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.     

Development of a BB-2590/U rechargeable lithium-ion battery

PolyStor has teamed with Hawker Eternacell (US) to develop a BB-2590/U rechargeable lithium-ion battery under contract with the US Army CECOM (Ft. Monmouth, NJ, USA). The concept involves using commercially available ICR-18650 cylindrical lithium-ion cells. The individual cells have a high specific energy of 135 Wh kg⁻¹ and an energy density of 335 Wh dm⁻³. Electronic circuitry was developed to provide pack protection, charge equalization and battery management (fuel gauging). PolyStor's rechargeable BB-2590/U battery provides 4.5 Ah at 28 V nominal or 9.0 Ah at 14 V nominal, translating into 108 Wh kg⁻¹ and 150 Wh dm⁻³. The key developments are discussed in this paper.     

Development of an optimal charging algorithm of a Ni-MH battery for stationary fuel cell/battery hybrid system application

When installed in stationary fuel cell/battery hybrid systems, sealed nickel-metal hydride (Ni-MH) battery packs have low rates of charging behavior at high temperatures. They can also be charged with surplus power from fuel cell system when they are part of a small-capacity fuel cell/battery hybrid system. Test results indicate that when subjected to high temperatures and low rates of charging current, a Ni-MH battery experiences a sharp reduction in discharge capacity but does not experience an increase in voltage. To solve these problems, we have applied a new charging algorithm based on this pulse charging method to a Ni-MH battery. The pulse charging method reduces the charging time by 2 hrs and has a charging efficiency of over 97%. The charging current factor (β) in this pulse charging method should influenced the controlling the charging rate to the battery with applied voltages. The results show a 27% increase in efficiency with the new charging method compared to the system efficiency of the conventional constant-voltage charging method. Such a pulse charging method is expected to increase the lifespan of a Ni-MH battery by inhibiting gas generation.     

Diffusion-limited model for a lithium/air battery with an organic electrolyte

A diffusion-limited transient mathematical model for a lithium/air cell, with the air cathode pores flooded with an organic electrolyte, has been developed. During cell discharge, the cathode pore radius profile is reflective of the distribution of the lithium peroxide product in the cathode. The cathode pore radius profile has been predicted as a function of time, current density, oxygen gas pressure, and cathode thickness for an assumed initial porosity and average cathode pore size. Transient concentration profiles of the dissolved oxygen in the electrolyte were also determined. Capacities of the lithium/air cell were predicted and compared favorably with literature experimental results.     

A modified Al2O3 coating process to enhance the electrochemical performance of Li(Ni1/3Co1/3Mn1/3)O2 and its comparison with traditional Al2O3 coating process

Al₂O₃-modified Li(Ni_1/3Co_1/3Mn_1/3)O₂ is synthesized by a modified Al₂O₃ coating process. The Al₂O₃ coating is carried out on an intermediate, (Ni_1/3Co_1/3Mn_1/3)(OH)₂, rather than on Li(Ni_1/3Co_1/3Mn_1/3)O₂. As a comparison, Al₂O₃-coated Li(Ni_1/3Co_1/3Mn_1/3)O₂ also is prepared by traditional Al₂O₃ coating process. The effects of Al₂O₃ coating and Al₂O₃ modification on structure and electrochemical performance are investigated and compared. Electrochemical tests indicate that cycle performance and rate capability of Li(Ni_1/3Co_1/3Mn_1/3)O₂ are enhanced by Al₂O₃ modification without capacity loss. Al₂O₃ coating can also enhance the cycle performance but cause evident capacity loss and decline of rate capability. The effect of Al₂O₃ coating and Al₂O₃ modification on kinetics of lithium-ion transfer reaction at the interface of electrode/electrolyte is investigated via electrochemical impedance spectra (EIS). The result support that the Al₂O₃ modification increase Li⁺ diffused coefficient and decrease the activation energy of Li⁺ transfer reaction but the traditional Al₂O₃ coating lead to depression of Li⁺ diffused coefficient and increase of activation energy.     

A binary ionic liquid system composed of N-methoxyethyl-N-methylpyrrolidinium bis(trifluoromethanesulfonyl)-imide and lithium bis(trifluoromethanesulfonyl)imide: A new promising electrolyte for lithium batteries

Room temperature ionic liquids are nowadays the most appealing research target in the field of liquid electrolytes for lithium batteries, due to their high thermal stability, ionic conductivity and wide electrochemical windows. The cation structure of such solvents strictly influences their physical and chemical properties, in particular the viscosity and conductivity.In this paper we report on the preparation and characterization of a complete series of solutions between lithium bis(trifluoromethanesulfonyl)imide (LiTFSI) and the promising N-methoxyethyl-N-methylpyrrolidinium bis(trifluoromethanesulfonyl)-imide (PY_1,2O1) ionic liquid. A wide molality range has been explored in order to identify the optimal compositions in terms of conductivity and electrochemical stability. Our thermal results show that the solutions are amorphous independently on the LiTFSI content. Up to salt concentration of 0.4 mol kg⁻¹ the solutions have a very low viscosity (η ∼ 36 cP), a high ionic conductivity, even at temperatures below 0 °C, and a good electrochemical stability. Cations transport numbers ranging between 0.05 and 0.39 have been determined as a function of LiTFSI content. The combination of these properties makes the PY_1,2O1-based solutions potentially attractive liquid electrolytes for lithium batteries.     

Development of new energy management strategy for a household fuel cell/battery hybrid system

This work aims to construct an efficient and robust fuel cell/battery hybrid operating system for a household application. The ability to dispatch the power demands, sustain the state of charge (SOC) of battery, optimize the power consumption, and more importantly, ensure the durability as well as extend the lifetime of a fuel cell system is the basic requirements of the hybrid operating system. New power management strategy based on fuzzy logical combined state machine control is developed, and its effectiveness is compared with various strategies such as dynamic programming (DP), state machine control, and fuzzy logical control with simulation. Experimental results are also presented, except for DP because of difficulties in achieving real‐time implementation and much faster response to load variation. The given current from the energy management system (EMS) as a reference of the fuel cell output current is determined by filtering out various harmful signals. The new power management strategy is applied to a 1‐kW stationary fuel cell/battery hybrid system. Results show that the fuel cell hybrid system can run much smoothly with prolonged lifetime.     

Development of an electrical model for a PV/battery system for performance prediction

This paper presents electrical model of a photovoltaic-battery system. This model helps to understand the behaviour of a solar-battery system under various load and irradiance conditions. And also it assists with investigation of the performance of the system. Hybrid energy systems use different energy sources such as solar and wind with a backup unit such as a battery or a diesel generator. They are an economical option in areas remote from national grid. In this context the performance of the system to supply electric power in an efficient way of operation is important. The problem comes from uncertain renewable energy supply and load and also non-linear characteristics of components in the system. The purpose of study we are involved in this relation is to see the behaviour of a solar-battery system under various load and irradiance conditions and to investigate the performance of the system. As a result an optimum system configuration and a correct and cost effective size of Balance of System (BOS) can be achieved. In this paper the complete electrical circuit of the entire hybrid system, the mathematical model and computational technique are presented.     

Electrochemical characteristics of manganese oxide/carbon composite as a cathode material for Li/MnO2 secondary batteries

Electrolytic manganese dioxide (EMD) recovered from a simulated leaching solution of spent alkaline batteries using a modified cyclone cell is tested as a cathode material for Li secondary batteries. An EMD/C(Super P) composite heat-treated at 400 °C after high-energy mechanical milling shows better electrochemical performance than that of pure EMD in terms of cycleability and capacity fading. The electrochemical characteristics of the EMD/C(Super P) composite are investigated by various analytical techniques. The irreversible capacity during the first cycle is mainly due to the formation of a Li₂MnO₃ phase. The carbon composite also retards the dissolution of Mn during cycling.     

Structural transformation of layered hydrogen trititanate (H2Ti3O7) to TiO2(B) and its electrochemical profile for lithium-ion intercalation

The thermally-induced structural transformation of layered hydrogen trititanate (H₂Ti₃O₇) to TiO₂(B) has been systematically studied by means of in situ X-ray diffraction (XRD) over a wide temperature range from 170 to 450 °C. Our data indicate a structural transition realized via continuous loss of interlayer water, which results in a series of non-stoichiometric hydrogen titanate compounds (3TiO₂·δH₂O). Electrochemical analysis of hydrogen titanates for lithium-ion intercalation shows that reversible specific capacity increases as calcination temperature increases, whereas cycling stability decreases during the continuous dehydration process.     

Fabrication and electrochemical characterization of a vertical array of MnO2 nanowires grown on silicon substrates as a cathode material for lithium rechargeable batteries

A complementary metal-oxide-semiconductor (CMOS) compatible process for fabricating on-chip microbatteries based on nanostructures has been developed by growing manganese dioxide nanowires on silicon dioxide (SiO₂)/silicon (Si) substrate as a cathode material for lithium rechargeable batteries. High aspect-ratio anodized aluminum oxide (AAO) template integrated on SiO₂/Si substrates can be exploited for fabrication of a vertical array of nanowires having high surface area. The electrolytic manganese dioxide (EMD) nanowires are galvanostatically synthesized by direct current (dc) electrodeposition. The microstructure of these nanowire arrays is investigated by scanning electron microscopy and X-ray diffraction. Their electrochemical tests show that the discharge capacity of about 150 mAh g⁻¹ is maintained during a few cycles at the high discharge/charge rate of 300 mA g⁻¹.     

Experimental evaluation of a passive fuel cell/battery hybrid power system for an unmanned ground vehicle

Unmanned vehicles are increasing the performance of monitoring and surveillance in several applications. Endurance is a key issue in these systems, in particular in electric vehicles, powered at present mainly by batteries. Hybrid power systems based on batteries and fuel cells have the potential to achieve high energy density and specific energy, increasing also the life time and safe operating conditions of the power system. The objective of this research is to analyze the performance of a passive hybrid power system, designed and developed to be integrated into an existing Unmanned Ground Vehicle (UGV). The proposed solution is based on six LiPo cells, connected in series, and a 200 W PEM fuel cell stack, directly connected in parallel to the battery without any limitation to its charge. The paper presents the characterization of the system behavior, and shows the main results in terms of performance and energy management.     

Synthesis and performance of carbon-coated Li3V2(PO4)3 cathode materials by a low temperature solid-state reaction

The carbon-coated monoclinic Li₃V₂(PO₄)₃ (LVP) cathode materials can be synthesized by a low temperature solid-state reaction route. The influences of different heat treatments on the LVP have been investigated using X-ray diffraction (XRD), scanning electron microscopy (SEM) and electrochemical methods. In the range of 3.0-4.3 V, both LVP/C electrodes present good rate capability and excellent cyclic performance. It is found that the sample (LVP1/C) prepared by the two-step heat treatment with pre-sintering at 350 °C delivers the initial discharge capacity of 99.8 mAh g⁻¹ at 10 C charge-discharge rate and still retains 95.8 mAh g⁻¹ after 300 cycles. For the sample (LVP2/C) synthesized by the one-step heat treatment, 95.9 and 90.0 mAh g⁻¹ are obtained in the 1st and 300th cycles at 10 C rate, respectively. Our results based on the XRD patterns and the SEM images suggest that the good rate capability and cyclic performance may be owing to the pure phases, small particles, large specific surface areas and residual carbon. In the range of 3.0-4.8 V, compared with the LVP2/C, the LVP1/C also exhibits better performance.     

A new approach of sizing battery energy storage system for smoothing the power fluctuations of a PV/wind hybrid system

In this paper, a new approach for optimally sizing the storage system employing the battery banks for the suppression of the output power fluctuations generated in the hybrid photovoltaic/wind hybrid energy system. At first, a novel multiple averaging technique has been used to find the smoothing power that has to be supplied by the batteries for the different levels of smoothing of output power. Then the battery energy storage system is optimally sized using particle swarm optimization according to the level of smoothing power requirement, with the constraints of maintaining the battery state of charge and keeping the energy loss within the acceptable limits. Two different case studies have been presented for different locations and different sizes of the hybrid systems in this work. The results of the simulation studies and detailed discussions are presented at the end to portrait the effectiveness of the proposed method for sizing of the battery energy storage system. Copyright © 2016 John Wiley & Sons, Ltd.     

The doping effect on the crystal structure and electrochemical properties of LiMnxM1−xPO4 (M = Mg, V, Fe, Co, Gd)

To substitute minor Mn²⁺ by the transition metal ion M = Mg²⁺, V³⁺, Fe²⁺, Co²⁺, or Gd³⁺, LiMn_0.95M_0.05PO₄ samples are synthesized by a solid-state reaction route. The interpretation of doping effects is complicated by the interrelations between doping microstructure and morphology, because the crystal structure would be affected by the doped elements. The lattice structure and deviation of Li-O bond lengths of the doped LiMnPO₄ are refined by XRD refinement. All the samples present a couple of oxidation and reduction peaks in cyclic voltammetry, corresponding to a redox Mn³⁺/Mn²⁺ reaction coupled with the extraction/reinsertion process of Li⁺ in LiMnPO₄ structure. During charge/discharge process, the electron flowing and Li⁺ cation diffusion in the various doped LiMnPO₄ samples should be different thermodynamic and kinetic process. For further studying which step in thermodynamic and kinetic process would affect or control the electrochemical performance, the initial charge/discharge capacities and cycleability of doped LiMnPO₄ samples are obtained under different voltage range (from 2.7 to the upper cut-off voltage 4.4, 4.6 and 4.8 V, respectively) and different environment temperatures (0, 25, and 50 °C). At relative higher measuring temperature, the discharge capacity of Co-doped LiMnPO₄ shows 151.9 mAh g⁻¹.     

Feasibility study and techno-economic analysis of an SOFC/battery hybrid system for vehicle applications

A feasibility study and techno-economic analysis for a hybrid power system intended for vehicular traction applications has been performed. The hybrid consists of an intermediate temperature solid oxide fuel cell (IT-SOFC) operating at 500–800 °C and a sodium–nickel chloride (ZEBRA) battery operating at 300 °C. Such a hybrid system has the benefits of extended range and fuel flexibility (due to the IT-SOFC), high power output and rapid response time (due to the battery). The above hybrid has been compared to a fuel cell-only, a battery-only and an ICE vehicle. It is shown that the capital cost associated with a fuel cell-only vehicle is still much higher than that of any other power source option and that a battery-only option would potentially encounter weight and volume limitations, particularly for long drive times. It is concluded that increasing drive time per day decreases substantially the payback time in relation to an ICE vehicle running on gasoline and thus that the hybrid vehicle is an economically attractive option for commercial vehicles with long drive times. In the case where the battery has reached volume production prices at £70 kWh⁻¹ and current fuel duty values remain unchanged then a payback time <2 years is obtained. For a light delivery van operating with 6 h drive time per day, a fuel cell system model predicted a gasoline equivalent fuel economy of 25.1 km L⁻¹, almost twice that of a gasoline fuelled ICE vehicle of the same size, and CO₂ emissions of 71.6 g km⁻¹, well below any new technology target set so far. It is therefore recommended that a SOFC/ZEBRA demonstration be built to further explore its viability.     

Synthesis and electrochemical performances of core-shell structured Li[(Ni1/3Co1/3Mn1/3)0.8(Ni1/2Mn1/2)0.2]O2 cathode material for lithium ion batteries

Micro-scale core-shell structured Li[(Ni_1/3Co_1/3Mn_1/3)_0.8(Ni_1/2Mn_1/2)_0.2]O₂ powders for use as cathode material are synthesized by a co-precipitation method. To protect the core material Li[Ni_1/3Co_1/3Mn_1/3]O₂ from structural instability at high voltage, a Li[Ni_1/2Mn_1/2]O₂ shell, which provides structural and thermal stability, is used to encapsulate the core. A mixture of the prepared core-shell precursor and lithium hydroxide is calcined at 770 °C for 12 h in air. X-ray diffraction studies reveal that the prepared material has a typical layered structure with an space group. Spherical morphologies with mono-dispersed powders are observed in the cross-sectional images obtained by scanning electron microscopy. The core-shell Li[(Ni_1/3Co_1/3Mn_1/3)_0.8(Ni_1/2Mn_1/2)_0.2]O₂ electrode has an excellent capacity retention at 30 °C, maintaining 99% of its initial discharge capacity after 100 cycles in the voltage range of 3-4.5 V. Furthermore, the thermal stability of the core-shell material in the highly delithiated state is improved compared to that of the core material. The resulting exothermic onset temperature appear at approximately 272  °C, which is higher than that of the highly delithiated Li[Ni_1/3Co_1/3Mn_1/3]O₂ (261 °C).     

Electrochemical characteristics of the interface between the metal hydride electrode and electrolyte for an advanced nickel/metal hydride battery

The characteristics of the negative electrode of a Ni/MH (metal hydride) battery are related to the charge transfer and mass transfer processes at the interface between the MH electrode and the electrolyte. With increasing number of charge/discharge cycles, the MH alloy powders micro-crack into particles that are several microns in diameter and this then influences the exchange current density. A polarization experiment was used to analyze the charge transfer and mass transfer processes. The exchange current densities of uncoated and Pd-coated Mm_0.95Ti_0.05Ni_3.85Co_0.45Mn_0.35Al_0.35 alloy electrodes increase with increasing number of charge/discharge cycles before reaching a constant value after 20–30 cycles.     

Temperature-controlled microwave solid-state synthesis of Li3V2(PO4)3 as cathode materials for lithium batteries

Monoclinic Li₃V₂(PO₄)₃ can be rapidly synthesized at 750 °C for 5 min (MW5m) by using temperature-controlled microwave solid-state synthesis method (TCMS). The carbon-free sample MW5m presents well electrochemical properties. In the cut-off voltage 3.0-4.3, MW5m presents a charge capacity 132 mAh g⁻¹, almost equivalent to the reversible cycling of two lithium ions per Li₃V₂(PO₄)₃ formula unit (133 mAh g⁻¹), and discharge capacity 126.4 mAh g⁻¹. In the cut-off voltage 3.0-4.8 V, MW5m shows an initial discharge capacity of 183.4 mAh g⁻¹, near to the theoretical discharge capacity. In the cycle performance, the capacity fade of Li₃V₂(PO₄)₃ is dependent on the cut-off voltage and the preparation method.