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At least 397 records · Page 22

Potentiodynamics of the Zinc and Proton Storage in Disordered Sodium Vanadate for Aqueous Zn-Ion Batteries

A rechargeable Zn-ion battery is a promising aqueous system, where coinsertion of Zn 2+ and H + could address the obstacles of the sluggish ionic transport in cathode materials imposed by multivalent battery chemistry. However, there is a lack of fundamental understanding of this dual-ion transport, especially the potentiodynamics of the storage process. Here, a quantitative analysis of Zn 2+ and H + transport in a disordered sodium vanadate (NaV 3 O 8 ) cathode material has been reported. Collectively, synchrotron X-ray analysis shows that both Zn 2+ and H + storages follow an intercalation storage mechanism in NaV 3 O 8 and proceed in a sequential manner, where intercalations of 0.26 Zn 2+ followed by 0.24 H + per vanadium atom occur during discharging, while reverse dynamics happens during charging. We find that such a unique and synergistic dual-ion sequential storage favors a high capacity (265 mA h g –1 ) and an energy density (221 W h kg –1 ) based on the NaV 3 O 8 cathode and a great cycling life (a capacity retention of 78% after 2000 cycles) in Zn/NaV 3 O 8 full cells.

36 MATERIALS SCIENCE↗

The computer simulation of automobile use patterns for defining battery requirements for electric cars

A Monte Carlo simulation process was used to develop the U.S. daily range requirements for an electric vehicle from probability distributions of trip lengths and frequencies and average annual mileage data. The analysis shows that a car in the U.S. with a practical daily range of 82 miles (132 km) can meet the needs of the owner on 95% of the days of the year, or at all times other than his long vacation trips. Increasing the range of the vehicle beyond this point will not make it more useful to the owner because it will still not provide intercity transportation. A daily range of 82 miles can be provided by an intermediate battery technology level characterized by an energy density of 30 to 50 watt-hours per pound (66 to 110 W-hr/kg). Candidate batteries in this class are nickel-zinc, nickel-iron, and iron-air. The implication of these results for the research goals of far-term battery systems suggests a shift in emphasis toward lower cost and greater life and away from high energy density.

Schwartz, H. J.↗

An improved method for analysis of hydroxide and carbonate in alkaline electrolytes containing zinc

A simplified method for titration of carbonate and hydroxide in alkaline battery electrolyte is presented involving a saturated KSCN solution as a complexing agent for zinc. Both hydroxide and carbonate can be determined in one titration, and the complexing reagent is readily prepared. Since the pH at the end point is shifted from 8.3 to 7.9 - 8.0, m-cresol purple or phenol red are used as indicators rather than phenolphthalein. Bromcresol green is recommended for determination of the second end point of a pH of 4.3 to 4.4.

Reid, M. A.↗

An improved method for analysis of hydroxide and carbonate in alkaline electrolytes containing zinc

A simplified method for titration of carbonate and hydroxide in alkaline battery electrolyte is presented involving a saturated KSCN solution as a complexing agent for zinc. Both hydroxide and carbonate can be determined in one titration, and the complexing reagent is readily prepared. Since the pH at the end point is shifted from 8.3 to 7.9-8.0, m-cresol purple or phenol red are used as indicators rather than phenolphthalein. Bromcresol green is recommended for determination of the second end point of a pH of 4.3 to 4.4.

Reid, M. A.↗

Battery workshop

Accelerated and nondestructive testing techniques for various type batteries - lead acid, sealed nickel, nickel cadmium, silver cadmium, and silver zinc cells

ELECTROCHEMICAL CELL↗

Use of Hydrogel Electrolyte in Zn-MnO2 Rechargeable Batteries: Characterization of Safety, Performance, and Cu2+ Ion Diffusion

Achieving commercially acceptable Zn-MnO2 rechargeable batteries depends on the reversibility of active zinc and manganese materials, and avoiding side reactions during the second electron reaction of MnO2. Typically, liquid electrolytes such as potassium hydroxide (KOH) are used for Zn-MnO2 rechargeable batteries. However, it is known that using liquid electrolytes causes the formation of electrochemically inactive materials, such as precipitation Mn3O4 or ZnMn2O4 resulting from the uncontrollable reaction of Mn3+ dissolved species with zincate ions. In this paper, hydrogel electrolytes are tested for MnO2 electrodes undergoing two-electron cycling. Improved cell safety is achieved because the hydrogel electrolyte is non-spillable, according to standards from the US Department of Transportation (DOT). The cycling of “half cells” with advanced-formulation MnO2 cathodes paired with commercial NiOOH electrodes is tested with hydrogel and a normal electrolyte, to detect changes to the zincate crossover and reaction from anode to cathode. These half cells achieved ≥700 cycles with 99% coulombic efficiency and 63% energy efficiency at C/3 rates based on the second electron capacity of MnO2. Other cycling tests with “full cells” of Zn anodes with the same MnO2 cathodes achieved ~300 cycles until reaching 50% capacity fade, a comparable performance to cells using liquid electrolyte. Electrodes dissected after cycling showed that the liquid electrolyte allowed Cu ions to migrate more than the hydrogel electrolyte. However, measurements of the Cu diffusion coefficient showed no difference between liquid and gel electrolytes; thus, it was hypothesized that the gel electrolytes reduced the occurrence of Cu short circuits by either (a) reducing electrode physical contact to the separator or (b) reducing electro-convective electrolyte transport that may be as important as diffusive transport.

25 ENERGY STORAGE↗

Amorphous zinc–molybdenum–sulfide chalcogel as a long-cycle, high-capacity electrode for lithium-ion batteries

The inherent limitations of intercalation-based electrodes in lithium-ion batteries have prompted the search for alternative materials with higher specific capacities and robust electrochemical stability. Sulfur-based electrodes, despite their high theoretical capacities (1672 mAh g −1 ), typically suffer from poor cycling performance. In this work, zinc molybdenum polysulfide (Zn x Mo 3 S 13 , 0.5 ≤ x), an amorphous semiconductor chalcogel, exhibits high specific capacity and excellent cycling stability. Synchrotron X-ray pair distribution function and extended X-ray absorption fine structure analyses reveal a short-range atomic structure comprising Mo–Mo, M–S (M = Mo, Zn), and S–S bonding motifs. The coordination environment of Mo and S closely resembles that of Mo 3 S 13 clusters, interconnected via S–S bridges and Zn 2+ cations. The Li/Zn x Mo 3 S 13 cell delivers an initial discharge capacity of 844 mAh g −1 at C/3, and retains 386.2 mAh g −1 after 1000 cycles with an average coulombic efficiency of 99.99%. The distribution of relaxation times analysis confirms the formation of a stable solid electrolyte interphase, which underpins the cell's long-term stability. In conclusion, this outstanding performance is attributed to the synergistic effects of the chalcogel's unique amorphous framework, semiconductive character, Zn-mediated polysulfide anchoring, and structural resilience, positioning Zn x Mo 3 S 13 chalcogel among the most durable pure metal sulfide cathodes reported for next-generation LIBs.

36 MATERIALS SCIENCE↗

Elucidating the Morphological Instability Mechanisms During Electrodeposition of Active Metals

The primary aim of this investigation is to elucidate the mechanisms by which a group of metals pertinent to battery technology exhibit unstable growth morphology during electrodeposition, which are crucial for the operational efficacy of batteries. The metals under consideration include alkali metals alongside zinc, all of which are characterized by high atomic mobility and reactivity with the electrolytes employed in battery systems. These materials represent promising electrode candidates for next-generation rechargeable batteries that are anticipated to deliver significantly enhanced energy density at a reduced cost. Nevertheless, the widespread occurrence of distinctly non-uniform morphologies, exemplified by the emergence of filamentous and moss-like structures, constitutes a significant impediment to their effective utilization, as it leads to accelerated capacity degradation and potential internal short circuits. This study addresses a critical question that has thus far garnered limited attention: Does the residual stress induced by the plating process play an instrumental role in inducing the morphological instability? Utilizing zinc as the primary model system, this project will be executed through three interconnected tasks: (1) the quantification of the relationship between plating stress and electroplating morphologies, (2) the three-dimensional imaging of the microstructure of the mossy structure at the nanoscale, and (3) the development of a mesoscale electroplating model to interpret empirical findings and generate additional predictive insights.

25 ENERGY STORAGE↗

An electric vehicle propulsion system's impact on battery performance: An overview

The performance of two types of batteries, lead-acid and nickel-zinc, was measured as a function of the charging and discharging demands anticipated from electric vehicle propulsion systems. The benefits of rapid high current charging were mixed: although it allowed quick charges, the energy efficiency was reduced. For low power (overnight) charging the current wave shapes delivered by the charger to the battery tended to have no effect on the battery cycle life. The use of chopper speed controllers with series traction motors resulted in a significant reduction in the energy available from a battery whenever the motor operates at part load. The demand placed on a battery by an electric vehicle propulsion system containing electrical regenerative braking confirmed significant improvment in short term performance of the battery.

Bozek, J. M.↗

Interspace and Vacancy Modulation: Promoting the Zinc Storage of an Alcohol-Based Organic–Inorganic Cathode in a Water–Organic Electrolyte

Expanding interspace and introducing vacancies are desired to promote the mobility of Zn ions and unlock the inactive sites of layered cathodes. However, this two-point modulation has not yet been achieved simultaneously in vanadium phosphate. Here, in this work, a strategy is proposed for fabricating an alcohol-based organic–inorganic hybrid material, VO 1–x PO 4 ·0.56C 6 H 14 O 4 , to realize the conjoint modulation of the d-interspace and oxygen vacancies. Peculiar triglycol molecules with an inclined orientation in the interlayer also boost the improvement in the conversion rate of V 5+ to V 4+ and the intensity of the P—O bond. Their synergism can ensure steerable adjustment for intercalation kinetics and electron transport, as well as realize high chemical reactivity and redox-center optimization, leading to at least 200% increase in capacity. Using a water–organic electrolyte, the designed Zn-ion batteries with an ultrahigh-rate profile deliver a long-term durability (fivefold greater than pristine material) and an excellent energy density of ≈142 Wh kg –1 (including masses of cathode and anode), thereby substantially outstripping most of the recently reported state-of-the-art zinc-ion batteries. This work proves the feasibility to realize the two-point modulation by using organic intercalants for exploiting high-performance new 2D materials.

25 ENERGY STORAGE↗

Power Sources Symposium, 31st, Atlantic City, NJ, June 11-14, 1984, Proceedings

The present conference on electrochemical power sources encompasses systems of such types as the thermoelectric, advanced rechargeable, lithium reserve, rechargeable, and nonrechargeable, nickel-cadmium and nickel-hydrogen rechargeable, lead-acid, nickel-zinc and nickel-iron rechargeable, nickel-cadmium and nickel-hydrogen rechargeable, and fuel cells. Attention is given to Si-Ge alloy multicouple technology, sodium-sulfur battery development status, the safety aspects of a rechargeable lithium C cell, fiber-structure electrodes for nickel-cadmium batteries, energy density improvements in Li/carbon monofluoride cells, zinc-air button cell technology, catalyzed cathodes for Li/SOCl2 cells, the effect of polymer structure on the rate capability of the lithium-iodine cell, and a methanol fuel cell powerplant.

Source record↗

Material Failure Mechanisms of Alkaline Zn Rechargeable Conversion Electrodes

Zinc (Zn) alkaline electrodes hold great importance and promise in the battery technology community, yet their behavior in real-world applications is still poorly understood. Here, we report a study of failure mechanisms and material evolution during cycling of 27 zinc–manganese dioxide (Zn–MnO 2 ) cells wherein the percent utilization of the Zn electroactive material is systematically varied between 1 and 16%. Cell fabrication is kept typical of the prevailing industrial cell design. The cycle life ranges from 2800 to 60, depending inversely on the Zn utilization. In all cases, the Zn material microstructure sheds the polytetrafluoroethylene (PTFE) binder and forms zinc oxide (ZnO) rods, with longer rods formed by lower current per Zn mass. Irreversible side reactions such as the hydrogen evolution reaction (HER), short circuits, or gas crossover cause the Zn anode’s charging efficiency to average 92% (as low as 86%), which in turn causes the baseload of metallic Zn to gradually disappear. Cell failure occurs after the baseload of metallic Zn is exhausted. The total lifetime discharge capacity remains constant near 12 ± 5 Ah/g Zn invariant of Zn utilization, which suggests that the aforementioned processes of Zn microstructural evolution and side-reaction destruction of baseload metallic zinc both progress linearly with cell capacity throughput. Manual reproduction of individual Zn failure mechanisms is performed in 22 fresh cells. Tight packing of the microstructure can lead to poor mass transfer, which causes supersaturation of soluble Zn and finally produces a high overvoltage during discharge. Here, the low charging current density yields poor coulombic efficiency due either to the competitive HER or soft short circuits.

25 ENERGY STORAGE↗

Li-ion EMU Battery Testing

A 45Ah Lithium ion (Li-Ion) battery comprised of 5 Yardney prismatic cells was evaluated to replace the silver-zinc cells in the Extra-vehicular Mobility Unit (EMU). Tests determined that the five cell battery can meet the mission objective of 500 duty cycles and maintain a minimum voltage of 16.0 V without an individual cell voltage dropping below 3.0V. Forty real time cycles were conducted to develop BOL trend data. Decision to switch to accelerated cycling for the remaining 460 cycles was made since Real Time cycling requires 1 day/cycle. Conclusions indicate that battery replacement would indeed be prudent.

Rehm, Raymond↗

Test Procedures for Characterizing, Evaluating, and Managing Separator Materials used in Secondary Alkaline Batteries

Secondary alkaline batteries, such as nickel-cadmium and silver-zinc, are commonly used for aerospace applications. The uniform evaluation and comparison of separator properties for these systems is dependent upon the measurement techniques. This manual presents a series of standard test procedures that can be used to evaluate, compare, and select separator materials for use in alkaline batteries. Detailed test procedures evaluating the following characteristics are included in this manual: physical measurements of thickness and area weight, dimensional stability measurements, electrolyte retention, resistivity, permeability as measured via bubble pressure, surface evaluation via SEM, chemical stability, and tensile strength.

Guasp, Edwin↗