The advanced lead–acid battery consortium—a worldwide cooperation brings rapid progress

The development of valve regulated lead–acid (VRLA) batteries has, in recent years, been carried forward rapidly through the collaborative efforts of a worldwide consortium of battery manufacturers and related elements of industry; the Advanced Lead–Acid Battery Consortium (ALABC). This group has set aside its competitive instincts in order to achieve acceptable goals in respect of those parameters that are key factors controlling the marketability of electric vehicles (EVs): cost, cycle life, specific energy, specific power and rate of recharge. This paper provides an overview of the principal themes of the ALABC research and development programme.     

A high performance lead–acid battery for EV applications

Some recent work in the development of a high energy density lead–acid battery for electric vehicle application is described. Two separate methods are used to achieve this objective. Significant total cell weight savings can be achieved by the use of an electrolyte management system. This minimises the quantity of water used in the electrolyte. The second feature concerns the form and utilization of the lead–paste active materials. The positive and negative pastes are carried as a slurry and are agitated during the charge/discharge cycle. This maximises the utilisation of the active materials and reduces premature sulphation.     

Power sources for hybrid buses: comparative evaluation of the state of the art

Due to their beneficial effect on environment, electric vehicles are an important factor for the improvement of urban traffic and, more particularly, for a healthier living environment. A particularly promising field of application is the hybrid-electric city bus, which offers unprecedented opportunities for reducing energy consumption and emissions. Nowadays, various hybrid bus configurations are being proposed and are being demonstrated in several European cities with the support of the European Union's ‘Thermie' programme. The most important hybrid bus project within Thermie is the Sagittaire project [EU Thermie Project Sagittaire, Newsletter 2, September 1998; EU Thremie project Sagittaire, unpublished documents], aiming to introduce hybrid buses in nine European cities: Luxembourg, Besançon, Alicante, Sintra, Stavanger, Trento, Savona, Athens and Bruges.     

Saft lithium-ion energy and power storage technology

Since they were first introduced in the early 1990s, lithium-ion batteries have enjoyed unprecedented growth and success in the consumer marketplace. Combining excellent performance with affordability, they have become the product of choice for portable computers and cellular phones. Building on the same energy and life cycle attributes which marked their consumer market success, but adding new high power storage capability, lithium-ion technology is now poised to play a similar role in the transportation sector. With major programmes in both high capacity and high power lithium-ion technology, Saft has developed a family of products which can address the power and energy storage needs for vehicles, utilities, aviation, satellites, and other applications where light weight, long life, and excellent energy or power storage capabilities are needed. Although further development and refinements are underway, Saft has made a major commitment to bring this technology to the market with the establishment of a major pilot and research facility in Bordeaux France. This paper discusses the performance of this family of products and their potential applications.     

Review on the research of failure modes and mechanism for lead–acid batteries

The lead–acid battery (LAB) has been one of the main secondary electrochemical power sources with wide application in various fields (transport vehicles, telecommunications, information technologies, etc.). It has won a dominating position in energy storage and load‐leveling applications. However, the failure of LAB becomes the key barrier for its further development and application. Therefore, understanding the failure modes and mechanism of LAB is of great significance. The failure modes of LAB mainly include two aspects: failure of the positive electrode and negative electrode. The degradations of active material and grid corrosion are the two major failure modes for positive electrode, while the irreversible sulfation is the most common failure mode for the negative electrode. Introduction of carbon materials to the negative electrodes of LAB could suppress sulfation problem and enhance the battery performance efficiently. This paper will attempt here to pull together observations made by previous research to obtain a more comprehensive and integrative view of LAB failure modes. Moreover, according to a detail investigation to the battery market, we have drawn an objective and optimistic conclusion of LAB prospect. Copyright © 2016 John Wiley & Sons, Ltd.     

Effects of preparation condition and particle size distribution on fumed silica gel valve-regulated lead–acid batteries performance

The effects of three types of fumed silica on the electrochemical properties of gelled electrolytes have been investigated by means of cyclic voltammetry (CV), electrochemical impedance spectroscopy (EIS), transmission electron microscope (TEM) and the Brunauer, Emmett and Teller (BET) technique. The CV and EIS results show that a moderate mechanical dispersion of fumed silica in the H₂SO₄ solution has important effects on the electrochemical properties of the gelled electrolyte. The optimal mechanical dispersion time is closely related to the operating temperature during preparation of gel, as well as the silica particle size and its distribution. A high stirring rate improves the electrode capacity and decreases the viscosity of the gelled electrolyte. With moderate mechanical dispersion, gelled electrolytes prepared from different fumed silica particles exhibit equal electrode capacities.     

Testing of a sodium/nickel chloride (ZEBRA) battery for electric propulsion of ships and vehicles

One of the promising future batteries for electric propulsion of vehicles and ships is the sodium/nickel chloride or ZEBRA (Zero Emission Battery Research Activities) battery. Despite some disadvantages with respect to the high temperature, the advantages with respect to specific energy and energy density are such that, especially in applications where the battery is used on a more or less continuous basis (e.g., in delivery vans and taxies) it is an interesting candidate battery. Another interesting application is on board of ships, like submarines or future electrical surface ships with electric propulsion. In 1995 a 2 year feasibility study, including experimental testing of a 10 kW h battery, was completed. This investigated the naval applicability of the sodium/sulphur battery, which is also a high temperature battery. Here the limited, experimentally proven, life-time of the batteries of about 1.5 years and this made naval application almost impossible. A paper about this study was presented at the 19th International Power Sources Symposium held at Brighton, England, in April 1995 [R.A.A. Schillemans, C.E. Kluiters, Sodium/sulphur batteries for naval applications, in: A. Attewell, T. Keily (Eds.), Power Sources 15, International Power Sources Symposium Committee, Crowborough UK, 1995. p. 421.]. Because of the more or less comparable specifications on specific energy and the more promising results of the life-time and field tests with sodium/nickel chloride batteries, a ZEBRA battery from AEG Anglo Batteries has been tested for naval applications. This was done by simulating the charge and discharge as it occurs in practice for the applications investigated. With respect to the electrical ship application (investigated for the Royal Netherlands Navy) the power versus time taken from the battery was simulated as well as the charge procedures. The same can be done for the vehicle application: in this case typical drive cycles for a van or taxi are translated to power versus time taken from the battery. The results of the tests for application of the battery in naval ships are very promising.     

Reliability of rechargeable batteries in a photovoltaic power supply system

We investigated the reliability of a rechargeable battery acting as the energy storage component in a photovoltaic power supply system. A model system was constructed for this that includes the solar resource, the photovoltaic power supply system, the rechargeable battery and a load. The solar resource and the system load are modelled as stochastic processes. The photovoltaic system and the rechargeable battery are modelled deterministically, and an artificial neural network is incorporated into the model of the rechargeable battery to simulate damage that occurs during deep discharge cycles. The equations governing system behaviour are solved simultaneously in the Monte Carlo framework, and a first passage problem is solved to assess system reliability.     

Project “High energy density lithium batteries for long range EV”

2015年科技部组织编制了新能源汽车试点专项实施方案并于11月12日发布了2016年项目指南,共支持19个项目,其中“1.1”为动力电池新材料新体系。通过竞争,中国科学院物理研究所牵头申请的“长续航动力锂电池新材料与新体系研究”项目,与北京大学牵头申请的“高比能动力电池的关键技术和相关基础科学问题研究项目”共同获得了支持。本文介绍了“长续航动力锂电池新材料与新体系研究”项目的目的和意义,研究目标,研究内容,技术指标,课题安排,研究基础,研究挑战和预期效益。     

Effects of functional electrolyte additives for Li-ion batteries

The electrochemical behaviour and thermal stability of functional electrolyte additives for Li-ion batteries is investigated. The Li-ion cell systems is comprised of an anode of mesocarbon microbeads (MCMB) and a cathode (LiCoO₂) in a solution of 1.1 M LiPF₆ dissolved in ethylene carbonate and ethylmethyl carbonate (EC:EMC; 4:6, v/v). Vinyl acetate (VA) and vinylene carbonate (VC) in an ionic electrolyte containing triphenylphosphate (TPP) are tested as functional electrolyte additives. The main analysis tools used in this study are cyclic voltammetry (CV), differential scanning calorimetry (DSC), electrochemical impedance spectroscopy (EIS), and scanning electron microscopy (SEM). Cells containing VA or VC exhibit excellent irreversible capacity, coulombic efficiency, rate capability and cycleability. These features confirming the effectiveness of VC addition for improving both the cell performance and the thermal stability of electrolytes in TPP-containing solutions for Li-ion batteries.     

Degradation of LiCoO2 in aqueous lithium–air batteries

The degradation behaviour of aqueous rechargeable lithium cobalt oxide–air batteries in 5 M LiNO₃ aqueous solution is observed by electrochemical characterizations. At lower scan rates of cyclic voltammetry, the three pairs of redox peaks at E _SCE = 0.79/0.67, 0.89/0.85 and 1.15/0.97 V are proven to produce good reversibility. The small separation of the peaks is proportionally consistent with the Li⁺ diffusion coefficients of 2.82 × 10^?7 cm² s^?1 (anodic) and 1.76 × 10^?7 cm² s^?1 (cathodic). The lithium cobalt oxide–air batteries have a higher initial specific discharge capacity of 114.35 mA h g^?1, which fades to 83% (after the first 10 cycles) and 52% (after 50 cycles). As the specific discharge capacity decreases, the resistance increases. The dissolution of Li⁺ is mainly attributed to these degradations. Further analyses of the batteries' degradation are performed by morphological and structural characterizations of the cathode material. Copyright © 2016 John Wiley & Sons, Ltd.     

The optimisation of grid designs for valve-regulated lead/acid batteries for hybrid electric vehicle applications

The design, construction and testing of valve-regulated lead/acid cells with grid designs optimised for high-rate partial state-of-charge cycling for hybrid electric vehicles are described. Computer modelling was used to develop the grid designs. This showed that designs with opposed tabs and terminals on the top and bottom of the cell were likely to have the best performance not only in terms of grid conductivity but also for uniformity of active material utilisation. Prototype cells were built and tested. Low rate performance was in line with the designs and the high-rate performance was substantially enhanced compared with conventional constructions. The cells were then tested to a shallow cycling regime and to a simplified hybrid electric vehicle cycle. The results showed excellent life under these conditions without the benefit of carbon or graphite additives to the negative active material that have also been shown to improve cycle life under these conditions.     

High‐performance porous lead/graphite composite electrode for bipolar lead‐acid batteries

In general, thicker active material bipolar electrode's specific capacity and cycle life are very poor owing to its low bonding strength between the active material and the substrate and the diffusion rate of the sulfuric acid electrolyte inside the active material. In this paper, we synthesize a novel attached and porous lead/graphite composite electrode for bipolar lead‐acid battery and can effectively solve these problems. The graphite/polytetrafluoroethylene emulsion is employed to improve the bonding strength and conductivity and the porous can provide electrolyte diffusion channels. The specific capacities of 2‐mm thick positive active material at 0.25, 0.5, 1 and 2 C can attain 75.99, 58.98, 47.97, and 33.36 mAh·g^?1. The discharge voltage platform is also relatively high and no rapid decline with increasing discharge rate. Furthermore, after 80 cycles, the specific capacity does not drop evidently. Copyright © 2017 John Wiley & Sons, Ltd.     

4-Bromobenzyl isocyanate versus benzyl isocyanate—New film-forming electrolyte additives and overcharge protection additives for lithium ion batteries

Electrochemical properties and working mechanisms of benzyl isocyanate compounds as polymerizable electrolyte additives for overcharge protection of lithium ion batteries have been studied by cyclic voltammetry, charge–discharge cycling, overcharge tests, accelerating rate calorimetry (ARC) and in situ Fourier transform infrared spectroscopy (FTIRS). The overcharge and FTIRS data clearly reveal that 4-bromobenzyl isocyanate (Br-BIC) can electrochemically polymerize at 5.5 V (versus Li/Li⁺) to form an overcharge-inhibiting (probably insulating) film on the cathode surface. In addition, is found the Br-BIC does slightly improve the charge/discharge performance of a lithium ion battery. Furthermore, Br-BIC and benzyl isocyanate show beneficial solid electrolyte interphase (SEI) formation behaviour on graphite in propylene carbonate based electrolyte solutions.     

Single and multi‐objective optimization for the performance enhancement of lead–acid battery cell

Electric energy storage systems are used considerably in industries and daily applications. The demand for batteries with high energy content has increased because of their use in hybrid vehicles. Lead–acid batteries have wide applications because of their advantages such as high safety factor and low cost of production. The major shortcoming of lead–acid batteries is low energy content and high dimension and weight. Nowadays, a common method to increase the energy content of lead–acid battery is the experimental method with trial and error, which is time consuming and expensive. In this paper, non‐isothermal one‐dimensional numerical simulation of lead–acid battery with finite volume method is performed. In addition, a cell with higher energy content and lower thickness is designed by using particle swarm optimization algorithm based on developed simulation code. The results of single objective optimization show that an optimal battery that has 27.6% higher energy can be made with the same cell dimension. The results also show that an optimum cell battery can be obtained with a decrease of 24% in thickness while keeping the energy the same. Moreover, a multi‐objective optimization algorithm is utilized to find Pareto optimal solutions while considering the energy content and thickness objectives simultaneously. Copyright © 2016 John Wiley & Sons, Ltd.     

Development of carbon conductive additives for advanced lithium ion batteries

The newly developed conductive carbon blacks C-NERGY™ Super C65 and C-NERGY™ Super C45 were studied with regard to their performance as conductive additives in positive lithium ion battery electrodes and compared to other reference conductive carbon blacks. The lowest electrical volume resistivity and highest compressibility were found for C-NERGY™ Super C45 dry-mixed with LiCoO₂ powder. Mixing by high shear forces in acetone dispersion improved the electrical resistivity and compressibility of the C-NERGY™ Super C65 containing LiCoO₂ mixture to the same level obtained for the C-NERGY™ Super C45 mixture in the same process. Acetone dispersions of C-NERGY™ Super C45 and LiCoO₂ showed the lowest viscosities attributed to the carbon black's specific BET surface area of 45 m² g⁻¹ being the lowest of all carbon blacks studied. The easy dispersibility of C-NERGY™ Super C45 in LiCoO₂ could be explained by its particular surface group chemistry characterized by time-of-flight secondary ion mass spectrometry. The electrical volume resistivity of the LiCoO₂/carbon black mixtures was in line with the high current rate performance of half-cells with related LiCoO₂ electrodes. Compared to the investigated carbon blacks, the electrical volume resistivity of the graphite conductive additives C-NERGY™ KS6L and C-NERGY™ SFG6L at different concentrations in LiCoO₂ powders showed higher critical volume fractions but lower ultimate resistivity levels. Adding one of these graphites to the carbon black conductive mass improved the electrode density and, at concentrations above the critical volume fraction of the graphite component, significantly decreased the ultimate resistivity level of the LiCoO₂ electrode mass.     

Alkaline aqueous electrolytes for secondary zinc–air batteries: an overview

New applications and emerging markets in electromobility and large‐scale stationary energy storage require the development of new electrochemical systems with higher energy density than current batteries. Rechargeable metal–air batteries, mainly lithium–air and zinc–air systems, are considered one of the most promising candidates. In contrast to lithium, zinc is abundant, inexpensive and its electrodeposition in aqueous electrolytes is relatively easy. Unfortunately, achieving a rechargeable zinc–air battery is still hindered by various technical problems related to the reversibility and lifetime of the electrodes. The most widely used electrolyte in zinc–air batteries has been the classical aqueous alkaline. In this context and with the main objective of providing a complete overview, we studied a wide number of articles starting from the beginning of the development of secondary zinc–air batteries (1970–1980s) to more recent works, with the aim of compiling all available information. It is essential to revise older papers to find relevant information that may get otherwise forgotten and not taken into account to develop new solutions. This information could also be applied in other storage systems based on zinc as nickel–zinc, zinc hybrid or zinc‐ion. Copyright © 2016 John Wiley & Sons, Ltd.     

Environmental assessment of vanadium redox and lead-acid batteries for stationary energy storage

The environmental impact of both the vanadium redox battery (vanadium battery) and the lead-acid battery for use in stationary applications has been evaluated using a life cycle assessment approach. In this study, the calculated environmental impact was lower for the vanadium battery than for the lead-acid one. The net energy storage efficiency of the vanadium battery was greater due to lower primary energy needs during the life cycle. Favourable characteristics such as long cycle-life, good availability of resources and recycling ability justify the development and commercialisation of the vanadium battery.     

A new dynamic SOH estimation of lead‐acid battery for substation application

State of Health (SOH) is one of the most important parameters of lead‐acid batteries. Most of the existing SOH estimation methods only take the influence of charge cycles into consideration, and the estimation accuracy is limited. Batteries in the substations have two typical states: one is the check‐discharge state, in which the batteries are discharged for 8 h at 0.1 C (Capacity) to determine whether the battery pack has certain reliability. The other is the floating charge state, in which the batteries are connected to the charger to maintain full power. This paper proposes a novel SOH estimation method based on the two states. In the check‐discharge state, the relationship between the voltage and the age of battery is analysed. The health index, which is introduced in this model, is affected by the age of battery. In the floating state, the relationship between the internal resistance and the age of battery is discussed. Another SOH model is established based on the change of the internal resistance. By combining the two models, the estimation method can achieve real‐time estimation and high accuracy for substation application. An accelerated life test is applied to verify the theoretical analysis. The experimental results demonstrate that the SOH estimation error is less than 3% which is very satisfactory for practical applications. Copyright © 2016 John Wiley & Sons, Ltd.