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Batteries, Volume 3, Issue 4 (December 2017) – 13 articles

Cover Story (view full-size image): It was shown, for the first time, that a thin film Al/nc–Si/Al structure with a porous top contact may spontaneously generate electromotive force (emf) up to 1V, upon interaction with water vapor in the surrounding atmosphere. The possibility of emf observation is denoted to the inequality of two aluminum electrodes. We investigated volt–ampere characteristics in different conditions and proposed a model of emf generation in the structures. View this paper
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2585 KiB  
Article
Effects of Cs2CO3 Additive in KOH Electrolyte Used in Ni/MH Batteries
by Shuli Yan, Jean Nei, Peifeng Li, Kwo-Hsiung Young and K. Y. Simon Ng
Batteries 2017, 3(4), 41; https://doi.org/10.3390/batteries3040041 - 18 Dec 2017
Cited by 6 | Viewed by 6924
Abstract
The effects of Cs2CO3 addition in a KOH-based electrolyte were investigated for applications in nickel/metal hydride batteries. Both MgNi-based and Laves phase-related body-centered cubic solid solution metal hydride alloys were tested as the anode active materials, and sintered β-Ni(OH) [...] Read more.
The effects of Cs2CO3 addition in a KOH-based electrolyte were investigated for applications in nickel/metal hydride batteries. Both MgNi-based and Laves phase-related body-centered cubic solid solution metal hydride alloys were tested as the anode active materials, and sintered β-Ni(OH)2 was used as the cathode active material. Certain amounts of Cs2CO3 additive in the KOH-based electrolyte improved the electrochemical performances compared with a conventional pure KOH electrolyte. For example, with Laves phase-related body-centered cubic alloys, the addition of Cs2CO3 to the electrolyte improved cycle stability (for all three alloys) and discharge capacity (for the Al-containing alloys); moreover, in the 0.33 M Cs2CO3 + 6.44 M KOH electrolyte, the discharge capacity of Mg52Ni39Co3Mn6 increased to 132%, degradation decreased to 87%, and high-rate dischargeability stayed the same compared with the conventional 6.77 M KOH electrolyte. The effects of Cs2CO3 on the physical and chemical properties of Mg52Ni39Co3Mn6 were characterized by Fourier transform infrared spectroscopy, X-ray diffraction, transmission electron microscopy, inductively coupled plasma, and electrochemical impedance spectroscopy. The results from these analyses concluded that Cs2CO3 addition changed both the alloy surface and bulk composition. A fluffy layer containing carbon was found covering the metal particle surface after cycling in the Cs2CO3-containing electrolyte, and was considered to be the main cause of the reduction in capacity degradation during cycling. Also, the Cs2CO3 additive promoted the formations of the C–O and C=O bonds on the alloy surface. The C–O and C=O bonds were believed to be active sites for proton transfer during the electrochemical process, with the C–O bond being the more effective of the two. Both bonds contributed to a higher surface catalytic ability. The addition of 0.33 M Cs2CO3 was deemed optimal in this study. Full article
(This article belongs to the Special Issue Nickel Metal Hydride Batteries 2017)
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10830 KiB  
Article
Electron Backscatter Diffraction Studies on the Formation of Superlattice Metal Hydride Alloys
by Shuli Yan, Kwo-Hsiung Young, Xin Zhao, Zhi Mei and K. Y. Simon Ng
Batteries 2017, 3(4), 40; https://doi.org/10.3390/batteries3040040 - 13 Dec 2017
Cited by 4 | Viewed by 6619
Abstract
Microstructures of a series of La-Mg-Ni-based superlattice metal hydride alloys produced by a novel method of interaction of a LaNi5 alloy and Mg vapor were studied using a combination of X-ray energy dispersive spectroscopy and electron backscatter diffraction. The conversion rate of [...] Read more.
Microstructures of a series of La-Mg-Ni-based superlattice metal hydride alloys produced by a novel method of interaction of a LaNi5 alloy and Mg vapor were studied using a combination of X-ray energy dispersive spectroscopy and electron backscatter diffraction. The conversion rate of LaNi5 increased from 86.8% into 98.2%, and the A2B7 phase abundance increased from 42.5 to 45.8 wt % and reduced to 39.2 wt % with the increase in process time from four to 32 h. During the first stage of reaction, Mg formed discrete grains with the same orientation, which was closely related to the orientation of the host LaNi5 alloy. Mg then diffused through the ab-phase of LaNi5 and formed the AB2, AB3, and A2B7 phases. Diffusion of Mg stalled at the grain boundary of the host LaNi5 alloy. Good alignments in the c-axis between the newly formed superlattice phases and LaNi5 were observed. The density of high-angle grain boundary decreased with the increase in process time and was an indication of lattice cracking. Full article
(This article belongs to the Special Issue Nickel Metal Hydride Batteries 2017)
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4232 KiB  
Article
A Bilevel Equalizer for Large Lithium Ion Batteries
by Ngalula Sandrine Mubenga, Zachary Linkous and Thomas Stuart
Batteries 2017, 3(4), 39; https://doi.org/10.3390/batteries3040039 - 7 Dec 2017
Cited by 8 | Viewed by 13637
Abstract
Due to variations among the cells, large lithium ion batteries (LIB) such as those in battery energy storage stations (BESS) and electric vehicles (EVs) must have an equalizer (EQU) circuit to balance the cell voltages. In spite of their significant losses and other [...] Read more.
Due to variations among the cells, large lithium ion batteries (LIB) such as those in battery energy storage stations (BESS) and electric vehicles (EVs) must have an equalizer (EQU) circuit to balance the cell voltages. In spite of their significant losses and other limitations, passive equalizers (PEQ) are used in most applications because they are relatively simple and low cost. Active equalizers (AEQ) reduce these PEQ problems, but are not as widely used due to their much higher cost and complexity. A new hybrid circuit called the Bilevel EQU (BEQ) combines the PEQ and AEQ to provide much higher performance than a pure PEQ but at a much lower cost than a pure AEQ. Full article
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3498 KiB  
Article
A Ni/MH Pouch Cell with High-Capacity Ni(OH)2
by Shuli Yan, Tiejun Meng, Kwo-Hsiung Young and Jean Nei
Batteries 2017, 3(4), 38; https://doi.org/10.3390/batteries3040038 - 4 Dec 2017
Cited by 7 | Viewed by 7223
Abstract
Electrochemical performances of a high-capacity and long life β-α core-shell structured Ni0.84Co0.12Al0.04(OH)2 as the positive electrode active material were tested in a pouch design and compared to those of a standard β-Ni0.91 [...] Read more.
Electrochemical performances of a high-capacity and long life β-α core-shell structured Ni0.84Co0.12Al0.04(OH)2 as the positive electrode active material were tested in a pouch design and compared to those of a standard β-Ni0.91Co0.045Zn0.045(OH)2. The core-shell materials were fabricated with a continuous co-precipitation process, which created an Al-poor core and an Al-rich shell during the nucleation and particle growth stages, respectively. The Al-rich shell became α-Ni(OH)2 after electrical activation and remained intact through the cycling. Pouch cells with the high-capacity β-α core-shell positive electrode material show higher charge acceptances and discharge capacities at 0.1C, 0.2C, 0.5C, and 1C, improved self-discharge performances, and reduced internal and surface charge-transfer resistances, at both room temperature and −10 °C when compared to those with the standard positive electrode material. While the high capacity of the core-shell material can be attributed to the α phase with a multi-electron transfer capability, the improvement in high-rate capability (lower resistance) is caused by the unique surface morphology and abundant interface sites at the β-α grain boundaries. Gravimetric energy densities of pouch cells made with the high-capacity and standard positive materials are 127 and 110 Wh·kg−1, respectively. A further improvement in capacity is expected via the continued optimization of pouch design and the use of high-capacity metal hydride alloy. Full article
(This article belongs to the Special Issue Nickel Metal Hydride Batteries 2017)
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6782 KiB  
Article
Nanostructured Networks for Energy Storage: Vertically Aligned Carbon Nanotubes (VACNT) as Current Collectors for High-Power Li4Ti5O12(LTO)//LiMn2O4(LMO) Lithium-Ion Batteries
by Fabian Pawlitzek, Holger Althues, Benjamin Schumm and Stefan Kaskel
Batteries 2017, 3(4), 37; https://doi.org/10.3390/batteries3040037 - 15 Nov 2017
Cited by 9 | Viewed by 10371
Abstract
As a concept for electrode architecture in high power lithium ion batteries, self-supported nanoarrays enable ultra-high power densities as a result of their open pore geometry, which results in short and direct Li+-ion and electron pathways. Vertically aligned carbon nanotubes (VACNT) [...] Read more.
As a concept for electrode architecture in high power lithium ion batteries, self-supported nanoarrays enable ultra-high power densities as a result of their open pore geometry, which results in short and direct Li+-ion and electron pathways. Vertically aligned carbon nanotubes (VACNT) on metallic current collectors with low interface resistance are used as current collectors for the chemical solution infiltration of electroactive oxides to produce vertically aligned carbon nanotubes decorated with in situ grown LiMn2O4 (LMO) and Li4Ti5O12 (LTO) nanoparticles. The production processes steps (catalyst coating, VACNT chemical vapor deposition (CVD), infiltration, and thermal transformation) are all scalable, continuous, and suitable for niche market production to achieve high oxide loadings up to 70 wt %. Due to their unique transport structure, as-prepared nanoarrays achieve remarkably high power densities up to 2.58 kW kg−1, which is based on the total electrode mass at 80 C for LiMn2O4//Li4Ti5O12 full cells. The tailoring of LTO and LMO nanoparticle size (~20–100 nm) and VACNT length (array height: 60–200 µm) gives insights into the rate-limiting steps at high current for these kinds of nanoarray electrodes at very high C-rates of up to 200 C. The results reveal the critical structural parameters for achieving high power densities in VACNT nanoarray full cells. Full article
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4004 KiB  
Article
Effects of Boron-Incorporation in a V-Containing Zr-Based AB2 Metal Hydride Alloy
by Shiuan Chang, Kwo-Hsiung Young, Taihei Ouchi, Jean Nei and Xin Wu
Batteries 2017, 3(4), 36; https://doi.org/10.3390/batteries3040036 - 14 Nov 2017
Cited by 9 | Viewed by 6327
Abstract
In this study, boron, a metalloid element commonly used in semiconductor applications, was added in a V-containing Zr-based AB2 metal hydride alloy. In general, as the boron content in the alloy increased, the high-rate dischargeability, surface exchange current, and double-layer capacitance first [...] Read more.
In this study, boron, a metalloid element commonly used in semiconductor applications, was added in a V-containing Zr-based AB2 metal hydride alloy. In general, as the boron content in the alloy increased, the high-rate dischargeability, surface exchange current, and double-layer capacitance first decreased and then increased whereas charge-transfer resistance and dot product of charge-transfer resistance and double-layer capacitance changed in the opposite direction. Electrochemical and gaseous phase characteristics of two boron-containing alloys, with the same boron content detected by the inductively coupled plasma optical emission spectrometer, showed significant variations in performances due to the difference in phase abundance of a newly formed tetragonal V3B2 phase. This new phase contributes to the increases in electrochemical high-rate dischargeability, surface exchange current, charge-transfer resistances at room, and low temperatures. However, the V3B2 phase does not contribute to the hydrogen storage capacities in either gaseous phase and electrochemical environment. Full article
(This article belongs to the Special Issue Nickel Metal Hydride Batteries 2017)
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3442 KiB  
Article
Performance Comparison between AB5 and Superlattice Metal Hydride Alloys in Sealed Cells
by John M. Koch, Kwo-Hsiung Young, Jean Nei, Chaolan Hu and Benjamin Reichman
Batteries 2017, 3(4), 35; https://doi.org/10.3390/batteries3040035 - 6 Nov 2017
Cited by 8 | Viewed by 6131
Abstract
High-power cylindrical nickel metal/hydride batteries using a misch metal-based Al-free superlattice alloy with a composition of La11.3Pr1.7Nd5.1Mg4.5Ni63.6Co13.6Zr0.2 were fabricated and evaluated against those using a standard AB5 metal hydride [...] Read more.
High-power cylindrical nickel metal/hydride batteries using a misch metal-based Al-free superlattice alloy with a composition of La11.3Pr1.7Nd5.1Mg4.5Ni63.6Co13.6Zr0.2 were fabricated and evaluated against those using a standard AB5 metal hydride alloy. At room temperature, cells made with the superlattice alloy showed a 40% lower internal resistance and a 59% lower surface charge-transfer resistance compared to cells made with the AB5 alloy. At a low temperature (−10 °C), cells made with the superlattice alloy demonstrated an 18% lower internal resistance and a 60% lower surface charge-transfer resistance compared to cells made with the AB5 alloy. Cells made with the superlattice alloy exhibited a better charge retention at −10 °C. A cycle life comparison in a regular cell configuration indicated that the Al-free superlattice alloy contributes to a shorter cycle life as a result of the pulverization from the lattice expansion of the main phase. Full article
(This article belongs to the Special Issue Nickel Metal Hydride Batteries 2017)
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3872 KiB  
Article
Comparison among Constituent Phases in Superlattice Metal Hydride Alloys for Battery Applications
by Kwo-Hsiung Young, Taihei Ouchi, Jean Nei, John M. Koch and Yu-Ling Lien
Batteries 2017, 3(4), 34; https://doi.org/10.3390/batteries3040034 - 31 Oct 2017
Cited by 11 | Viewed by 6955
Abstract
The effects of seven constituent phases—CeNi3, NdNi3, Nd2Ni7, Pr2Ni7, Sm5Ni19, Nd5Co19, and CaCu5—on the gaseous phase and electrochemical characteristics of a [...] Read more.
The effects of seven constituent phases—CeNi3, NdNi3, Nd2Ni7, Pr2Ni7, Sm5Ni19, Nd5Co19, and CaCu5—on the gaseous phase and electrochemical characteristics of a superlattice metal hydride alloy made by induction melting with a composition of Sm14La5.7Mg4.0Ni73Al3.3 were studied through a series of annealing experiments. With an increase in annealing temperature, the abundance of non-superlattice CaCu5 phase first decreases and then increases, which is opposite to the phase abundance evolution of Nd2Ni7—the phase with the best electrochemical performance. The optimal annealing condition for the composition in this study is 920 °C for 5 h. Extensive correlation studies reveal that the A2B7 phase demonstrates higher gaseous phase hydrogen storage and electrochemical discharge capacities and better battery performance in high-rate dischargeability, charge retention, and cycle life. Moreover, the hexagonal stacking structure is found to be more favorable than the rhombohedral structure. Full article
(This article belongs to the Special Issue Nickel Metal Hydride Batteries 2017)
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5411 KiB  
Article
Thermal Characteristics of Conversion-Type FeOF Cathode in Li-ion Batteries
by Liwei Zhao, Ayuko Kitajou and Shigeto Okada
Batteries 2017, 3(4), 33; https://doi.org/10.3390/batteries3040033 - 23 Oct 2017
Cited by 4 | Viewed by 7785
Abstract
Rutile FeOF was used as a conversion-type cathode material for Li-ion batteries. In the present study, 0.6Li, 1.4Li, and 2.7Li per mole lithiation reactions were carried out by changing the electrochemical discharge reaction depth. The thermal characteristics of the FeOF cathode were investigated [...] Read more.
Rutile FeOF was used as a conversion-type cathode material for Li-ion batteries. In the present study, 0.6Li, 1.4Li, and 2.7Li per mole lithiation reactions were carried out by changing the electrochemical discharge reaction depth. The thermal characteristics of the FeOF cathode were investigated by thermogravimetric mass spectrometric (TG-MS) and differential scanning calorimeter (DSC) systems. No remarkable HF release was detected, even up to 700 °C, which indicated a low toxic risk for the FeOF cathode. Changes in the thermal properties of the FeOF cathode via different conversion reaction depths in the associated electrolyte were studied by changing the cathode/electrolyte ratio in the mixture. LiFeOF was found to exothermically react with the electrolyte at about 210 °C. Similar exothermic reactions were found with charged FeOF cathodes because of the irreversible Li ions. Among the products of the conversion reaction of FeOF, Li2O was found to exothermically react with the electrolyte at about 120 °C, which induced the main thermal risk of the FeOF cathode. It suggests that the oxygen-containing conversion-type cathodes have a higher thermal risk than the oxygen-free ones, but controlling the cathode/electrolyte ratio in cells successfully reduced the thermal risk. Finally, the thermal stability of the FeOF cathode was evaluated in comparison with FeF3 and LiFePO4 cathodes. Full article
(This article belongs to the Special Issue Thermal and Safety Properties of Materials, Cells and Batteries)
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1485 KiB  
Article
Statistical Characterization of the State-of-Health of Lithium-Ion Batteries with Weibull Distribution Function—A Consideration of Random Effect Model in Charge Capacity Decay Estimation
by Chinedu I. Ossai and Nagarajan Raghavan
Batteries 2017, 3(4), 32; https://doi.org/10.3390/batteries3040032 - 16 Oct 2017
Cited by 17 | Viewed by 10273
Abstract
Effective prognosis of lithium-ion batteries involves the inclusion of the influences of uncertainties that can be incorporated through random effect parameters in a nonlinear mixed effect degradation model framework. This study is geared towards the estimation of the reliability of lithium-ion batteries, using [...] Read more.
Effective prognosis of lithium-ion batteries involves the inclusion of the influences of uncertainties that can be incorporated through random effect parameters in a nonlinear mixed effect degradation model framework. This study is geared towards the estimation of the reliability of lithium-ion batteries, using parametric effects determination involving uncertainty, using a multiphase decay patterned sigmoidal model, experimental data and the Weibull distribution function. The random effect model, which uses Maximum Likelihood Estimation (MLE) and Stochastic Approximation Expectation Maximization (SAEM) algorithm to predict the parametric values, was found to estimate the remaining useful life (RUL) to an accuracy of more than 98%. The State-of-Health (SOH) of the batteries was estimated using the Weibull distribution function, which is found to be an appropriate formulation to use. Full article
(This article belongs to the Special Issue Battery Management Systems)
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4785 KiB  
Article
Spontaneous Generation of Electromotive Force in Thin Film Al/Nanosilicon/Al Structures
by Sergey G. Dorofeev, Nikolay N. Kononov, Sergei S. Bubenov, Pavel A. Kotin, Aleksandr N. Zolotykh and Denis V. Grigoriev
Batteries 2017, 3(4), 31; https://doi.org/10.3390/batteries3040031 - 10 Oct 2017
Cited by 1 | Viewed by 5935
Abstract
Contemporary pursuits in electronics include the miniaturization as well as flexibilization of devices. Although there are a large number of different thin and flexible electrochemical batteries, only a few can boast the possibility of working in high humidity conditions. This paper reports on [...] Read more.
Contemporary pursuits in electronics include the miniaturization as well as flexibilization of devices. Although there are a large number of different thin and flexible electrochemical batteries, only a few can boast the possibility of working in high humidity conditions. This paper reports on the fabrication of structures consisting of films of silicon nanoparticles encased between two aluminium electrodes. The value of electromotive force (emf) measured depends on the temperature of the sample and on the pressure of water vapor in the storage atmosphere and reaches approximately 1 V. Volt-ampere characteristics were investigated at different conditions to yield a model of emf generation in these structures. It was found that the reaction of water with silicon nanoparticles is the prime reason behind emf generation. Such a source may be introduced into electronic paper, and employed in the next generation of smart cards. The structure may also be manufactured directly on the surface of silicon chips, such as on the back of crystals in microschemes. Full article
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4512 KiB  
Article
Effects of Alkaline Pre-Etching to Metal Hydride Alloys
by Tiejun Meng, Kwo-Hsiung Young, Chaolan Hu and Benjamin Reichman
Batteries 2017, 3(4), 30; https://doi.org/10.3390/batteries3040030 - 5 Oct 2017
Cited by 9 | Viewed by 6598
Abstract
The responses of one AB5, two AB2, four A2B7, and one C14-related body-centered-cubic (BCC) metal hydrides to an alkaline-etch (45% KOH at 110 °C for 2 h) were studied by internal resistance, X-ray diffraction, scanning [...] Read more.
The responses of one AB5, two AB2, four A2B7, and one C14-related body-centered-cubic (BCC) metal hydrides to an alkaline-etch (45% KOH at 110 °C for 2 h) were studied by internal resistance, X-ray diffraction, scanning electron microscope, inductively coupled plasma, and AC impedance measurements. Results show that while the etched rare earth–based AB5 and A2B7 alloys surfaces are covered with hydroxide/oxide (weight gain), the transition metal–based AB2 and BCC-C14 alloys surfaces are corroded and leach into electrolyte (weight loss). The C14-predominated AB2, La-only A2B7, and Sm-based A2B7 showed the most reduction in the internal resistance with the alkaline-etch process. Etched A2B7 alloys with high La-contents exhibited the lowest internal resistance and are suggested for use in the high-power application of nickel/metal hydride batteries. Full article
(This article belongs to the Special Issue Nickel Metal Hydride Batteries 2017)
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7438 KiB  
Article
Cell Performance Comparison between C14- and C15-Predomiated AB2 Metal Hydride Alloys
by Kwo-Hsiung Young, John M. Koch, Chubin Wan, Roman V. Denys and Volodymyr A. Yartys
Batteries 2017, 3(4), 29; https://doi.org/10.3390/batteries3040029 - 25 Sep 2017
Cited by 17 | Viewed by 6602
Abstract
The performance of cylindrical cells made from negative electrode active materials of two selected AB2 metal hydride chemistries with different dominating Laves phases (C14 vs. C15) were compared. Cells made from Alloy C15 showed a higher high-rate performance and peak power with [...] Read more.
The performance of cylindrical cells made from negative electrode active materials of two selected AB2 metal hydride chemistries with different dominating Laves phases (C14 vs. C15) were compared. Cells made from Alloy C15 showed a higher high-rate performance and peak power with a corresponding sacrifice in capacity, low-temperature performance, charge retention, and cycle life when compared with the C14 counterpart (Alloy C14). Annealing of the Alloy C15 eliminated the ZrNi secondary phase and further improved the high-rate and peak power performance. This treatment on Alloy C15 showed the best low-temperature performance, but also contributed to a less-desirable high-temperature voltage stand and an inferior cycle stability. While the main failure mode for Alloy C14 in the sealed cell is the formation of a thick oxide layer that prevents gas recombination during overcharge and consequent venting of the cell, the failure mode for Alloy C15 is dominated by continuous pulverization related to the volumetric changes during hydride formation and hysteresis in the pressure-composition-temperature isotherm. The leached-out Mn from Alloy C15 formed a high density of oxide deposits in the separator, leading to a deterioration in charge retention performance. Large amounts of Zr were found in the positive electrode of the cycled cell containing Alloy C15, but did not appear to harm cell performance. Suggestions for further composition and process optimization for Alloy C15 are also provided. Full article
(This article belongs to the Special Issue Nickel Metal Hydride Batteries 2017)
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