Rechargeable Alkaline Batteries Research Articles

Electrochemically Produced Zinc Oxide Electrode in Rechargeable Alkaline Batteries

The zinc electrode is a commonly used negative electrode in a host of commercially important battery systems such as Zinc- Manganese dioxide (Zn-MnO2) and Silver – Zinc (Ag2O-Zn) batteries. Out of these the Zn-MnO2 battery is a commercially successful non-rechargeable battery because of its inherent safety, low cost and relatively high energy density. Recent experimental work has shown that a rechargeable Zn-MnO2 battery is capable of giving 3000 cycles when cycled at 10% of the MnO2 theoretical 1 e- capacity and 1.5% Zn 2e- capacity. However, at higher zinc utilization the battery is short-lived. Dendrite shorting, shape change and MnO2 poisoning are some of the main mechanisms of zinc electrode failure. These failure mechanisms are closely related to the high electrochemical solubility and the unrestrained movement of zincate ions, formed at the anode on discharge. Therefore, it is imperative to immobilize zincate ion either via complexation or intercalation. Hydrotalcite-like layered materials are recently reported as anode active materials for Nickel -Zinc batteries and have been suggested to capture zinc ions into their structure. We report the cycling performance of Zinc Aluminum Bismuth hydrotalcite for 900 cycles at 10% zinc utilization in 6 M potassium hydroxide solution saturated with zinc oxide against Nickel oxyhydroxide cathode. X-ray diffraction results show the presence of zinc oxide on discharge and do not support the presence of a layered hydrotalcite after cycling, as has been reported in literature. This is attributed to the instability of the hydrotalcite crystal structure in concentrated alkaline electrolytes. The results of this study show improved performance because of zinc oxide saturated electrolyte. To inherently reduce the tendency of the zinc electrode for dendrite shorting and shape change we investigate a fundamental question of the difference between the cycling of a zinc electrode versus the cycling of an electrochemically formed zinc oxide electrode. A novel, first of its kind, battery cycling protocol is reported where manganese dioxide cathode is cycled against a zinc oxide anode formed in-situ. This is made possible by first deeply discharging the manganese dioxide against a metallic zinc electrode resulting in complete conversion of metallic zinc to zinc oxide. Subsequent cycling of the electrochemically formed zinc oxide anode and cathode is carried out at a shallow depth of discharge. Adopting this strategy has resulted in improved cycle life at 12% utilization of the zinc electrode. We dissect the cells at different cycles to see an evolution of the active material in the cell with metallic zinc and the cell with electrochemically formed zinc oxide. Bulk electrolyte analysis for zincate ion shows that the zinc oxide cell is under-saturated while the metallic zinc cell is saturated with zincate ions. Optical Microscopy images of the zinc oxide anode show the presence of finer zinc particles embedded inside a zinc oxide matrix. Preliminary analysis results show that cycling of electrochemically produced zinc oxide rather than metallic zinc anode reduces shape change and dendrites because of reduction of zincate ions in the bulk electrolyte.

Bio-mediated synthesis of α-Ni(OH)2 nanobristles on hollow porous carbon nanofibers for rechargeable alkaline batteries

Nickel hydroxide nanobristles were fabricated on the surface of hollow carbon nanofibers (HPCNFs) through a low cost and effective bio-mediated technology, where the eggshells with eggshell membrane were selected as multifunctional reactors to separate the precursor solution to control OH− ion diffusion in order to form α-Ni(OH)2 instead of β-Ni(OH)2. The as prepared Ni(OH)2/HPCNFs displays high capacity (283 mAh/g) and a remarkable cycle life (82% specific capacity retained after 5000 cycle numbers) in 1M KOH aqueous solution. Compared with literature reports, in which Ni(OH)2 are often considered for pseudocapacitors, we suggest our electrodes are good for rechargeable alkaline secondary batteries or as battery electrodes in hybrid supercapacitors, based on battery behavior observed in our electrochemical measurements. As battery electrodes in hybrid supercapacitors, an asymmetric supercapacitor was fabricated, in which Ni(OH)2/HPCNFs and activated carbon as positive and negative electrode, respectively (Ni(OH)2/HPCNFs//AC ASC), which displays intriguing electrochemical performances with a high energy density (31.3 Wh /kg at 300.5 W/ kg). The results demonstrate that the bio-mediated method for achieving Ni(OH)2/HPCNFs nanomaterials is becoming a promising technology in alkaline batteries.

Microwave-assisted synthesis of nano petal-like α-Ni(OH)2/RGO and its electrochemical performance

A nanoscale petal-like α-Ni(OH)2/reduced graphene oxide (α-Ni(OH)2/RGO) composite was synthesized with the one-step microwave method. α-Ni(OH)2 particles with sizes of approximately 200 nm are uniformly distributed on the reduced graphene oxide sheet in the sample. When used as an electrode for alkaline rechargeable batteries, the discharge capacity of the α-Ni(OH)2/RGO composite reaches 333.5 mAh/g at 0.2C and 247.1 mAh/g at 10 C, respectively, with an excellent rate capability. After 2000 cycles, the capacity of the electrode is insignificantly attenuated, indicating a high capacity retention and cycling stability. The outstanding electrochemical properties are attributed to the nanoscale petal-like structure α-Ni(OH)2 anchoring on the RGO sheets, which facilitates ion diffusion and increases the active surface, which is effectively reacting with the electrolyte. The nanoscale petal-like electrode material fabricated in this study provides clues to address the problem of energy applications of high-performance alkaline rechargeable batteries.

Frontispiz: Triple‐Shelled Manganese–Cobalt Oxide Hollow Dodecahedra with Highly Enhanced Performance for Rechargeable Alkaline Batteries

Frontispiz: Triple‐Shelled Manganese–Cobalt Oxide Hollow Dodecahedra with Highly Enhanced Performance for Rechargeable Alkaline Batteries

Frontispiece: Triple‐Shelled Manganese–Cobalt Oxide Hollow Dodecahedra with Highly Enhanced Performance for Rechargeable Alkaline Batteries

Frontispiece: Triple‐Shelled Manganese–Cobalt Oxide Hollow Dodecahedra with Highly Enhanced Performance for Rechargeable Alkaline Batteries

Effect of Sub-nanoparticle Architecture on Cycling Performance of MnO2 Battery Cathodes through Thermal Tuning of Polymorph Composition

Reversible cycling of MnO2 cathodes remains a challenge in alkaline rechargeable battery development. In prior work, we have developed new platelet shaped MnO2 nanoparticles with stable performance...

Recent Advances in Rational Electrode Designs for High‐Performance Alkaline Rechargeable Batteries

AbstractIn recent years, noticeable progress is achieved regarding alkaline rechargeable batteries (ARBs). Due to their merits of safety and low cost, ARBs are considered promising energy storage sources for large‐scale grid energy storage, electric vehicles, and hybrid electric vehicles, as well as wearable and portable devices. While previous reviews have focused on specific topics associated with ARBs, providing a comprehensive review on rechargeable alkaline batteries is both timely and worthwhile. In this review, the recent progress in ARBs is summarized and the strategies underlying rational electrode designs for cathodes and anodes are highlighted, as well as their applications in full cells including flexible batteries. This review may pave the way for further designs of high‐performance alkaline batteries.

Ultrafast Lithium Diffusion in Bilayer Buckled Graphene: A Comparative Study of Li and Na

A spectacular enhancement of the diffusion constant parallel to the folding axis is found. The ratio of the parallel to the perpendicular diffusion depends on the buckling direction and stacking type, and increases with the degree of buckling. The strongest anisotropy is observed in the case of fixed zig-zag edges. A comparison with the interlayer diffusion of Na suggests that the strong asymmetry in the vibrational states of buckled graphene and also the smaller mass of Li are likely to contribute to the observed diffusion enhancement. This work opens a new pathway to develop highly-efficient anodes for rechargeable alkaline batteries.

Thiocarboxylate-modified Ni(OH)2 nanosheets for high-performance alkaline batteries

Thiocarboxylate-modified Ni(OH)2 nanosheets present a superior electrochemical performance as an alkaline rechargeable battery cathode due to their highly conductive metal–sulfur bonds.

Triple-Shelled Manganese-Cobalt Oxide Hollow Dodecahedra with Highly Enhanced Performance for Rechargeable Alkaline Batteries.

Precisely carving of multi-shelled manganese-cobalt oxide hollow dodecahedra (Co/Mn-HD) with shell number up to three is achieved by a controlled calcination of the Mn-doped zeolitic imidazolate framework ZIF-67 precursor (Co/Mn-ZIF). The unique multi-shelled and polycrystalline structure not only provides a very large electrochemically active surface area (EASA), but also enhances the structural stability of the material. The residual C and N in the final structures might aid stability and increase their conductivity. When used in alkaline rechargeable battery, the triple-shelled Co/Mn-HD exhibits high electrochemical performance, reversible capacity (331.94 mAh g-1 at 1 Ag-1 ), rate performance (88 % of the capacity can be retained with a 20-fold increase in current density), and cycling stability (96 % retention over 2000 cycles).

Triple‐Shelled Manganese–Cobalt Oxide Hollow Dodecahedra with Highly Enhanced Performance for Rechargeable Alkaline Batteries

AbstractPrecisely carving of multi‐shelled manganese–cobalt oxide hollow dodecahedra (Co/Mn‐HD) with shell number up to three is achieved by a controlled calcination of the Mn‐doped zeolitic imidazolate framework ZIF‐67 precursor (Co/Mn‐ZIF). The unique multi‐shelled and polycrystalline structure not only provides a very large electrochemically active surface area (EASA), but also enhances the structural stability of the material. The residual C and N in the final structures might aid stability and increase their conductivity. When used in alkaline rechargeable battery, the triple‐shelled Co/Mn‐HD exhibits high electrochemical performance, reversible capacity (331.94 mAh g−1 at 1 Ag−1), rate performance (88 % of the capacity can be retained with a 20‐fold increase in current density), and cycling stability (96 % retention over 2000 cycles).

Ni(OH)2 nanoplates decorated on graphene nanosheets for alkaline secondary batteries

The β-nickel hydroxide/reduced graphene oxide (β-Ni(OH)2/RGO) nanocomposites were successfully synthesized by the microwave-assisted method. The as-obtained samples are composed of β-Ni(OH)2 nanoplates deposited homogeneously on the surfaces of the RGO layer. The discharge capacity of the β-Ni(OH)2/RGO composite decreases from 316.3 to 259.9 mA h/g at the discharge rate from 0.2 to 10 C, and the capacity decreases slightly by 17.8%. The excellent capacity and rate capability are assigned to the well-defined nanocrystallinity of the disorder hexagonal β-Ni(OH)2 nanoplates growing and anchoring on the surface of the RGO layer with the most numerous of available active sites, which provide more comfort spaces for protons and ions. The superior capacity of pseudocapacitive β-Ni(OH)2 and good conductivity of RGO make the β-Ni(OH)2/RGO composites a promising battery-type material for high-performance alkaline rechargeable batteries.

Novel Application of Repaired LiFePO4 as a Candidate Anode Material for Advanced Alkaline Rechargeable Batteries

The extensive application of LiFePO4 batteries for energy storage in recent years will result in a large number of spent LiFePO4 batteries in the future. How to properly recycle these spent LiFePO4...

“Carbon‐Glue” Enabled Highly Stable and High‐Rate Fe3O4 Nanorod Anode for Flexible Quasi‐Solid‐State Nickel–Copper//Iron Alkaline Battery

AbstractThe practical application of iron oxide anode in rechargeable alkaline batteries is greatly hampered by the poor electrochemical stability and low rate capability. In addition, flexible solid‐state iron anode‐based rechargeable batteries with distinctive counter electrode coupling are quite lacking. Herein, an interesting “carbon glue” penetration strategy toward Fe3O4 nanorod film anode is proposed. This design not only immobilizes the nanorods and maintains strong adhesion with the current collector but also ensures continuous electrically conductive pathway, resulting in dramatically increased stability (≈99% capacity retention after 1000 cycles) and excellent rate performance (1.2 min charging with ≈70.6% initial capacity kept). By pairing with a new‐type Ni0.49Cu0.51O nanowire array cathode, a unique 1.2 V flexible rechargeable nickel–copper//iron alkaline battery is further assembled, which stores energy based on redox electrochemistry of transition metal ions. It delivers high volumetric energy and power densities (7.21 mWh cm−3; 299.30 mW cm−3), and demonstrates outstanding stability up to 5000 cycles. In particular, with the utilization of quasi‐solid‐state electrolyte, the device still maintains good performance upon substantially bending and twisting. This work presents a new concept to design high stability iron anode‐based alkaline batteries and further pushes forward the development of emerging flexible energy storage systems.

(Invited) (More) Uniform Control of Oxidative Dissolution, Complexation, and Electrodeposition Using 3D Wiring of Aperiodic Zinc Sponge Anodes in Rechargeable Alkaline Batteries

Our team at the U.S. Naval Research Laboratory has solved the chronic impediment of cell-shorting dendritic growth that has thwarted development of rechargeable zinc alkaline batteries—particularly to depths of zinc utilization that can challenge lithium-ion energy density. We do so using architectural design in which zinc particles are fused into a porous, highly conductive, and 3D-wired “sponge” monolith, as verified by X-ray tomography. This architectural configuration controls the behavior of the zinc anode during cycling such that an inner core of metallic zinc persists—even when discharging >90% of the zinc present—thus permitting recovery of >95% of that deeply discharged metal upon electroplating recharge. An additional key to our ability to oxidize and then re-plate the zinc lies in retaining at the inner and outer surfaces of the sponge the secondary discharge product, namely the zinc oxide that precipitates out of solution when zincate ions (the primary discharge product) dehydrate upon reaching supersaturation concentrations. The more uniform reactivity of zinc sponge anodes will be demonstrated for rechargeable Ni–Zn, Ag–Zn, and Zn–air cells.

A Dendritic Nickel Cobalt Sulfide Nanostructure for Alkaline Battery Electrodes

AbstractA uniform dendritic NiCo2S4@NiCo2S4 hierarchical nanostructure of width ≈100 nm is successfully designed and synthesized. From kinetic analysis of the electrochemical reactions, those electrodes function in rechargeable alkaline batteries (RABs). The dendritic structure exhibited by the electrodes has a high discharge‐specific capacity of 4.43 mAh cm−2 at a high current density of 240 mA cm−2 with a good rate capability of 70.1% after increasing the current densities from 40 to 240 mA cm−2. At low scan rate of 0.5 mV s−1 in cyclic voltammetry test, the semidiffusion controlled electrochemical reaction contributes ≈92% of the total capacity, this value decreases to ≈43% at a high scan rate of 20 mV s−1. These results enable a detailed analysis of the reaction mechanism for RABs and suggest design concepts for new electrode materials.

Electrochemically Produced Zinc Oxide Electrode in Rechargeable Alkaline Batteries

The zinc electrode is a commonly used negative electrode in a host of commercially important battery systems such as Zinc-Manganese dioxide (Zn-MnO2) and Silver-Zinc (Ag2O-Zn) batteries. Out of these the Zn-MnO2 battery is a commercially successful non-rechargeable battery because of its inherent safety, low cost and relatively high energy density. Recent experimental work has shown that a rechargeable Zn-MnO2 battery is capable of giving 3000 cycles when cycled at 10% of the MnO2 theoretical 1 e- capacity and 1.5% of the Zn 2 e- capacity. However, at higher zinc utilization the battery is short-lived. Dendrite shorting, shape change and MnO2 poisoning are some of the main mechanisms of zinc electrode failure. These failure mechanisms are closely related to the high electrochemical solubility and the unrestrained movement of zincate ions, formed at the anode on discharge. Therefore, it is imperative to immobilize zincate ion either via complexation or intercalation. Hydrotalcite-like layered materials are recently reported as anode active materials for Nickel -Zinc batteries and have been suggested to capture zinc ions into their structure. We report the cycling performance of Zinc Aluminum Bismuth hydrotalcite for 900 cycles at 10% zinc utilization in 6 M potassium hydroxide solution saturated with zinc oxide against Nickel oxyhydroxide cathode. X-ray diffraction results show the presence of zinc oxide on discharge and do not support the presence of a layered hydrotalcite after cycling, as has been reported in literature. This is attributed to the instability of the hydrotalcite crystal structure in concentrated alkaline electrolytes. The results of this study show improved performance because of zinc oxide saturated electrolyte. To inherently reduce the tendency of the zinc electrode for dendrite shorting and shape change we investigate a fundamental question of the difference between the cycling of a zinc electrode versus the cycling of an electrochemically formed zinc oxide electrode. A novel, first of its kind, battery cycling protocol is reported where manganese dioxide cathode is cycled against a zinc oxide anode formed in-situ. This is made possible by first deeply discharging the manganese dioxide against a metallic zinc electrode resulting in complete conversion of metallic zinc to zinc oxide. Subsequent cycling of the electrochemically formed zinc oxide anode and cathode is carried out at a shallow depth of discharge. Adopting this strategy has resulted in improved cycle life at 12% utilization of the zinc electrode. We dissect the cells at different cycles to see an evolution of the active material in the cell with metallic zinc and the cell with electrochemically formed zinc oxide. Bulk electrolyte analysis for zincate ion shows that the zinc oxide cell is under-saturated while the control cell is saturated with zincate ions. Preliminary analysis results show that cycling of electrochemically produced zinc oxide rather than metallic zinc anode reduces shape change and dendrites because of reduction of zincate ions in the bulk electrolyte.

Iron oxide nanoconfined in carbon nanopores as high capacity anode for rechargeable alkaline batteries

Rechargeable aqueous batteries are attracting renewed attention due to flammability and high cost of lithium-ion cells. Extremely low cost, very high abundance and eco-friendliness of iron (Fe) anodes make them particularly attractive for aqueous chemistries. Unfortunately, traditional Fe anodes suffer from low capacity utilization, the need for formation pre-cycling and dissolution of active material when fully discharged. Known methods for synthesis of nanocomposite Fe anode are expensive and offer poor control over material properties and uniformity. We report on a novel low-cost synthesis route to produce nanocomposites with crystalline FeOx nanoparticles very uniformly distributed within individual nanoporous carbon particles. The conductivity enhancement and a very small size of FeOx particles (< 5 nm) effectively enhance the discharge capacity of Fe anodes up to 600 mAh g−1. In contrast to graphene-FeOx or carbon nanotube-FeOx, the large size of the produced nanocomposite particles allows them to be processed into electrodes the same way as supercapacitor electrodes are mass-produced by industry. The nanoconfinement suppresses side reactions, such as nanoFe dissolution and hydrogen evolution, resulting in capacity retention of up to ~85% after 200 cycles. When used in combination with novel In-based additives, reported anodes uniquely exhibited a single high-voltage discharge profile in full cells, which improves energy density of cells and simplifies battery management system.

Morphology and Phase Changes in Iron Anodes Affecting their Capacity and Stability in Rechargeable Alkaline Batteries

Rechargeable alkaline batteries may become attractive nonflammable alternatives to lithium-ion (Li-ion) batteries for applications where achieving the highest energy density is less critical than safety, environmental friendliness, and low cost of energy storage. The broad abundance and low price of iron (Fe) make it attractive as a rechargeable anode material for aqueous batteries. Through cyclic voltammetry and post-mortem analysis, we revealed four distinct stages of Fe anode evolution: development, retention, fading, and failure, where each stage is associated with very specific changes in the morphology and phase of Fe anodes. We observed the Fe particle fragmentation resulted in the capacity increase during the initial cycles of charge–discharge. Most importantly, we discovered the irreversible formation of maghemite (γ-Fe2O3) with low reactivity is responsible for the eventual Fe anode capacity fading. This unexpected discovery changes the paradigm on possible routes to stabilize Fe anodes and cont...

Enhanced Electrochemical Performance of CoB Amorphous Alloy through the Addition of Lanthanum

In order to investigate the effect of lanthanum on the electrochemical properties of CoB amorphous alloy, Co-Lax-B alloys (x = 0, 0.1, 0.5, and 1) were prepared by chemical reduction method. As negative electrodes in alkaline rechargeable batteries, Co-Lax-B alloys exhibit superior electrochemical properties. For Co-La0.1-B alloy, at the discharge current density of 100 mA/g, the initial discharge capacity is 830.6 mAh/g and the discharge capacity has remained around 317.3 mAh/g even after 100 cycles. Moreover, the high-rate discharge ability (HRD) of Co-La0.1-B alloy electrode at the discharge current density of 300 mA/g, 600 mA/g, and 900 mA/g is 98.16%, 95.17%, and 91.86%, respectively. The anodic polarization (AP) and the electrochemical impedance spectra (EIS) measurements indicate that the kinetics of electrochemical performance of the alloys is remarkably improved with the addition of lanthanum.