bluuebunny/crossref_metadata_2025_split huggingface dataset:
Transmission Line Model of Battery Cell's Impedance: Theory Vs. Experiments
Authors: Moskon Joze , Drvarič Talian Sara , Dominko Robert , Gaberscek Miran 
Published: December 2020

Electrochemical impedance spectroscopy (EIS) is arguably the most accurate electrochemical technique. It often appears as the main or, more commonly, an additional approach in experimental investigation of advanced batteries. To a large extent, the popularity of impedance technique is probably due to fully automized, easy-to-use modern devices and, also, due to user-friendly softwares that facilitate the basic analysis of measured spectra in terms of equivalent circuit fitting. On the negative side, the final result of such a standard approach is a set of parameters (resistors, capacitors, inductors) which are difficult to interpret in terms of physical processes occurring in the measured cell. In the worst case, assignment of equivalent circuit parameters to physical processes is carried out arbitrarily which frequently leads to erroneous intepretation of cell’s physics.
Interpretation of measured EIS spectra gets much more reliable if instead the equivalent circuit approach one relies on physical-chemical models that describe transport and reaction phenomena in given cell. The linearized physical-chemical models of electrochemical cells can be solved in three ways: (i) by finding an analytical solution, (ii) using conventional numerical procedures, (iii) using the transmission line approach which transcribes the physical equations into a large number of spatially distributed discrete visual elements that resemble the usual resistors and capacitors.
In this presentation we will demonstrate the power of transmission line approach when trying to resolve the physical meaning of measured impedance features of advanced battery cells. After explaining the transmission line methodology on conventional battery electrodes, such as LiCoO2, NMC, LiFePO4, the general applicability of the approach will be demonstrated on state of the art electrodes such as sulfur cathode, lithium rich fcc and magnesium batteries. In all cases discussed we will compare the actual measured spectra with theoretical predictions of the corresponding transmission line model. We will show that the latter is able to accurately predict the trends in both sizes and shapes of measured spectra when changing the experimental conditions (electrode thickness, concentration of salt, state of charge, cycle number, surface treatment of electrode, porosity of electrode etc.). Furthemore, the proposed model is also able to capture peculiar small details of measured impedance responses, some of which will be discussed and explained in order to further elucidate processes taking place in modern battery components.
Electrodeposited Zinc-Based Films As Anodes for Aqueous Zinc Batteries
Authors: Fayette Matthew , Chang Hee Jung , Rodriguez Perez Ismael , Li Xiaolin , Reed David 
Published: December 2020

In the past thirty years, there has been significant development in the search for alternative energy sources such as secondary battery systems. Zinc (fourth-most mined material) has attracted much attention due to its abundance, low-cost, and recyclability. More-over, as Zinc-based batteries can be manufactured with aqueous-based electrolytes, this allows for competition with Lithium-ion batteries, but with the advantage of enhanced safety. Zinc-based batteries (MnO2/Zinc) have been previously commercialized and are one of the dominant technologies in the battery market. However, the alkaline MnO2/Zinc battery is not currently considered re-chargeable due to the formation of zinc-dendrites, passivation of Zn metal, and cathode poisoning. In contrast to the alkaline system, the mild acidic system does not suffer from zinc passivation as there is negligible generation of zinc oxide/zinc hydroxide.
In this work, we report a proof-of concept work where electrodeposited zinc-based anodes (zinc and copper-zinc) are used in mild aqueous zinc batteries. The study provides a comparison of commercial zinc foil, and electrodeposited zinc/copper-zinc in a mild aqueous zinc battery. Prior to this comparison, electrodeposition conditions are determined by cyclic voltammetry. The three anodes are further compared structurally through X-ray diffraction and scanning electron microscopy. Further electrochemical characterization was carried out in coin cells as symmetric/asymmetric and full cells to evaluate the feasibility of each anode. The electrodeposited zinc-based anodes exhibit low electrode polarization (~0.025V), and stable cycling performance from 0.25-10 mA cm-2 compared to commercial zinc foil. Coulombic efficiencies at 1 mA cm-2 were over 98% for the electrodeposited zinc-based materials and were maintained for over 100 cycles. Furthermore, full cells with an electrodeposited zinc and brass anode, EMD MnO2 cathode, in 1M ZnSO4 + 0.1M MnSO4 delivered capacities of 96.3, and 163 mAh g-1, respectively, at a 100 mA g−
1
compared to 92.1 mAh g-1 for commercial zinc. Lastly, the zinc-based anodes also show better rate capability at a current density of up to 3 A g-1.
(Invited) Multivalent Battery Chemistries: Anodes, Cathodes, and Electrolytes
Authors: Gewirth Andrew A. , Ta Kim , Zhang Ruixian 
Published: December 2020

Multivalent batteries based on Mg2+, Al3+, Ca2+, or Zn2+ may have advantages over traditional lithium ion batteries, particularly in the area of volumetric capacity. Each of these chemistries, however, presents challenges which inhibit implementation. In this talk we discuss aspects of each chemistry. With regard to Mg and Ca, we discuss the essential features of electrolytes that support reversible cation deposition and stripping. The crucial feature is the presence of electrolyte components which depassivate the electrode. In the case of Mg, this depassivation is typically provided by Cl-. In the case of Ca, depassivation comes from hydride formation at the interface. In both cases, the necessity to form a depassivation product leads to altered deposition kinetics.
For Al and Zn we discuss cathodes. For Al, we report a new C3N4-based cathode, and on the mechanism of Al interaction with it. In particular, Al associates with C3N4 not as bare Al3+, but rather as a AlCl4
-. For Zn, we report a new series of spinels -- ZnAlxCo2-xO4 and ZnNixMnxCo2-2xO4 -- and discuss their utility as cathode materials for non-aqueous Zn-ion battery. The data show that the Zn2+ ions reversibly intercalate into the spinel structure during the charge/discharge processes, a compositional transformation directly correlated with a multiply reversible conversion between Co4+/Co3+ or Co4+/Co3+, Ni4+/Ni3+/Ni2+ and Mn4+/Mn3+ oxidation states within the lattice. The data suggest that Mn, Ni co-substitution for Co in ZnCo2O4 is an efficient method to facilitate Zn-deintercalation and enhance discharge capacity.
Highly Energy-Efficient Vanadium Redox Flow Batteries with Thermo-Chemically Activated Graphite Felt Electrodes
Authors: Neburchilov Vladimir , Tsay Ken , Fatih Khalid , Neagu Roberto , Kodra Oltion , Kjeang Erik , Vinicios Juvencio da Silva Caio 
Published: December 2020

The Vanadium Redox Flow Battery (VRFB) is a promising energy storage technology for large scale stationary applications that require a long cycle life of over 10 years. The specific feature of VRFB is the slower kinetics of redox reactions (V2+/V3+) on the negative electrode (NE) as compared to the kinetics of the redox reaction (VO2
+ /VO2+) on the positive electrode (PE) and poor kinetic reversibility.. The commonly used electrodes for VRFBs are graphite felt electrodes (GFE). One of the main challenges facing these GFEs is their activation that enhances a rate of redox reactions due to the increase of GFE wettability and surface area. Another challenge is capability to maintain GFE activation over cycling.
In this work, we report on thermal and thermo-chemical activation of GFEs which leads to the formation of functional groups (carboxyl C=O, phenolic C-O, and adsorbed O or H2O for the enhancement of the electrode wettability and active surface area. The physicochemical characterization of the activated GFEs was performed using X-ray photoelectron spectroscopy (XPS) and contact angle measurements. The electrochemical study was conducted by cyclic voltammetry (CV) measurements in 0.2M VOSO4/2M H2SO4 at 1 mV/s and cycling tests (50 cycles, three tests for every GFE) in a commercial 9cm2 VRFB ( Standard Energy Corp.) using a charge/discharge current density of 80 mA/cm2 at 20oC and a commercial vanadium electrolyte 1.6M [V]/2M H2SO4. The increase of temperature of GFE heat treatment of GFEs from 400 to 500oC resulted in the growth of the energy efficiency (EE) of VRFBs with such electrodes from 81.3 to 87.2%, respectively, due to the increase of adsorbed oxygen or water from 1.6 to 8.72% and C-O (C-OH) groups from 0.49 to 2.09%, respectively and wettability (contact angle (CA) decreases from 78.7 to 65.1o). Analysis of CVs of the redox reaction VO2
+ /VO2+ shows the decrease of the peak of potential separation ΔEp (Epa-Epc) from 0.357 to 0.345 V and the peak of current ratio (Jpa/Jpc) from 1.406 to 1.26, indicating lower polarization due to the increase of the electrode surface area, acceleration and reversibility of these redox reaction, respectively (Table 1). The proposed additional treatment of the heat treated GFE at 400oC (GFE400) in strong oxidants H2O2, H2SO4 and HNO3 for the decomposition of C=O and the enhancement of the content C-O groups and GFE wettability didnt result in the performance improvement (VRFB with GFE400+10%H2O2 - energy efficiency of 78%).
The thermal treatment of GFE at 500oC demonstrated improvement of VRFB cell performance, namely growth of energy efficiency to 87.2% and VE to 90.1%, % due to the increase of wettability and active surface area of GFEs.

Figure 1
(Invited) Calcium-Ion Cathode Materials
Authors: Kim Sanghyeon , Yin Liang , Parajuli Prakash , Blanc Lauren , Fister Timothy T , Park Haesun , Kwon Bob Jin , Zapol Peter , Klie Robert F , Kang Kisuk , Nazar Linda F , Lapidus Saul H. , Ingram Brian J. , Vaughey John T. 
Published: December 2020

Calcium-ion batteries (CIBs) could be an alternative to lithium-ion batteries (LIBs) for certain niche applications due to their theoretically high operating potentials and the high natural abundance of calcium. However, the development of CIBs has been limited by the lack of proper electrolytes and electrode materials due to the difficulties identifying Ca-ion insertion host materials. Previous efforts to develop CIB cathodes have been made mainly based on intercalation materials such as Prussian blue-based materials (1) , layered oxide materials (MoO3 (2), V2O5 (3), CaCo2O4 (4-5), and layered phosphates (VOPO4·2H2O) (6). In this discussion we will be reviewing the state of Ca-ion battery materials and delve into an analysis of several functional polyanionic materials that show promising properties and characteristics as CIB cathodes. The NASICON-type NaV2(PO4)3, derived from de-sodiation of Na3V2(PO4)3, has been shown to reversibly intercalate Ca2+ -ions (capacity 81 mA h g-1) above 3V (vs. Ca2+/Ca) with stable cycling performance. DFT calculations, XAS, XRD, and TEM studies were used to support the insertion of Ca-ions and give insights into the diffusion mechanism of the materials involved (7,8). The presentation will also provide insights into materials design aspects of CIB materials and note areas of need that would benefit the MV battery community.
References:
(1) Albert L. Lipson, Baofei Pan, Saul H. Lapidus, Chen Liao, John T. Vaughey,Brian J. Ingram “Odyssey of Rechargeable Ca-Ion Batteries: A New Energy Storage System”. Chem. Mat.
2015,
27
, 8442.
(2) Marta Cabello, Francisco Nacimiento, Ricardo Alcántara, Pedro Lavela, Carlos Pérez Vicente,José L. Tirado “Applicability of Molybdite as an Electrode Material in Calcium Batteries: A Structural Study of Layer-type CaxMoO3” Chem. Mat., 2018,
30, 5853−5861
(3) M. Bervas, L.C. Klein, G.G. Amatucci “Vanadium oxide–propylene carbonate composite as a host for theintercalation of polyvalent cations”. Solid State Ionics
2005
176, 2735–2747.
(4) A. Ponrouch, M.R. Palacin “On the road toward calcium-based batteries” Current Opinion in Electrochemistry
2018, 9, 1-7.
(5) Haesun Park, Yanjie Cui, Sanghyeon Kim, J. T. Vaughey, PeterZapol “Ca Cobaltites as Potential Cathode Materials for Rechargeable Ca-Ion Batteries: Theory and Experiment” J. Phys. Chem. C
2020,
124, 5902−5909
(6) J.J. Wang, S.S. Tan, F.Y. Xiong, R.H. Yu, P.H. Wu, L.M. Cui, Q.Y. An “VOPO4 2H(2)O as a new cathode material for rechargeable Ca-ion batteries” Chem Comm. 2020
56 3805.
(7) M.L. Mao, T. Gao, T, S.Y., Hou, C.S. Wang “A critical review of cathodes for rechargeable Mg batteries” Chem Soc Reviews
2018
47 8804.
(8) T.N. Chen, G.S. Gautam, W.X. Huang, G. Ceder, G “First-Principles Study of the Voltage Profile and Mobility of Mg Intercalation in a Chromium Oxide Spinel” Chem Mat
2018
30 152.
Characterization and Optimization of Co-Doped SnO2 As Anode for Lithium-Ion Batteries
Authors: Birrozzi Adele , Asenbauer Jakob , Ashton Thomas , Groves Alexandra R. , Darr Jawwad , Bresser Dominic 
Published: December 2020

Tin oxide-based materials have been intensively investigated as alternative anodes for lithium-ion batteries due to their high specific capacity, environmental friendliness, non-toxicity, and ease of handling.[1] However, the initial formation of Li2O upon lithiation is essentially irreversible, which has a severe effect on the first cycle coulombic efficiency and the reversibly achievable capacity in general.[2] It has been shown that the incorporation of transition metal dopants can address this issue, as it enables the reversible formation and reformation of Li2O.[3] The choice of the dopant, however, plays a critical role for the long-term cycling stability, rate capability, and eventual energy density of the resulting lithium-ion cells.[4]

Herein, we show that the addition of specific combination of different dopants allows for further tailoring the electrochemical properties. We also demonstrate the production of such materials using a scalable continuous hydrothermal flow method. The performance of the best composition (Sn0.9Co0.05Mn0.05O2, SCMO) was further improved by applying a carbonaceous coating. The electrochemical investigation of the coated anode material was conducted in half-cells and in high-energy full-cells using high-voltage LiNi0.5Mn1.5O4 (LNMO) as active material for the cathode (Figure 1).[5] The performance of the full-cells was further enhanced by carefully optimizing the anode composition and fine-tuning the full-cell design, considering electrolytes and different pre-lithiation degrees.

Reference
s
:

[1] F. Zoller, D. Böhm, T. Bein, D. Fattakhova-Rohlfing, ChemSusChem.,
1

2

, 4140 (2019)
[2] I.A. Courtney and J.R. Dahn, J Electrochemical Soc., 144
, 2045 (1997)
[3] D. Bresser, S. Passerini and B. Scrosati, Energy Environ. Sci.
,

9
, 3348 (2016)
[4] Y. Ma et al, Sustain. Energy Fuels,
2
, 2601 (2018)
[5] A. Birrozzi et al., Batter. Supercaps,
3
, 284 (2020).

Figure 1
Quenching Method and Performance of High Voltage Layered Lithium Rich Nickel Manganese Oxides
Authors: Burke Sven , Whitacre Jay 
Published: December 2020

Due to their promise of high specific capacity layered lithium rich nickel manganese oxide materials have a large body of literature dedicated to their structure, and electrochemical behaviors[1–5]. Yet these materials have often been marred by significant capacity losses, rate capability limitations, and structural instability over the course of cycling. Several techniques involving surface and structural modifications have been used to mitigate these capacity losses[6–8]. In this work we used a hybrid acetate/nitrate precursors and sol-gel/combustion synthesis to conduct an unprecedented combined survey of the composition of Li(NixLi(1/3-2x/3)Mn(2/3-x/3))O2, and synthetic quench rates to elucidate the effects of these variables on electrochemical cycling behavior, bulk morphology, and surface morphology of the layered lithium rich manganese oxides. We find that the electrochemical behavior of these materials is dependent on both the nickel content as well as the quenching method, with a lower limit on the nickel content beyond which the effects of quenching are minimal. Despite XRD revealing loss of super lattice peaks indicating a loss of transition metal ordering, often associated with capacity loss, galvanostatic cycling of samples saw improved capacities over the course of cycling. SEM found bulk morphology of cathodes differs across nickel contents, yet it did not experience large changes over the course of cycling. The use of TEM found that the surfaces of Li(NixLi(1/3-2x/3)Mn(2/3-x/3))O2 powders is highly sensitive to quenching method, and comparison of surfaces over the course of cycling provided incites into the effects of quenching and nickel content on electrochemical cycling behaviors of the cathode materials. This investigation reveals that careful considerations in synthesis are required for the realization of high-performance layered lithium rich nickel manganese oxides.
[1] Y. J. Park, Y.-S. Hong, X. Wu, K. S. Ryu, S. H. Chang, J. Power Sources
2004, 129, 288.
[2] Z. Lu, L. Y. Beaulieu, R. A. Donaberger, C. L. Thomas, J. R. Dahn, J. Electrochem.
Soc.
2002, 149, A778.
[3] Z. Lu, J. R. Dahn, J. Electrochem. Soc.
2002, 149, A1454.
[4] M. Jiang, B. Key, Y. S. Meng, C. P. Grey, Chem.
Mater.
2009, 21, 2733.
[5] J. Bréger, N. Dupré, P. J. Chupas, P. L. Lee, T. Proffen, J. B. Parise, C. P. Grey, J. Am. Chem. Soc.
2005, 127, 7529.
[6] D. Eum, B. Kim, S. J. Kim, H. Park, J. Wu, S. P. Cho, G. Yoon, M. H. Lee, S. K. Jung, W. Yang, W. M. Seong, K. Ku, O. Tamwattana, S. K. Park, I. Hwang, K. Kang, Nat.
Mater.
2020, 19, 419.
[7] H. Z. Zhang, Q. Q. Qiao, G. R. Li, S. H. Ye, X. P. Gao, J. Mater. Chem.
2012, 22, 13104.
[8] Y. Wu, A. Manthiram, Solid State Ionics
2009, 180, 50.
A Maturation Process or Binders Based on Coordination Chemistry to Boost the Mechanical Strength and Cyclability of Si-Based Electrodes
Authors: Huet Lucas , Kana Nassima , Mazouzi Driss , Vanpeene Victor , Devic Thomas , Maire Eric , Roué Lionel , Lestriez Bernard 
Published: December 2020

Silicon is attractive as negative electrode material for Li-ion batteries (LIBs) to increase their energy density [1]. The main challenge is to deal with the large silicon volume expansion induced by its lithiation, which damages the mechanical integrity of the electrode, and produces an unstable solid electrolyte interphase (SEI).
Recently, we have discovered a post-processing treatment, called maturation, which very significantly improves the mechanical and electrochemical stabilities of silicon-based electrodes made with polycarboxylic acid binders [2-4]. It consists of storing the electrode in a humid atmosphere for a few days before drying and cell assembly. We found that during maturation, the atmospheric-induced corrosion of the current collector releases oxidized copper species that migrate into the electrode to physically crosslink the binder phase, substantially modifying its resiliency to the silicon volume variation as shown by various in situ and operando characterizations. The pre-addition of a small amount of copper or zinc salt in the electrode slurry allows to reach similar improvement of electrochemical performance than maturation [5]. This reveals that there is great potential to explore coordination chemistry to design new, more efficient binders through the medium strength and dynamic nature of coordination bonds [6].

Acknowledgments

The authors thank the Natural Sciences and Engineering Research Council of Canada (NSERC) (grant RGPIN-2016-04524) and Transition Énergétique Québec (TEQ) (grant Techno-0040-0001) for financial support of this work.

References

[1] M.N. Obrovac, Si-alloy negative electrodes for Li-ion batteries. Current Opinion in Electrochemistr, 2018, 9, 8–17.
[2] Z. Karkar et al., How silicon electrodes can be calendered without altering their mechanical strength and cycle life J. Power Sources, 2017, 371, 136-147.
[3] C. Real Hernandez et al., A Facile and Very Effective Method to Enhance the Mechanical Strength and the Cyclability of Si-Based Electrodes for Li-Ion Batteries, Adv. Energy Mater, 2017, 1701787.
[4] V. Vanpenne et al., Adv. Energy Mater, Dynamics of the morphological degradation of Si-based anodes for Li-ion batteries characterized by in-situ synchrotron X-ray tomography, Adv. Energy Mater. 9, 2019, 1803947
[5] D. Mazouzi et al., CMC-citric acid Cu(II) cross-linked binder approach to improve the electrochemical performance of Si-based electrodes Electrochimica Acta, 2019, 304, 495-504.
[6] T. Devic, B. Lestriez, L. Roué, Silicon Electrodes for Li-Ion Batteries. Addressing the Challenges through Coordination Chemistry, ACS Energy Letters, ACS Energy Lett., 2019, 4, 550−557.
Abundant Natural Dye-Based Organic Molecule As Sole Redox Active Material for Symmetric Aqueous Redox Flow Battery
Authors: Nambafu Gabriel , Shao Minhua 
Published: December 2020

Organic redox flow batteries (ORFBs) are considered potential substitutes to their traditional metal-based counterparts for application as large scale energy storage device[1] . This is in consideration to the merits offered by organic redox active materials i.e. inexpensive, environment friendly, high solubility and existence in diverse molecular structures that facilitates synthetic tunability to design molecules with the desired physicochemical properties[2] . However, capacity fade as result of cross-contamination has been one of the main challenges hindering development of this energy storage technology[3] . Symmetric redox flow batteries that employs a single redox active material in both electrolytes have the potential to address this challenge making them very attractive[4] .
In this work, a low-cost organic dye is coupled with a radical organic molecule to form a sole bifunctional redox active material that can be used as both negoyte (-0.71V) and posolyte (0.52V versus Hg/Hg2SO4) in an organic symmetric aqueous redox flow battery. Cyclic voltammetry studies of the combined bifunctional molecule reveal reversible redox reactions of the redox couples leading to a theoretical cell voltage of 1.23V. A symmetric pumped cell testing demonstrated over 100 consecutive charge/discharge cycles with nearly 85% coulombic efficiency at current density of 2.5 mAcm-2. The battery utilizes a pH neutral supporting electrolyte (NaCl in water) which is inexpensive, non-corrosive and non-flammable resulting to a low-cost, durable, safe and environmental-friendly redox flow battery.