Liquid Electrolyte Cells Research Articles

Polymer-Ion Interaction Prompted Quasi-Solid Electrolyte for Room-Temperature High-Performance Lithium-Ion Batteries.

Lithium-ion batteries using quasi-solid gel electrolytes (QSEs) have gained increasing interest due to their enhanced safety features. However, their commercial viability is hindered by low ionic conductivity and poor solid-solid contact interfaces. In this study, a QSE synthesized by in situ polymerizing methyl methacrylate (MMA) in 1,2-dimethoxyethane (DME)-based electrolyte is introduced, which exhibits remarkable performance in high-loading graphite||LiNi0.8Co0.1Mn0.1O2 (NCM811) pouch cells. Owing to the unique solvent-lacking solvation structure, the graphite exfoliation caused by the well-known solvent co-intercalation is prohibited, and this unprecedented phenomenon is found to be universal for other graphite-unfriendly solvents. The high ionic conductivity and great interfacial contact provided by DME enable the quasi-solid graphite||NCM811 pouch cell to demonstrate superior C-rate capability even at a high cathode mass loading (17.5mgcm-2), surpassing liquid carbonate electrolyte cells. Meanwhile, the optimized QSE based on carbonates exhibits excellent cycle life (92.4% capacity retention after 1700 cycles at 0.5C/0.5C) and reliable safety under harsh conditions. It also outperforms liquid electrolytes in other high-energy-density batteries with larger volume change. These findings elucidate the polymer's pivotal role in QSEs, offering new insights for advancing quasi-solid-state battery commercialization.

Exploring the Role of Coordinating Environments on Durability of Nickel-Based Catalysts for Hydrogen Evolution Reactions

Ni-based platinum-group-metal (PGM)-free catalysts for hydrogen evolution reaction have been considered viable for the commercialization of alkaline exchange membrane water electrolysis (AEMWE) due to their high activity and low cost. Even though several highly active Ni-based catalysts have been developed in recent years, their long-term stability under commercially relevant conditions was not systematically assessed, preventing a direct comparison with the currently used catalysts. While not as active, the current commercial PGM-free catalysts are highly stable, with an operational life measured in decades. However, conducting durability assessments through long-term durability studies can take over 10,000 hours which is impractical. Consequently, accelerated stress tests (ASTs) specifically targeting the catalyst and simulating uncontrolled shutdown and high overpotential scenarios are needed to further improve AEMWE technology.In this presentation, the ASTs of several Ni-based catalysts with different coordination environments (nickel molybdenum, nickel cupferron1, Ni-NiO, and a novel high surface area de-alloyed Ni catalyst) will be explored. The catalysts were subjected to high overpotentials and uncontrolled shutdown cycles in both liquid electrolyte and AEMWE cells. The structure of these catalysts was observed using in situ Raman spectroscopy, XRD, TEM, and BET gas adsorption analysis and correlated to changes in electrochemical performance. The determination of the catalyst structure during these ASTs is paramount in designing durable PGM-free catalysts for improved AEMWE performance.1) Doan, H.; Kendrick, I.; Blanchard, R.; Jia, Q.; Knecht, E.; Freeman, A.; Jankins, T.; Bates, M. K.; Mukerjee, S. Functionalized Embedded Monometallic Nickel Catalysts for Enhanced Hydrogen Evolution: Performance and Stability. J. Electrochem. Soc. 2021, 168 (8), 084501. https://doi.org/10.1149/1945-7111/ac11a1.

Quasi-Solid-State Electrolyte Induced by Metallic MoS2 for Lithium-Sulfur Batteries.

Lithium-sulfur (Li-S) batteries are a promising high-energy-density technology for next-generation energy storage but suffer from an inadequate lifespan. The poor cycle life of Li-S batteries stems from their commonly adopted catholyte-mediated operating mechanism, where the shuttling of dissolved polysulfides results in active material loss on the sulfur cathode and surface corrosion on the lithium anode. Here, we report in situ formation of a quasi-solid-state electrolyte (QSSE) on the metallic 1T phase molybdenum disulfide (MoS2) host that extends the lifetime of Li-S batteries. We find that the metallic 1T phase MoS2 host is able to initiate the ring-opening polymerization of 1,3-dioxolane (DOL), forming an integrated QSSE inside batteries. Nuclear magnetic resonance analysis reveals that the QSSE consists of ∼13% liquid DOL in a solid polymer matrix. The QSSE efficiently mediates sulfur redox reactions through dissolution-conversion chemistry while simultaneously suppressing polysulfide shuttling. Therefore, while ensuring high sulfur utilization, it avoids degradation of both electrodes, as well as the concomitant electrolyte consumption, leading to enhanced cycling stability. Under a practical lean electrolyte condition (electrolyte-to-sulfur ratio = 2 μL mg-1), Li-S pouch cell batteries with the QSSE demonstrate a capacity retention of 80.7% after 200 cycles, much superior to conventional liquid electrolyte cells that fail within 70 cycles. The QSSE also enables Li-S pouch cell batteries to operate across a wider temperature range (5 to 45 °C), together with improved safety under mechanical damage.

Solid-state lithium batteries composed of hematite and oxide electrolyte

As Li-ion battery anode materials, two types of hematite (Fe2O3(big), Fe2O3(ultrafine)) were evaluated by using liquid electrolyte and oxide-based solid electrolyte. Although the anode using Fe2O3(ultrafine) with larger specific surface area showed a high initial reversible capacity in the liquid-electrolyte cell, there was a steep capacity decay in the cycling test. In the solid-electrolyte cell, we obtained very low reversible capacities of 40 mA h g−1 for the anode using Fe2O3(big) with smaller specific surface area. In contrast, the capacity of Fe2O3(ultrafine) anode was as high as 400 mA h g−1 at the 20th cycle. This is the first demonstration of charge–discharge reactions for Fe2O3 anode in oxide-based solid-state batteries. The Fe2O3(ultrafine) particles were dispersed relatively uniformly between solid electrolyte in the active layer, suggesting that the contact area between Fe2O3 and solid electrolyte becomes large. Consequently, Fe2O3(ultrafine) could benefit from larger contact area delivering the suitable reaction site for Li+ to improve the anode performance.

Degradation of Styrene-Poly(ethylene oxide)-Based Block Copolymer Electrolytes at the Na and K Negative Electrode Studied by Microcalorimetry and Impedance Spectroscopy

The electrode-electrolyte interface of alkali metal electrodes and solid polymer electrolytes (SPE) is challenging to access because solid electrolytes are difficult to remove without damaging the interphase region. Herein, the two non-invasive techniques isothermal microcalorimetry (IMC) and electrochemical impedance spectroscopy (EIS) are combined to explored degradation processes of reactive sodium and potassium metal electrodes in contact with SPEs. Comparison of the parasitic heat flows and interfacial resistances at different current densities with a liquid electrolyte (LE) system showed marked differences in aging behaviour. The data also suggest that the electrochemically active surface area of alkali metal electrodes increase with cycling, leading to larger parasitic heat flows and indicating morphological changes. SPE-based cells exhibit similar levels of parasitic heat flow at different current densities, which is in stark contrast to the LE cell where a strong correlation between the two is evident. The ambiguity of EIS spectra is challenging due to the overlapping time constants of the underlying electrode processes. However, equivalent circuit modelling can be used to follow trends in resistance evolution, for example to track the rapidly increasing cell impedance in K/K symmetric cells during a 48 h equilibration interval prior to cycling, which abruptly disappeared once cycling begins.

Limitations of Liquid Electrolyte RDE Experiments for the Determination of OER Catalyst Activity: The Effect of the Catalyst Layer Thickness

Developing novel oxygen evolution reaction (OER) noble metal catalysts with a low metal packing density is key for the wider large-scale implementation of polymer electrolyte membrane water electrolysis (PEMWE). OER activities of these new catalysts are commonly measured in liquid electrolytes using half-cell configurations, such as rotating-ring-disk electrodes (RDE). Recent studies in liquid electrolyte cells showed that the accumulation of microscopic oxygen bubbles within the OER catalyst layer causes shielding of active catalyst sites. In this study, three different OER catalysts were screened for their activity at different loadings in a liquid electrolyte RDE setup. Potential sweeps using bare Ir black, a commercially available IrO2/TiO2 and a homemade Ir/ATO (antimony doped tin oxide) catalyst with different loadings were performed. It was demonstrated that the mass activity of the Ir/ATO catalyst decreases by more than 50% with a catalyst loading increase, which is attributed to the accumulation of microscopic oxygen bubbles within the catalyst layer and was correlated to the coating thickness of the catalyst layer. We suggest screening the OER catalyst activity of low packing catalyst materials in a loading analysis by testing minimum three different loadings within the kinetic Tafel slope region to avoid underestimation of the catalyst activity.

Binary Atomic Sites Enable a Confined Bidirectional Tandem Electrocatalytic Sulfur Conversion for Low-Temperature All-Solid-State Na-S Batteries.

The broader implementation of current all-solid-state Na-S batteries is still plagued by high operation temperature and inefficient sulfur utilization. And the uncontrollable sulfur speciation pathway along with the sluggish polysulfide redox kinetics further compromise the theoretical potentials of Na-S chemistry. Herein, we report a confined bidirectional tandem electrocatalysis effect to tune polysulfide electrochemistry in a novel low-temperature (80 °C) all-solid-state Na-S battery that utilizes Na3 Zr2 Si2 PO12 ceramic membrane as a platform. The bifunctional hollow sulfur matrix consisting binary atomically dispersed MnN4 and CoN4 hotspots was fabricated using a sacrificial template process. Upon discharge, CoN4 sites activate sulfur species and catalyze long-chain to short-chain polysulfides reduction, while MnN4 centers substantially accelerate the low-kinetic Na2 S4 to Na2 S directly conversion, manipulating the uniform deposition of electroactive Na2 S and avoiding the formation of irreversible products (e.g., Na2 S2 ). The intrinsic synergy of two catalytic centers benefits the Na2 S decomposition and minimizes its activation barrier during battery recharging and then efficiently mitigate the cathodic passivation. As a result, the stable cycling of all-solid-state Na-S cell delivers an attractive reversible capacity of 1060 mAh g-1 with a high CE of 98.5 % and a high energy of 1008 Wh kgcathode -1 , comparable to the liquid electrolyte cells.

Binary Atomic Sites Enable a Confined Bidirectional Tandem Electrocatalytic Sulfur Conversion for Low‐Temperature All‐Solid‐State Na−S Batteries

AbstractThe broader implementation of current all‐solid‐state Na−S batteries is still plagued by high operation temperature and inefficient sulfur utilization. And the uncontrollable sulfur speciation pathway along with the sluggish polysulfide redox kinetics further compromise the theoretical potentials of Na−S chemistry. Herein, we report a confined bidirectional tandem electrocatalysis effect to tune polysulfide electrochemistry in a novel low‐temperature (80 °C) all‐solid‐state Na−S battery that utilizes Na3Zr2Si2PO12 ceramic membrane as a platform. The bifunctional hollow sulfur matrix consisting binary atomically dispersed MnN4 and CoN4 hotspots was fabricated using a sacrificial template process. Upon discharge, CoN4 sites activate sulfur species and catalyze long‐chain to short‐chain polysulfides reduction, while MnN4 centers substantially accelerate the low‐kinetic Na2S4 to Na2S directly conversion, manipulating the uniform deposition of electroactive Na2S and avoiding the formation of irreversible products (e.g., Na2S2). The intrinsic synergy of two catalytic centers benefits the Na2S decomposition and minimizes its activation barrier during battery recharging and then efficiently mitigate the cathodic passivation. As a result, the stable cycling of all‐solid‐state Na−S cell delivers an attractive reversible capacity of 1060 mAh g−1 with a high CE of 98.5 % and a high energy of 1008 Wh kgcathode−1, comparable to the liquid electrolyte cells.

Structure and Activity-Durability Tradeoff of Coated Fe-N-C Catalysts for the Oxygen Reduction Reaction

Fe-based catalysts stand out for oxygen reduction reactions among the platinum group metal (PGM)-free catalysts for reducing the reliance on expensive and scarce platinum. With the endeavor of a PGM-free community, the state-of-the-art Fe-N-C catalysts have demonstrated encouraging initial activity in Proton Exchange Membrane Fuel Cell (PEMFC) 1-2. However, their long-term stability and durability remain a challenge, both in acidic liquid electrolyte cells and in single-cell PEMFCs3. Recently, a novel approach has demonstrated improved durability of Fe-N-C catalysts during ORR, which consisted of coating a pre-existing Fe-N-C with a thin carbon overlayer obtained via chemical vapor deposition of a metal-organic framework (ZIF-8), at 1100 °C4. However, the underlying mechanism for enhanced durability remains unclear. One of the keys to improved stability lies in the specific structure of the catalysts, including the coordination of the ORR-active iron atoms and the structure of the nitrogen-doped carbon matrix, especially the structure located at the top surface of catalysts. The CVD conditions that affect the structure of FeNC must be optimized, to achieve the optimal activity-durability trade-off.This presentation will report on the structure, activity, and durability trends of a suite of FeNC catalysts coated at different CVD conditions. The key parameters have been investigated, such as deposition temperature, overlayer thickness, and iron speciation on their ORR activity and durability. The coated Fe-N-C catalysts have been evaluated for their activity/durability (in oxygenated environments) both in liquid electrolyte cells and PEMFCs. The coated Fe-N-C demonstrated inferior initial activity and improved durability (Figure 1). The correlation between the structural information derived from multiple techniques (XRD, Mossbauer spectroscopy, TEM, Raman spectroscopy, N2 sorption, etc) and their electrochemical behaviors will be discussed.References Jiao, L.; Li, J.; Richard, L. L.; Sun, Q.; Stracensky, T.; Liu, E.; Sougrati, M. T.; Zhao, Z.; Yang, F.; Zhong, S.; Xu, H.; Mukerjee, S.; Huang, Y.; Cullen, D. A.; Park, J. H.; Ferrandon, M.; Myers, D. J.; Jaouen, F.; Jia, Q., Nature Materials 2021, 20 (10), 1385-1391.Mehmood, A.; Gong, M.; Jaouen, F.; Roy, A.; Zitolo, A.; Khan, A.; Sougrati, M.-T.; Primbs, M.; Bonastre, A. M.; Fongalland, D.; Drazic, G.; Strasser, P.; Kucernak, A., Nature Catalysis 2022, 5 (4), 311-323.Martinez, U.; Komini Babu, S.; Holby, E. F.; Zelenay, P., Current Opinion in Electrochemistry 2018, 9, 224-232.Liu, S.; Li, C.; Zachman, M. J.; Zeng, Y.; Yu, H.; Li, B.; Wang, M.; Braaten, J.; Liu, J.; Meyer, H. M.; Lucero, M.; Kropf, A. J.; Alp, E. E.; Gong, Q.; Shi, Q.; Feng, Z.; Xu, H.; Wang, G.; Myers, D. J.; Xie, J.; Cullen, D. A.; Litster, S.; Wu, G., Nature Energy 2022, 7 (7), 652-663. Figure 1

Nafion-Based Quasi-Solid-State Polymer Electrolyte for Lithium-Sulfur Batteries

Lithium-sulfur batteries are considered a strong contender for next-generation high-energy battery systems given their high gravimetric energy density. However, this battery chemistry is still facing challenges such as the polysulfide shuttle effect caused by the high solubility of long-chain lithium polysulfides (Li2Sn) resulting in active material loss and compromised cycle life. Solid-state polymer electrolytes (SPEs) represent a promising pathway to address this issue by preventing the formation and transport of these undesirable polysulfide intermediates.1,2 Moreover, the application of flexible polymer electrolytes promotes safe high energy batteries for smart textiles.In this study, single lithium-ion conducting solid polymer electrolytes (SLIC-SPEs) based on lithiated Nafion membrane have been investigated, utilizing the chemical and thermal stability of this kind of ionomers. Among others, a mixture of ethylene carbonate (EC) and propylene carbonate (PC) was tested as organic aprotic swelling solvent offering advantageous characteristics such as great chemical stability and high ion mobility while avoiding phase separation issues and undesired leaching.Sulfur-infiltrated ultramicroporous carbon composite cathodes were utilized in combination with the investigated SLIC-SPEs, facilitating a quasi-solid-state lithium-sulfur full cell with carbonate-solvent compatibility and high active material utilization.3 Electrochemical performance of the full cell was investigated elaborately and compared with a reference system using solely the liquid EC:PC solvent. While rapid capacity fading can be observed for the liquid electrolyte cell, an enduring high capacity is found in the lithiated-Nafion system. For better understanding of these effects, cycling analysis was accompanied by implementing impedance spectroscopy upon galvanostatic cycling. The electrochemical characterization indicates the formation of a stable film and high degree of reversibility during cycling of the lithiated-Nafion cell whereas an increased film resistance due to sulfur cross-over and electrolyte decomposition was observed within the liquid electrolyte system.(1) Z. Li, W. Lu, N. Zhang, Q. Pan, Y. Chen, G. Xu, D. Zeng, Y. Zhang, W. Cai, M. Yang, J. Mater. Chem. A 2018, 6 (29), 14330-14338.(2) X. Hao, H. Wenren, X. Wang, X. Xia, J. Tu, J. Colloid Interface sci. 2020, 558, 145-154,(3) M. Nojabaee, B. Sievert, M. Schwan, J. Schettler, F. Warth, N. Wagner, B. Milow, K. A. Friedrich, J. Mater. Chem. A 2021, 9 (10), 6508-6519,

Computational Investigation of Halide Solid Electrolytes for Na-Based Batteries

Significant scientific and economic challenges are presented by developing battery systems with increased energy storage capacity. Geopolitical issues might pose supply chain risks for lithium (Li)-ion batteries, which are frequently used in portable electronics. As an alternative, sodium-ion batteries (NIBs), have drawn attention from researchers all over the world due to the perspective of being lower cost systems[1]. In comparison to lithium-ion batteries, solid-state sodium-ion batteries (SSSBs) promise as a safe, scalable, and environmentally friendly alternative. For the production of robust and adaptable SSSBs, the development of highly conductive, electrochemically stable, and chemically stable solid electrolytes (SEs) is essential [2]. With greater durability, adaptability, and safety, solid-state batteries with inorganic solid electrolytes are being heavily investigated as safer and perhaps more energy-dense alternatives to liquid electrolyte cells.Sulfides solid electrolytes have been extensively investigated due to their mechanical softness and high ionic conductivity. However, the electrochemical oxidation stability of those materials are as low as 2 V (vs. Na+/Na)[3]. Alternatively, the excellent ion conductivities and stability at high potentials have made halide compounds, intriguing candidates for solid electrolytes in batteries. These compounds offer fast ion transport, good stability at highly oxidative potentials, and are easily processed. A wide range of chemistries, such as A3MX6 (A = Li, Na; M = Sc, In, Y, Yb, Er, Hf, Ho, Dy, Al, Zr; X = F, Cl, Br, I), have been synthesized with tunable properties and the characterizations of those materials shows relevant electrochemical proprieties [2].In our work, we investigate different Na-based chloride compounds by Density Functional Theory (DFT). We expand beyond the reported compositions to consider possible cation-substituted compounds. Here, we report on the structures, ionic conduction pathways and ionic conductivity (computed by molecular dynamics methods) expected for such compounds. In the next months, we will also evaluate the compounds´ chemical and electrochemical stability. Our work moves us one step closer towards the development of stable and highly conductive solid electrolytes for Na-based solid-state batteries.References :[1] J. Mater. Chem. A, 2021,9, 281-292[2]J. Mater. Chem. A, 2022,10, 21565-21578[3] ACS Energy Lett. 2022, 7, 10, 3293–3301

Highly cyclable voltage control of magnetism in cobalt ferrite nanopillars for memory and neuromorphic applications

Tuning the properties of magnetic materials by voltage-driven ion migration (magneto-ionics) gives potential for energy-efficient, non-volatile magnetic memory and neuromorphic computing. Here, we report large changes in the magnetic moment at saturation (mS) and coercivity (HC), of 34% and 78%, respectively, in an array of CoFe2O4 (CFO) epitaxial nanopillar electrodes (∼50 nm diameter, ∼70 nm pitch, and 90 nm in height) with an applied voltage of −10 V in a liquid electrolyte cell. Furthermore, a magneto-ionic response faster than 3 s and endurance >2000 cycles are demonstrated. The response time is faster than for other magneto-ionic films of similar thickness, and cyclability is around two orders of magnitude higher than for other oxygen magneto-ionic systems. Using a range of characterization techniques, magnetic switching is shown to arise from the modulation of oxygen content in the CFO. Also, the highly cyclable, self-assembled nanopillar structures were demonstrated to emulate various synaptic behaviors, exhibiting non-volatile, multilevel magnetic states for analog computing and high-density storage. Overall, CFO nanopillar arrays offer the potential to be used as interconnected synapses for advanced neuromorphic computing applications.

(Invited) In-Situ/Operando X-Ray Absorption Spectroscopy: Methods and Challenges in Electrocatalysts Characterization

During the last decades X-ray absorption spectroscopy (XAS) has proved to be a fundamental tool for understanding the nature of active catalytic species, especially in the form of highly dispersed, amorphous phases, and in the case of single atom catalysts. [1-4] The efforts in developing this technique under working conditions are justified by the extraordinary information that can be obtained on the identity of active species, reaction intermediates and activation/degradation phenomena. Clearly, the challenges embrace many fields: 1) catalysts can be very complex materials, comprising different, even disordered, phases; 2) it is a technique that uses synchrotron radiation, and the design of an appropriate experimental set-up requires know-how, but also synergy with a beamline team; 3) a rigorous interpretation of the XAS data requires high level of expertise to avoid easy misinterpretations, and the continuous development of new data analysis methods.This talk aims to discuss in-situ/operando XAS studies to investigate the activity and stability of novel catalysts during electrochemical reactions in proton exchange membrane fuel cell (PEMFC) devices and during CO2 reduction. In most studies with operando XAS, electrochemical studies have been performed in liquid electrolyte cells. While instructive, the performance and stability observed in liquid electrolyte at room temperature is however never directly transferable to the performance in a PEMFC device, operating at high temperature, high current density, and with a solid-polymer electrolyte interface. This current limitation can be overcome by the design of an appropriate cell able to isolate and extract the signal coming from the area where the reactions take place.Part of the talk will also be devoted to some time-resolved structural probing techniques to follow a reaction pathway under high temperature or pressure conditions. M. Elmaalouf,M. Odziomek, S. Duran, M. Gayrard, M. Bahri, C. Tard, A. Zitolo, B. Lassalle-Kaiser, J.Y. Piquemal, O. Ersen, C. Boissière, C. Sanchez, M. Giraud, M. Faustini and J. Peron Nat Commun 2021, 12 , 3935 D. Karapinar, N.H. Tran, N.R. Sahraie, J. Li, D. Wakerley, N. Touati, S. Zanna, D. Taverna, L.H. Galvão Tizei, A. Zitolo, F. Jaouen, V. Mougel, M. Fontecave, Angewandte Chemie International Edition 2019, 58(42), 15098-15103 Zitolo, A.; Ranjbar-Sahraie, N.; Mineva, T.; Li, J.; Jia, Q.; Stamatin, S.; Harrington, G. F.; Lyth, S. M.; Krtil, P.; Mukerjee, S.; Fonda, E.; Jaouen, F., Nat Commun 2017, 8 (1), 957 A. Zitolo, V. Goellner, V. Armel, M. T. Sougrati, T. Mineva, L. Stievano, E. Fonda, F. Jaouen, Nature Materials 2015, 14, 937-942

Unlocking Stable Multi‐Electron Cycling in NMC811 Thin‐Films between 1.5 – 4.7 V

AbstractAmong cathode materials, LiNi0.8Mn0.1Co0.1O2 (NMC811) is the most discussed for high performance Li‐ion batteries, thanks to its capacity of ≈200 mAh g‐1 and low Co content. Here, it is demonstrated that NMC811 can reversibly accommodate more than one Li‐ion per formula unit when coupled with a solid‐state electrolyte, thus significantly increasing its capacity. Sputtered Li‐rich NMC811 cathodes are tested with lithium–phosphorus–oxynitride as a solid‐state electrolyte in a thin‐film architecture, which is a simplified 2D model with direct access to the cathode‐electrolyte interface. The solid‐state electrolyte helps to stabilize the interface and prevents capacity fading, voltage decay, and interface resistance growth, thus allowing cycling at extended voltage ranges of 1.5–4.7 V. While the liquid electrolyte cells suffer from rapid capacity decay, the Li‐rich NMC811 cells with the solid‐state electrolyte can cycle at a fast rate and an initial capacity of 149 mAh g‐1 from 1.5 to 4.3 V for 1000 cycles. The all‐solid‐state thin‐film cells with a lithium metal anode yield a discharge capacity of up to 350 mAh g‐1 at C/10 because of multi‐electron cycling with a coulombic efficiency of 90.1%. The results demonstrate how solid‐state electrolytes that are stable against NMC811 cathodes can unlock the full potential of this Li‐rich and Ni‐rich cathode class.

In situ gel electrolyte network guaranteeing ionic communication between solid electrolyte and cathode

Solid electrolytes are regarded as promising candidates replacing organic liquid electrolyte due to much enhanced safety, which is able to use lithium metal as an anode material for high energy system. Among several solid electroytes, garnet-type solid electrolyte has wide electrochemical window as well as high chemical stability and ionic conductivity at room temperature. However, from an assembled full cell's point of view, high interfacial resistance between electrode and solid electrolyte is a huge obstacle which should be overcome. Herein, we synthesize high ionic conductivy of Gallium-doped garnet-type solid electrolyte (Li6.25Ga0.25La3Zr2O12) having 1.2 mS cm-1 at room temperature and then applied gel polymer electrolyte into cathode by in situ gelation method for a full cell system. The interfacial resistance is reduced by about 260 times and rate capability from 0.05C to 1C was 80%, which is superior to a hybrid of liquid electrolyte and LGLZO cell system. Initial capacity retaines 89% even after 800 cycles at 0.5C.

Kinetic Diagnostics and Synthetic Design of Platinum Group Metal-Free Electrocatalysts for the Oxygen Reduction Reaction Using Reactivity Maps and Site Utilization Descriptors.

The experimental development of catalytically ever-more active platinum group metal (PGM)-free materials for the oxygen reduction reaction (ORR) at fuel cell cathodes has been until recently a rather empirical iteration of synthesis and testing. Here, we present how kinetic reactivity maps based on kinetic descriptors of PGM-free single-metal-site ORR electrocatalysts can help to better understand the origin of catalytic reactivity and help to derive rational synthetic guidelines toward improved catalysts. Key in our analysis are the catalytic surface site density (SD) and the catalytic turnover frequency (TOF) in their role as controlling kinetic parameters for the ORR reactivity of PGM-free nitrogen-coordinated single-metal M-site carbon (MNC) catalysts. SD-TOF plots establish two-dimensional reactivity maps. We also consider the ratio between SD and the total number of single-metal sites in the bulk, referred to as the site utilization factor, which we propose as another guiding parameter for optimizing the synthesis of MNC catalysts. Exemplified by two sets of FeNC, CoNC, and SnNC catalysts prepared using two distinctly different N- and C-precursor material classes (Zn-based zeolitic imidazolate frameworks and covalent polyaniline), we comparatively diagnose the intrinsic kinetic ORR parameters as well as structural, morphological, and chemical properties. From there, we derive and discuss possible synthetic guidelines for further improvements. Our approach can be extended to other families of catalysts and may involve kinetic performance data of idealized liquid-electrolyte cells as well as gas diffusion layer-type flow cells.

Brushed Metals for Rechargeable Metal Batteries.

Battery designs are swiftly changing from metal-ion to rechargeable metal batteries. Theoretically, metals can deliver maximum anode capacity and enable cells with improved energy density. In practice, these advantages are only possible if the parasitic surface reactions associated with metal anodes are controlled. These undesirable surface reactions are responsible for many troublesome issues, like dendrite formation and accelerated consumption of active materials, which leads to anodes with low cycle life or even battery runaway. Here, a facile and solvent-free brushing method is reported to convert powders into films atop Li and Na metal foils. Benefiting from the reactivity of Li metal with these powder films, surface energy can be effectively tuned, thereby preventing parasitic reaction. In-operando study of P2 S5 -modified Li anodes in liquid electrolyte cells reveals a smoother electrode contour and more uniform metal electrodeposition and dissolution behavior. The P2 S5 -modified Li anodes sustain ultralow polarization in symmetric cell for >4000 h, ≈8× longer than bare Li anodes. The capacity retention is ≈70% higher when P2 S5 -modified Li anodes are paired with a practical LiFePO4 cathode (≈3.2mAhcm-2 ) after 340 cycles. Brush coating opens a promising avenue to fabricate large-scale artificial solid-electrolyte-interphase directly on metals without the need for organic solvent.

Unraveling the Stable Cathode Electrolyte Interface in all Solid‐State Thin‐Film Battery Operating at 5 V

AbstractSpinel‐type LiNi0.5Mn1.5O4 (LNMO) is one of the most promising 5 V‐class cathode materials for Li‐ion batteries that can achieve high energy density and low production costs. However, in liquid electrolyte cells, the high voltage causes continuous cell degradation through the oxidative decomposition of carbonate‐based liquid electrolytes. In contrast, some solid‐state electrolytes have a wide electrochemical stability range and can withstand the required oxidative potential. In this work, a thin‐film battery consisting of an LNMO cathode with a solid lithium phosphorus oxynitride (LiPON) electrolyte is tested and their interface before and after cycling is characterized. With Li metal as the anode, this system can deliver stable performance for 600 cycles with an average Coulombic efficiency >99%. Neutron depth profiling indicates a slight overlithiated layer at the interface prior to cycling, a result that is consistent with the excess charge capacity measured during the first cycle. Cryogenic electron microscopy further reveals intimate contact between LNMO and LiPON without noticeable structure and chemical composition evolution after extended cycling, demonstrating the superior stability of LiPON against a high voltage cathode. Consequently, design guidelines are proposed for interface engineering that can accelerate the commercialization of a high voltage cell with solid or liquid electrolytes.

Effects of Coating on the Electrochemical Performance of a Nickel-Rich Cathode Active Material

Due to their safety and high power density, one of the most promising types of all-solid-state lithium batteries is the one made with the argyrodite solid electrolyte (ASE). Although substantial efforts have been made toward the commercialization of this battery, it is still challenged by some technical issues. One of these issues is to prevent the side reactions at the interface of the ASE and the cathode active material (CAM). A solution to address this issue is to coat the CAM particles with a material that is compatible with both ASE and CAM. Prior studies show that the lithium niobate, LiNbO3, (LNO) is a promising material for coating CAM particles to reduce the interfacial side reactions. However, no systematic study is available in the literature to show the effect of coating LNO on CAM performance. This paper aims to quantify the effect of LNO coating on the electrochemical performance of a nickel-rich CAM. The electrochemical performance parameters that are studied are the capacity, cycling performance, and rate performance of the coated-CAM; and the effectiveness of the coating to prevent the side reactions at the ASE and CAM interface is out of the scope of this study. To eliminate the effect of side reactions at the ASE and CAM interface, we conduct all tests in the organic liquid electrolyte (OLE) cells to solely present the effect of coating on the CAM performance. For this purpose, 0.5 wt.% and 1 wt.% LNO are used to coat the LiNi0.6Mn0.2Co0.2O2 (NMC-60) CAM through two synthesizing methods. Consequently, the effects of the synthesizing method and the coating weight percentage on the NMC-60 performance are presented.

Single versus poly-crystalline layered oxide cathode materials for solid-state battery applications - a short review article

The recent developments in the application of single-crystalline (SC) cathode materials in solid-state batteries are discussed in this mini-review. The characteristics of SC and poly-crystalline (PC) cathode materials are explored, with emphasis on the kinetic and mechanical properties. The critical factors influencing their performance in liquid electrolyte and solid-state battery cells are investigated. Finally, the advantages and disadvantages of both morphologies are discussed and considerations to ensure a fair comparison between SC and PC cathodes in different systems are raised.