Chinese Advanced and Cheap Rechargeable Battery

Chapter 9 - Rechargeable Batteries and Their Management

To the Editor, Proper laryngeal illumination is a crucial component of providing optimal conditions for tracheal intubation under direct laryngoscopy. Intubating equipment is often used and checked on a daily basis in the operating room; however, laryngoscopes often lie inactive for prolonged periods in emergency airway kits for the general wards, the emergency room, critical care units, or out-of-hospital use. Limited data are published on the life span of laryngoscope batteries or the safe storage period for emergency airway kits. We undertook to evaluate the useful ‘‘shelf life’’ of a commonly used laryngoscope device without battery recharging between uses. Institutional research ethics board approval was unnecessary for this simple bench test of a single laryngoscope to evaluate battery life between full charges. A new Heine 3.5 volt Xenon laryngoscope handle with a new nickel metal hydride (NiMH) battery and a new Heine Macintosh #3 Classic reusable fibreoptic stainless steel blade (Herrsching, Germany) was evaluated. The rechargeable battery was fully charged at the start of this study. The light intensity delivered from the handle and blade unit was tested daily using a previously described testing chamber and light meter. Light output was recorded after 30 sec of usage on each day (Figure). Testing was stopped on day 181 after the light output had dropped to 2,000 lux. This bench-top test shows that new NiMH battery sets can hold their charge for prolonged periods of time without requiring recharging. Testing was stopped arbitrarily once the light output had reached 2,000 lux as this is the threshold level that our institution had deemed as a minimum safe light requirement prior to introduction of the new International Organization for Standardization (ISO) guidelines of 500 lux. Our observations are limited by the fact that we tested a single new device with only one type of rechargeable battery (i.e., NiMH vs lithium or nickel cadmium batteries), and we did not examine battery ‘‘memory’’ effects. Despite these limitations, these observations over 181 days do help to characterize performance of these new laryngoscopes over prolonged storage periods under minimal usage conditions. These data should be useful to other institutions for equipment life cycle management and planning and for establishing quality control testing protocols for emergency airway equipment.

1.Introduction After the end of life of hybrid electric vehicle (HEV), there is a possibility that some of the Nickel-metal hydride (Ni-MH) batteries for HEV remain capacity and we could reuse these batteries without any trouble. In order to utilize these reusable batteries, the capacity estimation method to reuse used batteries is essential. Ni-MH battery capacity decreases during the actual usage. Then we reported that the low capacity retention batteries caused by the negative electrode could be sorted out by the electrochemical impedance spectroscopy (EIS) in a charge state [1.2].On the other hand, it is well known that there are low capacity retention batteries caused by aging of NiOOH in the positive electrode. Among them, the most important thing to consider for reusing the Ni-MH batteries is low capacity retention batteries caused by “memory effect” [3]. When the memory effect occurs, the charging voltage at each SOC increased in accordance with history of the battery. The increase of charging voltage accelerates the side reaction. As a result, capacity decreases due to memory effect. Generally, the memory effect can be eliminated by low rate (0.3C-0.4C) charge and discharge refresh cycles. However, in order to completely eliminate the memory effect, it is necessary that charge and discharge cycles. As a result, it takes a long time to eliminate the memory effect. Thus, in order to determine quickly if the used battery could be reused, it is demanded that the easy method to detect the degree of capacity decrease due to the memory effect. In this study, we would like to report the quick and accurate method to detect the degree of capacity decrease due to the memory effect by EIS. 2.Experimental We used a Ni-MH battery for HEV (1.2 V - 6.5 Ah) as an experimental cell. In order to get the various degrees of capacity decrease due to the memory effect, the cells were charged and discharged for several cycles at constant current of 3 C rate at 35 oC in the range from SOC 0 % to SOC 20 %, SOC 40 %, SOC 60 %, and SOC 80 %. After the accumulated discharge capacity reached 2600 Ah, AC impedance measurements were carried out at SOC 60 %. The AC impedance spectra were obtained with 0.15 C of AC signal in the frequency range of 100 kHz to 0.01 Hz. All measurements were performed at 25 oC. We defined the degree of memory effect as the sum of difference of charging voltage (∫ΔVoltage) between the initial cell and the cycled cell. 3.Results and discussion Fig.1 (a) shows the charge curves of the cells which was obtained on test condition detailed before. We can see the charge curves difference by changing in the range of SOC. Fig.1 (b) shows the AC impedance spectra of these cells. Impedance spectrum of the Ni-MH battery shows semicircle which indicates the charge electron transfer reaction and linear part which indicates the diffusion process. The semicircle in impedance spectrum of the Ni-MH battery is mainly attributed to the negative electrode and the linear part is mainly attributed to the positive electrode. We found that the radius of semicircle in impedance spectrum decreased after cycled which indicate the resistance of electron transfer reaction of negative electrode decreased due to the activation of the negative electrode. On the other hand, in the linear part, we found that the imaginary value on each frequency get higher with the memory effect on the positive electrode. In order to confirm the relationship between the memory effect and impedance spectrum, we calculated (ΔZ"/Δ(ω-1))-1 [AsV-1] as the frequency response of the imaginary components of the linear part. Fig.1(c) shows the relationship between (ΔZ"/Δ(ω-1))-1 and the degree of memory effect (∫ΔVoltage). As shown in Fig.1 (c), (ΔZ"/Δ(ω-1))-1 correlates with the degree of memory effect. Thus, we can estimate the degree of memory effect by calculating (ΔZ"/Δ(ω-1))-1 from the linear part in impedance spectrum, suggesting that it is possible that the degree of capacity decrease due to memory effect can be detected by using (ΔZ"/Δ(ω-1))-1. Reference [1]H. Nishi, D. Koba, S. Ito, T. Yao, D. Mukoyama, H. Nara, S. Tsuda, T. Momma, T. Osaka, The 56rd Battery Symposium in Japan, 1M25 (2015)[2]D. Koba, H. Nishi S. Ito, T. Yao, D. Mukoyama, H. Nara, S. Tsuda, T. Momma, T. Osaka, The 56rd Battery Symposium in Japan, 1M26 (2015) [3] Y. Sato, S. Takeuchi, K.Kobayakawa, J. Power Sources 93 (2001) 20-24 Figure 1

Pyrometallurgical recycling of Li-ion, Ni–Cd and Ni–MH batteries: A minireview

With the increasing popularity of hybrid vehicles, which were initially commercialized from Japan, the use of nickel‐metal hydride (NiMH) batteries has also increased dramatically. This will inevitably lead to a large number of NiMH batteries in the future. This makes the reuse and recycling of these waste NiMH batteries an urgent concern. Nevertheless, the environmental burden generated from the reuse and recycling processes has not been clarified. Moreover, many NiMH batteries are exported from Japan to developing countries and will eventually be landfilled. Such problems severely weaken the efficiency of the waste battery recycling system in Japan. This research aims to analyze the environmental impact of a NiMH battery under each type of waste treatment strategy using the life cycle assessment (LCA) method. Then, a fleet‐based LCA is performed to show how exactly the collection rate of waste batteries affects the efficiency of the recycling industry. The results show that, if we can reuse or recycle a waste NiMH battery instead of it being directly landfilled, the absolute environmental impact of the NiMH battery can be decreased. Especially in the reuse and recycle scenario, approximately 83 kg of CO 2 emissions, 1.37 kg of resource depletion, 0.044 m 3 of landfill volume, and 1611 MJ energy consumption will be conserved for each NiMH battery. Moreover, the efficiency of the Japanese recycling industry would significantly improve if more waste NiMH batteries can be recycled or reused in Japan instead of being exported to developing countries.

Electric vehicles (EVs) are becoming more popular than internal combustion engines for reasons such as ease of use, durability, efficiency, and speed. Electric motors aim to improve the efficiency of energy storage systems and be more environmentally friendly. Due to the growing population, the number of vehicles in use is also increasing, leading to higher carbon dioxide (CO2) and hydrocarbon emissions. This demand has positively affected the battery market in the EV industry. Battery electric vehicles (BEVs), hybrid electric vehicles (HEVs), and plug-in hybrid electric vehicles (PHEVs), along with lead-acid batteries, nickel–metal hydride (NiMH) batteries, and lithium-ion batteries, are frequently preferred in the EV industry. NiMH batteries contain approximately 35–50% nickel (Ni), 5–20% rare earth elements (REEs), and 10% iron (Fe) by weight. Considering the supply and demand gap for REEs, often called “vitamins of modern industry”, the recovery of REEs from waste NiMH batteries, which contain high amounts of these elements, becomes important. In this review article, literature on EVs, their types, and EV battery types is presented. In addition, the recycling process of NiMH batteries, which are very rich in REEs and precious metals, such as Ni, cobalt (Co), and manganese (Mn), is discussed, and the enrichment methods effective in the recycling process of NiMH batteries are examined.

In a society that increasingly relies on mobile electronics, demand is rapidly growing for both primary and rechargeable batteries that power devices from cell phones to vehicles. Existing batteries utilize lightweight active materials that use electrochemical reactions of ions such as H(+), OH(-) and Li(+)/Mg(2+) to facilitate energy storage and conversion. Ideal batteries should be inexpensive, have high energy density, and be made from environmentally friendly materials; batteries based on bulk active materials do not meet these requirements. Because of slow electrode process kinetics and low-rate ionic diffusion/migration, most conventional batteries demonstrate huge gaps between their theoretical and practical performance. Therefore, efforts are underway to improve existing battery technologies and develop new electrode reactions for the next generation of electrochemical devices. Advances in electrochemistry, surface science, and materials chemistry are leading to the use of nanomaterials for efficient energy storage and conversion. Nanostructures offer advantages over comparable bulk materials in improving battery performance. This Account summarizes our progress in battery development using a combination of lightweight elements and nanostructured materials. We highlight the benefits of nanostructured active materials for primary zinc-manganese dioxide (Zn-Mn), lithium-manganese dioxide (Li-Mn), and metal (Mg, Al, Zn)-air batteries, as well as rechargeable lithium ion (Li-ion) and nickel-metal hydride (Ni-MH) batteries. Through selected examples, we illustrate the effect of structure, shape, and size on the electrochemical properties of electrode materials. Because of their numerous active sites and facile electronic/ionic transfer and diffusion, nanostructures can improve battery efficiency. In particular, we demonstrate the properties of nanostructured active materials including Mg, Al, Si, Zn, MnO(2), CuV(2)O(6), LiNi(0.8)Co(0.2)O(2), LiFePO(4), Fe(2)O(3), Co(3)O(4), TiS(2), and Ni(OH)(2) in battery applications. Electrochemical investigations reveal that we generally attain larger capacities and improved kinetics for electrode materials as their average particle size decreases. Novel nanostructures such as nanowires, nanotubes, nanourchins, and porous nanospheres show lower activation energy, enhanced reactivity, improved high-rate charge/discharge capability, and more controlled structural flexibility than their bulk counterparts. In particular, anode materials such as Si nanospheres and Fe(2)O(3) nanotubes can deliver reversible capacity exceeding 500 mA.h/g. (Graphite used commercially has a theoretical capacity of 372 mA x h/g.) Nanocomposite cathode materials such as NiP-doped LiFePO(4) and metal hydroxide-coated Ni(OH)(2) nanotubes allow us to integrate functional components, which enhance electrical conductivity and suppress volume expansion. Therefore, shifting from bulk to nanostructured electrode materials could offer a revolutionary opportunity to develop advanced green batteries with large capacity, high energy and power density, and long cycle life.

One of the key components of a hybrid electric vehicle (HEV) drive train is its secondary energy storage device. The automotive industry is still in the process of debating on the fact, as to which device provides the best option in HEVs, for the purpose of load leveling. This paper aims at providing a fair idea with regards to the selection of secondary energy sources, based on vehicle performance characteristics and overall drive train efficiency. The performances of lead-acid (PBA), lithium-ion (Li-Ion), nickel-cadmium (Ni-Cd), nickel-metal hydride (Ni-MH), and nickel-zinc (Ni-Zn) batteries, as well as ultra-capacitors (UC) are investigated over city and highway driving schedules for a heavy-duty diesel-parallel hybrid transit bus application. Based on the simulation studies for the above-mentioned storage devices, the Ni-MH, PBA, and the ultra-capacitor technologies demonstrate best results in terms of fuel economy and percentage drive train efficiency. On the other hand, the Ni-Zn and Li-Ion batteries show much promise, but still demand a great deal of research and development work, before they become a viable option for HEV applications. Finally, the paper compares and summarizes critical performance characteristics for the energy storage devices under investigation.

Nickel metal hydride (Ni-MH) batteries have demonstrated key technology advantages for applications in new-energy vehicles, which play an important role in reducing greenhouse gas emissions and the world’s dependence on fossil fuels. However, the poor high-rate dischargeability of the negative electrode materials—hydrogen storage alloys (HSAs) limits applications of Ni-MH batteries in high-power fields due to large polarization. Here we design a hybrid electrode by integrating HSAs with a current collector of three-dimensional bicontinuous nanoporous Ni. The electrode shows enhanced high-rate dischargeability with the capacity retention rate reaching 44.6% at a discharge current density of 3000 mA g−1, which is 2.4 times that of bare HSAs (18.8%). Such a unique hybrid architecture not only enhances charge transfer between nanoporous Ni and HSAs, but also facilitates rapid diffusion of hydrogen atoms in HSAs. The developed HSAs/nanoporous metals hybrid structures exhibit great potential to be candidates as electrodes in high-performance Ni-MH batteries towards applications in new-energy vehicles.

A simplified equivalent circuit model for simulation of Pb–acid batteries at load for energy storage application

The status of research and development on advanced batteries in Japan is reviewed. The three types of batteries attracting the most interest are: (1) nickel-metal hydride batteries, (2) secondary lithium batteries, and (3) secondary batteries using solid electrolytes. The advances made in the development of these batteries are described from the viewpoint of the application of new materials. The materials used for batteries come from multidisciplinary research. Hydrogen-storage alloys and conducting polymers are examples of materials with interdisciplinary origins.< <ETX xmlns:mml="http://www.w3.org/1998/Math/MathML" xmlns:xlink="http://www.w3.org/1999/xlink">&gt;</ETX>

Synthesis and electrochemical characterizations of the nanocrystalline Ti[Co xMg 1−x] ( x = 0.65) material as a hydrogen storage alloy

Depletion of fossil fuels and concerns over CO2 emission have driven the development of electric vehicles (EVs) with high-energy efficiencies and low emissions. Lithium-ion rechargeable batteries, compared to lead acid, nickel cadmium, nickel metal hydroxide, and other popular rechargeable batteries, are considered as the most promising candidates for EVs for their high operating voltage and high energy density. Silicon nanowires are considered as lithium-ion battery anodes for their ultra high capacity at 4200 mAh·g-1 (10× higher than conventional graphite anode), as well as stress accommodation for reversible lithiation and delithiation. Silicon nanowires were fabricated via metal assisted electroless etching, and conductive nickel monosilicides ohmic contacts were created via simple one-step thermal annealing procedure between nanowires and nickel electrodes for integration. Composite anodes were prepared from electrolessly fabricated silicon nanowires for lithium-ion batteries, and an addition of only 15 % silicon nanowires results in a two-fold increase in reversible capacities for 15 cycles. Silicon anodes with hydride, methylated and siloxane surface terminations were prepared and tested in lithium-ion cells; another silicon anode was cycled with 5 % trimethoxymethylsilane. Analyses showed methylated and siloxane terminations lead to passivated surfaces, and hydride-terminated nanowires were relatively more reactive with electrolytes. The addition of silane additive results in more OPFx compounds and Si-O-Si bonds at the silicon surface with significantly higher capacities (3287 mAh·g-1). AFM nano-indentation analyses also showed a significant increase in contact stiffness with silane additive, and the increase in contact stiffness may improve the anode’s ability to withstand large volume changes. Although the chemical composition of the SEI is altered with silane additives, performance improvements were mainly associated mechanical effects.

With rapidly mounting environmental concerns, coupled with increased energy demand and impending depletion of fossil fuel reserves, there has been a strong focus on developing advanced technologies for a renewable energy infrastructure. Alternative energy sources, though environmentally friendly, are intermittent thus require large-scale energy storage to buffer the temporal mismatch between power generation and power consumption. Flow batteries are a leading candidate for this role due to their decoupled energy and power capacity [1]. Since they were first proposed by NASA in the 1970’s, numerous iterations have been made, but commercialization has been hindered by their high cost, but there is hope this can be addressed by better cell designs [2]. The energy and power density of flow batteries are generally lower than that of lead-acid, lithium-ion and nickel metal hydride batteries [3]. Decreasing the various resistances within the flow battery system via improving electrical conductivity of the electrode is a promising route to improve cell performance. Improving the electrical conductivity of the electrode will result in higher efficiency of the cell, as current flow more easily reducing ohmic losses. Improving efficiency means more power can be obtained from a given amount of electrolyte. Therefore, performance will be improved and capital cost will be lowered as less electrolyte will now be required to meet a specific power generation targets. The electrospining technique has been recently investigated as a means of producing high performance electrodes, via small fibers and very high porosity [4]. High porosity means presence of much less solid material, which in turn leads to higher resistance within the electrode as fewer electron flow paths exist. This presentation will report the developments made towards increasing the electrical conductivity of high porosity electrospun fibers of polyacrylonitrile, such as varying the sintering/carbonization conditions, impregnating the fibrous mat with conductive filler, and pre-treating the material prior to carbonization to improve inter-fiber contacts. Figure 1 & 2 show SEM images for electrospun fibers of polyacrylonitrile before and after pre-treatment prior to carbonization. The developed materials were characterized for their structural (i.e. fibre morphology, porosity) and transport properties (i.e. diffusivity, permeability). These parameters closely correlate with cell performance and are crucial for the developmental phase, before the final product can be tested in a pilot scale test cell. As improving electrical conductivity is the primary focus of the research, Figure 3 shows a graph of how the developments of this research have enhanced the previously mentioned property. REFERENCES [1] A. Z. Weber, M. M. Mench, J. P. Meyers, P. N. Ross, J. T. Gostick, and Q. Liu, “Redox flow batteries: A review,” J. Appl. Electrochem., vol. 41, no. 10, pp. 1137–1164, 2011. [2] L. H. Thaller, “Electrically rechargeable REDOX flow cell,” US3996064 A, 07-Dec-1976. [3] M. R. Mohamed, S. M. Sharkh, and F. C. Walsh, “Redox flow batteries for hybrid electric vehicles: Progress and challenges,” 5th IEEE Veh. Power Propuls. Conf. VPPC ’09, pp. 551–557, 2009. [4] S. Liu, M. Kok, Y. Kim, J. L. Barton, F. R. Brushett, and J. Gostick, “Evaluation of Electrospun Fibrous Mats Targeted for Use as Flow Battery Electrodes,” J. Electrochem. Soc., vol. 164, no. 9, pp. A2038–A2048, 2017. Figure 1

This study investigates the electrochemical characteristics of nanostructured LaNi5 intermetallic synthesized via the sol-gel method for application as an anode material in nickel-metal hydride (Ni-MH) batteries. A comparison with a commercial counterpart produced by fusion synthesis with mechanical grinding revealed that the nanostructured material, with primary particle sizes of 300–700 nm, exhibits significantly improved kinetic properties, including reduced charge transfer resistance and more efficient mass transport. The synthesized LaNi5 demonstrates rapid activation, reaching a maximum capacity of 180 mAh/g by the 5th cycle, although degradation to 130 mAh/g is observed by the 50th cycle. In contrast, the commercial sample exhibits slow activation, with a gradual capacity increase to 190 mAh/g followed by stabilization. This discrepancy between enhanced kinetic properties and cycle stability in the nanostructured material presents a promising direction for optimizing anode materials in Ni-MH batteries.