Advanced Lead Acid Battery Research Articles

Influence of basic carbon additives on the electrochemical performance of lead-carbon batteries

Enhancement of the dynamic charge acceptance (DCA) of advanced lead-acid batteries for micro- and mild-hybrid cars is essential to improve the fuel consumption and CO2 emissions by recuperation of the braking energy. In this work, the effect of carbon surface basicity on the electrochemical activity and the DCA of lead-carbon electrodes is revealed. Five different activated carbons (AC) with different pH values ranging from 9.5 to 11.1 were prepared by ammonia and hydrogen gas treatments. These ACs were used as additives in the negative electrodes of 2 V lead-acid cells. The cyclic voltammetry of the pure carbon as well as lead-carbon (negative) electrodes demonstrates that the hydrogen evolution reaction (HER) activity is increased via higher surface basicity of the ACs. A correlation between the surface basicity of carbon and the DCA can be established in the electrochemical performance. A remarkable impact of carbon pH on the charge currents after the charge history (Ic) as well as final DCA (IDCA) is observed. In case of the charge currents after the discharge history (Id) and during simulated Stop/Start microcycles (Ir), the carbon content in the negative electrodes affects the charge currents. This work demonstrates that the DCA of advanced lead-carbon batteries can be improved by using carbon additives with higher pH in the negative electrodes.

Performance and Charging-Discharging Behavior of AGM Lead Acid Battery according to the Improvement of Bonding between Active Material/Substrate using Sand-Blasting Method

To cope with automobile exhaust gas regulations, ISG (Idling Stop & Go) and charging control systems are applied to HEVs (Hybrid Electric Vehicle) for the purpose of improving fuel economy. These systems require quick charge/discharge performance at high current. To satisfy this characteristic, improvement of the positive electrode plate is studied to improve the charge/discharge process and performance of AGM(Absorbent Glass Mat) lead-acid batteries applied to ISG automotive systems. The bonding between grid and A.M (Active Material) can be improved by applying the Sand-Blasting method to provide roughness to the surface of the positive grid. When the Sand-Blasting method is applied with conditions of ball speed 1,000 rpm and conveyor speed 5 M/min, ideal bonding is achieved between grid and A.M. The positive plate of each condition is applied to the AGM LAB (Absorbent Glass Mat Lead Acid Battery); then, the performance and ISG life characteristics are tested by the vehicle battery test method. In CCA, which evaluates the starting performance at -18 °C and 30 °C with high current, the advanced AGM LAB improves about 25 %. At 0 °C CA (Charge Acceptance), the initial charging current of the advanced AGM LAB increases about 25 %. Improving the bonding between the grid and A.M. by roughening the grid surface improves the flow of current and lowers the resistance, which is considered to have a significant effect on the high current charging/discharging area. In a Standard of Battery Association of Japan (SBA) S0101 test, after 300 A discharge, the voltage of the advanced AGM LAB with the Sand-Blasting method grid was 0.059 V higher than that of untreated grid. As the cycle progresses, the gap widens to 0.13 V at the point of 10,800 cycles. As the bonding between grid and A.M. increases through the Sand Blasting method, the slope of the discharge voltage declines gradually as the cycle progresses, showing excellent battery life characteristics. It is believed that system will exhibit excellent characteristics in the vehicle environment of the ISG system, in which charge/discharge occurs over a short time.

Evaluation of ancillary services in distribution grid using large‐scale battery energy storage systems

Battery energy storage systems (BESSs) are being presented as a prominent solution to the various imminent issues associated with the integration of variable renewable energy sources in the distribution system. Performance of grid-connected BESS depends on the type of application (power and energy), grid operating parameters and level of interconnection point, which shows the necessity of benefit assessment of BESS technology and its applications in terms of economic and grid operations before investment at a larger scale. In this study, real-time analysis and evaluation of two different battery technologies connected in a medium voltage (MV) distribution system are carried out. The main objective of this paper is focused on the impact analysis of large-scale BESS on MV distribution feeder. A real case of installation of lithium-ion and advanced lead-acid battery systems into the Indian distribution system has been considered for this study. Different operational strategies of BESS such as frequency regulation and energy time-shift have been performed with real-time data. The effectiveness in usage of BESS with these functionalities has been verified in terms of peak shaving, improvement in voltage profile and reduction in power losses in the feeder.

A techno-economic assessment of battery business models in the UK electricity market

The UK's transition to a zero-carbon economy is inevitably leading to an electricity grid with a high penetration of intermittent renewable energy generation, resulting in the need to install grid-scale energy storage systems at an accelerating rate. This study has taken the perspective of a business owner to assess the profitability of deploying battery technologies in the UK electricity market by analysing arbitrage in electricity markets, capacity market auctions, and ancillary services (frequency response and reserve). Additional work was conducted for integrating battery arbitrage cycling with solar and wind generation, comparing the utilisation of a linear programming model against a simplistic threshold cycling model. An overall economic assessment of value streams found that the lowest payback periods for premium ancillary services were 3.3 years (advanced lead-acid battery providing fast reserve) and 6.6 years (lithium-ion battery providing frequency response). Moreover, this research has demonstrated promising returns on investment for stacking short-term operating reserve with arbitrage in the balancing market. In the near future, battery systems will likely attain accelerated deployment due to reforms in ancillary service structures, cost reductions in battery technologies, greater price volatility in the balancing market, and effective policy incentives introduced by the UK government.

Techno-Economic Analysis of the Sabatier Electrolyzer: CO2-to-Methane Using Proton-Conducting Ceramics

As intermittent renewable-electricity generation achieves higher market penetration, the need for quick and efficient storage and dispatch of this energy becomes more pronounced. In this report, we present our techno-economic analysis of a Sabatier Electrolyzer based on proton-conducting ceramic materials. The Sabatier Electrolyzer technology is illustrated in the figure, and integrates steam electrolysis and hydrogen production with CO2 hydrogenation into a single reactor based on protonic-ceramic electrolysis cells (PCECs) and Sabatier catalysts. CO2 and H2O are fed to fuel and steam electrodes, respectively, of a protonic-ceramic electrolysis cell. An external power source drives H2O splitting at the steam electrode. The product O2 is exhausted from the cell. The product protons are driven across the protonic-ceramic membrane to the fuel electrode, where they react with CO2 to form CH4 and H2O. The combination of processes can match the exothermicity of CO2 hydrogenation with the endothermicity of H2O electrolysis to facilitate thermal balance and high efficiency.When powered by solar and / or wind energy, the Sabatier Electrolyzer has the potential to store intermittent renewable electricity in the form of commodity chemicals while simultaneously reducing carbon dioxide emissions, thereby addressing two principle societal concerns in a single device. Methane presents an attractive energy-storage method; it is stable, integrates well with our existing infrastructure, and can be dispatched quickly for energy generation. In addition to our experimental demonstrations presented in another report, we explore the market potential of the Sabatier electrolyzer through techno-economic analysis (TEA) of a 1.3-MW PCEC electrolysis plant that methanates CO2 produced from a Greenfield coal-fired power plant with a three-ton-per-day coal feedstock. Preliminary models establish a levelized-cost of storage (LCOS) for synthesized methane produced by the PCEC plant. This LCOS represents the required sale price of 1 MWh of synthesized methane to enable “break-even” investment of the SOEC plant over a 30-year plant life. We estimate LCOS of just under 400 $/ MWhe of synthesized methane, less than that of lithium-ion batteries, lead-acid batteries, and advanced lead-acid batteries for commercial and industrial standalone applications.The techno-economic model includes extensive cost estimates for PCEC balance of plant components taken from the literature, the Energy Information Administration, and the U.S. Department of Energy. Our sensitivity analyses show that PCEC Faradaic efficiency and methane selectivity have the largest impact on the Levelized Cost of Storage. A 20% reduction in methane selectivity raises LCOS of the plant by 258 $/MWh, or more than 50%. Further, a 20% decrease in Faradaic efficiency increases LCOS by nearly the same amount. Of the many model inputs, these two parameters prove most critical in estimating the Levelized Cost of Storage.Building on this result, we are now developing a Life Cycle Assessment using the well-established CO2U analysis from the DOE National Energy Technology Laboratory. LCA results will also be presented as part of this talk. Figure 1

Field study on operational performance and economics of lithium-polymer and lead-acid battery systems for consumer load management

This paper presents long-term field test results of lithium-polymer and advanced lead-acid battery systems for consumer load management. The battery systems aimed to minimize electricity bills of an industrial consumer by shifting its load to lower priced time-zones and regulating its peak. Annual and daily peak reduction effects and operating revenues are examined under a time-of-use tariff and battery promotional incentive. Capacity degradations of the batteries are calculated to estimate the actual lifetime. Based on actually earned revenue during the field test and predicted service life for the each type of the batteries, total expected revenue per unit installation capacity is estimated and compared with investment cost per capacity to perform the economics of the tested battery systems for consumer load. This analysis found that the profitability cannot be assured under the considered time-of-use pricing alone but can be expected when adequate incentive is provided. It is also revealed that the batteries in real use conditions lose their capacity considerably quicker than suggested by manufacturers. Therefore, it is recommended to consider actual fading pattern of the battery for accurate economic evaluation at the design stage and to reflect the battery degrading cost into the charge-discharge scheduling model to optimize operating revenue.

Can flow batteries scale in the behind-the-meter commercial and industrial market? A techno-economic comparison of storage technologies in California

Flow batteries have different performance characteristics than established storage technologies such as lithium-ion and lead-acid. We model advanced lead-acid, lithium-ion, and flow batteries for commercial and industrial customers under various tariff scenarios providing retail and wholesale market services to determine if flow batteries can compete in the retail market. We find that flow batteries are uncompetitive with lithium-ion and lead-acid batteries across a range of use cases and modelling assumptions. Flow batteries at a 4-h duration must be less expensive than their competitors on a dollar per installed kWh basis, often by 20–30%, to break even with shorter duration li-ion or lead-acid despite allowing for deeper depth of discharge and superior cycle life. Our results are robust to assumptions of tariff rates, battery round-trip efficiencies, amount of solar generation and whether the battery can participate in the wholesale energy and ancillary services markets.

Corrosion Resistant Polypyrrole Coated Lead-Alloy Positive Grids for Advanced Lead-Acid Batteries

We herein report a method for reducing lead-alloy positive grid corrosion in lead acid batteries by developing a polypyrrole (ppy) coating on to the surface of lead-alloy grids through potentiostatic polymerization technique. The experimental results demonstrate that the presence of ppy coating significantly enhances the corrosion resistance and inhibits the oxygen evolution rate as compare to bare grids. C-rate studies of 2 V/2.6 Ah lead-acid cells show ∼15–20% improvement in capacity at low charge-discharge rates (C/20- C/5) and ∼10% at high C rates (C/2 and 3C) for the cells with ppy coating grids in relation to conventional lead-acid cells.

Nano Structured Rgo - TiO2 Composite As Negative Electrode Additive for High Performance Lead Acid Batteries

Lead acid batteries (LAB) continues to be the major energy storage system for variety of applications such as stationary, uninterruptible power supplies, telecommunications, automotive and even in hybrid and electric vehicles. Besides, LABs are of low cost, >98 % recycling, safety, high abundance of the materials. In spite of being randomly optimized its various aspects in the past, lead acid battery researchers are still facing major challenges of sulfation at the both positive and negative plates. Besides, positive electrode grid corrosion, longer curing as well as formation time of the positive plate and also its low energy density because of high atomic weight of lead (Pb) limits its application [1]. Besides, the major issue of negative plate operating under partial-state-of-charge (PSoC) conditions are sulfation and low charge acceptance. PSoC can quickly diminish the overall life of a battery, which results in frequent, costly battery replacements. So the current research in LAB is directed to achieve high energy density, long-cycle life and to reduce sulfation [2-3]. Different forms of carbon (such as graphene, graphite, carbon nanotubes etc.) additives to the negative active mass (NAM) was used to decrease the lead sulfate formation, increase the conductivity of negative active material by forming conductive network with lead sulfate crystals. Beside carbon acts as a capacitor. This capacitive property of carbon is useful in charge-discharge operations conditions at high rate to provide high voltage [4-5]. In this work we present reduced graphene oxide (rGO) - TiO2 as an ideal additive for advanced LABs operating under HRPSoC conditions. Nano structured TiO2 grown (decorated) on reduced graphene oxide (rGO-TiO2) has been successfully synthesized from the solvothermal method. Optimized 0.5 wt. % of rGO-TiO2 employed as NAM additive to enhance the initial discharge capacity, decreases the hard sulfation, improves the charge acceptance and more utilization of the NAM. Addition of 0.5 wt. % of rGO - TiO2 to the NAM in composition of rGO: TiO2 is 1:10 and 1:3 (Hereafter rGO-TiO2-1:10, 1:3) delivers > 67% and 85 % increase in capacity during the first formation cycle compared to conventional lead-acid cell (LAC). The rGO - TiO2 additive based cells are formed in one cycle whereas conventional electrode takes about 3 cycles to achieve the full capacity. 0.5 wt. % of rGO - TiO2 additive LAC delivers 20% more capacity compared to the conventional cell at all C-rates (C/20 to 2C). Presence of rGO in the negative plate to increases the charge acceptance of the cell. Cycling study was performed on 2V/2.1 Ah conventional and 0.5 wt. % of rGO, TiO2, and rGO-TiO2 (1:100, 1:10, 1:3) additive cell at 1C rate shows an increase in capacity of about 40% was observed with rGO - TiO2 additive based cells as compared to conventional cells. This could be due to the reversibility of PbSO4 to lead. As cycling progresses at the 1C rate, conventional cell has poor capacity retention due to the formation of PbSO4 at the negative plate and does not convert into the active material (Pb). It leads to the early evolution of hydrogen at the negative plate and rapidly decreases the capacity. Significant amount of RGO in the active material shows the capacitive phenomenon. During high rate charging, charging occurs at electrical double layer of the surface of the rGO. Besides addition of rGO - TiO2 in NAM could limit the sulfation of negative plates, due to the high porosity of RGO which could acts as an electrolyte reservoirs in the interior of the negative plates. This helps the active sites for the migration of PbSO4 to Pb during charge and inhibition of PbSO4 during cycling. Beside, TiO2 Nano particles occupies the pores of the active mass and also supplies electrolyte to the bulk. The combination of both rGO and TiO2 in the active mass helps to improve more active material utilization of NAM during 1C rate cycling. HRPSoC cycling increases to 22630 cycles for rGO-TiO2 additive cell compared to the 7614 cycles of conventional LAC. Acknowledgements: Financial support for this project work from Clean Energy Research Initiative (CERI) under Department of Science and Technology (DST), Govt. of India (Project Code: DST/TM/CERI/C141) gratefully acknowledged.

Choice of battery energy storage for a hybrid renewable energy system

There are certain unelectrified villages across the Indian subcontinent where providing supply through the grid is difficult due to forest cover or mountainous terrain. The most feasible option is to provide off-grid electrification through renewable energy resources such as solar or wind energy. These intermittent sources do not promise a 24 $\times $ 7 supply system. Thus, along with solar or wind energy systems, it becomes important to use a renewable resource, such as biomass, which is available in abundance in rural areas. The need for battery energy storage becomes mandatory in order to store the surplus energy produced by renewable resources and supply it at a time of insufficiency. Currently, many battery technologies are evolving with better characteristics than conventional battery systems in terms of efficiency, response time, deep cycle discharge, lifecycle, etc. The aim of this study is, firstly, to design and model a hybrid renewable energy system (HRES), using photovoltaic (PV)-Biogas (BG) system with HOMER software. Secondly, we aim to test this model using three different battery types: advanced lead acid (LA) batteries, lithium ion (LI) batteries, and zinc-bromine (Zn-Br) flow batteries (FB), used individually. Using these three battery technologies, the HRESs are then compared in terms of system sizing, economy, technical performance, and environmental stability. A case study for the unelectrified village of Madhya Pradesh (MP) is discussed to suggest the practical aspect of the comparative analysis. The results demonstrate that the HRES using LI batteries is the most favorable choice. Using this configuration, the economic parameters, including total net present cost (NPC) and levelized cost of energy (LCOE), are found to be lowest. The technical parameters, including battery state of charge (SOC), capacity shortage, and environmental parameters (CO$_{2}$ emissions) are found to be optimum.

Dynamic charge acceptance and hydrogen evolution of a new MXene additive in advanced lead-acid batteries via a rapid screening three-electrode method.

A methodology to screen additives in lead-acid batteries is critical. We developed a three-electrode system that can rapidly check the dynamic charge acceptance (DCA) and hydrogen evolution of electrodes. The electrode with 2% MXene and 0.2% carbon black shows a better DCA, which indicates its great potential in the start-stop technology.

Cloud energy storage for grid scale applications in the UK

In this paper, the UK's electricity market and battery technologies were researched to determine the economics of aggregating domestic batteries for grid-scale services. A feasibility study was conducted under three scenarios in order to estimate the value of Advanced Lead-Acid (ALA) and Lithium-Ion (LI) batteries for domestic households in the UK. A profit optimization model was built using historical market data, and technical parameters of the batteries. An aggregated system of 5000 batteries was simulated and used to compare and stack value streams of seven different grid-scale services in the UK, including energy arbitrage, reserve and frequency regulation services.The results showed that using a battery system for domestic services is currently not economically viable, however grid-scale provision of dynamic frequency response and fast reserve services yield sufficient annual revenue to compensate for these losses. The annual profit margin per household obtained was £ 532/692 for ALA and LI batteries respectively, allowing a shared margin of £ 230–300 after accounting for household costs.The promotion of an aggregated storage system is hindered by current regulatory barriers in the UK, such as a double payment structure for storage operators, lack of subsidy and lack of separate definition for storage devices.

Novel core–shell structure of a lead-activated carbon (Pb@AC) for advanced lead–acid battery systems

To enhance the power and energy densities of advanced lead–acid batteries (Ad-LAB), a novel core–shell structure of lead-activated carbon (Pb@AC) was prepared and used as a negative electrode active material. The AC could be formed as a shell around a core of Pb nanoparticles. The active core–shell structures were synthesized using a simple chemical process to overcome the limitations in the negative Pb electrode, specifically the large crystallization of lead sulfate (PbSO4) that leads to a short cycle life. The key role of the carbon material in the negative electrode is to enhance the electrochemical performances and decrease the formation of PbSO4. The X-ray diffraction study reveals that the formation of lead oxide was prevented by the AC during the synthetic process. The novel core–shell structure of Pb@AC was confirmed through transmission electron microscopy. In order to obtain high-performance Ad-LAB, a high surface area of the AC is necessary to provide a super capacitive effect in the negative electrode. The unit cell performance of the as-prepared active materials exhibits significant increased discharge capacity at 1C rate. The unit cell with the Pb@AC negative electrode has a capacity per unit volume of 0.0165 Ah/cc. Hence, the low cost of AC and the simple synthetic core–shell structure of Pb@AC make this material a promising negative electrode active material for Ad-LAB applications.

Preparation and characterization of Pb nanoparticles on mesoporous carbon nanostructure for advanced lead-acid battery applications

To enhance the electrochemical energy performance, the lead nanoparticles on mesoporous carbon (Pb on MPC) were prepared and characterized for advanced lead acid battery (Ad-LAB) applications. At present, Ad-LAB garners significant attention in energy storage devices because of its high charge acceptance. However, the major problem has associated with the large crystallization of PbSO4 in negative electrode during unit cell operation. To minimize this issue, Pb nanoparticles have incorporated on MPC in this present investigation. The Pb on MPC has prepared through facile chemical reduction process. The structural analysis of Pb, MPC, and Pb on MPC have confirmed by X-ray diffraction analysis. The specific surface area (SSA) and pore size distribution of MPC and Pb on MPC has obtained through Brunauer-Emmett-Teller measurements. The obtained SSA is 245.38 and 32.42 m2 g−1 for MPC and Pb on MPC, respectively. Additionally, the incorporation of Pb on MPC has confirmed by the microstructural analysis of high resolution transmission electron microscopy. The obtained particle sizes of the Pb nanoparticles are ~5 nm. Based on the structural, microstructural and cyclic voltammetry analysis, we suggest that Pb on MPC can be used as an efficient active material for negative electrode in Ad-LAB systems.

A test system for advanced lead acid battery state-of-charge and state-of-health research

A test system for advanced lead acid battery state-of-charge and state-of-health research

Carbon honeycomb grids for advanced lead-acid batteries. Part III: Technology scale-up

The carbon honeycomb grid technology employs new carbon/carbon composites with ordered 3D structure instead of the classic lead-acid battery current collectors. The technology is laboratory scaled up from small size grids corresponding to electrodes with a capacity of 3 Ah to current collectors suitable for assembly of lead-acid batteries covering the majority of the typical lead-acid battery applications. Two series of 150 grids each (one positive and one negative) are manufactured using low-cost lab-scale equipment. They are further subjected to pasting with active materials and the resulting battery plates are assembled in 12 V AGM-VLRA battery mono-blocks for laboratory testing and outdoor demonstration in electric scooter replacing its original VRLAB pack. The obtained results demonstrate that the technology can replace successfully the state of the art negative grids with considerable benefits. The use of the carbon honeycomb grids as positive plate current collectors is limited by the anodic corrosion of the entire structure attacking both the carbon/carbon composite part and the electroplated lead-tin alloy coating.

Carbon honeycomb grids for advanced lead-acid batteries. Part II: Operation of the negative plates

The article presents the recent progress in the carbon honeycomb grid technology for valve-regulated lead-acid batteries with absorptive glass-mat separators (AGM-VRLAB). The work is focused on the development of negative current collectors using industrial grade composite honeycomb precursors. The developed model AGM-VRLA cells comprised of one prototype honeycomb negative electrode and two conventional traction positive counter-electrodes show high utilisation of the negative active material and long cycle life both in high-rate partial state of charge (HRPSoC) cycling mode and in deep cycling mode. The analysis of the results from the cycle-life tests and the tear-down analysis indicate that the benefits delivered by the novel grids can be related to the low mesh size of the grid, low γ-coefficient, as well as the use of milled carbon fibre additive. The combination of the three, results in the reversibility of the negative active material sulfation process when the electrolyte concentration in the cells is lower than the one traditionally used in the AGM-VRLAB technology. The negative plates show no signs of irreversible degradation after more than 900 cycles in deep cycling mode and more than 2000 capacity turnovers (equivalent cycles) in HRPSoC cycling mode.

Advanced Lead–Acid Batteries and the Development of Grid-Scale Energy Storage Systems

This paper discusses new developments in lead-acid battery chemistry and the importance of the system approach for implementation of battery energy storage for renewable energy and grid applications. The described solution includes thermal management of an UltraBattery bank, an inverter/charger, and smart grid management, which can monitor the state of charge (SoC) and the state of health (SoH) of the battery during system operation. With such features, it can allow the battery to operate within an optimum SoC window and thus can further maximize the longevity of the UltraBattery. Importantly, the smart battery management can trend the SoH of the battery and allow cell replacement at a convenient time without affecting the system operation. Furthermore, the advanced system package allows remote monitoring and control of operation, thus reducing the running cost of the system. It is clear that the widespread use of renewable-energy systems, in turn, would lead to a reduction in global consumption of the limited supplies of the fossil fuels and in the associated production of greenhouse-gas emissions.

Electrification Boost for Downsized Gasoline Engine

Vehicle, engine, and system experts from many organisations collaborated within the Hyboost project, which was co-funded by the UK government-backed Technology Strategy Board. Led by Ricardo UK, the project’s partners included Ford, Controlled Power Technologies (CPT), Valeo, the European Advanced Lead Acid Battery Consortium, and Imperial College London. The project’s goal was to develop an extremely efficient gasoline powertrain delivering a CO2 emission level of ≤100 g/km over the NEDC in a family size vehicle. This was to be achieved without noticeably impacting the vehicle’s driveability in comparison to the same model with a conventional, naturally aspirated gasoline engine. The basic concept of the research project was to use aggressive downsizing in combination with DI. In order to maintain driveability, an electric supercharger, an additional energy capture and storage function, plus a higher voltage level (12+x V) were added to the powertrain.

Electrification of a Downsized Boosted Gasoline Engine

Vehicle, engine, and system experts from many organisations collaborated within the Hyboost project, which was co-funded by the UK government-backed Technology Strategy Board. Led by Ricardo UK, the project’s partners included Ford, Controlled Power Technologies (CPT), Valeo, the European Advanced Lead Acid Battery Consortium, and Imperial College London. The project’s goal was to develop an extremely efficient gasoline powertrain delivering a CO2 emission level of ≤100 g/km over the NEDC in a family size vehicle. This was to be achieved without noticeably impacting the vehicle’s driveability in comparison to the same model with a conventional, naturally aspirated gasoline engine. The basic concept of the research project was to use aggressive downsizing in combination with DI. In order to maintain driveability, an electric supercharger, an additional energy capture and storage function, plus a higher voltage level (12+x V) were added to the powertrain.