possible vacancy sites in the two crystal structures at 0K and ab inito molecular dynamic temperatures. We calculate the activation energy barrier for the various diffusion modes by employing the nudge elastic band (NEB) method. We then seek to correlate these diffusion characteristics to the results of neutron scattering experiments to further understand the Li ion hopping mechanisms in a more complex structure amorphous electrolyte via AIMD simulations at high temperatures.
5:45 PM - ES3.2.05
Synthesis and Optimization of High Energy Cathode Material LiVOPO4 with Enhanced Electronic and Ionic Conductivity
Yong Shi 1 , Hui Zhou 1 , Yiqing Huang 1 , Qiyue Yin 2 , Youngmin Chung 1 , Fengxia Xin 1 , Fredrick Omenya 1 , Natalya Chernova 1 , Guangwen Zhou 2 , M Stanley Whittingham 1 3
1 Chemistry and Materials Science, Binghamton University, Vestal, New York, United States, 2 Department of Mechanical Engineering & Materials Science and Engineering Program, Binghamton University, Binghamton, New York, United States, 3 NorthEast Center for Chemical Energy Storage (NECCES), Binghamton University, Binghamton, New York, United States
Show AbstractLithium ion batteries (LIBs) have been widely used in many fields as power suppliers for mobile equipment. Recently, ε-LiVOPO4 has been regarded as a promising multi-electron cathode material that is capable to intercalate two Li per vanadium to achieve a very high theoretical capacity of 318 mAh/g, which exceeds any cathode material in the market today. However, it has been reported that ε-LiVOPO4 has poor electrical and ionic conductivity, which causes a severe polarization and poor utilization of this material. In this study, pure LiVOPO4 was successfully synthesized by an optimized solid-state reaction. To build up fast electronic and ionic pathways, we introduce three methods to increase conductivity, namely, particle nanosizing, carbon additive optimization and ionic conductor coating. The results demonstrate that the optimized ε-LiVOPO4 has achieved great improvements of electrochemical performance in terms of capacity, rate capability, reversibility and cyclibilty.
This project is supported by the U.S. Department of Energy’s Office of Energy Efficiency and Renewable Energy (EERE) program under Award No. DE-EE0006852.
ES3.3: Poster Session
Session Chairs
Wednesday AM, April 19, 2017
Sheraton, Third Level, Phoenix Ballroom
9:00 PM - ES3.3.01
Commercial Graphite Surface Modified by Lithium Titanate for the Research of Lithium Ion Battery in Fast Charge/Discharge Application
Lung-Hao Hu 1
1 Department of Mechanical Engineering, Southern Taiwan University of Science and Technology, Tainan Taiwan
Show AbstractThe advantages of traditional lithium titanate (LTO, Li4Ti5O12) as the anode material for lithium ion battery are good rate capability, low cost and high safety; however, the drawbacks include its high redox voltage ~ 1.5V and low theoretical capacity (175 mAhg-1) and low surface conductivity. The commercial anode material for lithium ion battery is artificial graphite whose advantages are low cost, low discharge voltage and relatively high capacity (300~370 mAhg-1); however, its disadvantage is poor rate capability that the graphite anode collapses to cause the failure of full battery system owing to graphene interlayer expansion during fast intercalation/de-intercalation cycling process. This research is to utilize anatase TiO2 incorporated with lithium salt via wet physical method to surface-modify the commercial graphite and then the LTO surface-modified graphite is calcined at 700°C under nitrogen gas environment to form LTO/graphite composite. The stoichiometric ratio of lithium titanate is Li4Ti5O12 coated on the surface of the commercial graphite examined by X-ray diffraction. Due to the poor surface conductivity of LTO, after LTO/graphite composite formed, we use sugar as the carbon source to coat an amorphous carbon film on the surface of the LTO/graphite composite via carbon thermal reduction process. The goal is to make the carbon coated LTO/graphite composite (cLTO/graphite) have good electrochemical properties such as the high rate capability, low redox potential and long cycle life. The LTO layer protects the graphene interlayer expansion during fast charging/discharging from the collapse of graphite and modify its SEI formation. The initial data shows that the specific capacity of the cLTO/graphite composite can remain above 300 mAhg-1 under high current density, 2Ag-1 during charge and discharge cycling. The redox potential of cLTO/graphite composite remains below one volt much lower that than of the traditional lithium titanate.
9:00 PM - ES3.3.02
Facile Synthesis of Novel Interconnected Nanosheets Structure of Nickel Hydroxide and Copper for High-Performance Supercapacitor Application
Diwen Shi 1 , Hao Gong 1
1 , National University of Singapore, Singapore Singapore
Show AbstractIn this work, an advanced interwoven architecture of pseudo-active nickel hydroxide and conductivity reinforcement copper metal was fabricated through a facile single-step chemical method. In the concurrently formed structure, copper nanosheets network growing together with nickel hydroxide nanosheets provides efficient electron-transportation highway throughout the electrode, which facilitates a high utilization of electroactivity of nickel hydroxide especially at high charging/discharging rates. As a result, an ultrahigh areal capacitance of 7.95 F cm-2 was achieved at 2 mA cm-2, 79.5% (6.34 F cm-2) of which still retains at the high current density of 30 mA cm-2. The hybrid material also exhibits an outstanding cycling stablity with nearly full capacitance retention (98.5%) after being charged and discharged at different current densities for 3500 cycles. What’s more, the high areal capacitances and superior energy densities aquried from the corresponding full cell test further confirms the hybrid’s high potential in practical application. The involved mechanisms are analyzed and discussed.
9:00 PM - ES3.3.03
Hydrated WO3 for High Power and High-Volumetric Capacitance Electrochemical Capacitors
James Mitchell 1 , William Lo 1 , Veronica Augustyn 1
1 Materials Science and Engineering, North Carolina State University, Raleigh, North Carolina, United States
Show AbstractThis research investigates the role of interlayer structural water in bulk, layered WO3 for high power, high-volumetric and areal capacitance for pseudocapacitive energy storage. Structural water in bulk, hydrated oxides exists as a 2-D, liquid-like layer that could lead to enhanced interfacial charge transfer and solid-state ion transport. The use of bulk hydrated oxides and high mass loadings could result in high areal and volumetric capacitance, which are important metrics for energy-storage device applications.
Hydrated WO3, WO3 *2H2O, was synthesized via precipitation of a tungstate salt in acid, and the structural water content was further controlled through thermal dehydration to yield WO3 *H2O and WO3. Morphology and structure of the obtained materials were characterized through electron microscopy, X-ray diffraction, and Raman spectroscopy. Electrochemical characterization was performed with slurry-cast electrodes and high mass loadings (> 4 mg cm-2) using three-electrode cyclic voltammetry at sweep rates from 1 to 200 mV s-1. These results show that hydrated WO3 exhibits excellent capacity retention, and more importantly, improved energy efficiency at high rates compared to the anhydrous material. The excellent high rate capability of hydrated WO3 is attributed to the presence of interlayer structural water and a semiconductor-to-metal transition upon proton intercalation. In addition, this research explored the effect of electrode architecture on the volumetric capacitance of hydrated WO3. Overall, the results present a new design strategy for high-power, high-energy density storage based on bulk hydrated transition metal oxides.
9:00 PM - ES3.3.04
Intercalation Mechanisms of Manganese-Rich Layered Sodium Oxides in Aqueous Electrolytes
Shelby Boyd 1 , Veronica Augustyn 1
1 , North Carolina State University, Raleigh, North Carolina, United States
Show AbstractAqueous sodium-ion batteries operating in neutral pH electrolytes offer the potential for low cost, low toxicity, high safety, and high power-density energy storage for large-scale applications, such as those needed to store electricity from renewable energy sources. However, the mechanisms of ion intercalation into solid state electrodes operating in neutral pH aqueous electrolytes are not well understood. This work investigates the intercalation mechanisms and effect of composition in a moisture-stable, layered P2-type oxide, NaxNi0.22Mn0.66Co0.11O2 (NaNMC). Layered, Mn-rich sodium oxides are promising electrode materials because of the abundance and safety of manganese. The electrochemical performance of NaNMC in neutral pH electrolytes is investigated, and the energy storage mechanism is further probed with ex situ X-ray diffraction and in situ Raman spectroscopy. Furthermore, a systematic investigation of the effect of transition metal doping is performed to reduce the amount of Co and Ni, and tune the redox potential and capacity for aqueous ion intercalation. The results show that NaNMC is redox-active in neutral-pH electrolytes and that there is a profound impact of transition metal substitution on the structure and stability of layered P2-type sodium oxides in aqueous electrolytes. This work demonstrates the fundamental relationships between composition, structure, and electrochemical behavior in layered sodium oxides that must be optimized in order to achieve high capacity and sustainable aqueous ion intercalation electrodes.
9:00 PM - ES3.3.05
High Ion Conducting Nanohybrid Solid Polymer Electrolytes via Single-Ion Conducting Mesoporous Organosilica in Poly(Ethylene Oxide)
Youngdo Kim 1 , Taehoon Kim 1 , Suk Jin Kwon 1 , Hye-kyeong Jang 1 , Byung Mun Jung 1 , Sang Bok Lee 1 , U Hyeok Choi 2 1
1 , Korea Institute of Materials Science, Changwon Korea (the Republic of), 2 Macromolecular Engineering, Pukyoung National University, Busan Korea (the Republic of)
Show AbstractA novel mesoporous silica-based single ion conductor for lithium ion batteries was prepared via two-step selective functionalization of designated silica precursors into the inner pore wall of mesoporous silica. 2-[(trifluoromethane-sulfonylimido)-N-4-sulfonylphenyl]ethyl (TFSISPE) group was firstly incorporated as a silica precursor having anionic weak-binding imide group and a dense brush of oligo-poly(ethylene glycol) (PEG) moieties, solvating Li+, was co-grafted to produce functionalized mesoporous silica (FMS-TFSISPE) nanoparticles. FMS-TFSISPE showed a 2D hexagonal nanopore structure and a regular spherical shape with an average diameter of 50 nm. Poly(ethylene oxide) (PEO) was used to form a dispersion of the mesoporous silica nanoparticles into the polymer matrix. This new polymer-mesoporous silica nanohybrid solid electrolyte with the sole mobile Li ions (FMS-TFSISPE-PEO) exhibits attractive electrical, mechanical, and electrochemical properties. The ionic conductivity and storage modulus both increase simultaneously upon addition of FMS-TFSISPE nanoparticles. 30 wt% FMS-TFSISPE nanoparticles lead to the highest ionic conductivity (~10^-3 S/cm at 25 0C) and storage modulus (~10^4 at 30 0C) with a high lithium ion transference number (~0.9). Compared to conventional non-porous silica nanoparticles-incorporated PEO matrix (SiO2-TFSISPE-PEO), FMS-TFSISPE-PEO exhibits 2 orders of magnitude higher ionic conductivity with lower activation energy, suggesting that the facile transportation of lithium ions is achieved through the continuous weak-binding and solvating nanopore channel of the mesoporous silica retaining a high surface area and pore volume.
9:00 PM - ES3.3.06
MetILs3—A Strategy for Maximizing Energy Density in Flow Battery Electrolytes
Leo Small 1 , Harry Pratt 1 , Cy Fujimoto 1 , Travis Anderson 1
1 , Sandia National Laboratories, Albuquerque, New Mexico, United States
Show AbstractThe performance of nonaqueous redox flow batteries is currently limited by the solubility of the redox-active species, constraining the ultimate achievable energy density of the battery. To address this limitation, we present a strategy to maximize the energy density of the electrolyte whereby redox activity is introduced into all parts of the electrolyte, creating an inherently energy dense electrochemical fuel. This broadly applicable strategy is exemplified using an ionic liquid with a metal coordination cation (MetIL), incorporating redox activity into all aspects of the MetIL: the metal ion core, the ligands, and the anion. This yields an electrochemical fuel with 7.4 moles of redox-active electrons available per liter of MetIL, a nearly 3x increase compared to the 2.5 M typical of aqueous vanadium chemistries. We leverage square wave voltammetry at a carbon fiber microelectrode to evaluate the electrochemical redox behavior of a series of these energy dense MetILs, allowing effective electrochemical evaluation of the reversibility of this energy dense fuel not only at the literature standard dilute concentrations, but also at more realistic neat concentrations demanded for flow battery application. Testing of these MetILs3 in a flow cell shows Coulombic efficiencies greater than 96% and a slow decrease in capacity over time, attributed to crossover of the cobaltocene anolyte chosen for initial testing. Further research into this area, optimizing electrolyte viscosity, melting point, and conductivity might yield >14 moles redox active electrons per liter.
Sandia National Laboratories is a multi-mission laboratory managed and operated by Sandia Corporation, a wholly owned subsidiary of Lockheed Martin Corporation, for the U.S. Department of Energy’s National Nuclear Security Administration under contract DE-AC04-94AL85000.
Symposium Organizers
Veronica Augustyn, North Carolina State University
Doron Aurbach, Bar-Ilan University
Y. Shirley Meng, University of California, San Diego
Naoaki Yabuuchi, Tokyo Denki University
Symposium Support
Bio-Logic USA
M. Braun Inc.
Pine Research Instrumentation
WITec Instruments Corp
ES3.4: Mg Intercalation
Session Chairs
Wednesday AM, April 19, 2017
PCC North, 200 Level, Room 226 A
9:00 AM - *ES3.4.01
The Mg-Ion Storage Capability of MXenes
Mengqiang Zhao 1 , Maria Lukatskaya 1 , Sankalp Kota 1 , Chang Ren 1 , Michel Barsoum 1 , Yury Gogotsi 1
1 , Drexel University, Philadelphia, Pennsylvania, United States
Show AbstractThe increasing interest in energy storage technologies has generated the need for alternative rechargeable magnesium-ion batteries due to their innate merits in terms of raw material abundance, theoretical capacity, and operational safety. However, their development has been greatly hindered by the lack of efficient cathode materials for bivalent Mg-ions storage. In 2011, our group discovered a large family of two-dimensional (2D) early transition metal carbides and nitrides, named MXenes.[1-2] The MXenes have shown great promise as hosts for reversible intercalation of a variety of mono- and multi-valent cations. However, MXenes have not been previously tested as cathode materials for Mg-ion batteries.
Density functional theory (DFT) calculations indicate that MXenes can show high capacities (> 500 mAh/g) for intercalation of Mg ions.[3-4] A sacrificial template method was utilized to fabricate a macroporous MXene-based architecture, to improve its electrolyte accessibility in laboratory tests. In an all phenyl complex (APC) electrolyte, a capacity of ~200 mAh/g was achieved at 50 mA/g by a macroporous Ti3C2Tx film cathode vs. Mg metal anode. At higher current densities of 100 and 500 mA/g, the capacities were retained at 140 and 50 mAh/g, respectively. At 200 mAh/g, a higher capacity was achieved by the Mo2CTx film cathode at 100 mA/g. Mechanistic investigations indicated that both Mg-ion intercalation and redox reaction contributed to the energy stored in a MXene-based Mg-ion battery. Considering ~20 different MXenes have been synthesized, this work opens the door of exploring a very large family of potential Mg-ion battery cathode materials.
References:
[1] Naguib, M.; Kurtoglu, M.; Presser, V.; Lu, J.; Niu, J.; Heon, M.; Hultman, L.; Gogotsi, Y.; Barsoum, M. W., Two-Dimensional Nanocrystals Produced by Exfoliation of Ti3AlC2. Adv. Mater. 2011, 23 (37), 4248-4253.
[2] Naguib, M.; Mochalin, V. N.; Barsoum, M. W.; Gogotsi, Y., 25th Anniversary Article: MXenes: A New Family of Two-Dimensional Materials. Adv. Mater. 2014, 26 (7), 992-1005.
[3] Eames, C.; Islam, M. S., Ion Intercalation into Two-Dimensional Transition-Metal Carbides: Global Screening for New High-Capacity Battery Materials. J. Am. Chem. Soc. 2014, 136 (46), 16270-16276.
[4] Xie, Y.; Dall'Agnese, Y.; Naguib, M.; Gogotsi, Y.; Barsoum, M. W.; Zhuang, H. L.; Kent, P. R. C., Prediction and Characterization of MXene Nanosheet Anodes for Non-Lithium-Ion Batteries. ACS Nano 2014, 8 (9), 9606-9615.
9:30 AM - ES3.4.02
Controlling Interlayer Interactions in Vanadium Pentoxide-Poly(ethylene oxide) Nanocomposites for Enhanced Magnesium-Ion Charge Transport and Storage
Christopher Rhodes 1 , Sanjaya Perera 1 , Randall Archer 1 , Craig Damin 1 , Shraddha Acharya 1
1 , Texas State University, San Marcos, Texas, United States
Show AbstractRechargeable magnesium batteries have attracted significant attention based on their lower cost and improved safety compared with lithium-ion batteries. Layered materials have been shown to electrochemically store Mg-ions, however additional research is needed to increase the Mg-ion capacity and understand the nature of interlayer interactions. We have investigated hydrated vanadium pentoxide (V2O5) xerogels that incorporate poly(ethylene oxide) (PEO) between the layers as an approach to improve Mg-ion charge storage and understand interlayer structure and dynamics. V2O5 nanosheets were grown in the presence of PEO to allow inimate interaction with the V2O5 layers and provide control of the PEO content in V2O5-PEO nanocomposites. X-ray diffraction and high resolution transmission electron microscopy show that the interlayer spacing between V2O5 layers was increased by incorporating PEO within the layers. The Mg-ion diffusion cofficient was determined to be strongly dependent on not only interlayer spacing, but also interlayer composition. With specific amounts of the polymer within the V2O5-PEO nanocomposites, the Mg-ion diffusion cofficient was significantly increased compared with V2O5 xerogels. Raman spectroscopy supports that the polymer interacts with the V2O5 lattice leading to interlayer water that is less strongly bound to the V2O5 lattice. The V2O5-PEO nanocomposites with specific amounts of PEO showed significant improvements in Mg-ion specific capacities over V2O5 xerogels, improved rate capabilities, and higher capacity retention upon cycling. Our work supports that beyond interlayer spacing the nature of interlayer interactions between the V2O5 lattice, PEO, H2O and Mg-ions are key factors to control Mg-ion charge transport and storage. The design of layered materials with controlled interlayer interactions provides a novel route to significantly improve charge storage and transport in multivalent cathode materials.
9:45 AM - ES3.4.03
First-Principles Design of Cathode Materials for Mg Batteries—The Role of Anion Doping and Nanostructuring
Liwen Wan 1 , David Prendergast 1
1 , Lawrence Berkeley National Lab, Berkeley, California, United States
Show AbstractOne of the bottlenecks to design new Mg battery system and to achieve comparable performance as Li-ion batteries is to find or develop “new” cathode materials that can reversibly intercalate Mg. The success of the first working Mg battery relies on the use of low-voltage Chevrel phase cathode (Mo6S8). Apart from this, only a handful of material systems are shown capable of intercalating Mg and the MoO3 compound is one of them. However, very sluggish Mg diffusion is observed in bulk MoO3 and thus strategies such as anion doping or reducing particle size are proposed in order to improve Mg diffusivity. In this work, we discuss how anion doping and nanostructuring will affect Mg mobility in alpha-MoO3 based on density functional simulations. It is found that replacing a small fraction of oxygen with fluorine facilitates Mg diffusion, especially through the fluorine site. In contrast to anion doping, in which the effects are fairly localized, nanostructuring results in more homogeneous response of the lattice to Mg diffusion. However, creating a nanostructure will inevitably increase the surface/bulk ratio and therefore the behavior of Mg migration through the cathode surfaces need to be carefully evaluated. Here, we demonstrate how the MoO3 surface chemistry plays a significant role to dissociate Mg from its strongly coordinated counterions and to initiate Mg migration through the surfaces.
This work is supported by the Joint Center for Energy Storage Research (JCESR), an Energy Innovation Hub funded by the U.S. Department of Energy, Office of Science, Basic Energy Sciences.
10:00 AM - *ES3.4.04
Activating Layered LiNi0.5Co0.2Mn0.3O2 as a Host for Mg Intercalation in Rechargeable Mg Batteries
Kisuk Kang 1
1 , Seoul National University, Seoul Korea (the Republic of)
Show AbstractLayered crystal structure is one of the most intensively studied intercalation hosts for guest ion insertion. Regarding the Mg insertion, layered transition metal sulfides or selenides have been often demonstrated for reversible Mg intercalation, however, far less intercalation hosts have been found for layered oxides probably due to the strong interaction between Mg2+ and the oxide host. Here, we show that layered LixNi0.5Co0.2Mn0.3O2 (NCM523), which is one of the important commercial electrodes for Li ion batteries but has been regarded electrochemically inactive in rechargeable Mg batteries, can function as a reversible host for Mg2+, if water opens up the layers and screens the electrostatic interaction between Mg2+ and the host. Upon the formation of water-intercalated NCM523, the discharge capacity dramatically increases utilizing the multi-redox reaction of Ni2+/Ni3+/Ni4+ which exhibits the average voltage of ~3.1 V (vs. Mg/Mg2+) in rechargeable Mg batteries with the energy density of 589 Wh kg-1 in the first discharge. This is the first demonstration of the Ni multi-redox reaction combined with the multi-valent Mg2+ intercalation in rechargeable battery system. Also, it proposes a new avenue to utilize various layered oxides as Mg intercalation host by a structural tailoring of the layered crystal with water incorporation.
10:30 AM - ES3.4.05
Systematic Electron Microscopy Study Investigating Mg Intercalation of Tunnel Structured ζ-V2O5 Polymorph
Arijita Mukherjee 1 , Gene Nolis 1 , Hyun Deog Yoo 1 , Justin Andrews 2 , Sarbajit Banerjee 2 , Jordi Cabana 1 , Robert Klie 1
1 , University of Illinois at Chicago, Chicago, Illinois, United States, 2 Chemistry, Texas A&M University, College Station, Texas, United States
Show AbstractBatteries using a Mg metal anode and a suitable high voltage intercalation cathode can provide a competitive alternative to current Li ion battery technology. Mg metal anode can achieve even higher specific volumetric capacity (3833 mAh/cm3) than that for Li metal anode(2046 mAh/cm3), is non dendrite forming hence safer than Li metal anode, and can be a more cost effective option as well [1] . Research is underway to look for high voltage cathodes that can reversibly intercalate Mg. Vanadium Pentoxide(V2O5) is a promising candidate for Mg ion based batteries based on recent simulation efforts [2] . Recent work has also identified a novel polymorph, ζ-V2O5 ,whose structure consists of one dimensional tunnels as opposed to the layered framework of α-V2O5. It has been shown that these ζ-V2O5 nanowires can intercalate Li and Mg chemically.[3]
This contribution will focus on systematic characterization of ζ-V2O5 nanowires employing electron microscopy techniques such as aberration-corrected scanning transmission electron microscopy (STEM) imaging, electron energy-loss spectroscopy (EELS) and energy dispersive X ray spectroscopy (EDX). Starting from the pristine material, a thorough study will be presented primarily focusing on electrochemically cycled samples with Mg. Comparisons will also be made on the Mg intercalation behavior of this tunnel structured polymorph with our previous results on orthorhombic α-V2O5 .[4] Since nature of electrochemical reactions of Mg with oxide based cathodes can be quite complicated, it would be particularly interesting to compare the Mg intercalation sites in ζ-V2O5 to those in α-V2O5. ζ-V2O5 has also demonstrated reversible electrochemical cycling with Li and Na and shows promise as a versatile intercalation cathode host.
References
[1] Yoo, Hyun Deog, et al. "Mg rechargeable batteries: an on-going challenge." Energy & Environmental Science 6.8 (2013): 2265-2279.
[2] Sai Gautam, Gopalakrishnan, et al. "The Intercalation Phase Diagram of Mg in V2O5 from First-Principles." Chemistry of Materials 27.10 (2015): 3733-3742.
[3] Marley, Peter M., et al. "Emptying and filling a tunnel bronze." Chemical Science 6.3 (2015): 1712-1718.
[4]Mukherjee, Arijita, et al. “Direct Investigation of Mg intercalation into orthorhombic V2O5 cathode using Atomic resolution Electron Microscopy Methods.” [To be submitted to Chemistry Of Materials]
ES3.5: Mg Ion Batteries I
Session Chairs
Jordi Cabana
Rana Mohtadi
Wednesday PM, April 19, 2017
PCC North, 200 Level, Room 226 A
11:15 AM - *ES3.5.01
Rechargeable Magnesium Batteries—Advancements and Bottlenecks
Rana Mohtadi 1 , Oscar Tutusaus 1 , Timothy Arthur 1 , Hikaru Aso 1
1 , Toyota, Ann Arbor, Michigan, United States
Show AbstractThe urge to access a battery system which combines high energy density with lower costs and improved safety has been driving interests in rechargeable magnesium batteries. These batteries, while in principle are very promising, remain confined to research laboratories. This is despite the numerous breakthroughs made thus far.[1] Herein, we will explain the bottleneck challenges that continue to face this technology and explain contributions made by our group targeted towards creating a path forward to overcoming these in addition to offering a technological assessment of these batteries.[2,3,4,5]
References
[1] a) H. D. Yoo, I. Shterenberg, Y. Gofer, G. Gershinsky, N. Pour, D. Aurbach, Energy Environ. Sci. 2013, 6, 2265-2279; b) R. Mohtadi, F. Mizuno Beilstein J. Nanotechnol. 2014, 5, 1291–1311, c) Choi, J. W. & Aurbach, D. Nature Reviews Materials 1, 2016, 16013 1-16.
[2] R. Mohtadi, M. Matsui, T. S. Arthur, S.-J. Hwang, Angew. Chem. Int. Ed. 2012, 51, 9780 –9783
[3] a) T. J. Carter, R. Mohtadi, T. S. Arthur, F. Mizuno, R. Zhang, S. Shirai, J. W. Kampf, Angew. Chem. Int. Ed. 2014, 53, 3173-3177;
[4] O. Tutusaus, R. Mohtadi, ChemElectroChem. 2015, 2, 51-57.
[5] O. Tutusaus, R. Mohtadi, T. Arthur. F. Mizuno, Angew. Chem., Int. Ed. 2015, 54, 7900-7904.
11:45 AM - ES3.5.02
Electrochemical Stability of Magnesium-Based Anodes for Batteries
Jodie Yuwono 1 , Nick Birbilis 1 , Nikhil Medhekar 1
1 , Monash University, Clayton, Victoria, Australia
Show AbstractThe use of light electropositive metal anodes offers a promising breakthrough in the development of a rechargeable battery technology. Magnesium (Mg) with a divalent charge carrier (Mg2+) has long been viewed as an alternative metal for the replacement of Li based batteries. However, key challenges in addressing the electrochemical stability of Mg pose questions regarding the feasibility of Mg use as the anode. The inadequate understanding of active mechanisms in Mg dissolution and the formation of insulating Mg(OH)2 film lead to an inconsistent electrochemical performance contrary to what is expected for the practical battery anodes. In the present study, we found that the surface hydroxylation exhibited the increasing Mg activity (self-catalytic) of anodic behavior. The molecular paths and the associated activation energies of the interfacial reaction of Mg/water have been investigated through density functional theory (DFT), in order to comprehensively identify the key reaction pathways. We observed an improved performance of Mg anode through the alloying with group 14 and 15 elements. The alloying elements were found to control the anodic behavior, which is mainly achieved by disrupting the water dissociation reaction on the surface. These new findings in the electrochemical stability of Mg, thus, not only provide a practical importance for improving the battery anodes reliability but also the corrosion performance of Mg for other applications.
12:00 PM - ES3.5.03
Nanostructure Cathode and Anode Materials for Mg-Ion Batteries
Kostiantyn Kravchyk 1 2 , Maryna Bodnarchuk 2 , Maksym Kovalenko 1 2
1 , ETH Zurich, Laboratory of Inorganic Chemistry, Zurich Switzerland, 2 , Empa - Swiss Federal Laboratories for Materials Science and Technology, Dübendorf Switzerland
Show AbstractDue to limited natural abundance of lithium, novel battery technologies are needed for large-scale, stationary storage of electricity [1]. Such batteries can then be combined with renewable sources of electricity, for the best integration of a variety of sources into electrical grid. We will discuss the utility of nanoscale inorganic materials as cathode and anode materials in Mg-ion batteries. In particular, the focus will be on a balance between the performance, material’s synthesis costs and natural abundance of the constituting elements. Owing to the reduced diffusivity of Mg-ions in most materials, nanostructuring has been identified to be of drastically higher importance than in the case of alkali-ion (Li, Na) batteries. The cathodic side of a battery remains the bottleneck. In this regard, we present several metal sulfides, delivering capacities of up to 160 mAh g-1, with plateau voltages of 1.1-1.2V [2]. On the anode side, we present Bi nanostructures as convenient anodes for research purposes. In particular, Bi-based anodes operate in a variety of electrolytes, in which metallic Mg is non-operational due to oxidative passivation [3].
References
[1] H.D. Yoo, et al. Energy & Environmental Science, 2013, 6, 2265-2279.
[2] K.V. Kravchyk, et al. Nature Energy, 2016, submitted.
[3] K.V. Kravchyk, et al. ASC Nano, 2016, submitted.
12:15 PM - *ES3.5.04
Are Spinel Oxides Viable for the Reversible Intercalation of Divalent Ions? An Update
Jordi Cabana 1
1 , University of Illinois at Chicago, Chicago, Illinois, United States
Show AbstractElectrochemical energy storage was an important enabler of the wireless revolution and it is touted as a key component of a society that shifts away from its dependence on fossil fuels. Li-ion batteries are the primary technology when high energy devices are required. However, despite their improved functionality over older systems (e.g. lead-acid car batteries), they do not quite yet meet the emerging energy demands in transportation and grid markets. This roadblock sparked interest in the development of batteries that utilize divalent cations (i.e. Ca2+, Mg2+, Zn2+) as ionic carriers. Theoretical predictions indicate that couples exist between a Mg metal negative electrode and oxide positive electrodes that could surpass the current practical limits of current devices. Among the candidate oxides, those showing a spinel structure have been predicted as the most suitable for the reversible intercalation of ions such as Mg2+ or even Ca2+ [1], the critical reaction in the positive electrode. However, experimental validation, while incipient [2], has not been fully achieved. In this talk, we will present the most up-to-date insight into the ability of spinel oxides to diffuse and reversibly intercalation divalent ions, with a focus on Mg2+. Characterization of chemical and physical phenomena using a combination of tools providing information at different scales is vital in this task. We will rely on data from X-ray diffraction, spectroscopy and scattering, electron microscopy and nuclear magnetic resonance to probe the reactions that occur when spinel oxides are used as working electrodes in cells with electrolytes containing divalent ions such as Mg2+. The rationale for the choice of techniques and the key pieces they provided to complete the picture will be discussed. Our ultimate aim in the talk will be to establish relationships between crystal-chemistry, charge carrier and outcomes of the electrochemical reaction.
1. Liu, M., et al., Energy Environ. Sci. 2015, 8, 964.
2. Kim, C. et al., Adv. Mater. 2015, 27, 3377.
ES3.6: Mg Ion Batteries II
Session Chairs
Veronica Augustyn
Maximilian Fichtner
Wednesday PM, April 19, 2017
PCC North, 200 Level, Room 226 A
2:45 PM - *ES3.6.01
Magnesium Sulfur Battery—Its Beginning and Recent Progress
Maximilian Fichtner 1
1 , Helmholtz Institute Ulm (HIU), Ulm Germany
Show AbstractMg has emerged as a promising candidate in the search for alternatives to Li, mostly due to its high theoretical volumetric capacity, its abundance and environmental friendliness and the fact that no dendrites form at the metal surface during stripping and plating. The absence of dendrites allows a combination of a dense metal anode and a liquid electrolyte, without compromising the safety. The combination of magnesium and sulfur would be particularly attractive, due to its sustainable composition, low cost of the active materials and the high volumetric capacity in comparison to the Li-S system.
While early work on secondary Mg batteries was done using electrolytes with strong reduction properties (i.e. nucleophilic electrolytes) based on Grignard compounds and Lewis acid-base adducts, these first systems were not compatible with sulfur which would immediately be reduced in contact with the electrolyte. A first breakthrough was achieved by a modified electrolyte concept using a Hauser base which was less nucleophilic and the first two cycles were reported, however, at low discharge voltage.
Further progress was made when a similar system was introduced with a much broader electrochemical window and a discharge voltage close to the theoretical voltage of the Mg-S system. With that, the first cells cycling dozens of times were presented. As in the case of Li-S, a decrease of the reversible capacity was observed upon cycling and several attempts have been made in the meantime to understand the origin of this behaviour, and to improve the cyclic stability.
3:15 PM - ES3.6.02
Multivalent Metal/Sulfur Chemistries for High Energy Density Rechargeable Battery
Tao Gao 1 , Chunsheng Wang 1
1 , University of Maryland, College Park, Maryland, United States
Show AbstractThe increasing demand for high energy density batteries urges the community to seek novel chemistries. Among them, Li/S and Li-O2 have received the most attentions due to their great potential and the community's extensive experience in Li chemistry. In contrast, multivalent chemistries (Mg and Al) attract less attention despite of their unique and remarkable advantages. Although their higher reduction potentials (Mg=-2.36V vs SHE; Al=-1.3V vs SHE) compromises battery voltages, their less reactive nature has enabled a better (elec)chemical compatibility at the metal/electrolyte interface, which eliminates any surface layer and leads to a high coulombic efficiency (100%) for metal deposition/striping. This is crucial for a rechargeable battery chemistry based on metal anode, because the formation of surface layer would cause continuous consumption of electrolyte during repeated cycling. Furthermore, the deposition of multivalent metal (Mg and Al) shows uniform morphology with no whiskers (‘dendrite’) below Sand’s time, which eliminates the possibility of whiskers penetrating through separators and internal short circuit of the battery. This feature allows multivalent metal batteries to function in a much safer manner than Li metal batteries.
The success of multivalent battery chemistry relies on development of proper electrolytes and cathode materials. While great progress has been made regarding the former, few advance was seen in the latter. In this presentation, we will introduce our latest achievement in tackling the cathode challenges. Our study has focused on metal/sulfur chemistries, because 1) they provide close or even higher volumetric energy density than Li/S chemistry; 2) the potentially fast reaction kinetics of the non-topotactic reaction compared with intercalation reaction.
ES3.7: Anion Redox
Session Chairs
Alexis Grimaud
Naoaki Yabuuchi
Wednesday PM, April 19, 2017
PCC North, 200 Level, Room 226 A
4:30 PM - *ES3.7.01
Anionic Redox Processes for Energy Storage—Mastering the O-O Bond Formation
Alexis Grimaud 1 2
1 Chimie du Solide et de l’Energie, College de France, Paris France, 2 Réseau sur le Stockage Electrochimique de l’Energie, Centre National de la Recherche Scientifique, Amiens France
Show AbstractThe design of new materials for electrochemical devices is a pivotal question for the development of the next generation of energy storage materials. Recently, it appeared simultaneously in two fields considered so far as antagonist, namely Li-ion batteries (LIBs) relying on bulk reversible redox processes and water oxidation electrocatalysis relying on surface adsorption processes, that the use of anionic redox processes in place of the traditionally considered cationic redox may enhance the electrochemical performances of transition metal oxides (TMOs).1 More specifically, realizing that oxygen can be loss from the oxide decomposition at high potential, mastering the reaction of lattice oxygen evolution becomes critical for the development of electrochemical energy storage devices. Through recent findings in both fields of LIBs and water splitting, we will discuss in this presentation the different situations, from the case where oxygen pairs can be stabilized on the surface of TMOs to the case where they are unstable and lattice oxygen is evolved. Example of the latter case will be given with a special emphasis paid to the structural reorganization triggered by such oxygen loss and to the control of reactive surface oxygen for the design of enhanced water oxidation catalysts. Finally, we will show how the mechanism of O-O bond formation can be modulated through the specific interaction of oxygen intermediates with species in solution.
1. Grimaud, A., Hong, W. T., Shao-Horn, Y. & Tarascon, J.-M. Anionic redox processes for electrochemical devices. Nat. Mater. 15, 121–126 (2016).
5:00 PM - ES3.7.02
A Joint Experimental and Theoretical Approach to the Question of Anion Redox in Lithium-Rich Layered Oxides
William Gent 1 2 , Yufeng Liang 3 , Qinghao Li 2 , Kipil Lim 1 4 , Jihyun Hong 1 4 , Yiyang Li 1 , Jongwoo Lim 1 , David Kilcoyne 2 , David Vine 2 , Michael Toney 4 , Wanli Yang 2 , David Prendergast 3 , William C. Chueh 1 4
1 , Stanford University, Stanford, California, United States, 2 Advanced Light Source, Lawrence Berkeley National Laboratory, Berkeley, California, United States, 3 The Molecular Foundry, Lawrence Berkeley National Laboratory, Berkeley, California, United States, 4 , SLAC National Accelerator Laboratory, Stanford, California, United States
Show AbstractThe concept of oxygen anions acting as redox couples in the high energy density lithium-rich layered oxide positive electrode materials has been the focus of intense debate in recent years. While it is known that transition metal oxidation does not account for the extended high voltage plateau capacity during the first charge, there is still little consensus on the exact mechanism of charge compensation in this regime. Early on it was proposed that oxygen evolution compensated the removal of lithium ions during the plateau, but more recently it has been suggested that an oxide/peroxide redox couple accounts for the bulk redox capacity. More recent still is the hypothesis that the formation of localized oxygen holes compensates lithium ion extraction in the bulk. In this work, we resolve the controversy by employing a variety of experimental and theoretical tools to develop a multi-length scale understanding of the anion redox phenomenon in lithium-rich layered oxide electrodes. Through Scanning Transmission X-ray Microscopy operating at the oxygen K and transition metal L edges, we observe a dichotomy in the behavior of the surface and the bulk of individual primary particles, confirming that multiple anionic redox processes occur during the plateau. By coupling the spatially resolved X-ray absorption spectra with ab initio spectroscopy simulation and super-resolution Resonant Inelastic X-ray Scattering, we develop a holistic understanding of the complex behavior of these materials encompassing structure, redox, and electrochemistry.
5:15 PM - ES3.7.03
Strong Oxygen Participation in the Redox Governing the Structural and Electrochemical Properties of Na-Rich Layered Oxide Na2IrO3
Arnaud Perez 1 2 , Dmitry Batuk 1 3 , Matthieu Saubanere 1 4 5 , Gwenaelle Rousse 1 2 5 , Dominique Foix 6 5 , Eric McCalla 1 5 8 , Erik Berg 9 , Romain Dugas 1 5 , Karel Van den Bos 3 , Marie-Liesse Doublet 4 5 , Danielle Gombeau 6 5 , Artem Abakumov 3 7 , Gustaaf Van Tendeloo 3 , Jean-Marie Tarascon 1 2 5
1 , Collège de France, Paris France, 2 , Sorbonne Universités, PARIS France, 3 , EMAT, Antwerp Belgium, 4 , Institut Charles Gerhardt, Montpellier France, 5 , RS2E, Amiens France, 6 , IPREM/ECP, Pau France, 8 , CEMS, Minneapolis, Minnesota, United States, 9 , Paul Scherrer Institut, Villigen Switzerland, 7 , Skoltech Center for Electrochemical Energy Storage, Moscow Russian Federation
Show AbstractThe Na-ion technology appears as an interesting alternative to the widespread Li-ion systems for large scale energy storage applications. Its success will largely rely on the development of new cathode materials with higher energy density. The Na-based layered oxides, with NaxMO2 formula (M = transition metals), are currently the focus of intense research activity as they provide a great versatility of compositions and structure (O3, P2, P3).1 However, most of these layered oxides present a limited energy density because of their low Na content (x<1) and low redox potential.
One of the strategies to surpass this limitation is to use the recent knowledge on anionic redox activity obtained from Li-rich layered oxides.2 To avoid any problem related to cationic migration or O2 release observed with 3d/4d transition metals,3,4 Na2IrO3 appeared as an ideal compound to study the reversibility of the anionic process. Indeed, the strong overlap between Ir(5d) and O(2p) orbitals stabilizes the anionic redox process, as observed in the parent compound Li2IrO3.5
Na2IrO3 shows the reversible intercalation of 1.5 Na+ through two well-defined plateaus at 2.7 V and 3.7 V. This large capacity could be accounted for by cumulative cationic and anionic redox activity as deduced by complementary X-ray photoemission spectroscopy, X-ray/neutron diffraction and transmission electron microscopy measurements. Upon deintercalation of Na, Na2IrO3 undergoes well-defined structural changes which appeared to be driven by the strong cationic repulsions in the material. Lastly, the long-term cyclability of Na2IrO3 was found to be highly dependent on the cell configuration, with a complete reversibility obtained in a full Na-ion cell using hard carbon as an anode. These results will help defining new directions for developing high energy Na-rich layered oxides based on more sustainable elements than Ir.
(1) Kubota, K. et al. Layered Oxides as Positive Electrode Materials for Na-Ion Batteries. MRS Bulletin 2014, 39 (5), 416–422.
(2) Sathiya, M. et al. Reversible Anionic Redox Chemistry in High-Capacity Layered-Oxide Electrodes. Nat Mater 2013, 12 (9), 827–835.
(3) Sathiya, M. et al. Origin of Voltage Decay in High-Capacity Layered Oxide Electrodes. Nat Mater 2015, 14 (2), 230–238.
(4) Koga, H. et al. Operando X-Ray Absorption Study of the Redox Processes Involved upon Cycling of the Li-Rich Layered Oxide Li1.20Mn0.54Co0.13Ni0.13O2 in Li Ion Batteries. J. Phys. Chem. C 2014, 118 (11), 5700–5709.
(5) McCalla, E. et al. Visualization of O-O Peroxo-like Dimers in High-Capacity Layered Oxides for Li-Ion Batteries. Science 2015, 350 (6267), 1516–1521.
5:30 PM - ES3.7.04
An Intermediate Temperature Solid Oxide Iron-Air Redox Battery Operated on O2--Chemistry and Loaded with Pd-Catalyzed Iron-Based Energy Storage Material
Cuijuan Zhang 1 , Kevin Huang 1
1 , University of South Carolina, Columbia, South Carolina, United States
Show AbstractThe solid-oxide iron-air redox battery (SOIARB) operated on high-temperature O2--chemistry is an emerging all-solid-state battery suitable for large-scale energy storage with strong advantages in rate capacity and safety. However, it faces a serious challenge, particularly at lower temperatures, in rechargeability controlled by sluggish reduction kinetics of iron oxide. This work demonstrates that the slow iron oxide reduction kinetics can be significantly enhanced by loading Pd nanoparticles into Fe-based energy storage material, achieving high cycle efficiency at high energy and power density. A representative result shows that at 500 oC and C/5.3 (10 mA cm-2, or 239.6 mA g-1-Fe) rate, the battery delivers a discharge specific energy of 960.3 Wh kg-1-Fe at 80% iron utilization (UFe), and ~600 Wh kg-1-Fe at UFe = 50% with an average cycle efficiency of 62.9% over 25 cycles.
5:45 PM - ES3.7.05
Regenerative Hydrogen Electrodes for Energy Storage
Sanjeev Mukerjee 1 , Huong Doan 1 , Shraboni Ghoshal 1
1 , Northeastern University, Boston, Massachusetts, United States
Show AbstractRegenerative hydrogen electrode (HOR/HER) are an attractive option for energy storage in aqueous electrolytes accross the two extreme ends of the pH scale. At the low pH scale applications in Hydrogen Bromine flow batteries offers high energy density compared to most of the other competitive reox based approaches such as the Vanadium redox system. However the principle catalytic challenge lies in ensuring immunity towards anion poisoning at the hydrogen regenerative catalyst. The first part of this talk will focus on some recent success in engendering such anion immunity (halide ions) to regenerative hydrogen electrode exhibiting orders of magnitude higher tolerance towards deactivation when compared with the standard Pt/C system. Both fundamental and translational aspects of this effort will be presented. Use of in situ x-ray absorption spectroscopy (XAS) together wiith the advanced rendition of this technique for elucidating surface effects such as nature of adsorbed species measured under operando conditions will be shown together with in situ Raman spectra. Single cell cycling results relative to Pt/C reference will be presented.
On the high end of the pH scale similar efforts will be presented in the context of non noble metal catalysts. In this case the much debated role of hydrogen bonding affinity will be presented as a principle determinant for explaining HOR activity. Interfacial models will be used to explain both HER and HOR activities in the context of non noble metal oxide composites. As in the low pH case, use of in situ and operando XAS and Raman will be described to provide a molecular level perspective of the electrocatalysis.
Symposium Organizers
Veronica Augustyn, North Carolina State University
Doron Aurbach, Bar-Ilan University
Y. Shirley Meng, University of California, San Diego
Naoaki Yabuuchi, Tokyo Denki University
Symposium Support
Bio-Logic USA
M. Braun Inc.
Pine Research Instrumentation
WITec Instruments Corp
ES3.8: Multivalent Chemistry Mg and Beyond
Session Chairs
Brian Ingram
Arumugam Manthiram
M. Rosa Palacin
Yan Yao
Thursday AM, April 20, 2017
PCC North, 200 Level, Room 226 A
9:00 AM - *ES3.8.01
On the Road towards Ca-Based Batteries
Alexandre Ponrouch 1 , Fanny Barde 2 , Deyana Tchitchekova 1 , Carles Frontera 1 , Elena Arroyo 3 , M. Rosa Palacin 1
1 , ICMAB CSIC, Barcelona Spain, 2 , Toyota Motor Europe, Zaventem Belgium, 3 , Universidad Complutense, Madrid Spain
Show AbstractAside from controversial debates on lithium availability and cost, some general arguments could be raised against a possible generalized blind implementation of lithium based technology at large scale. While research in Na-ion batteries has recently boosted, less attention has been paid to the viability of an analogous technology based on divalent cations as charge carriers. The main caveat in such concept is the slow diffusion of multivalent elements, which penalizes the expected power performance. This has been addressed by using more covalent hosts for insertion, as coulombic interactions diminish if electrons are less localized in the M-X bonds. Along this line, the progresses done in the development of secondary magnesium based batteries using covalent host positive materials and complex electrolyte solutions are worth mentioning. An alternative technology based on calcium appears as an attractive option. Calcium is the fifth most abundant element on earth crust and its standard reduction potential is only 170 mV above that of lithium, thus enabling significantly larger cell potential than that achievable with magnesium. Moreover, the low polarizing effect (charge/radius) would a priori present some advantages towards the latter with respect to reaction kinetics and resulting power performances.
The feasibility of a calcium metal based technology had been poorly explored as it was generally admitted that calcium deposition was virtually impossible due to the lack of calcium ion transport through the surface layer formed at the electrode interface in conventional electrolyte solutions. The talk will revisit these aspects discussing the feasibility of reversible calcium plating/stripping using conventional alkylcarbonate electrolytes which impacts the prospects of developing new calcium based rechargeable battery technology. In addition, research aimed at unraveling cathode materials guided by DFT calculations will also be presented.
9:30 AM - ES3.8.02
Rechargeable Al-Ion Battery in Ionic Liquid Electrolytes—Toward Multivalent Ion Secondary Batteries
Myungjun Kim 1 , Seonhee Lee 1 , Changdeuck Bae 1 2 , Hochul Nam 1 , Eunsoo Kim 1 , Hyunjung Shin 1
1 Department of Energy Science, Sungkyunkwan University, Suwon Korea (the Republic of), 2 , Integrated Energy Center for Fostering Global Creative Researcher (BK 21 Plus) Sungkyunkwan University, Suwon Korea (the Republic of)
Show AbstractThe paradigm shifts in energy storage system from small portable electronics to large-scale applications, such as electrical vehicles (EVs) and stationary energy storage systems (ESSs), have led to an increase in demand for rechargeable batteries with cost-effectiveness, safety, cycling stability and high energy density. One of the most promising solutions to the issue is to develop novel rechargeable batteries based on multivalent (MV) ion (e.g., Mg2+, Ca2+, Zn2+, and Al3+). Rechargeable battery utilizing such MV ions can have high energy density of 3,833 Ah/L for Mg, 2,073 Ah/L for Ca and 8,040 Ah/L for Al, respectively. Among those various MV metals, Al is attractive alternative because it is the most abundant metal in earth’s crust leading to its low cost. Furthermore, Al-ion based redox couple provides gravimetric and nearly 3 - 4 times higher volumetric capacity compared to lithium-ion case since it involves three electrons transfer during its electrochemical reaction. In this study, adequate non-aqueous electrolytes, stable deposition/stripping of Al anodes and possible cathode materials were investigated.
Electrochemical properties of ionic liquid electrolytes were explored. The CV curves of AlCl3/1-ethyl-3-methylimidazolium chloride ([EMIm]Cl) ionic liquids varying with mole fraction of 1.1, 1.3 and 1.5 were measured in Al/GC (glassy carbon) cell in potential range of 0 - 2.5 V. Electrolytes with AlCl3/[EMIm]Cl = 1.3 showing the lowest current level were used in this study. CV curves of Al deposition/dissolution on Mo foil with the potential range between -1 V and 2 V in AlCl3/[EMIm]Cl ionic liquid electrolyte were obtained. Reduction peak with small over-potential of about 0.2 V and oxidation peak were clearly observed indicating reversible Al deposition/stripping in the electrolyte on the Mo foil. It is worth noting that the morphology of deposited Al is not dendritic but granular. CV curve of the Al-ion battery using stainless steel (SUS316L) as a current collector revealed many peaks while large electrochemical window between 0 – 2.3 V was observed for Mo foils. As a result, it is shown that Mo current collector was stable in AlCl3/[EMIm]Cl ionic liquid electrolyte and stainless steel was not appropriate for a current collector. The electrochemical activity of α-MoO3 cathode prepared by a simple powder method was demonstrated. It was shown that the reversible capacity of the Al/α-MoO3 cell was ~24 mAh/g at current rate of 10 mA/g and stable cycling performance with 98% coulombic efficiency up to more than 120 cycles. Current research work provides guidance on how to design cathode materials for Al-ion rechargeable battery using ionic liquid electrolyte.
9:45 AM - ES3.8.03
Synthesis and Electrochemical Characterization of Anhydrous and Hydrated WO3 for Mg-Ion Intercalation in Non-Aqueous Electrolytes
Ruocun Wang 1 , Veronica Augustyn 1
1 , North Carolina State University, Raleigh, North Carolina, United States
Show AbstractThere is a high demand for low-cost energy storage devices with high energy density and excellent safety. To achieve energy densities greater than those of Li-ion batteries with better safety and lower cost, multivalent batteries, such as those based on Mg2+, are under active investigation. The primary motivations for investigating Mg-based batteries are due to the divalent charge of Mg cations, which may allow higher practical capacity given a certain amount of ion storage sites available in a host structure. In addition, Mg is more cost efficient than Li and Mg metal could safely be used as an anode material as it does not form dendrites during electrochemical cycling. One of the biggest challenges for Mg-ion batteries is the lack of cathode materials operating at high potentials and with high capacities, and in reality, most cathode materials for Li-ion batteries performed poorly when the intercalating species were changed to Mg2+. This has been attributed to the higher cation charge/radius ratio of Mg2+, which results in a high desolvation barrier at the electrode/electrolyte interface and introduces difficult redistribution of charges in the host lattice and significant Coulombic repulsion between the intercalating species upon intercalation into the host structure. The modification of the interlayer spacing of transition metal compounds with water has been shown to improve the kinetics of Mg2+ intercalation. This research focuses on the systematic investigation of interlayer structural water in a model transition metal oxide for Mg-ion batteries, WO3. In this study, WO3·2H2O was synthesized by acid precipitation and WO3·H2O and WO3 were obtained by heat treatment. Raman spectroscopy, X-ray diffraction (XRD), scanning electron microscopy (SEM), and thermal gravimetric analysis (TGA) were applied to study the structure of the obtained products. The electrochemical behavior of the obtained materials was investigated by cyclic voltammetry in a three-electrode cell in both Li+ and Mg2+ non-aqueous electrolytes to elucidate the effect of the divalent charge on ion intercalation in hydrated structures in non-aqueous electrolytes.
10:00 AM - *ES3.8.04
Multivalent Ions as the Next Energy Storage Frontier
Brian Ingram 1
1 , Argonne National Laboratory, Chicago, Illinois, United States
Show AbstractNon-aqueous multivalent (MV) intercalation batteries offer energy density limitations, cost, and safety improvements relative to state-of-the-art Li-ion battery technology. As an emerging field, there are specific scientific questions that must be answered before MV batteries are commercially available. A marriage of theoretical and experimental approaches helps to expedite this process as part of the Joint Center for Energy Research (JCESR). MV-ion battery research indicates the successful generation of fundamental understanding of multivalent battery systems, including the metallic anode interface, electrolyte, and cathode for Mg, Ca, and Zn systems. This talk will focus on two topics: bulk MV ion speciation electrolytes and the proposed role these species play in efficient electrochemical process, and the development of new intercalation host structures with emphasis on high voltage cathodes for high energy densities MV batteries.
11:00 AM - *ES3.8.05
Assessing the Practicality of Multi-Valent-Ion Insertion/Extraction into Hosts by Chemical Methods
Arumugam Manthiram 1 , Watchareeya Kaveevivitchai 1
1 , University of Texas at Austin, Austin, Texas, United States
Show AbstractRechargeable batteries have aided the revolution in portable electronics. Their continued use in portable devices and their adoption for electrifying the transportation sector and storing the electricity generated from renewable sources require a balance among cost, cycle life, safety, energy density, power density, and environmental impact. With an aim to lower the cost and increase the energy density, rechargeable batteries based on multi-valent working ions (e.g., Mg, Zn, Ca, Al, and Y) have become appealing in recent years. However, rechargeable batteries based on multi-valent ions are met with numerous challenges, including lack of practically viable electrolytes or electrode hosts. The lack of appropriate electrolytes often leads to the dilemma of whether the poor electrochemical performance encountered originates from the electrode or electrolyte or both. Moreover, fabricating cells and evaluating them can often be time-consuming.
To overcome the above challenges, this presentation will focus on the development and use of simple chemical methods to rapidly assess the insertion/extraction of multi-valent ions into potential electrode host materials. Such an assessment can serve as a screening method without requiring the electrolytes for multi-valent working ions or the assembly of the electrochemical cells. For example, extraction of multi-valent ions from potential electrode hosts with the oxidizer nitronium tetrafluoroborate in acetonitrile medium and insertion of multi-valent ions into potential hosts with a microwave-assisted solvothermal process will be presented. In selected cases containing trivalent manganese ions, the disproportionation reaction of trivalent manages ions in dilute acidic environment into (i) divalent manganese ions and their leaching out into solution and (ii) tetravalent manganese ions and their retention in the electrode hosts will be presented. The approach reveals the challenges of utilizing close-packed structures like the spinel, particularly with an ionic oxide lattice, as a potential host for Mg or Zn. The electrostatic repulsions encountered by the diffusing multi-valent ions with the highly charged host cations in an oxide prevent their extraction, unlike in their lithium-ion counterparts. Such diffusional limitations are minimized on passing from a highly ionic oxide host to a less ionic sulfide host. On the other hand, the microwave-assisted solvothermal process offers a rapid approach to assess the insertion of multi-valent working ions. Choosing appropriate solvents allows a tuning of the reducing power during the microwave-assisted solvothermal process. Based on the chemical multi-valent-ion insertion/extraction methods presented, the identification of new electrode materials along with their electrochemical performances will be presented.
11:30 AM - ES3.8.06
Two-Dimensional Vanadium Carbide (MXene) as a High Capacity Cathode Material for Rechargeable Aluminum Batteries
Armin VahidMohammadi 1 , Majid Beidaghi 1
1 Materials Engineering, Auburn University, Auburn, Alabama, United States
Show AbstractLarge-scale utilization of electricity produced from renewable sources is limited by the intermittent nature of these sources and the lack of low-cost, efficient and safe technologies to store the generated electricity. Li-ion battery is the most mature battery technology and is used widely for portable electronics. However, their application for electrical transportation and grid-scale storage in the future is limited due to their high cost, limited Li metal resources, and their increasingly concerning safety issues. High energy rechargeable batteries based on multivalent ions could be a possible solution for the energy storage problems of the future. Among multivalent ion batteries, the aluminum battery has certain attributes that hold promise for electric transportation and large-scale stationary applications. Aluminum can exchange three electrons during electrochemical processes that can potentially be harnessed for higher charge storage. Additionally, aluminum is a lightweight metal and the most abundant in the Earth's crust. Also, aluminum has four times higher volumetric capacity compared to lithium (8040 mAhcm-3) with a reasonably high gravimetric capacity of 2980 mAhg-1. However, similar to other multivalent ion batteries, development of reliable aluminum batteries is dependent on finding high capacity cathode materials and suitable electrolytes with high voltage stabilities. Here, we report on a rechargeable Al-ion battery with two-dimensional (2D) vanadium carbide (V2C) as the cathode material. V2C is a member of a recently discovered family of 2D and layered transition metal carbides, called MXenes. A battery assembled with V2C cathode and Al metal anode shows reversible charge and discharge behavior with a charge plateau at around 1.5 V and a distinct discharge plateau at around 1.2 and a stable capacity of about 150 mAh/g for more than 50 cycles. Our detailed studies on the battery performance and identification of intercalated species will be presented at the conference. The results of our study represent an important step towards finding efficient cathode materials for Al batteries.
11:45 AM - *ES3.8.07
Development of Cathode Materials for Rechargeable Magnesium Batteries
Yan Yao 1 2
1 , University of Houston, Houston, Texas, United States, 2 , TcSUH, Houston, Texas, United States
Show AbstractRechargeable magnesium batteries (RMBs) have attracted tremendous attention in the past several years due to dendrite-free Mg anodes. One major hurdle for magnesium rechargeable batteries is the lack of an efficient Mg-ion intercalation cathode. Most existing cathodes suffer from sluggish diffusion of Mg-ion at room temperature. In this talk, I present three cathode design strategies to tackle this challenge. The first approach is an interlayer distance expansion strategy in layered metal chalcogenide to transform a Mg-inactive cathode approaching its theoretical capacity. The second approach relies on Mg complex cation as intercalating species with high reversible capacity of 260 mAh/g and two orders faster diffusivity at room temperature. The final approach takes advantage of redox-active polymers with coordination reaction mechanism. We hope to identify new directions towards overcoming the challenges facing multivalent-ion batteries.
12:15 PM - *ES3.8.08
Probing Efficient Mg Metal Electrodeposition and Dissolution with Weakly Coordinated Anions
Kevin Zavadil 1 , Nathan Hahn 1 , Tylan Watkins 1 , Artem Baskin 2 , Liwen Wan 2 , David Prendergast 2 , Nav Nidhi Rajput 2 , Kristin Persson 3
1 , Sandia National Labs, Albuquerque, New Mexico, United States, 2 , Lawrence Berkeley National Lab, Berkeley, California, United States, 3 , University of California Berkeley, Berkeley, California, United States
Show AbstractA viable rechargeable Mg battery requires a non-chloride electrolyte in which oxide cathodes are stable. Reported near-unit Coulombic efficiency electrolytes are all chloro-magnesium complex formers. The question arises as to whether Mg2+ can be efficiently deposited in the absence of chloride and, more generally, as a “naked” cation. In this presentation, the challenges of delivering Mg2+ as “naked” cation are explored through the use of select magnesium salts composed of weakly coordinating anions, including the 1-carbadodecaborate (monocarborane) anion. Raman, XAS, and multi-nuclear NMR demonstrate the Mg dication is coordinated by the solvent (e.g., the glyme series) not the anion throughout a wide range of salt concentration. Despite the lack of an anion in the first shell coordination sphere for the monocarborane, voltammetry and chronopotentiometry at microelectrodes show that Mg is deposited at the Mg:glyme interface at a Coulombic efficiency of greater than 99% and at overpotentials no larger those measured using chloro-magnesium complexes. Such observations change our view of the role that chloride plays as being beneficial but not essential for facile, efficient Mg deposition. The role of the anion, solvent and chloride will also be discussed in terms of Mg dissolution and passivation.
This work was supported as part of the Joint Center for Energy Storage Research, an Energy Innovation Hub funded by the U.S. Department of Energy, Office of Science. Sandia is a multiprogram laboratory managed and operated by Sandia Corporation, a wholly owned subsidiary of Lockheed Martin Company, for the U.S. DOE’s NNSA under contract DE-AC04-94AL85000.
12:45 PM - ES3.8.09
Nano-Sized Titanium Sulfide as Cathode Materials for Rechargeable Aluminum Ion Battery
Linxiao Geng 1 , Juchen Guo 1
1 , University of California, Riverside, Riverside, California, United States
Show AbstractRechargeable aluminum battery system is very intriguing due to the following reasons: First of all, aluminum has high capacity due to its trivalency. And aluminum is very easy to get since it is the most abundant metal element in earth’s crust.1 As a result, rechargeable aluminum battery can be very promising in large scale energy storage application. One of the main reasons that hinders the development of rechargeable aluminum battery is the lacking of electrolyte that can enable facile deposition and dissolution of aluminum in the anode side. On the other hand, facile electrochemical deposition and dissolution of aluminum can be achieved in room temperature ionic liquid (molten salt) synthesized by mixing aluminum chloride (AlCl3) with organic salts such as 1-butylpyridinium chloride, 1-ethyl-3-methylimidazolium chloride, etc. at a certain ratio.2,3 Utilizing ionic liquid as electrolyte marks a new stage of investigation on developing rechargeable aluminum battery system. In a previous research, our group proposed Chevrel phase Mo6S8 as the first conventional intercalation type cathode material.4 The logic of choosing transition metal sulfide instead of transition metal oxide as cathode material for aluminum ion battery is very important. Due to the strong coulombic effect, the energy barrier of multivalent ions transportation in the crystal structure is very high.5 Thus, a softer anionic framework is needed. Sulfide has a much lower electronegativity than oxide, which makes transition metal sulfide a very promising cathode candidate for rechargeable aluminum ion battery. Herein, we report the synthesis of nano sized layered TiS2 and cubic Ti2S4 as well as investigated their electrochemical properties as cathode materials for ionic liquid electrolyte based rechargeable aluminum ion battery at both room temperature and 50 °C. We further confirmed the aluminum intercalation in the TiS2 and Ti2S4 crystal structure using ex-situ XRD and XPS. The proposed titanium sulfide cathode materials showed decent reversible capacity and a higher working potential. More importantly, it further validates the feasibility of finding transition metal sulfide cathode materials for rechargeable aluminum ion battery.
1. Li, Q.; Bjerrum, N. J. J. Power Sources 2002, 110, 1.
2. Endres, F. ChemPhysChem 2002, 3, 144.
3. Jiang, T.; Chollier Brym, M. J.; Dube, G.; Lasia, A.; Brisard, G. M. Surf. Coat. Technol. 2006, 201, 1.
4. Geng, L.; Lv, G.; Xing, X. Guo, J. 2015, 27, 4926−4929.
5. Rong, Z.; Malik, R.; Canepa, P.; Sai Gautam, G.; Liu, M.; Jain, A. Persson, K.; Ceder, G. Chem. Mater., 2015, 27 (17), pp 6016–6021.
ES3.9: Electrochemical Capacitors
Session Chairs
Veronica Augustyn
Majid Beidaghi
Chunxu Pan
Christopher Rhodes
Thursday PM, April 20, 2017
PCC North, 200 Level, Room 226 A
2:30 PM - ES3.9.01
Facet Dependent Electrochemical Behavior of β-MnO2 Nanowires and Micro-Rods
Wentao Yao 1 , Yifei Yuan 2 , Hasti Asayesh-Ardakani 1 , Zhennan Huang 3 , Fei Long 1 , Craig Friedrich 1 , Khalil Amine 2 , Jun Lu 2 , Reza Shahbazian-Yassar 3 1
1 Mechanical Engineering-Engineering Mechanics, Michigan Technological University, Houghton, Michigan, United States, 2 Chemical Science and Engineering Division, Argonne National Laboratory, Chicago, Illinois, United States, 3 Mechanical and Industrial Engineering, University of Illinois at Chicago, Chicago, Illinois, United States
Show AbstractManganese dioxide has been widely used in the field of energy storage, such as supercapacitors, cathode material for lithium ion batteries, catalyst for lithium-air batteries and fuel cells, etc. The performance of the MnO2 materials is highly related to their size, morphology, and exposed crystal surfaces. Improving their electrochemical performances is in need of critical control and deep understanding of the synthesis process, especially for β-MnO2 materials. Although several modeling works have compared the properties of different crystal surfaces of the β-MnO2 material, no experimental results have been reported to control the exposed crystal surfaces and test the electrochemical properties of the different surfaces.
In this work, the lateral surfaces of hydrothermally grown β-MnO2 nanowires and micro-rods were examined by high-resolution transmission electron microscopy (HRTEM) as well as aberration-corrected scanning transmission electron microscopy (STEM). A mutual surface-energy-controlled mechanism was revealed to dominate the evolution of the lateral surfaces in the two β-MnO2 morphologies. Changing of the lateral surfaces followed the elimination of {100} surfaces and the increased occupancy of the stable {110} surfaces. The elimination of the {100} surfaces happened with both self-growth and oriented attachment of the nanowires and micro-rods along their {100} surfaces. The β-MnO2 micro-rods with higher occupancy of {100}/{110} lateral surfaces showed a higher capacitance than the micro-rods with low occupancy of lateral surfaces. The revealed mechanism is highly informative for the facet-controlled growth of β-MnO2 materials with other applications as well, such as intercalation cathode for lithium ion batteries or effective catalyst for lithium-air batteries.
2:45 PM - ES3.9.02
Tuning the Interlayer of Transition Metal Oxides for High Rate and Multivalent Energy Storage
Ruocun Wang 1 , James Mitchell 1 , William Lo 1 , Veronica Augustyn 1
1 , North Carolina State University, Raleigh, North Carolina, United States
Show AbstractLayered transition metal oxides are widely investigated for energy storage in batteries and electrochemical capacitors. In these materials, tuning of the interlayer region via the presence of structural water or other polar solvent molecules presents an opportunity to integrate a 2D, liquid-like layer into a solid state structure and improve the kinetics of interfacial charge transfer and solid state ion intercalation. Such structures would be particularly advantageous for high rate (< 5 minute) applications and energy storage with multivalent cations. This presentation will describe the synthesis of oxides with interlayer structural water and solvent molecules and the effect of these on the electrochemical energy storage behavior of two model oxides, WO3 and MoO3. In acidic electrolytes, hydrated WO3 offers improved energy efficiency at very fast sweep rates (< 30 seconds) over anhydrous WO3. Moreover, the electrochemical performance is achieved with particles that are several hundred nm in diameter and with mass loadings of > 5 mg cm-2 in traditional slurry electrodes. Hydrated MoO3 is solvent-exchanged with n-alkylamines to yield oxides with extremely large interlayer spacings of > 20 Å. These materials are then characterized for Mg2+ intercalation in non-aqueous electrolytes, where it has been found that the divalent charge presents significant energy barriers for desolvation at the interface and solid-state diffusion within the host structure. The ability to tune the interlayer spacing of layered oxides presents an important design tool for the development of both high rate and multivalent energy storage electrodes.
3:00 PM - ES3.9.03
Titanium Disulfide-Carbon Nanotube Electrodes Enable High Energy Density Pseudocapacitors
Xining Zang 1 2 , Caiwei Shen 1 2 , Emmeline Kao 1 2 , Mohan Sanghadasa 3 , Adam Schwartzberg 4 , Liwei Lin 1 2
1 Berkeley Sensor and Actuator Center, University of California, Berkeley, Berkeley, California, United States, 2 Mechanical Engineering, University of California, Berkeley, Berkeley, California, United States, 3 , U.S. Army RDECOM AMRDEC, Redstone Arsenal, Alabama, United States, 4 Molecular Foundry, Lawrence Berkeley National Laboratory, Berkeley, California, United States
Show AbstractMaterials in the transition metal dichalcogenide (TMDC) family are known to have high surface areas in favor of electrochemical energy storage systems. Among them, Titanium disulfide (TiS2) is the lightest and cheapest one with the potential for high energy density devices. It has been shown that lithium ions have very fast diffusion rates into and out of the TiS2 crystal lattices in favor of energy storages but the mechanical degradation after multiple cycles has been a key problem. This work shows a conformal coating process via the atomistic layer deposition (ALD) of TiN onto vertically aligned carbon nanotube (VACNT) forests and a follow-up sulfur vapor annealing process to convert TiN to TiS2. Experimental results exhibit excellent properties of high conductivity and energy density electrodes for supercapacitors with good stability over 10,000 charge/discharge cycles. We attribute this to the intercalation voltage of TiS2 is 2 Volts vs Li/Li+ to sustain a high electrochemical operation window of 3 Volts in the 21 M LiTFSI electrolyte. This system has achieved 195 F/g in specific capacitance, 60.9 Wh/kg in energy density, and 1250 W/kg in power Density. A flexible supercapacitor is constructed by transferring the TiS2-CNT forest film onto a Kapton tape using the LiTFSI/PVA/H2O electrolyte to have a high device projection capacitance of 60 mF/cm2.
3:15 PM - ES3.9.04
Complementary Electrochromic Supercapacitor for Multifunctional Smart Window
Feichi Zhou 1 , Yang Chai 1
1 , HK Polytechnic University, Hong Kong Hong Kong
Show AbstractComplementary Electrochromic Supercapacitor for Multifunctional Smart Window
Feichi ZHOU1, Feng Pan1, and Yang Chai1
1. Department of Applied Physics, The Hong Kong Polytechnic University, Hung Hom, Hong Kong.
Electrochromic supercapacitors, which incorporate the electrochromism and energy storage function, not only enable the real-time monitoring of the amount of energy stored or consumed in the device, but also allow dynamic light control through the device.1 WO3 based electrochromic supercapacitors have been demonstrated with a good trade-off between the electrochromic properties and the energy storage abilities, such as fast color change, high coloration efficiency, strong color contrast between fully charged (deep blue) and uncharged state (transparent), good capacity, power density and energy density. In the previous works, WO3 cathodic electrochromic layer was employed as both electrochromic and energy storage layer (WO3+H++e →HWO3), while the energy storage in the anodes (e.g.WO3, carbon nanotube (CNT), and CNT-WO3) is achieved by double-layer capacitance.2,3 To improve the energy storage capability and enhance the electrochromic performance, we employ NiO anodic electrochromic layer (NiO + OH- → NiOOH + e) as the complementary electrode instead of the WO3 anode.
In this work, the electrochromic supercapacitors in three different configurations have been investigated and compared: WO3/LiOH/PVA/WO3 (type A), NiO/LiOH/PVA/NiO (type B), and WO3/LiOH/PVA/NiO (type C). We examined both electrochromic performances and energy storage capabilities in the three devices. Type C device exhibits higher areal capacitance, energy density and coloration efficiencies compared with those of type A and B, indicating that the use of both anodic and cathodic electrochromic layers enables improved energy storage capability and wide range of color-changing. We also design a perovskite photovoltachromic supercapacitor by integrating the type C device (top) with a perovskite solar cell (bottom). The colored and fully charged supercapacitor can protect the solar cell from long-time exposure and enhance the photo-stability of solar cell.1
1. Zhou, F., Ren, Z., Zhao, Y., Shen, X., Wang, A., Li, Y. Y., Surya, C., Chai, Y., Perovskite Photovoltachromic Supercapacitor with All Transparent Electrodes. ACS nano 2016.
2. Sun, P., Deng, Z., Yang, P., Yu, X., Chen, Y., Liang, Z., Meng, H., Xie, W., Tan, S., Mai, W., Freestanding CNT–WO 3 hybrid electrodes for flexible asymmetric supercapacitors. Journal of Materials Chemistry A 2015, 3 (22), 12076-12080.
3. Yang, P., Sun, P., Chai, Z., Huang, L., Cai, X., Tan, S., Song, J., Mai, W., Large Scale Fabrication of Pseudocapacitive Glass Windows that Combine Electrochromism and Energy Storage. Angewandte Chemie International Edition 2014, 53 (44), 11935-11939.
3:30 PM - ES3.9.05
Direct Graphenic Nanocarbon Growth on Silicon for Miniaturised Supercapacitors
Mohsin Ahmed 1 , Bei Wang 1 , John Boeckl 2 , Nunzio Motta 3 , Francesca Iacopi 4
1 , Griffith University, Nathan, Queensland, Australia, 2 , Air Force Research Laboratory, Dayton, Ohio, United States, 3 , Queensland University of Technology, Brisbane, Queensland, Australia, 4 , University of Technology Sydney, Broadway, New South Wales, Australia
Show AbstractThe current silicon-based miniaturised devices need a stand-alone energy source, such as Li-ion battery for continuous powering [1]. The silicon technology is yet to develop seamlessly integrated energy storage systems. Here, we present a novel approach to fabricate on-silicon energy storage devices in the form of a supercapacitor, enabled by cubic silicon carbide (3C-SiC) on silicon. A nickel-assisted graphitization technique is used to grow graphene on 3C-SiC with high surface area to fabricate on-silicon supercapacitors. During annealing, 3C-SiC acts as both template and source of graphenic carbon, while, simultaneously, the nickel induces porosity on the surface by forming silicides which are subsequently removed. The surface of the SiC is made further porous by implementing a novel multi-step annealing and etching, leading to a very conductive surface over an accessible and porous SiC frame. This methods yields a few-layer discontinuous graphenic carbon electrode, which demonstrates a double-layer capacitance with a specific energy and power density of 0.15 Wh cm-3 and 9.0 W cm-3, respectively, and about 88% capacitance retention over 10,000 cycles.
Reference:
[1] F. Leng, C.M. Tan, M. Pecht, Effect of Temperature on the Aging rate of Li Ion Battery Operating above Room Temperature, Scientific Reports, 5 (2015) 12967.
3:45 PM - ES3.9.06
Fiber-Shaped Asymmetric Supercapacitors with Ultrahigh Energy Density for Flexible/Wearable Energy Storage
Li Yong 1 , Xiaoqin Yan 1 , Yue Zhang 1
1 , University of Science and Technology Beijing, Beijing China
Show AbstractThe increasing demand for energy and environmental protection has stimulated intensive research into energy storage and conversion from alternative energy sources. Supercapacitors (SCs), also called electrochemical capacitors or ultracapacitors, have attracted significant interest during the past few decades because of their high power density, super-long cycling life and safe operation. By offering rapid charging and discharging rates, and the ability to sustain millions of cycles, SCs bridge the gap between batteries and conventional electrolytic capacitors. Thus, SCs support a broad field of applications, ranging from consumer electronics, renewable energy storage systems, electronic textiles to transport vehicles.
As a new family of SCs, FSCs utilize cylindrically shaped fibers with diameters ranging from micrometers to millimeters as electrodes and they are generally light in weight and small in size. FSCs have attracted considerable attention since 2011 and have shown great application potential either as micro-scale devices to complement or even replace micro-batteries in miniaturized electronics and microelectromechanical systems or as macro-scale devices for wearable electronics or smart textiles.Further, compared with conventional SCs, FSCs have great potential to be easily integrated with other fiber
shaped energy harvesting devices or sensors to form integrated multifunctional or self-powered systems. However, compared to conventional SCs, research on FSCs is still in its infancy and it remains challenging to increase the energy density without sacrificing power density and cycling life. A common research goal is to develop flexible FSCs while preserving or even surpassing their electrochemical characteristics as compared to conventional SCs.
Here a fiber-shaped asymmetric supercapacitor (FASC) with high energy density has been developed successfully using CNT@ZnO-NWs@MnO2 fibers as the positive electrode and CNT fibers as the negative electrode. Due to the high capacitances and excellent rate performances of CNT@ZnO-NWs@MnO2 fibers and CNT fibers, such an asymmetric cell exhibits superior electrochemical performances. An optimized FASC can be cycled reversibly in the voltage range of 0–1.8 V, and exhibits a maximum energy density of 13.25 mW h cm�2, which is much higher than those reported for fiber-shaped supercapacitors. Owing to the rational structure design, the all-solid-state FASCs demonstrate excellent mechanical and electrochemical stability. Over 1000 bending cycles, 96.7% of the initial capacitance can still be retained.
4:30 PM - ES3.9.07
Direct Integration of an Anodic Molybdenum Trioxide Pseudocapacitor on a Screen-Printed Silicon Solar Cell for On-Module Energy Storage
Shi Nee Lou 1 , Zi Ouyang 1 , Derwin Lau 1 , Rose Amal 1 , Yun Hau Ng 1 , Alison Lennon 1
1 , University of New South Wales, Sydney, New South Wales, Australia
Show AbstractEffective harnessing of solar energy potential using photovoltaic (PV) energy generation systems requires practical coupling with advanced energy storage (ES) systems to mitigate the fluctuating availability of sunlight and the actual energy demand. Here, we demonstrate a novel hybrid solar energy harvesting-storage architecture that can address the instability of PV energy generation using a pseudocapacitive component to buffer the solar cell energy output when sunlight is insufficient to meet demand. Most existing reports of such photo-rechargeable ES systems are based on dye-sensitized solar cell (DSSC) and capacitor hybrids or some other DSSC-ES alternatives like redox flow batteries or Li-ion batteries. In this work, for the first time, we monolithically integrate a nanostructured molybdenum trioxide (MoO3) pseudocapacitive electrode on a rear Al electrode of an industrial screen-printed crystalline Si (c-Si) solar cell. The c-Si solar cell and pseudocapacitor hybrid combines the merits of both components, as: (i) the crystalline silicon solar cells are of high efficiency, 25 year lifespan, and market dominating and; (ii) the pseudocapacitors have higher power densities than batteries and better energy densities than electric double layer capacitors (EDLCs), satisfying the requirements for solar energy storage and discharge. As a result, our c-Si solar cell-pseudocapacitor hybrid achieves an average capacitance of 15 mF/cm2, energy density of 79 µJ/cm2 and capacity of 1.2 mC/cm2 from the light charge-galvanostatic discharge tests. This energy storage represents a 1 to 4 orders of magnitude increase over previous c-Si cell-ES hybrids such as those reported by Westover et al.[1] for porous Si EDLC on c-Si cells (14 µF/cm2 and 4.2 µJ/cm2) and Thekkekara et al.[2] for laser scribed graphene oxide supercapacitors on c-Si cells (~1 µF/cm2 and ~1.34 µC/cm2). Our three-electrode architecture uses the solar cell’s granular Al rear electrode as a textured substrate for the capacitor electrode, and the solar cell’s photocurrent was used to uniformly anodize a sputtered Mo layer to form the pseudocapacitive MoO3 surfaces on the solar cell. The enhanced charge storage performance of our hybrid device is attributed to the three-terminal architecture realized by the common screen-printed Al electrode which: (i) simplifies the fabrication process; (ii) shortens the charge transfer path and reduces losses associated with the transfer; (iii) acts as an electronic barrier preventing degradation of the solar cell’s open-circuit voltage during the pseudocapacitor’s electrode fabrication; and (iv) effectively increases the surface area of MoO3 though its rough granular texture creating more active surface sites for redox and intercalation charge storage.
References:
[1] A. S. Westover et. al. Applied Physics Letters 2014, 104, 213905.
[2] L. V. Thekkekara et. al. Applied Physics Letters 2015, 107, 031105.
4:45 PM - ES3.9.08
Graphene-AgVO3 Composite for Supercapacitor Applications
Jiaqian Qin 1
1 , Chulalongkorn University, Bangkok Thailand
Show AbstractIn this work, the graphene-AgVO3 composites were successfully synthesized by precipitation methods from graphene, AgNO3, and NH4VO3. The electrode was prepared from polytetrafluoroethylene (PTFE), conductive carbon, and the prepared materials with weight ratio of 1:1:8. The cyclic voltammetry (CV), electrochemical impedance spectroscopy (EIS), and Galvanostatic charging-discharging (GCD)methods were performed to study the prepared electrode by an Autolab Type III. The results show that the specific capacitance of the composite electrode is higher than that of graphene, and the cycle stability and rate capability could be both improved with AgVO3 addition. Furthermore, the supercapacitor device was also fabricated from two electrodes with filter paper as separator. The GCD shows that specific capacitance, cycle stability, and rate capability of the supercapacitor device can be enhanced with AgVO3 incorporation.
5:15 PM - ES3.9.10
Role of Redox Additives in Inducing Three Times Higher Electrochemical Activity in Supercapacitors Based on Co3O4 Nanorods
Md. Aqueel Akhtar 1 , Amreesh Chandra 1
1 , Indian Institute of Technology Kharagpur, Kharagpur India
Show AbstractThe electrochemical activity in crystalline cobalt oxide (Co3O4) based nanostructures is largely attributed to the associated redox reactions. This paper reports a simple processing technique to stabilize porous morphologies of Co3O4. The hierarchical nanorods of Co3O4 depicting a broom like microstructure, was observed by FESEM analysis. The growth mechanism is carefully monitored and reported in the paper. The electrochemical performance of such porous nanorods is appreciably higher than corresponding solid structures. Recently, it is suggested that the use of redox additives needs to be revisited, as it may provide an easy and economical strategy for improving the electrochemical performance of supercapacitors. We present the use of synergetic potassium ferricyanide K3Fe(CN)6 as redox additive in 2 M KOH electrolyte to achieve nearly 3.5 times increase in the specific capacitance in the three electrode cell based on porous Co3O4. Specific capacitance as high as 2000 F/g could be obtained in such cells. In addition, the coulombic efficiency is significantly improved and remains high, even after 3000 charge-discharge cycles. It is believed that Fe(CN)63-/Fe(CN)64- redox couple, having high reversibility, in conjugation with Co2+/Co3+, act as a facile electron relaying agent at the interface of electrode and redox additive supported electrolyte. This leads to reduced hindrance toward electron transfer. These electrochemical cells based on porous electrodes and supported by redox additives thus have great promise for application in next generation supercapacitors.
5:30 PM - ES3.9.11
Design of Miura Folding Based Micro-Supercapacitor Arrays with Higher Areal Densities as Foldable and Miniaturized Energy Storage Units
Bo Song 1 , Yun Chen 1 , Kyoung-sik Moon 1 , CP Wong 1
1 , Georgia Institute of Technology, Atlanta, Georgia, United States
Show AbstractMicro-supercapacitors (MSCs) are gaining increasing popularity as high-demand energy storage sources for on-chip or wearable electronics. The MSCs are fabricated by patterning the interdigitated micro-electrodes in planar substrates, which significantly shortens the ionic diffusion pathways and provides higher power/energy densities. The 2D design also enables to fabricate low profile energy storage devices resulting in system miniaturization. In addition, as highly porous carbon nanomaterials, functionalized graphene IS employed as electrodes, and its wide range of fabricapability coupled with arbitrary substrates leads to flexible energy storage components. For the next generation portable and wearable electronics, the areal size of the energy storage units should be further shrunk down.
Here we developed a novel approach to fabricate foldable MSC based on the art of paper folding (Miura folding) to realize considerable increase in areal energy densities. The Miura folding is a method to fold a flat surface into crease patterns consisting of parallelograms with smaller areas. Previously, Miura-origami patterns have been applied to fold maps and make solar panels; while in this report, the first prototype of MSC-based miniaturized energy storage systems were demonstrated. Each MSC patterns were made by thin-layer deposition (<100 nm) of conductive graphene sheets followed by plasma etching to form the interdigitated patterns. Paper or Kapton FPC (flexible printed circuits) were used as the substrates. The functionalized graphene inks and silver nanowires were chosen as the current collector since they can maintain good conductivity after many cycles of mechanical deformations. The aqueous polymer gels and ionic liquid-based ionogels were used as the solid-state electrolytes for easy pattern folding and preventing leakage. To test the electrochemical properties of the MSC array after folding, the polypropylene separator was introduced. The area of the MSC array would decrease by a factor of 8 by 3 times of folding. The cyclic voltammetry study showed that the capacitance of each pattern had a negligible decrease upon folding, while the areal energy density increased dramatically. Moreover, the materials of the components (electrodes, current collectors and substrates) were tailored and the folding lines were carefully designed to avoid cracking or delamination. Finally, a more complicated Miura folding was used to fold a 4×4 MSC arrays with 16 layers of a single pattern, and results indicated the areal energy density increased up to 10 times. The fabrication of a novel Miura folding pattern based MSC and their charge storage capability, the cycling performance and their practical applications will be presented. In addition, future study on folding algorithms and mechanical analysis to transform current foldable MSC arrays into 3D structures to further miniaturize the volume of devices and boost the volumetric energy density will be discussed.