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At least 127 records · Page 7

Low-cost iron trichloride cathode for all-solid-state lithium-ion batteries

The dominant chemistries of lithium-ion batteries on the market today still rely on flammable organic liquid electrolytes and cathodes containing scarce metals, such as cobalt or nickel, raising safety, cost and environmental concerns. Here we show a FeCl 3 cathode that costs as little as 1% of the cost of a LiCoO 2 cathode or 2% of a LiFePO 4 cathode. Once coupled with a solid halide electrolyte and a lithium-indium (Li–In) alloy anode, it enables all-solid-state lithium-ion batteries without any liquid components. Notably, FeCl 3 exhibits two flat voltage plateaux between 3.5 and 3.8 V versus Li + /Li, and the solid cell retains 83% of its initial capacity after 1,000 cycles with an average Coulombic efficiency of 99.95%. Combined neutron diffraction and X-ray absorption spectroscopy characterizations reveal a Li-ion (de)intercalation mechanism together with a Fe 2+ /Fe 3+ redox process. Further, our work provides a promising avenue for developing sustainable battery technologies with a favourable balance of performance, cost and safety.

25 ENERGY STORAGE↗

Molten sodium batteries: advances in chemistries, electrolytes, and interfaces

The need for clean, renewable energy has driven the expansion of renewable energy generators, such as wind and solar. However, to achieve a robust and responsive electrical grid based on such inherently intermittent renewable energy sources, grid-scale energy storage is essential. The unmet need for this critical component has motivated extensive grid-scale battery research, especially exploring chemistries “beyond Li-ion”. Among others, molten sodium (Na) batteries, which date back to the 1960s with Na-S, have seen a strong revival, owing mostly to raw material abundance and the excellent electrochemical properties of Na metal. Recently, many groups have demonstrated important advances in battery chemistries, electrolytes, and interfaces to lower material and operating costs, enhance cyclability, and understand key mechanisms that drive failure in molten Na batteries. For widespread implementation of molten Na batteries, though, further optimization, cost reduction, and mechanistic insight is necessary. In this light, this work provides a brief history of mature molten Na technologies, a comprehensive review of recent progress, and explores possibilities for future advancements.

25 ENERGY STORAGE↗

Magnesium production by molten salt electrolysis with liquid tin cathode and multiple effect distillation

Low-cost clean primary production of magnesium metal is important for its use in many applications, from light-weight structural components to energy technologies. This work describes new experiments and cost and emissions analysis for a magnesium metal production process. The process combines molten salt electrolysis of MgO using MgF₂-CaF₂ electrolyte and a reactive liquid tin cathode, with gravity-driven multiple effect thermal system (G-METS) distillation to separate out the magnesium product, and re-use of the tin. Electrolysis experiments with carbon anodes showed current yield above 90%, while a yttria-stabilized zirconia solid oxide membrane (SOM) anode experiment showed 84% current yield. G-METS distillation is an important component of the envisioned process. It can potentially lower costs and energy use considerably compared with conventional magnesium distillation. Techno-economic analysis including detailed mass and energy balances shows that this electrolyte composition could lower costs by utilizing CaO, which is the primary impurity in MgO, as the Hall-Héroult process uses the sodium impurity in alumina. Analysis options include: raw material types (magnesite rock vs. brine or seawater), drying and calcining using electricity vs. natural gas, and carbon vs. SOM anode type. Using SOM inert anodes results in a cost premium around 10%–15%, mostly due to higher electrical energy usage resulting from membrane resistance, and reduces GHG emissions by approximately 1 kg CO₂/kg Mg product. Capital and operating cost estimates, and cradle to gate greenhouse gas (GHG) emissions analysis under several raw material and process technology scenarios, show comparable costs and emissions to those of aluminum production.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Rapid Laser Reactive Sintering of Garnet Li 6.4 La 3 Zr 1.4 Ta 0.6 O 12 and Li 6.1 La 3 Zr 2 Al 0.3 O 12 and Solid-State Electrolytes

All solid-state lithium-ion batteries (ASSLIBs) have gained significant interest in recent years due to their wide range of applications, including mobile devices, electric vehicles, and grid storage. Garnet-type Li 7 La 3 Zr 2 O 12 (LLZO) solid-state electrolyte (SSE) continues to be a significant player in the fabrication of ASSLIBs with excellent ionic conductivity on the order of 10 -3 S•cm -1 with the integration of dopants and sintering aids to assist conductivity and structural evolution during the sintering procedure. Traditional sintering techniques, such as solid-state sintering (SSS), have been proven to yield desirable crystal structures. However, the low ionic conductivity results from inferior microstructure, and lithium loss is a significant challenge. Recently, a relatively novel sintering process called rapid laser sintering (RLS) has shown great potential for achieving fully dense solid oxide electrolytes with less lithium loss, resulting in high ionic conductivity [1] [2] [3] [4]. Here, we applied a modified RLS method using precursor powders instead of pre-synthesized LLZO powders to fabricate Al-doped LLZO (Li 6.1 La 3 Zr 2 Al 0.3 O 12 + 13 wt% Li 2 CO 3 ) and Ta-doped LLZO (Li 6.4 La 3 Zr 1.4 Ta 0.6 O 12 + 5 wt% LiOH•H 2 O) dense electrolytes. This rapid laser reactive sintering (RLRS) could potentially reduce the number of processing steps and therefore lower the manufacturing cost. We hope the rapid high-temperature sintering can densify the electrolyte and avoid the lithium loss for achieving high lithium-ion conductivity. In this work, we optimized a combination of laser parameters (speed and power), initial precursor composition, and controlled atmospheres to discover the optimal conditions for reaching the efficacious crystal structure, microstructure, and ionic conductivity.

25 ENERGY STORAGE↗

Oxidative instability of ionomers in hydroxide-exchange-membrane water electrolyzers

Hydroxide-exchange membrane (HEM) electrolyzers can produce green H 2 with only earth-abundant catalysts and electrolyte-free (nominally pure) water feed, significantly decreasing system cost and complexity. However, HEM technology suffers from short lifetimes, attributed in part to poor stability of anion-exchange polymers used in the membrane and catalyst layers. We use electrochemical analysis and ex situ characterization techniques to study anion-exchange-polymer degradation in electrolyzers. Using multiple ionomers, catalyst-layer additives, and electrolyte feed, we show how anode-ionomer oxidation is the dominant degradation mechanism for all HEM-based electrolyzer cells tested. Here, we find improved device stability using oxidation-resistant catalyst-layer binders and propose new design strategies for advanced ionomer and catalyst-layer development.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Understanding the reversible electrodeposition of aluminum in low-cost room-temperature molten salts

Aluminum is the most earth-abundant metal, trivalent, and inert in ambient air; it also has a density approximately five times that of lithium at room temperature, making it attractive for cost-effective, long-duration storage in batteries. Here, we investigate structural requirements and physicochemical and transport properties of ionic liquid (IL) electrolytes thought to enable high reversibility of Al battery anodes. We find that intentionally designed, low-cost IL analogs, including ammonium-based molten salts, offer comparable Al anode reversibility to state-of-the-art imidazolium-based IL melts. A critical ratio of solvated Al-ion species is required to balance the effects of Lewis acidity needed to continuously etch native Al 2 O 3 and form a stable solid electrolyte interphase on Al. Our findings open new opportunities for developing simple, cost-effective, room-temperature Al batteries that enable long-duration electrical energy storage.

25 ENERGY STORAGE↗

Ultrahigh coulombic efficiency electrolyte enables Li||SPAN batteries with superior cycling performance

Raising the coulombic efficiency of lithium metal anode cycling is the deciding step in realizing long-life rechargeable lithium batteries. Here, we designed a highly concentrated salt/ether electrolyte diluted in a fluorinated ether: 1.8 M LiFSI in DEE/BTFE (diethyl ether/bis(2,2,2-trifluoroethyl)ether), which realized an average coulombic efficiency of 99.37% at 0.5 mA cm -2 and 1 mAh cm -2 for more than 900 cycles. This electrolyte also maintained a record coulombic efficiency of 98.7% at 10 mA cm -2 , indicative of its ability to provide fast-charging with high cathode loadings. Morphological studies reveal dense, dendrite free Li depositions after prolonged cycling, while surface analyses confirmed the formation of a robust LiF-rich SEI layer on the cycled Li surface. Moreover, we discovered that this ether-based electrolyte is highly compatible with the low-cost, high-capacity SPAN (Sulfurized polyacrylonitrile) cathode, where the constructed Li||SPAN cell exhibited reversible cathode capacity of 579 mAh g -1 and no capacity decay after 1200 cycles. A cell where a high areal loading SPAN electrode (>3.5 mAh cm -2 ) is paired with only onefold excess Li was constructed and cycled at 1.75 mA cm -2 , maintaining a coulombic efficiency of 99.30% for the lithium metal. Computational simulations revealed that at saturation, the Li-FSI complex forms contact ion pairs, with a first solvation shell comprising DEE molecules, and a second solvation shell with a mix of DEE/BTFE. This study provides a path to enable high energy density Li||SPAN batteries with stable cycling.

36 MATERIALS SCIENCE↗

A dynamically bare metal interface enables reversible magnesium electrodeposition at 50 mAh cm −2

Understanding and facilitating pure magnesium nucleation/growth electrodeposition behavior with ultrahigh Coulombic efficiency is complicated by the phenomenon of solid electrolyte interphase (SEI) formation in state-of-the-art, halogen-free magnesium electrolytes. Defining the electrolyte properties necessary to achieve ideal electrodeposition/stripping (E/S) thus remains elusive. Here, in this work, we reveal for the first time, rapid magnesium electrodeposition behavior that forms densely aligned, micron-sized thin platelets by establishing a dynamic bare magnesium/electrolyte interface during high-rate net plating. This effectively “SEI-free” interface allows facile magnesium diffusion and migration in stripping with near-unity E/S efficiency under demanding conditions over long-term cycling. The intrinsic electrolyte stability of the salt/solvent at the molecular level is the key to forming such an interface. The efficacy of the dynamic bare interface and an electrodeposited, free-standing magnesium anode is demonstrated in a high-areal-capacity full cell. These findings provide new design principles and fundamental understanding of interfacial chemistry in multivalent metal batteries.

Mg full cell↗

Design of robust and versatile hydrocarbon-based single-ion-conducting polymer electrolytes

Hydrocarbon-based polymers offer several advantages, including lower environmental impacts, cost effectiveness, and the ability to finely tune properties. Here, we have developed trifluoromethanesulfonimide (TFSI)-functionalized poly(norbornene) (PNB) polymers utilizing a specifically designed oxa-Michael addition of a vinyl TFSI anion to an alcohol. Our results reveal that PNB-TFSI derivatives exhibit superior thermal stability and mechanical robustness compared with Nafion. The optimized PNB-TFSI-H-48 polymer (IEC 1.86 mmol/g) exhibits equivalent performance to Nafion as an anode ionomer in a proton exchange membrane fuel cell. Exchanging the counter ion to Li + enables PNB-TFSI to be used for Li-ion battery applications. Propylene carbonate plasticized PNB-TFSI derivatives achieve an Li-ion conductivity of over 10 −5 S/cm at 30°C. This Li polymer electrolyte exhibits excellent electrochemical stability (5 V vs. Li + /Li) and good cycling in a Li symmetric cell. These results highlight the potential and rational design of PNB-TFSI polymers for next-generation energy storage and conversion technologies.

08 HYDROGEN↗

All Solid State Batteries Enabled by Multifunctional Electrolyte Materials

Solid Power has teamed with University of California San Diego to develop a high energy, long life, low cost, and safe all-solid-state-battery (ASSB). The battery is enabled by a multifunctional solid state electrolyte (SSE). The project enables scalable production of large format solid state batteries required by the vehicle market and building domestic battery manufacturers as leaders in the global vehicle ASSB production. In the project, the multifunctional SSE materials have been developed and optimized with ionic conductivity ≥ 5 mS/cm and electrochemical stability 0 – 4.5V. SSE separator films have been coated by using a roll-to-roll process with thickness ≤ 40 µm. All-solid-state NMC-Li pouch cells containing the developed SSE have been assembled. A cycle life of > 750 at 100% DOD and 45 °C has been demonstrated in a full pouch cell.

25 ENERGY STORAGE↗

Composite biopolymer electrolytes for high-performance reversible zinc-air batteries

Zinc-air batteries (ZABs) are regarded as one of the most promising candidates for next-generation energy storage systems due to their inherent safety, high energy density, and low cost. In this study, we optimized the composition of gel polymer electrolytes (GPEs), which play a crucial role in enhancing ZAB reversibility due to their water retention capabilities. The GPEs are synthesized using a combination of polyacrylic acid (PAA), polyacrylamide (PAM), and biopolymer kappa-carrageenan (KC), with and without additional additives. Among these, the composite GPE containing KC, PAA, and PAM demonstrated superior ionic conductivity (6.68 mS/cm at 30 °C) and enhanced water retention compared to the PAA–PAM-based GPE. Furthermore, this composite electrolyte operates within a wider electrochemical window of −1.0 V–2.2 V. A bifunctional catalyst, nickel–iron layered double hydroxide (NiFe-LDH), is electrochemically synthesized on a modified activated carbon cloth (CC). The catalyst loading is optimized based on oxygen evolution reaction (OER) performance, showing an overpotential of 555 mV. The oxygen reduction reaction (ORR) occurred at a half-wave potential of 0.620 V, which is lower than that of Pt/C (0.852 V), indicating better catalytic activity. The KC based cell exhibit better cycling stability than PAA–PAM-based GPE. The electrochemical performance of ZAB cells is evaluated under various atmospheres: ambient air and humid conditions and temperatures. Notably, in a humid environment, the cells achieved extended cycling stability, operating for over 500 h—significantly longer than under open-air conditions. Overall, this study highlights the importance of tailored GPE design and efficient bifunctional catalysts to enhance the performance and longevity of zinc-air batteries for long-duration energy storage applications.

Catalyst↗

Ultrahigh-Loading Manganese-Based Electrodes for Aqueous Batteries via Polymorph Tuning

Manganese-based aqueous batteries utilizing Mn 2+ /MnO 2 redox reactions are promising choices for grid-scale energy storage due to their high theoretical specific capacity, high power capability, low-cost, and intrinsic safety with water-based electrolytes. However, the application of such systems is hindered by the insulating nature of deposited MnO 2 , resulting in low normalized areal loading (0.005–0.05 mAh cm -2 ) during the charge/discharge cycle. Here, in this work, the electrochemical performance of various MnO 2 polymorphs in Mn 2+ /MnO 2 redox reactions is investigated, and ε-MnO 2 with low conductivity is determined to be the primary electrochemically deposited phase in normal acidic aqueous electrolyte. It is found that increasing the temperature can change the deposited phase from ε-MnO 2 with low conductivity to γ-MnO 2 with two order of magnitude increase in conductivity. It is demonstrated that the highly conductive γ-MnO 2 can be effectively exploited for ultrahigh areal loading electrode, and a normalized areal loading of 33 mAh cm -2 is achieved. At a mild temperature of 50 °C, cells are cycled with an ultrahigh areal loading of 20 mAh cm -2 (1–2 orders of magnitude higher than previous studies) for over 200 cycles with only 13% capacity loss.

25 ENERGY STORAGE↗

Understanding water management in platinum group metal-free electrodes using neutron imaging

Platinum group metal-free (PGM-free) catalysts are a low-cost alternative to expensive PGM catalysts for polymer electrolyte fuel cells. However, due to the low volumetric activity of PGM-free catalysts, the catalyst layer thickness of the PGM-free catalyst electrode is an order of magnitude higher than PGM based electrodes. The thick PGM-free electrodes suffer from increased transport resistance and poor water management, which ultimately limits the fuel cell performance. This manuscript presents the study of water management in the PGM-free electrodes to understand the transport limitations and improve fuel cell performance. Here, in-operando neutron imaging is performed to estimate the water content in different components across the fuel cell thickness. Water saturation in thick PGM electrodes, with similar catalyst layer thickness to PGM-free electrodes, is lower than in the PGM-free electrodes irrespective of the operating conditions, due to high water retention by PGM-free catalysts. Improvements in fuel cell performance are accomplished by enhancing water removal from the flooded PGM-free electrode in three ways: (i) enhanced water removal with a novel microporous layer with hydrophilic pathways incorporated through hydrophilic additives, (ii) water removal through anode via novel GDL in the anode, and (iii) lower water saturation in PGM-free electrode structures with increased catalyst porosity.

25 ENERGY STORAGE↗

Stacked Low-Inertia Converter or Solid-State Transformer: Modeling and Model Predictive Priority-Shifting Control for Voltage Balance

This paper presents control challenges of stacked low-inertia converter (SLIC) or cascaded reduced dc-link solid-state transformer (SST) and proposes a novel model predictive priority-shifting (MPPS) control with implicit modulator and a discrete-time large-signal model for voltage balancing and dc-link regulation. Low-inertia converters, featuring small electrolytic capacitor-less dc links, dramatically reduce cost, size, and weight compared to conventional solutions. However, without a large dc-link buffer, the input and output are tightly coupled, leading to significant control challenges. The control becomes even more challenging with these converters stacked input-series output-parallel (ISOP) for medium-voltage (MV) grid, which causes coupling between the modules besides the coupling within each module. This paper analyzes the multi-objective, multi-degree of freedom control problem, using the modular soft-switching solid-state transformer (M-S4T) as an example of the SLIC. First, distribution of control efforts under controller saturation is critical because multiple control objectives can be conflicting, especially when the module voltages are unbalanced and are being restored. The MPPS can shift the priorities to address this issue. Second, due to the low inertia and high dc-link ripple, classic space vector pulse-width modulation (SVPWM), average model with small-ripple assumption, and control design based on small-signal model cannot accurately modulate, model, and control the nonlinear reduced dc link. Therefore, a discrete-time large-signal model of the M-S4T is established to derive the predictive control in the MPPS. The MPPS and the PI control are compared in MV simulations to show the issue of applying the PI to the SLIC and the effectiveness of the MPPS for voltage balancing and dc-link regulation in a deadbeat manner. Finally, the proposed control is tested on a 5 kV ISOP SiC SST prototype to verify priority shifting to address controller saturation issue and fast and robust voltage balancing.

14 SOLAR ENERGY↗

Ghostbusters for Batteries

End-of-life lithium-ion batteries are Class 9 hazardous materials due to flammability of electrolyte and lithium. It is why the transportation cost ranges from $2.49/kg - $7.20/kg for civilian and defense disposition, that is over 50% of the cost of recycling. Damaged batteries have many times greater transportation cost. Dead batteries require costly bunker-storage that occupies real estate and personnel that could be used for productive purposes. Insurance is expensive and accidents are almost assured even with relatively low volumes of waste. Tipping fees on top of this adds an unpredictable, inflated cost for the EV industry, which is very cost sensitive for survival. Transforming lithium-ion into a class of non-hazardous material reduces transportation cost to $0.10/kg, providing a value opportunity of ~$2/kg to ~$6/kg for civilian and defense disposition respectively. OnTo can eliminate the risk of thermal runaway with a brief, non-toxic treatment to eliminate flammability and toxic risks in most any battery, except Pb, which is inherently toxic. With the service, OnTo also can provide rigorous certainty that cells are rendered inert. OnTo’s patented and patent pending deactivation technology improves the cost and safety for disposition of end-of-life lithium-ion battery packs and cells. Deactivation uses non-toxic chemical processing to remove inherent risks in lithium-ion and other primary and secondary chemistries. The technology has been demonstrated and developed through DOE contract with OnTo Technology LLC (EE0008475).

25 ENERGY STORAGE↗

Recent developments in catalyst-related PEM fuel cell durability

Cost and durability remain the two major barriers to the widespread commercialization of polymer electrolyte membrane fuel cell (PEMFC)-based power systems, especially for the most impactful but challenging fuel cell electric vehicle (FCEV) application. Commercial FCEVs are now on the road; however, their PEMFC systems do not meet the cost targets established by the U.S. Department of Energy, primarily due to the high platinum loading needed on the cathode to achieve the requisite performance and lifetime. Furthermore, while the activities of a number of commercial Pt-based alloy cathode catalysts exceed the beginning-of-life (BOL) targets, these activities, and the overall cathode performance, degrade via a variety of mechanisms described herein. Degradation is mitigated in current FCEVs by utilizing a cathode catalyst with a lower BOL activity (e.g., much lower transition metal alloy content and larger BOL nanoparticle size), necessitating higher catalyst loadings, and through the utilization of system controls that avoid conditions known to exacerbate degradation processes, such as limiting the fuel cell stack voltage range. The design and development of active and robust materials and eliminating the need for vehicle mitigation strategies would greatly simplify the operating system, allowing for greater transient operation, avoiding large hybridization, and curtailing of fuel cell power. Although system mitigation strategies have provided the near-term pathway for FCEV commercialization, material-specific solutions are required to further reduce costs and improve operability and efficiency. Future material developments should focus on stabilization of the electrode structure and minimization of the catalyst particle susceptibility to dissolution caused by oxide formation and reduction over PEMFC cathode-relevant operating potentials plus minimization of support corrosion. Ex situ accelerated stress tests have provided insight into the processes responsible for material and performance degradation and will continue to provide useful information on the relative stability of materials and benchmarks for robust and stable materials-based solutions not requiring system mitigation strategies to achieve adequate lifetime.

25 ENERGY STORAGE↗

Electrolytic Renewable Fuel Production Optimal Operation Investigation - H2@Scale: Cooperative Research and Development Final Report, CRADA Number CRD-19-00818

This work explored the optimal design and operation of electrolytic hydrogen production from renewable power. While there are many financial incentives for renewable hydrogen, this work investigated the effects of Low Carbon Fuel Standards (LCFS) on the hydrogen breakeven cost. To this end, this project developed optimized operational strategies for electrolytic hydrogen facilities in the California. Four specific model projects were used as the basis for the analysis. Three model projects will be located in California and one in Texas or the Midwest to be determined during the project. All projects include interconnection to the natural gas grid as a method of transport for the product fuel and the hydrogen cases will also consider alternative modes of transport. The operational optimization will maximize project return through fuel production and grid services based on future scenarios for the value of each. The effort will rely on modeling tools developed by NREL and the UCI for grid modeling as well as the integrated resource planning tool (IRP), RESOLVE, which is the official IRP tool used by the California Public Utility Commission (CPUC). The development of this project can help to inform future hydrogen deployment, policy and regulation makers, research and development decisions, and private and public investment.

08 HYDROGEN↗

Zinc–air batteries in neutral/near-neutral electrolytes

The need to fully utilize intermittent renewable energy and have energy security, large-scale batteries are necessary. The aqueous zinc–air battery (ZAB) is a promising potential candidate for its safety, low-cost, and theoretical capacity. This research on ZAB mainly focused on alkaline electrolytes. These are favored for their conductivity, but greatly reduce the stability of the battery by zinc corrosion from the hydrogen evolution reaction (HER), dendrite formation, and carbonate formation. To address these issues, recently neutral and near-neutral electrolytes have been applied to aqueous ZAB to suppress HER, dendrite formation, and minimize carbonate formation. These include the use of chloride-based, potassium nitrate, aqueous organic, solid-state electrolytes supplemented with additives to improve the performance and stability. This field is still young with significant opportunities available for research.

25 ENERGY STORAGE↗