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At least 163 records · Page 9

In-situ polymerized and crosslinked electrolytes with interchangeable Li/Na transport for battery applications

The next generation of batteries requires electrolytes with high conductivity, mechanical stability, good adhesion with electrodes, wide electrochemical windows, and scalability. The present study introduces a concept of doped quasi single-ion conducting copolymers based on methacrylate-(trifluoromethanesulfonyl)imide (TFSI) and vinyl ethylene carbonate which at room temperature are mechanically robust and display ionic conductivities of ~0.1 mS/cm. These electrolytes can be polymerized/crosslinked in-situ, making them easily implementable in current battery manufacturing technologies. They also allow for switching between Li + and Na + transport using simple chemistry procedures. To demonstrate their potential for battery applications, the newly developed Li conductors have been tested in symmetric cells, exhibiting overall impedance below 350 Ohm and plating/stripping stability up to 1 mA/cm 2 . Moreover, lithium metal batteries incorporating this electrolyte and high-voltage Lithium Nickel Manganese Cobalt Oxide (NMC) cathodes show good capacity retention (~79%) during charging and discharging for 80 cycles at C/10 rate and a Coulombic efficiency close to 100% in the entire measurement range. The compositional, mechanical and electrochemical versatility of these electrolytes opens new venues for the design of polymer-based batteries capable of fast charging and extended cycle life, aligning with the current global green energy storage strategies.

Polymer electrolytes↗

Safe, Low-Cost, High Energy-Density, Solid-State Li-Ion Batteries

We developed intrinsically safe, robust, low-cost, high-energy-density solid-state Li-ion batteries, by integrating high conductivity garnet-type solid Li ion electrolytes and several different cathodes in tailored microstructures, fabricated by low-cost supported thin-film ceramic techniques, to overcome the primary technological barriers to next generation battery technology. In this ARPA-E project we employed Li-garnet solid-state electrolytes pioneered by one of the co-investigators (Thangadurai) which has room temperature (RT) conductivity of ~10 -3 S cm -1 . The highly stable garnet SSE allowed the use of S, NMC, and other cathodes with Li metal anodes without stability or flammability concerns. We studied the garnet’s stability when exposed to CO 2 and humidity (with or without an ALD coating) and showed that the material can be processed in ambient air for most steps prior to battery assembly, significantly reducing production costs. We extensively studied and scaled up the synthesis of the powder and explored external suppliers of garnet to determine the best pathway for commercial success. We used low-cost and scalable tapecasting fabrication methods to create porous-dense-porous “trilayer” solid electrolyte microstructures with a ~20 μm separating dense layer, and >70% porosity porous layers to host the electrodes. These scalable multilayer ceramic fabrication techniques, without need for dry rooms or vacuum equipment, also provide for dramatically reduced manufacturing costs. The tailored microstructured electrode supports (scaffold) increased interfacial area ~50x, overcoming the high impedance typical of planar geometry SSLiBs, resulting in record-setting 10 mA/cm 2 lithium cycling in a symmetric cell. We expanded our tapecasting ability and showed tapes >25m in length by the end of the project. We demonstrated the ability to sinter garnet without the use of a garnet powderbed, which could have been a major obstacle and waste of material at scale. At the same time, we expanded the size of our trilayers from coin cells (0.7 cm 2 ) to the full format design (30 cm 2 ). To develop full cells, we demonstrated 250 Wh/kg at room temperature with commercial NMC electrode films in a bilayer configuration. Similarly, we demonstrated 280 Wh/kg trilayer Li-S cells at room temperature with >90% capacity retention over 300 cycles. At 90°C we demonstrated 350 Wh/kg with a Li-S trilayer. The high thermal stability of the garnet electrolyte also enabled extended cycling (400 cycles) of a Li-TiS 2 cell at 150 °C, showcasing the exceptional safety and nonflammability of the solid-state trilayer batteries. Ion Storage Systems has taken this technology and knowledge to produce trilayer garnet electrolytes and is building out facilities to commercialize high performance solid state batteries. ISS has hired a strong staff, identified and communicated with a large number of potential partners, and successfully secured follow-on funding.

25 ENERGY STORAGE↗

Designing carbon wetting layers with inorganic salts as additives for enhanced adhesion and molten sodium wettability in electrochemical application

ß” alumina solid-state electrolyte (BASE) is considered one of the most promising materials for sodium batteries due to its high ionic conductivity and exceptional stability with molten sodium. However, at lower operating temperatures, the poor physical contact at the liquid-solid interface between molten sodium and BASE results in high interfacial resistance. In this study, we explore the optimization of carbon wetting layers with various salt additives to enhance adhesion and improve molten sodium wettability. Using a spray-coating method, carbon layers incorporating sodium hexametaphosphate (Na6(PO3)6, SHMP) as an additive demonstrate superior adhesion, mechanical stability, and enhanced wettability with molten sodium. Scanning Electron Microscopy (SEM) analysis reveals that SHMP preserves the porous carbon network required for efficient sodium transport while minimizing structural defects such as cracks and voids. Electrochemical testing using Na symmetric cells confirms that SHMP-modified layers significantly reduce interfacial resistance and overpotential, outperforming No salts counterparts. These findings highlight that the strategic incorporation of suitable additives, such as SHMP, in the design of microscale carbon layers could significantly enhance the performance of molten sodium batteries at lower operating temperatures.

Han, Henry H.↗

Creating and Preserving Nanoparticles during Co-Sintering of Solid Oxide Electrodes and Its Impact on Electrocatalytic Activity

A novel processing method that creates and preserves ceramic nanoparticles in solid oxide electrodes during co-sintering at traditional sintering temperatures is introduced. Specifically, carbon templated samarium-doped ceria nanoparticles (nSDC) were successfully integrated with commercial lanthanum strontium cobalt ferrite (LSCF) and commercial SDC powders, producing LSCF-SDC-nSDC cathodes upon processing. The effect of nSDC concentration on cathode electrocatalytic activity was investigated at low operational temperatures, 600 °C–700 °C, with symmetrical cells. Low nSDC loadings, ≤5 wt% nSDC, significantly decreased cell polarization resistance whereas higher loadings increased it. The best electrochemical performance was achieved with 5 wt% nSDC, lowering the polarization resistance by 41% at 600 °C. Fuel cell tests demonstrate that adding 5 wt% nSDC increased the maximum fuel cell power density by 38%. Electrochemical impedance spectra showed substantial improvements in both fuel cell polarization resistance and ohmic resistance, indicating that nSDC increased the electrocatalytically active area of the cathode. This work demonstrates a simple, novel method for effectively increasing electrocatalytic activity of solid oxide electrodes at low operational temperatures.

Muhoza, Sixbert P. (ORCID:0000000299864241)↗

Composite Membrane for Sodium Polysulfide Hybrid Redox Flow Batteries

Non-aqueous redox flow batteries (NARFBs) using earth-abundant materials, such as sodium and sulfur, are promising long-duration energy storage technologies. NARFBs utilize organic solvents, which enable higher operating voltages and potentially higher energy densities compared with their aqueous counterparts. Despite exciting progress throughout the past decade, the lack of low-cost membranes with adequate ionic conductivity and selectivity remains as one of the major bottlenecks of NARFBs. Here, we developed a composite membrane composed of a thin (<25 µm) Na+-Nafion coating on a porous polypropylene scaffold. The composite membrane significantly improves the electrochemical stability of Na + -Nafion against sodium metal, exhibiting stable Na symmetric cell performance for over 2300 h, while Na + -Nafion shorted by 445 h. Additionally, the composite membrane demonstrates a higher room temperature storage modulus than the porous polypropylene scaffold and Na + -Nafion separately while maintaining high Na + conductivity (0.24 mS/cm at 20 °C). Our method shows that a composite membrane utilizing Na + -Nafion is a promising approach for sodium-based hybrid redox flow batteries.

25 ENERGY STORAGE↗

Molecular Layer Deposition of Crosslinked Polymeric Lithicone for Superior Lithium Metal Anodes

In this work, we for the first time developed a novel lithium-containing crosslinked polymeric material, a lithicone that enables excellent protection effects over lithium (Li) metal anodes. This new lithicone was synthesized via an accurately controllable molecular layer deposition (MLD) process, in which lithium tert -butoxide (LTB) and glycerol (GL) were used as precursors. The resultant LiGL lithicone was analyzed using a suite of characterizations. Furthermore, we found that the LiGL thichicone could serve as an exceptional polymeric protection film over Li metal anodes. Our experimental data revealed that the Li electrodes coated by this LiGL lithicone can achieve a superior cycling stability, accounting for an extremely long cyclability of >13,600 Li-stripping/plating cycles and having no failures so far in Li/Li symmetric cells at a current density of 5 mA/cm 2 and an areal capacity of 1 mAh/cm 2 . We found that, with a sufficient protection by this LiGL coating, Li electrodes could realize long-term stable cyclability with little formation of Li dendrites and solid electrolyte interphase. This novel LiGL represents a facile and effective solution to the existing issues of Li anodes and potentially paves a technically feasible route for lithium metal batteries.

Meng, Xiangbo↗

Simultaneous Improvements in Efficiency and Stability of Organic Solar Cells via a Symmetric‐Asymmetric Dual‐Acceptor Strategy

Abstract Simultaneously achieving improvements in power conversion efficiency (PCE) and stability is the main task of the current development stage of organic solar cells (OSCs). This work reports a symmetry–asymmetry dual‐acceptor (SADA) strategy to construct ternary devices, which is found to be feasible for increasing both the PCE and the operational lifetime of OSCs. In this contribution, the symmetric acceptor L8‐BO and the asymmetric acceptor BTP‐S9 are blended in equal proportions with polymer donor PM6 for the consideration of absorption spectrum complementarity and cascade energetic alignment. In addition, the features of crystallinity and miscibility of the dual‐acceptor deliver optimized morphology lead to a high PCE of 18.84%. In addition, the asymmetric acceptor BTP‐S9 with a larger dipole moment shows tighter molecular stacking and longer crystal correlation length, which favor intrinsic molecular photostability, and further consolidate the operational lifetime of OSCs when coordinated with L8‐BO. This work demonstrates the efficacy of the SADA strategy for constructing efficient and stable OSCs.

Chemistry↗

Scaleup and manufacturability of symmetric-structured metal-supported solid oxide fuel cells

Metal-supported solid oxide fuel cells with symmetric architecture, having metal supports on both sides of the cell, are scaled up from button cell size to large 50 cm 2 active area cell size. The cells remain flat after sintering assisted by the symmetric structure. Equivalent performance is achieved for button cells and large cells, and thermal cycling and redox cycling tolerance are demonstrated for the large cells. The catalyst infiltration process is improved to enable high-throughput manufacturing. The cumbersome lab-scale molten nitrate infiltration process is replaced with a room-temperature process in which a shelf-stable aqueous solution of nitrate salts is applied to the cell by spraying, painting, or other scalable techniques. Here, a fast-ramp thermal conversion of the nitrate salts to the final oxide catalyst composition is implemented, allowing many infiltration cycles to be accomplished in a single work shift. Increasing the number of infiltration cycles from 5 to 10 led to an increase in peak power density from approximately 0.3 to 0.52 W cm -2 .

25 ENERGY STORAGE↗

Redox-stable symmetrical solid oxide fuel cells with exceptionally high performance enabled by electrode/electrolyte diffuse interface

Here, in this study, we report a high performance and redox-stable symmetrical solid oxide fuel cell (SOFC) based on (Ba 0.5 Sr 0.5 ) (Mo 0.1 Fe 0.9 )O 3-δ (BSMF) electrode and La 0.8 Sr 0.2 Ga 0.8 Mg 0.2 O 3-δ (LSGM) electrolyte. BSMF is able to operate both as anode and cathode. Excellent electrocatalytic activity has been achieved on BSMF towards hydrogen oxidation and oxygen reduction. Due to its closely matched lattice parameter to LSGM electrolyte, a unique diffuse interface is formed between BSMF and LSGM. Compared to a clean interface, e.g. BSMF/gadolinium doped ceria interface, this diffuse interface promotes the performance of BSMF electrode 1–1.8 times in 600–800 °C. Polarization resistance of the BSMF/LSGM specimen is as low as 0.047 and 0.007 Ωcm 2 in humidified H 2 and in air at 800 °C, respectively. On the BSMF/LSGM/BSMF symmetrical cell, a maximum power density of 2.28 W/cm 2 is achieved at 800 °C, the highest among with redox-stable ceramic electrodes to the best of our knowledge. Redox stability of this cell is confirmed. The role of anode and cathode is reversed back and forth in different operation modes. No apparent degradation is observed through 4 cycles within a 110 h operation period. These findings demonstrate that (Ba 0.5 Sr 0.5 ) (M o0.1 Fe 0.9 )O 3-δ coupled with LSGM electrolyte is an excellent choice to build a high performance, redox-stable SOFC.

25 ENERGY STORAGE↗

Dynamic operation of metal-supported solid oxide electrolysis cells

Symmetric-structure metal-supported solid oxide fuel cells and electrolysis cells (MS-SOFCs, MS-SOECs) offer several advantages over conventional solid oxide cells, including the use of inexpensive materials, high mechanical strength, and rapid ramp-up ability. Aggressive operation of MS-SOCs in fuel cell mode is well-established, including extremely fast start-up, redox tolerance, and imbalanced pressure. Here, we extend dynamic operation to MS-SOCs in SOEC mode with high steam content for both small button cells and a large rectangular cell, including: steam cycling, thermal cycling, redox cycling and power cycling. Steam cycling entailed switching between 3:97 and 50:50 steam:hydrogen ratio. For thermal cycling, the temperature was rapidly varied between 150°C and 700°C for 50 cycles. Redox cycling involved switching the steam side gas between 50 % humidified H 2 and 50 % humidified N 2 for 5 cycles. Power cycling was performed by operating the cell under variable current density, resulting in cell voltage between 1.3V and 2.8V. Degradation rates for each testing strategy were compared to a baseline cell, and found to be similar. In conclusion, the excellent tolerance to dynamic operation increases confidence that MS-SOECs will be compatible with dynamic or intermittent renewable resources.

08 HYDROGEN↗

Lithium Cyano Tris(2,2,2-trifluoroethyl) Borate as a Multifunctional Electrolyte Additive for High-Performance Lithium Metal Batteries

Lithium cyano tris(2,2,2-trifluoroethyl) borate (LCTFEB) has been synthesized and investigated as a new electrolyte additive for high performance of lithium metal batteries. LCTFEB is prepared by the reaction of tris(2,2,2-trifluoroethyl) borate with lithium cyanide. Incorporation of LCTFEB into carbonate-based electrolyte has been investigated. The electrochemical performance of NCM523/Li cells as well as symmetric Li/Li cells are significantly improved upon incorporation of LCTFEB (5 wt.%) into the electrolyte. Various characterizations of lithium metal morphology and the solid electrolyte interphase (SEI) on the lithium metal anode have been conducted using by FE-SEM, cryo-TEM and XPS suggesting the generation of a thin (≈ 10 nm) LiF rich SEI with low concentrations of B and N-compounds. The different SEI structure is formed by the preferential reductive decomposition of LCTFEB resulting in improved electrochemical performance. As a result, the new electrolyte additive provides insight into innovative approaches for multi-functional electrolyte additive design.

25 ENERGY STORAGE↗

Sulfide glass solid-state electrolyte separators for Li metal batteries: using an interlayer to increase rate performance and reduce stack pressure

We report on the solubility of (Li 2 S) 60 (SiS 2 ) x (P 2 S 5 ) 40–x , (0 ≤ x ≤ 40) sulfide glass solid-state electrolytes in the 1:1 (v/v) DME:DOL solvent mixture, a popular choice for lithium metal battery liquid electrolytes. SiS 2 -rich glasses within the compositional range of (Li 2 S) 60 (SiS 2 ) x (P 2 S 5 ) 40–x (28 ≤ x ≤ 40) were found to be functionally insoluble in DME:DOL. Hybrid symmetric test cells with a thin liquid electrolyte layer (0.6 M LiTFSI + 0.4 M LiNO 3 in 1:1 (v/v) DME:DOL) at the interface between lithium metal electrodes and an insoluble (Li 2 S) 60 (SiS 2 ) 28 (P 2 S 5 ) 12 glass wafer were tested. Hybrid test cells delivered a critical current density of 3.0 mA cm –2 at 25 °C and 0.1 MPa, which is nearly double the CCD of comparable dry symmetric test cells cycled at 10× higher stack pressure.

25 ENERGY STORAGE↗

Influence of Calendering on the Electrochemical Performance of LiNi 0.9 Mn 0.05 Al 0.05 O 2 Cathodes in Lithium-Ion Cells

Electrode calendering is a necessary process used in industry to improve the volumetric capacity of lithium-ion batteries. However, calendering high-nickel cathodes leads to electrode particle pulverization, raising concerns of a reduced cycle life due to parasitic side reactions. We present here an investigation of the impact of calendering on the morphology and electrochemical performance of the cobalt-free layered oxide cathode LiNi 0.9 Mn 0.05 Al 0.05 O 2 (NMA-90). We find that secondary particle pulverization and fusion simultaneously occur at sufficiently high pressures. The initial surface area of the cathode is shown to increase with the degree of calendering, despite the higher likelihood of secondary particle fusion. Long-term cycling of full coin cells assembled with the NMA-90 cathode and the graphite anode indicates that cells with higher degrees of cathode calendering exhibit lower capacity fade compared to uncalendered cathodes. Hybrid pulse-power tests demonstrate that the usable capacity range of cells with calendered cathodes far exceeds those with uncalendered cells after long-term cycling. The improved capacity retention and pulse-power performance are attributed to the enhanced mechanical properties of the electrode after calendering that prevents loss of the primary particle contact during long-term cycling. As a result, we find that calendering high-nickel NMA-90 to industrially relevant densities does not have a detrimental effect on capacity fade, marking an important step toward commercial adoption.

25 ENERGY STORAGE↗

Electrochemical conversion of methane to ethylene, olefins, and paraffins using metal-supported solid oxide cells

Electrochemical oxidative coupling of methane (E-OCM) with Sr 2 Fe 1·5 Mo 0·5 O 6–δ (SFM) catalyst is demonstrated with metal-supported solid oxide cells (MS-SOC). SFM anode and Pr 6 O 11 cathode catalysts are loaded into a porous symmetric-architecture cell by infiltration and firing. The most effective chelating agent (citric acid/ethyl glycol) and optimal firing/reducing temperatures (850 °C/750 °C) for the SFM catalyst precursor solution are selected and confirmed by cell testing. Operating temperature, cell voltage, and oxygen concentration at the cathode greatly affect the methane conversion rate and product selectivity by controlling the oxygen ion flow. CH 4 conversion of 85.8% is obtained, with C 2 H 4 , C 2 H 6 , and H 2 concentrations of 10.5%, 12.3%, and 25.6% at 800 °C, respectively, in the product exhaust gas. Reasonable stability of the current density and methane conversion is demonstrated during 200 h operation. Furthermore, this research demonstrates technical progress in catalyst and device development for the E-OCM reaction to synthesize valuable chemicals.

30 DIRECT ENERGY CONVERSION↗

A Carboranyl Electrolyte Enabling Highly Reversible Sodium Metal Anodes via a “Fluorine‐Free” SEI

Abstract Realization of practical sodium metal batteries (SMBs) is hindered due to lack of compatible electrolyte components, dendrite propagation, and poor understanding of anodic interphasial chemistries. Chemically robust liquid electrolytes that facilitate both favorable sodium metal deposition and a stable solid‐electrolyte interphase (SEI) are ideal to enable sodium metal and anode‐free cells. Herein we present advanced characterization of a novel fluorine‐free electrolyte utilizing the [HCB 11 H 11 ] 1− anion. Symmetrical Na cells operated with this electrolyte exhibit a remarkably low overpotential of 0.032 V at a current density of 2.0 mA cm −2 and a high coulombic efficiency of 99.5 % in half‐cell configurations. Surface characterization of electrodes post‐operation reveals the absence of dendritic sodium nucleation and a surprisingly stable fluorine‐free SEI. Furthermore, weak ion‐pairing is identified as key towards the successful development of fluorine‐free sodium electrolytes.

Tomich, Anton W.↗

A Carboranyl Electrolyte Enabling Highly Reversible Sodium Metal Anodes via a “Fluorine-Free” SEI

Realization of practical sodium metal batteries (SMBs) is hindered due to lack of compatible electrolyte components, dendrite propagation, and poor understanding of anodic interphasial chemistries. Chemically robust liquid electrolytes that facilitate both favorable sodium metal deposition and a stable solid-electrolyte interphase (SEI) are ideal to enable sodium metal and anode-free cells. Herein we present advanced characterization of a novel fluorine-free electrolyte utilizing the [HCB 11 H 11 ] 1- anion. Symmetrical Na cells operated with this electrolyte exhibit a remarkably low overpotential of 0.032 V at a current density of 2.0 mA cm -2 and a high coulombic efficiency of 99.5 % in half-cell configurations. Additionally, surface characterization of electrodes post-operation reveals the absence of dendritic sodium nucleation and a surprisingly stable fluorine-free SEI. Furthermore, weak ion-pairing is identified as key towards the successful development of fluorine-free sodium electrolytes.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Precautions of Using Three-Electrode Configuration to Measure Electrode Overpotential in Solid Oxide Electrochemical Cells: Insights from Finite Element Modeling

Accurate determination of electrode overpotentials is essential to assess the performance of the electrode and understand the rate-limiting steps involved. Three-electrode configuration with the use of a reference electrode at a fixed potential is a standard way to measure overpotential of a specific electrode in liquid electrochemical systems. However, application of such three-electrode configuration to solid electrochemical cells for overpotential determination is not straightforward and requires extra caution. Here we report a theoretical Finite Element Analysis on the geometrical requirements for which the reference electrode can be applied to anode- or electrolyte-supported solid oxide button cells. The modeling results suggest that the symmetry of the working and counter electrodes is the key factor determining if a reference electrode is suitable to use. For anode-supported fuel cells with asymmetrical working and counter electrodes, reference electrode cannot be used under all circumstances. To use reference electrode for overpotential measurements, electrolyte-supported cells with symmetrical semicircular-shaped electrodes are preferred. A data processing procedure has also been presented to obtain the electrode overpotential from the measured potential using the three-electrode scheme in solid oxide electrochemical cells.

25 ENERGY STORAGE↗