bluuebunny/crossref_metadata_2025_split huggingface dataset:
Novel Sulfonated Aromatic Polymer Membranes for Breaking the Coulombic and Voltage Efficiency Trade-Off Limitation in Vanadium Redox Flow Battery
Authors: Kim Sangil , Wang Tongshuai , Han Junyoung , Kim Kihyun , Munchinger Andreas , Kreuer Klaus-Dieter , Bae Chulsung 
Published: February 2020

Vanadium redox flow batteries (VRFBs) have received extensive attention due to its attractive features for the large-scale energy storage because of their design flexibility, absence of intercalation/deintercalation and stress build-up in electrodes, and safe operation. One of the most critical components in VRFB is an ion exchange membrane which can prevent cross mixing of the multivalence vanadium ions, while it still allows the transport of protons (or anions) to complete the circuit. However, the trade-off relationship of proton exchange membrane limits the energy efficiency (EE) of the VRFB due to low coulombic efficiency (CE) caused by vanadium ion cross over through the membrane or high membrane resistances. Anion exchange membrane suffers from poor chemical stability and low voltage efficiency due to low ion conductivity.
In this study, we synthesized a series of novel sulfonated aromatic polymer membranes having high proton conductivity as well as selectivity which surpass the proton conductivity-selectivity trade-off relationship. The effect of the pendent group structure on the membrane ion selectivity and battery performance was investigated. It was found that the incorporation of aromatic structures on the pendent groups effectively improved the proton conductivity and selectivity. The membrane with aromatic pendent groups (BPAr-F4) shows 3 times higher vanadium/proton ion selectivity than Nafion 212. As a result, the VRFB single cell equipped with the 80um-thick BPAr-F4 membrane shows significantly better performance in comparison to the cell with Nafion membranes, as high as 97.18% CE, 95.91% VE and 93.20% EE (vs. 75.14% CE, 96.12% VE and 72.22% EE of Nafion 212; 91.30% CE, 95.63% VE and 87.62% EE of Nafion 117) at 20 mA/cm2. Small-angle X-ray scattering (SAXS) studies indicates that their unique morphologies with narrow aqueous ionic domains which are well organized with acidic -SO3H groups results in the high proton selectivity and VRFB performance.
Stabilizing NaCrO2 By Sodium Site Doping with Calcium
Authors: Zheng Lituo , Bennett J. Craig , Obrovac M. N. 
Published: February 2020

O3-type NaCrO2 is a promising cathode material as it offers decent energy density and is easy to synthesize from abundant elements. A capacity fade of ~20% in 50 cycles is usually observed for NaCrO2 in organic solvents [1–3]. Research regarding improving the capacity retention of NaCrO2 includes coating the NaCrO2 particle with carbon [1,2], or increasing grain boundary content by nanosizing the grains [3]. In this study, NaCrO2 was Na-site doped with calcium to improve cycling retention in Na cells.
A series of [Na1-2xCax]CrO2 materials were synthesized using a solid state method. Figure 1(a) shows the XRD pattern and Rietveld refinement of [Na0.9Ca0.05]CrO2. A single O3 phase was obtained with no observable impurity. Figure 1(b) shows the capacity and coulombic efficiency versus cycle number for NaCrO2 and [Na0.9Ca0.05]CrO2 when cycled in the voltage range of 2 V – 3.6 V. Both materials have similar initial capacity, However the capacity retention of Na0.9Ca0.05CrO2 is significantly improved, compared to NaCrO2. The coulombic efficiency of Na0.9Ca0.05CrO2 is also constantly higher than NaCrO2. It is speculated that calcium substitution results in a more stable structure during sodium (de)intercalation. The effect of calcium substitution on structural changes during cycling and air-stability will be discussed.
[1] J.J. Ding, Y.N. Zhou, Q. Sun, Z.W. Fu, Cycle Performance Improvement of NaCrO2 Cathode by Carbon Coating for Sodium Ion Batteries, Electrochem. Commun. 22 (2012) 85–88.
[2] C.Y. Yu, J.S. Park, H.G. Jung, K.Y. Chung, D. Aurbach, Y.K. Sun, S.T. Myung, NaCrO2 Cathode for High-Rate Sodium-Ion Batteries, Energy Environ. Sci. 8 (2015) 2019–2026.
[3] Y. Tsuchiya, A.M. Glushenkov, N. Yabuuchi, Effect of Nanosizing on Reversible Sodium Storage in a NaCrO2 Electrode, ACS Appl. Nano Mater. 1 (2018) 364–370.

Figure 1
Fast-Charging All-Solid-State 3D Li-Ion Battery with Ultra-Thin Lipon and High-Capacity Electrodes Using Large-Area Atmospheric-Pressure Spatial ALD
Authors: Ameen Mahmoud , Poplawski Mateusz , Haverkate Lucas , Grob Frank , Anothumakkool Bihag , Hermes Dorothee , Khandan del Sepideh , Roozeboom Fred , Unnikrishnan Sandeep 
Published: February 2020

The key challenges in next-generation all-solid-state Li-ion battery technology are related to the energy and power densities required, fast charging constraints, battery lifetime, while keeping the cost low by high-volume manufacturing. Currently, EVs are based on Li-ion batteries that often utilize highly flammable and toxic components such as liquid organic electrolyte, thus imposing a potential threat in case of failure. There is high pressure on developing batteries that are safer, smaller, and cheaper.
Here, we report on innovative materials and architectural approaches that have the potential to disrupt current Li-ion battery technology, especially by combining high-capacity with high charging/discharging rates. We aimed at improving 3D battery performance by using large area atmospheric pressure spatial atomic layer deposition (sALD) for further tuning the electrode and electrolyte layers at the nanometer-scale. Apart from enabling high charge/discharge rates, 3D electrode architectures pave the way for the use of high-capacity materials without long-term cycling challenges. We will show the potential of the intrinsically safe 3D all-solid-state batteries that can be extended to energy densities required for automotive (850 Wh/l and 375 Wh/kg at cell level).
However, novel architectures demand newer processing techniques, especially for conformal layer stacks over 3D structures. In this regard, we will present the results on high-rate 3D Li-ion battery electrodes coated using our patented sALD technology, which enables charging times below 10 minutes. Next, we will discuss the first-ever sALD-based LiPON electrolyte material, deposited at least 10x faster than the current technologies using conventional ALD systems, and exhibiting high Li-ion conductivity > 10-7 S/cm and very low electronic conductivity (< 10-12 S/cm). The LiPON layers are pinhole-free and demonstrated to be cycled without shorts. Such electrolytes are also relevant for the development of protection layers in wet electrolyte-based lithium ion batteries, as well as for enabling thin-film planar and 3D solid-state batteries with ultrathin electrolyte layers (few 10’s of nanometers). Highlighted during the presentation will also be the attribute of the sALD technique to produce conformal and upscalable coatings that can be applied in roll-to-roll processing using metal foils to further enable the innovative and cost-effective 3D battery layers.
Computation-Guided Exploration for New-Chemistry Solid Electrolyte with Fast Ion Conduction and Good Electrochemical Stability
Authors: Mo Yifei 
Published: February 2020

A key challenge in enabling all-solid-state Li-ion batteries is the development of solid electrolyte materials with high Li ionic conductivity and good electrochemical stability.Current research efforts on solid-state Li-ion conductors focus mostly on oxides and sulfides. Unfortunately, oxide and sulfide chemistries have an undesirable trade-off between ionic conductivity and stability. New solid-state chemistries that can exhibit a low activation energy, good stability, and other desirable properties are a promising research direction for new solid electrolytes in solid-state batteries.
Using ab initio computation, we systematically explored new anion chemistries beyond oxides and sulfides, such as nitrides and halides. Our computation found nitride anion chemistry exhibits unique stability against Li metal, which is either thermodynamically intrinsic or a result of stable passivation. Many nitrides materials can serve as promising lithium metal protection materials to achieve long-term stability.
In addition, our first principles computation study confirmed that chlorides and bromides exhibit fast Li-ion conduction, wide electrochemical stability, and good cathode interface compatibility. We found Cl and Br anion chemistries can achieve fast Li-ion conduction in a variety of anion sublattices, and do not require the rare bcc anion lattice as in current fast ion-conducting sulfides or the concerted migration mechanism in current fast-conducting oxides. Further, we found chlorides and bromides generally exhibit wide electrochemical windows, poor electronic conductivity, and good cathode interface compatibility, and thus hold desirable conducting and stability properties for SE applications.
Our presentation highlight nitrides, chlorides and bromides as highly promising alternative chemistries for solid electrolytes in solid-state batteries.
References:
Shuo Wang, Qiang Bai, Adelaide M. Nolan, Yunsheng Liu, Sheng Gong, Qiang Sun, and Yifei Mo, “Lithium Chlorides and Bromides as Promising Solid-State Chemistries for Fast Ion Conductors with Good Electrochemical Stability”, Angewandte Chemie (online)
Adelaide Nolan, Yizhou Zhu, Xingfeng He, Qiang Bai, Yifei Mo, “Computation-Accelerated Design of Materials and Interfaces for All-Solid-State Lithium-Ion Batteries”, Joule, 2, 2016-2046 (2018)
Yizhou Zhu, Xingfeng He, Yifei Mo, “Strategies Based on Nitride Materials Chemistry to Stabilize Li Metal Anode”, Advanced Science, 1600517 (2017)
Molecular-Level Organic-Inorganic Hybrid Solid State Electrolyte
Authors: Li Yejing , Liu Ping 
Published: February 2020

All-solid-state batteries (ASSB) are of great interest due to their unique chemical/physical properties, such as non-flammability, no liquid leakage and gas generation, and a broad operating temperature range. Solid state electrolyte (SSE) can be divided into two categories: solid inorganic and polymer electrolytes. Inorganic electrolytes possess high ionic conductivities but are generally brittle and difficult to process. In contrast, polymer electrolytes are inherently flexible and easy to process but their ionic conductivities are generally low. Thus, extensive research has been devoted to combining the inorganic electrolyte and polymer electrolyte to achieve a balance in ionic conductivity and mechanical flexibility. The mechanical flexibility also enables hybrid solid electrolyte (HSE) to achieve an intimate contact/ improved interface with solid-state electrode. HSE has so far been fabricated by mechanical mixing of inorganic and polymeric materials which result in a heterogeneous mixture. It is often observed that interfacial issues between the components result in ionic conductivities far less than the values estimated from volume fractions and pure material performance.
Here we report the synthesis of a sulfide based HSE via an in-situ polymerization reaction. An inorganic Li-P-S electrolyte is used to trigger the polymerization of a sulfur containing precursor. As a result, the resultant composite achieved molecular bonding at the interface between the inorganic and the polymeric electrolytes. The interfacial structure was confirmed by the cryogenic-transmission electron microscopy and cryogenic-scanning transmission electron microscopy-energy-dispersive X-ray spectroscopy. Owing to this molecular level interaction, the ionic conductivity of this HSE is as high as 2.91*10-5 S cm-1 at room temperature, which is very close to the value expected from the volume fractions of the components. An ASSB fabricated with the HSE along with LiNi0.80Co0.15Al0.05O2 as the cathode and Li-In alloy as the anode demonstrated stable cycling shown in Figure 1. Our work shows that molecular engineering at the interface is a promising approach to fabricate flexible HSEs with high ionic conductivity for ASSBs.

Figure 1
Construction of Porphyrin-Sensitized Solar Cells Containing Toray™/TGP-H-060 Carbon - Based Cathodes
Authors: Manríquez Juan , Barroso-Martínez Jaxiry Shamara , Ortega-Díaz David , Bustos Erika , Gutiérrez-Granados Silvia 
Published: February 2020

In this work, we present the construction and photovoltaic response of porphyrin-sensitized solar cells containing TorayTM/TGP-H-060 carbon – modified indium-doped tin oxide (ITO) cathodes (ITO/C), as a viable alternative for substituting platinum oxides – modified ITO cathodes (ITO/PtOx), which are traditionally employed for designing dye-sensitized solar cells. In this case, a binary mixture (75:25) of propylene carbonate (PC) : 3-methoxypropionitrile (MPN), containing 0.015M I2 plus 0.285M LiI was employed as electrolyte for filling the photo-cells.
On one hand, our experimental results demonstrated that both cathodic systems, ITO/C and ITO/PtOx, had a very comparable electron transfer kinetics when studied the cathodic semi-reaction I3
- + 2e­
- --> 3I- at these electrode surfaces.

Table 1. Electron transfer constants (k°) and cathodic transfer coefficients (∝c) obtained for the semi-reaction I3
- + 2e­
- --> 3I- at ITO/C and ITO/PtOx cathodes. Electrolyte: 0.015M I2 plus 0.285M LiI contained in a binary mixture 75:25 of PC:MPN at 25°C. A polycrystalline Pt cathode was also employed for comparison purposes.

cathode

Electron transfer kinetic parameters

k°/10-4 (cm/s) and ∝

c

Pt
5.31
0.27

ITO/PtOx

3.35
0.26

ITO/C
2.70
0.23

On the other hand, a detailed revision of Table 2 reveals that the photovoltaic responses of porphyrin-sensitized solar cells containing ITO/C and ITO/PtOx cathodes were comparable under simulated solar light (AM1.5, 100mW/cm2). These interestingly results confirmed that TorayTM/TGP-H-060 carbon – modified ITO cathodes are promising to substitute those PtOx – modified ITO cathodes typically employed for constructing dye-sensitized solar cells.

Table 2. Photovoltaic responses obtained for porphyrin-sensitized solar cells containing ITO/C and ITO/PtOx cathodes, where: Eoc, jsc, ff and ξ are open-circuit potential, short-circuit photocurrent, fill-factor and global conversion efficiency, respectively, under simulated solar light (AM1.5, 100mW/cm2).

cathode

Eoc

(V)

jsc (m
A/cm2)

ff

ξ(%)

ITO/PtOx

-0.30
1.23
0.39
0.17

ITO/C
-0.35
1.18
0.40
0.19

References
U.López-García, O.A.Castellanos, L.A.Godínez, J.Manríquez, “Electrophoretically-Assisted Deposition of Mesoporphyrin IX on Nanoparticulate TiO2 Films for Constructing Efficient Dye-Sensitized Solar Cells”, Journal of The Electrochemical Society, 158 (2011) F100-F105.
Complex Capacitance Analysis on Electrochemical Properties of Passive Film Formed on Rebar in Concrete
Authors: Inohira Kanaho , Hoshi Yoshinao , Shitanda Isao , Itagaki Masayuki 
Published: February 2020

Reinforced concrete structures have been widely used for the social infrastructures because the rebar embedded in concrete shows high corrosion resistance due to the formation of passive film formed on the rebar. The monitoring of the conditions of the passive film formed on the rebar is important to ensure the proper maintenance and management of reinforced concrete structures. An electrochemical impedance spectroscopy (EIS) is a useful method to evaluate the corrosion state of reinforced concrete nondestructively1, 2). In the present study, the stability of passive film formed on the rebar was evaluated in the concrete simulated environment by the EIS.
A saturated calcium hydroxide solution was used to simulate the environment in concrete. The chloride ion concentration was adjusted to 3.8 mmol dm-3 and 16 mmol dm-3 by adding sodium chloride to a saturated aqueous solution of calcium hydroxide. The electrochemical impedance measurement was carried out by a three electrode system. A rod electrode made of cylindrical carbon steel (SR345) that has the same composition as rebar SD345, as is often used in actual structures, was adopted as a working electrode. A saturated KCl silver / silver chloride electrode and a platinum wire were used as a reference electrode and a counter electrode respectively. The electrochemical impedance was measured every 12 hours during immersion. The 3D impedance was measured in order to investigate the time-dependent change of the thickness of the passive film. An electrochemical measurement system (HZ-7000, Hokuto Denko Corporation) was used as the measurement device. The measurement frequency range was 10 kHz to 10 mHz with 5 points per logarithmic sweep.
By plotting the admittance and capacitance calculated from the impedance of carbon steel on the complex plane, the resistance and capacitance of the passive film formed on the carbon steel were evaluated. The changes of thickness of passive film formed on the carbon steel with time were discussed.

References

1) J. L. Dawson et al., Proceedings of NACE Corrosion / 78, Paper No. 125 (1978).
2) Yoshinao Hoshi et al., Electrochemistry, 87, 78-83, (2019)
3) Masayuki Itagaki et al., Electrochemistry, 75, 649-655, (2007).
(Invited) Implementation of Three-Dimensional Solid State Battery
Authors: Heo Jin S. , Park Hwi-Yeol , Jeong Huisu , Kim Kyounghwan , Lim Sungjin , Shon Jeong-Kuk , Yang Ho-Jung 
Published: February 2020

While increasing the multifunction of wearable devices such as smart watch, earphone, and glasses, the run-time of battery is getting more important to be a competitive product in the wearable market. In order to get more reliable and longer lasting battery, the concepts of 3D battery architecture have been suggested to improve energy density [1].
Several 3D microbattery architectures have been proposed to maximize the areal energy density and rate discharge capability by maintaining short ion-transport distances between cathode and anode [2]. However, the implementation of high areal capacity 3D electrode is difficult to fabricate due to the limitation of manufacturing processing [3]. Moreover, conventional fabrication technology of the thin film electrolyte cannot make good step coverage of the 3D conformal electrolyte.
In this research, we propose technical approaches to fabricate a high energy density 3D battery structure with good step coverage of the 3D conformal electrolyte. First, we developed a high aspect ratio (=h/w, where h is height and w is width of cathode) 3D cathode which consists of only LiCoO2 with high electrode density without any binder and conductive additives. And then, two kinds of different solid electrolyte layers, LLZO and LiPON, were applied to the 3D conformal coating on the 3D cathode by sol-gel and CVD processing. The process of sol gel and CVD efficiently improved step coverage of 3D conformal electrolyte. Subsequently, Li-metal was evaporated to make a bed for striping and plating as anode. Finally, the 3D solid state battery was evaluated and analyzed for the feasibility study of a next generation battery.

References

[1] Jeffrey W. Long et al, Chemical review, 104 (2004) 4463-4492
[2] Stefania Ferrari et al, J. Power Sources, 286 (2015) 25-46
[3] Matthew Roberts et al, J. Mater. Chem, 21 (2011) 9876-90
(Invited) Construction of Flexible Interfacial Layer for Solid-State Li Batteries
Authors: Yang Yong 
Published: February 2020

There is a growing interest in all-solid-state lithium batteries(ASLBs) for their safety and high energy density. However, the power density for ASLBs is still far away from satisfactory on the account of high interfacial resistance at electrode / solid electrolyte interface.
For example, Garnet-type solid-state electrolytes (SSEs) are considered as a good choice for solid-state batteries, yet the interfacial issues with metallic Li limit their applications. In my group, we propose an ultra-simple and effective strategy to enhance the interfacial connection between garnet SSEs and Li metal just by drawing a graphite-based soft interface with a pencil[1]. Both experimental analysis and theoretical calculations confirm that the reaction between graphite-based interfacial layer and metallic lithium forms a lithiated connection interface with good lithium-ionic and electronic conductivity. Compared to the reported interfacial materials, the graphite material provides a soft interface with better ductility and compressibility. With the improvement by this soft interface, the impedance of symmetric Li cells significantly decreases from 1350 to 105Ωcm2 and the cell can cycle for over 1000hoursat a current density of 300 μA/cm2 at room temperature. Moreover, a solid-state battery with Li-metal anode, ternary cathode NCM523 and graphite-based interface modified garnet SSEs is fabricated and displays excellent rate capability and long cycling performance.
In addition, LGPS-type materials show extremely high Li+ conductivity. But when in contact to Li metal, they can be reduced to produce Li2S, Li3P and Li-M alloy and form a mixed ionic and electronic conducting layer at the interface, which hinders the application of Li metal in such solid electrolyte system. We report on a simple approach for the modification of the interface between Li and Li10SnP2S12 sulfide solid electrolyte by utilizing ionic liquid[2]. Our study shows that the addition of 1.5M LiTFSI/Pyr13TFSI ionic liquid can not only promote intimate contact but can in-situ form a stable SEI layer at the interface between Li and solid electrolyte as well. A stable SEI layer instead of mixed conducting layer can prevent sulfide solid electrolyte from further decomposition and improve the cycle performance of batteries.

References:

1) Y.J. Shao, H.C.Wang, et al ; ACS Energy Lett.; 2018, 3, 1212-1218
2) B.Z. Zheng; J.P.Zhu, et al; ACS Applied Mater. & Interfaces; 2018, 10, 25473-25482
(Keynote) Where are Batteries Going?
Authors: Crabtree George 
Published: February 2020

Lithium-ion batteries are expanding well beyond their initial market in personal electronics, to encompass electric vehicles, the electricity grid and some forms of electric flight. These new applications require new standards for higher performance, lower cost and greater safety. Batteries have several promising options to meet these challenges, including incremental improvements to the basic lithium-ion platform, substantial modifications of the lithium-ion platform, (often called advanced lithium-ion) and entirely new concepts beyond the lithium-ion platform. The challenges, opportunities and applications of each option will be considered.
This work was supported as part of the Joint Center for Energy Storage Research (JCESR), an Energy Innovation Hub funded by the US Department of Energy, Office of Science, Basic Energy Sciences.
(Keynote) Taking a Closer Look at SEI Chemistry
Authors: Xu Kang C. 
Published: February 2020

Interphases enables the electrodes to operate at potentials beyond what thermodynamic stability limits of non-aqueous electrolytes would allow. The most prominent example of interphases is perhaps solid-electrolyte-interphase (SEI) on graphitic anodes in Li-ion batteries, which ensures the reversibility of Li-ion intercalation chemistries. In typical electrolytes, chemical building blocks of SEI mainly come from solvents decomposition products, and, although we often acknowledge that many aspects of SEI remains unknown, we thought we at least have establish the following foundation beyond doubt: (1) semi-carbonates from the single-electron reduction of carbonate solvents constitutes the major portion of SEI; (2) the formation of SEI is irreversible; and (3) SEI is ionic conductor and electron insulator. However, when taking a closer look at the “olde SEI” using a series of new techniques, we found some of those principles might need to be re-written.
In this work, I will summarize the newest understanding of this “least understood” component in Li-ion battery that were achieved in my own group and my collaborators.