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At least 973 records · Page 54

A stable cathode-solid electrolyte composite for high-voltage, long-cycle-life solid-state sodium-ion batteries

Rechargeable solid-state sodium-ion batteries (SSSBs) hold great promise for safer and more energy-dense energy storage. However, the poor electrochemical stability between current sulfide-based solid electrolytes and high-voltage oxide cathodes has limited their long-term cycling performance and practicality. Here, we report the discovery of the ion conductor Na 3-x Y 1-x Zr x Cl 6 (NYZC) that is both electrochemically stable (up to 3.8 V vs. Na/Na + ) and chemically compatible with oxide cathodes. Its high ionic conductivity of 6.6 × 10 –5 S cm –1 at ambient temperature, several orders of magnitude higher than oxide coatings, is attributed to abundant Na vacancies and cooperative MCl 6 rotation, resulting in an extremely low interfacial impedance. A SSSB comprising a NaCrO 2 + NYZC composite cathode, Na 3 PS 4 electrolyte, and Na-Sn anode exhibits an exceptional first-cycle Coulombic efficiency of 97.1% at room emperature and can cycle over 1000 cycles with 89.3% capacity retention at 40 °C. These findings highlight the immense potential of halides for SSSB applications.

99 GENERAL AND MISCELLANEOUS↗

Cycle life characteristics of Li-TiS2 cells

The development of lithium ambient temperature rechargeable cells is discussed. During the development process, we hope to gain a greater understanding of the materials and the properties of the Li-TiS2 cell and its components. The design will meet the requirements of 100 Wh/Kg and 1000 cycles, at 50 percent depth-of-discharge, by 1995.

Deligiannis, Frank↗

Incorporating Solvate and Solid Electrolytes for All‐Solid‐State Li 2 S Batteries with High Capacity and Long Cycle Life

Abstract The development of all‐solid‐state lithium–sulfur batteries is hindered by the poor interfacial properties at solid electrolyte (SE)/electrode interfaces. The interface is modified by employing the highly concentrated solvate electrolyte, (MeCN) 2 −LiTFSI:TTE, as an interlayer material at the electrolyte/electrode interfaces. The incorporation of an interlayer significantly improves the cycling performance of solid‐state Li 2 S batteries compared to the bare counterpart, exhibiting a specific capacity of 760 mAh g −1 at cycle 100 (330 mAh g −1 for the bare cell). Electrochemical impedance spectroscopy shows that the interfacial resistance of the interlayer‐modified cell gradually decreases as a function of cycle number, while the impedance of the bare cell remains almost constant. Cross‐section scanning electron microscopy (SEM)/ energy dispersive X‐ray spectroscopy (EDS) measurements on the interlayer‐modified cell confirm the permeation of solvate into the cathode and the SE with electrochemical cycling, which is related to the decrease in cell impedance. In order to mimic the full permeation of the solvate across the entire cell, the solvate is directly mixed with the SE to form a “solvSEM” electrolyte. The hybrid Li 2 S cell using a solvSEM electrolyte exhibits superior cycling performance compared to the solid‐state cells, in terms of Li 2 S loading, Li 2 S utilization, and cycling stability. The improved performance is due to the favorable ionic contact at the battery interfaces.

Shin, Minjeong↗

Conductive Ink with Circular Life Cycle for Printed Electronics

Electronic waste carries energetic costs and an environmental burden rivaling that of plastic waste due to the rarity and toxicity of the heavy-metal components. Recyclable conductive composites are introduced for printed circuits formulated with polycaprolactone (PCL), conductive fillers, and enzyme/protectant nanoclusters. Circuits can be printed with flexibility (breaking strain ≈80%) and conductivity (≈2.1 × 10 4 S m -1 ). These composites are degraded at the end of life by immersion in warm water with programmable latency. Approximately 94% of the functional fillers can be recycled and reused with similar device performance. The printed circuits remain functional and degradable after shelf storage for at least 7 months at room temperature and one month of continuous operation under electrical voltage. Here, the present studies provide composite design toward recyclable and easily disposable printed electronics for applications such as wearable electronics, biosensors, and soft robotics.

36 MATERIALS SCIENCE↗

Li 3 PO 4 Matrix Enables a Long Cycle Life and High Energy Efficiency Bismuth-Based Battery

Bismuth is a lithium-ion battery anode material that can operate at an equilibrium potential higher than graphite and provide a capacity twice as high as that of Li 4 Ti 5 O 12 , making it intrinsically free from lithium plating that may cause catastrophic battery failure. However, the potential of bismuth is hampered by its inferior cyclability (limited to tens of cycles). Here, we propose an “ion conductive solid-state matrix” approach to address this issue. By homogeneously confining bismuth nanoparticles in a solid-state γ-Li 3 PO 4 matrix that is electrochemically formed in situ, the resulting composite anode exhibits a reversible capacity of 280 mA hours per gram (mA h/g) at a rate of 100 mA/g and a record cyclability among bismuth-based anodes up to 500 cycles with a capacity decay rate of merely 0.071% per cycle. We further show that full-cell batteries fabricated from this composite anode and commercial LiFePO 4 cathode deliver a stable cell voltage of ~2.5 V and remarkable energy efficiency up to 86.3%, on par with practical batteries (80–90%). This work paves a way for harnessing bismuth-based battery chemistry for the design of high capacity, safer lithium-ion batteries to meet demanding applications such as electric vehicles.

25 ENERGY STORAGE↗

High rate, long cycle life battery electrode materials with an open framework structure

A battery includes a cathode, an anode, and an aqueous electrolyte disposed between the cathode and the anode and including a cation A. At least one of the cathode and the anode includes an electrode material having an open framework crystal structure into which the cation A is reversibly inserted during operation of the battery. The battery has a reference specific capacity when cycled at a reference rate, and at least 75% of the reference specific capacity is retained when the battery is cycled at 10 times the reference rate.

25 ENERGY STORAGE↗

V2O5 nanowires-graphene composite as an outstanding electrode material for high electrochemical performance and long-cycle-life supercapacitor

Highlights: • V{sub 2}O{sub 5} nanowires anchored on the surface of rGO sheets using facile hydrothermal method for energy storage application. • High gravimetric capacitance of 1002 F g{sup −1} has been achieved at the current density of 1 A g{sup −1} in an aqueous electrolyte. • Exceptionally high energy density of 116 Wh kg{sup −1} has been obtained using supercapacitor coin cell. • Composite (V{sub 2}O{sub 5}-NW-G) exhibits excellent cyclic stability with 83.94 % capacitance retention after 5000 GCD cycles. - Abstract: A composite of V{sub 2}O{sub 5} nanowires with reduced graphene oxide (V{sub 2}O{sub 5}-NW-G) has been prepared using facile hydrothermal method and tested for charge storage supercapacitor application. Morphological and structural aspects of as prepared materials has been studied using material characterization techniques like transmission electron microscope (TEM), scanning electron microscope (SEM), X-ray photoelectron spectroscopy (XPS), Raman spectroscopy, X-ray diffraction (XRD) and Fourier transform infrared spectroscopy (FTIR). The nanosized wires like structure of V{sub 2}O{sub 5} anchored on the graphene (rGO) sheets possesses improved electrical conductivity and high surface area. Electrochemical properties of the synthesized materials have been studied using cyclic voltammetry (CV), galvanostatic charge-discharge (GCD) and electrochemical impedance spectroscopy (EIS). Composite (V{sub 2}O{sub 5}-NW-G) exhibits exceptional properties like high gravimetric capacitance of 1002 F g{sup −1} along with good cyclic stability of 83.94% capacitance retention after 5000 repetitive GCD cycles. Excellent energy density of 116 Wh kg{sup −1} has been obtained at the power density of 1520 W kg{sup −1}.

75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗

Polysulfides capture-copper additive for long cycle life lithium sulfur batteries

Copper powder was introduced into the lithium sulfur battery system to capture intermediate polysulfides and Cu x S (x = 1 or 2) species was generated depending on the chain length of polysulfides. This phenomenon was verified by X-ray absorption near edge structure technique. The results indicated that copper can be oxidized to CuS by Li 2 S x (x ≥ 6), and a mixture of Cu 2 S and CuS was obtained when x ranges from 3 to 6. While Cu 2 S is eventually formed in the presence of Li 2 S 3 . After several cycles activation, the polysulfide-shuttle effect and self-discharge phenomenon which hinder the application of lithium sulfur batteries are found nearly eliminated Further experiments demonstrated that in the case of Cu 2 S generation, a high specific sulfur capacity of 1300 mAh g –1 could be delivered, corresponding to 77.6% sulfur utilization, while the Coulombic efficiency approximates around 100%. As a result, self-discharge experiment further demonstrated that polysulfides almost disappear in the electrolyte, which verified the polysulfide-capture capability of copper.

25 ENERGY STORAGE↗

Use of fiber like materials to augment the cycle life of thick thermoprotective seal coatings

Some experimental and analytical studies of plasma sprayed ZrO2-Y2O3 thick seal thermoprotective materials over NiCrAlY bond coats with testing to 1040 deg C in a Mach 0.3 burner flame are reviewed. These results indicate the need for material to have both compliance and sufficient strength to function successfully as a thick thermoprotective seal material. Fibrous materials may satisfy many of these requirements. A preliminary analysis simulating the simplified behavior of a 25 mm cylindrical SiO2-fiber material indicated significant radial temperature gradients, a relatively cool interface and generally acceptable stresses over the initial portion of the thermal cycle. Subsequent testing of these fiberlike materials in a Mach 0.3 Jet A/air burner flame confirmed these results.

Hendricks, R. C.↗

All-solid-state interpenetrating network polymer electrolytes for long cycle life of lithium metal batteries

A star-shape polymer of 3-armed poly(ethylene glycol) methyl ether methacrylate-co-glycidyl methacrylate copolymer (3PPEGM-co-GMA) was synthesized using an atom transfer radical polymerization (ATRP) technique. All-solid-state interpenetrating network polymer electrolytes (INSPEs) were fabricated by simultaneous reaction of 3PPEGM-co-GMA and bisphenol A diglycidyl ether (BPDE) with polyetherdiamine (ED2003) in the presence of lithium bis(trifluoromethane) sulfonamide (LiTFSI). The INSPEs exhibited ionic conductivities higher than 10 -5 S cm -1 at room temperature, a high oxidation stability of 4.5 vs. Li/Li + and remarkable stability towards lithium metal. Li metal batteries with LiFePO 4 as the cathode and INSPEs as the electrolyte cycled at a current rate of 0.1C at 60 °C showed a high initial discharge capacity of 156.2 mA h g -1 and a stable cycling performance over 200 cycles with a high coulombic efficiency of 99%. In conclusion, the results demonstrate that the interpenetrating network polymer electrolytes are promising electrolytes for next generation lithium-based batteries with high ionic conductivity, improved safety, and stable electrochemical performance.

25 ENERGY STORAGE↗

An Ordered P2/P3 Composite Layered Oxide Cathode with Long Cycle Life in Sodium-Ion Batteries

Developing stable cathode materials represents a crucial step toward long-life sodium-ion batteries. P2-type layered oxides are important as cathodes for their reversibility, but their long-term performance in full cells remains a key challenge. Herein, we report Na 0.75 Co 0.125 Cu 0.125 Fe 0.125 Ni 0.125 Mn 0.5 O 2 with an intergrowth of ordered P2 and P3 phases, studied by neutron diffraction and Rietveld refinement. A stable electrochemical performance is achieved in Na half cells with 100% capacity retention at a rate of C/10 after 100 cycles (initial capacity of 90 mAh/g), 96% capacity retention at a rate of 1 C after 500 cycles (initial capacity of 70 mAh/g), and 85% capacity retention at a rate of 5 C after 1000 cycles (initial capacity of 55 mAh/g). Stable full cell performance is achieved with 84.2% capacity retention after 1000 cycles at a rate of 1 C. Synchrotron X-ray diffraction, spectroscopy, and imaging are applied to elucidate the relationship between chemical/structural evolution and battery performance. A reversible local and global structural evolution is observed during initial cycles. Meanwhile, the challenges with enabling prolonged cycling (beyond 1000 cycles) may be associated with Fe dissolution and formation of a copper oxide phase. This study implies that cathodes with complex chemical and structural formations may stabilize electrochemical performance and highlights the importance of decoupling the contribution of each transition metal to performance degradation.

25 ENERGY STORAGE↗

Progress Towards Extended Cycle Life Si-based Anodes: Investigation of Fluorinated Local High Concentration Electrolytes

Silicon (Si) anodes are promising candidates for Li-ion batteries due to their high specific capacity and low operating potential. Implementation has been challenged by the significant Si volume changes during (de)lithiation and associated growth/regrowth of the solid electrolyte interphase (SEI). In this report, fluorinated local high concentration electrolytes (FLHCEs) were designed such that each component of the electrolyte (solvent, salt, diluent) is fluorinated to modify the chemistry and stabilize the SEI of high (30%) silicon content anodes. FLHCEs were formulated to probe the electrolyte salt concentration and ratio of the fluorinated carbonate solvents to a hydrofluoroether diluent. Higher salt concentrations led to higher viscosities, conductivities, and contact angles on polyethylene separators. Electrochemical cycling of Si-graphite/NMC622 pouch cells using the FLHCEs delivered up to 67% capacity retention after 100 cycles at a C/3 rate. Post-cycling X-ray photoelectron spectroscopy (XPS) analyses of the Si-graphite anodes indicated the FLHCEs formed a LiF rich solid electrolyte interphase (SEI). The findings show that the fluorinated local high concentration electrolytes contribute to stabilizing the Si-graphite electrode over extended cycling.

36 MATERIALS SCIENCE↗

Calcium-Doped High-Voltage Spinel Cathode for Long Cycle Life Lithium-Ion Batteries

With the promises of low cost, high operating voltage, and excellent rate capability, the high-voltage spinel material with the formula of LiNi 0.5 Mn 1.5 O 4 (LNMO) has been considered as one of the most promising cathode materials for nextgeneration lithium-ion batteries (LIBs). However, the adoption of LNMO into practical LIBs is greatly hindered due to its rapid capacity decay associated with its bulk structural instability and interfacial side reactions. To address these issues, we proposed to use the cost-effective calcium (Ca) element as a dopant to stabilize the oxygen framework and surface of the LNMO crystal. The experimental results showed that, with moderate Ca doping, the obtained cathode (Ca 0.05 LNMO) retained a specific capacity of ∼121 mAh/g (∼94.4% capacity retention) after 500 cycles at 0.5 C, compared to ∼73% for the baseline bare sample. Furthermore, the Ca 0.05 LNMO cathode retained ∼84% of its initial capacity, vs the baseline with ∼69%, after 150 cycles at the high temperature of 55 °C. The excellent battery performance of the moderately Ca-doped LNMO cathode is ascribed to its structural and kinetic advantages.

25 ENERGY STORAGE↗

A Highly Reversible Zn Anode with Intrinsically Safe Organic Electrolyte for Long-Cycle-Life Batteries

Dendrite has puzzled the metal anodes including Li and Zn for rechargeable batteries more than decades of years. Here we bypass this obstacle via adopting non-flammable Trimethyl Phosphate (TMP) safe organic electrolyte to build zinc ion batteries. The graphene-like form Zn deposit was gained via TMP surfactant and Zn3(PO4)2 molecular template. This novel morphology Zn anode demonstrates highly stable and reversible plating/stripping for more than 2000 hours without dendrite, and a remarkably high Coulombic efficiency (CE) of 99.57 %. Addition of Dimethyl Carbonate (DMC) to TMP enhanced the stability of Zn/Zn symmetric cells to over 5000 hours without sacrificing the CE (99.15 %) of Zn deposition/dissolution. Moreover, non-aqueous Zn-VS2 battery delivered a specific capacity of 146.6 mA h g-1 with a capacity retention of 94.38 % over 500 cycles. Excellent anodic stability, high CE and cycling stability of the full cell expands the scope for developing low cost, safe and high performance non-aqueous Zn batteries.

Naveed, Ahmad↗

Stress-Tolerant Nanoporous Germanium Nanofibers for Long Cycle Life Lithium Storage with High Structural Stability

Nanowires (NWs) synthesized via chemical vapor deposition (CVD) process have demonstrated significant improvement in lithium storage performance along with their outstanding accommodation of large volume changes during charge/discharge process. Nevertheless, the NW electrodes have been only confined to research level due to the lack of scalability and severe side reactions by their high surface area. Here, we present nanoporous Ge nanofibers (NPGeNFs) having moderate nanoporosity via a combination of simple electrospinning and low energetic zincothermic reduction reaction. In contrast with the CVD assisted NW growth, our method provides high tunability of macro/microscopic morphologies such as a porosity, length, and diameter of the nanoscale 1D structures. Significantly, the customized NPGeNFs showed highly suppressed volume expansion less than 15% (for electrodes) after full lithation and excellent durability with high lithium storage performance over 500 cycles. Our approach in this work offers effective 1D nanostructuring with highly customized geometries and can be extended to other applications including optoelectronics, catalysis, and energy conversion.

1D nanostructures↗

WBS 1.2.3.405 - Life Cycle Assessment of Storage Technologies

Recent commitments by the Biden administration have established targets to achieve a net-zero energy system by 2050. Meeting these targets will spur a rapid transition to clean energy technologies and a commensurate need to develop and deploy energy storage technologies at scale. Pumped Storage Hydro (PSH) is expected to be part of this solution because its ability to provide grid flexibility and stability and enable the dispatching of disparate variable renewable energy technologies. Despite PSH being a mature technology with a history of deployment dating back several decades, there is very little information on the greenhouse gas (GHG) implications of PSH as compared to other storage technologies. The objective of this project is to perform a full lifecycle assessment (LCA) of new PSH projects in the U.S. This LCA includes all project phases (resource extraction, construction, operation, maintenance, end-of-life). The functional unit for this study is 1 kWh electricity delivered by system to grid substation connection point and the estimated lifetime for our base case is 80 years. Data used in this study are based on over 30 potential PSH projects that are in preliminary planning phases and are represent a wide range of potential closed-loop PSH systems in terms of location, technology, and capacity. The project approach, data sources, and modeling assumptions have been informed by a technical review committee of stakeholders that include experts from academia, national and international government, industry, and utilities. The GHGs and energy return on investment (EROI) from PSH will be compared to other storage technologies (e.g., stationary battery storage). Results from this project will improve the PSH community's understanding of the environmental impacts and sustainability of new PSH projects and how PSH compares to other storage technologies. The approach used in this project relies on open-source programming. The analysis framework (source code and data) and will be made publicly available at the end of the project. In addition to reporting results for the base case, we will perform rigorous sensitivity analysis to identify the major drivers, understand impacts of different configurations, and future energy markets. Results from this project will be published in a suitable journal.

ENERGY PLANNING, POLICY, AND ECONOMY,HYDRO ENERGY↗

Life Cycle Systems Engineering Approach to NASA's 2nd Generation Reusable Launch Vehicle

The overall goal of the 2nd Generation RLV Program is to substantially reduce technical and business risks associated with developing a new class of reusable launch vehicles. NASA's specific goals are to improve the safety of a 2nd- generation system by 2 orders of magnitude - equivalent to a crew risk of 1 -in- 10,000 missions - and decrease the cost tenfold, to approximately $1,000 per pound of payload launched. Architecture definition is being conducted in parallel with the maturating of key technologies specifically identified to improve safety and reliability, while reducing operational costs. An architecture broadly includes an Earth-to-orbit reusable launch vehicle, on-orbit transfer vehicles and upper stages, mission planning, ground and flight operations, and support infrastructure, both on the ground and in orbit. The systems engineering approach ensures that the technologies developed - such as lightweight structures, long-life rocket engines, reliable crew escape, and robust thermal protection systems - will synergistically integrate into the optimum vehicle. Given a candidate architecture that possesses credible physical processes and realistic technology assumptions, the next set of analyses address the system's functionality across the spread of operational scenarios characterized by the design reference missions. The safety/reliability and cost/economics associated with operating the system will also be modeled and analyzed to answer the questions "How safe is it?" and "How much will it cost to acquire and operate?" The systems engineering review process factors in comprehensive budget estimates, detailed project schedules, and business and performance plans, against the goals of safety, reliability, and cost, in addition to overall technical feasibility. This approach forms the basis for investment decisions in the 2nd Generation RLV Program's risk-reduction activities. Through this process, NASA will continually refine its specialized needs and identify where Defense and commercial requirements overlap those of civil missions.

Thomas, Dale↗