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Batteries, Volume 5, Issue 1 (March 2019)

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Cover Story (view full-size image) Aqueous zinc ion batteries (AZIBs), a type of multivalent ion battery, have received attention [...] Read more.
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Open AccessArticle
Combining a Fatigue Model and an Incremental Capacity Analysis on a Commercial NMC/Graphite Cell under Constant Current Cycling with and without Calendar Aging
Received: 21 December 2018 / Revised: 11 March 2019 / Accepted: 13 March 2019 / Published: 21 March 2019
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Abstract
Reliable development of LIBs requires that they be correlated with accurate aging studies. The present project focuses on the implementation of a weighted ampere-hour throughput model, taking into account the operating parameters, and modulating the impact of an exchanged ampere-hour by the well-established [...] Read more.
Reliable development of LIBs requires that they be correlated with accurate aging studies. The present project focuses on the implementation of a weighted ampere-hour throughput model, taking into account the operating parameters, and modulating the impact of an exchanged ampere-hour by the well-established three major stress factors: temperature, current intensity (rated), and state of charge (SoC). This model can drift with time due to repeated solicitation, so its parameters need to be updated by on-field measurements, in order to remain accurate. These on-field measurements are submitted to the so-called Incremental Capacity Analysis method (ICA), consisting in the analysis of dQ/dV as a function of V. It is a direct indicator of the state of health of the cell, as the experimental peaks are related to the active material chemical/structural evolution, such as phase transitions and recorded potential plateaus during charging/discharging. It is here applied to NMC/graphite based commercial cells. These peaks’ evolution can be correlated with the here-defined Ah-kinetic and t -kinetic aging, which are chemistry-dependent, and therefore, has to be adjusted to the different types of cells. Full article
(This article belongs to the Special Issue Batteries and Supercapacitors Aging)
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Open AccessArticle
Recycling of Alkaline Batteries via a Carbothermal Reduction Process
Received: 12 December 2018 / Revised: 1 February 2019 / Accepted: 8 March 2019 / Published: 19 March 2019
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Abstract
Primary battery recycling has important environmental and economic benefits. According to battery sales worldwide, the most used battery type is alkaline batteries with 75% of market share due to having a higher performance than other primary batteries such as Zn–MnO2. In [...] Read more.
Primary battery recycling has important environmental and economic benefits. According to battery sales worldwide, the most used battery type is alkaline batteries with 75% of market share due to having a higher performance than other primary batteries such as Zn–MnO2. In this study, carbothermal reduction for zinc oxide from battery waste was completed for both vacuum and Ar atmospheres. Thermodynamic data are evaluated for vacuum and Ar atmosphere reduction reactions and results for Zn reduction/evaporation are compared via the FactSage program. Zn vapor and manganese oxide were obtained as products. Zn vapor was re-oxidized in end products; manganese monoxide and steel container of batteries are evaluated as ferromanganese raw material. Effects of carbon source, vacuum, temperature and time were studied. The results show a recovery of 95.1% Zn by implementing a product at 1150 °C for 1 h without using the vacuum. The residues were characterized by Atomic Absorption Spectrometer (AAS) and X-ray Diffraction (XRD) methods. Full article
(This article belongs to the Special Issue Circular Economy of Batteries Production and Recycling)
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Open AccessReview
Methods for Durability Testing and Lifetime Estimation of Thermal Interface Materials in Batteries
Received: 28 December 2018 / Revised: 19 February 2019 / Accepted: 2 March 2019 / Published: 18 March 2019
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Abstract
To ensure sufficient thermal performance within electric vehicle (EV) batteries, thermal interface materials (TIMs), such as pastes or adhesives, are widely used to fill thermally insulating voids between cells and cooling components. However, TIMs are composite materials that are subject to degradation over [...] Read more.
To ensure sufficient thermal performance within electric vehicle (EV) batteries, thermal interface materials (TIMs), such as pastes or adhesives, are widely used to fill thermally insulating voids between cells and cooling components. However, TIMs are composite materials that are subject to degradation over the battery’s lifetime. Using TIMs for battery applications is a new and emerging topic, creating the need to rapidly acquire knowledge about appropriate lifetime testing and evaluation methods, in close collaboration with the battery manufacturers. This paper reviews suitable methods for durability testing as well as basic modeling approaches which allow for the transfer of laboratory results to the longtime behavior of interface materials during a vehicle’s lifetime. Full article
(This article belongs to the Special Issue Thermal and Safety Properties of Materials, Cells and Batteries)
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Open AccessArticle
Fast Electrical Characterizations of High-Energy Second Life Lithium-Ion Batteries for Embedded and Stationary Applications
Received: 31 January 2019 / Revised: 7 March 2019 / Accepted: 12 March 2019 / Published: 14 March 2019
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Abstract
This paper focuses on the fast characterization of automotive second life lithium-ion batteries that have been recently re-used in many projects to create battery storages for stationary applications and sporadically for embedded applications. Specific criteria dedicated to the second life are first discussed. [...] Read more.
This paper focuses on the fast characterization of automotive second life lithium-ion batteries that have been recently re-used in many projects to create battery storages for stationary applications and sporadically for embedded applications. Specific criteria dedicated to the second life are first discussed. After a short review of the available state of health indicators and their associated determination techniques, some electrical characterization tests are explored through an experimental campaign. This offline identification aims to estimate the remaining ability of the battery to store energy. Twenty-four modules from six different commercial electric vehicles are analyzed. Well-known methodologies like incremental capacity analysis (ICA) and constant voltage phase analysis during CC-CV charge highlight the difficulty—and sometimes the impossibility—to apply traditional tools on a battery pack or on individual modules, in the context of real second life applications. Indeed, the diversity of the available second life batteries induces a combination of aging mechanisms that leads to a complete heterogeneity from a cell to another. Moreover, due to the unknown first life of the battery, typical state of health determination methodologies are difficult to use. A new generic technique based on a partial coulometric counter is proposed and compared to other techniques. In the present case study, the partial coulometric counter allows a fast determination of the capacity aging. In conclusion, future improvements and working tracks are addressed. Full article
(This article belongs to the Special Issue Batteries and Supercapacitors Aging)
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Open AccessArticle
Improved Discharge Capacity of Zinc Particles by Applying Bismuth-Doped Silica Coating for Zinc-Based Batteries
Received: 11 January 2019 / Revised: 8 March 2019 / Accepted: 11 March 2019 / Published: 14 March 2019
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Abstract
Corrosion and discharge behavior of battery-grade zinc particles coated with a silica layer doped with bismuth was investigated and compared with untreated zinc powder. Electrochemical investigations were carried out in half-cell configuration. The electrolyte was 6 M KOH in excess. Coated zinc particles [...] Read more.
Corrosion and discharge behavior of battery-grade zinc particles coated with a silica layer doped with bismuth was investigated and compared with untreated zinc powder. Electrochemical investigations were carried out in half-cell configuration. The electrolyte was 6 M KOH in excess. Coated zinc particles provided a discharge capacity of 737 mAh g−1 (89.9% DoD) versus 633 mAh g−1 (77.2% DoD) of untreated zinc particles after a dwell time of 1 h in KOH. The silica coating reduced the direct contact of the zinc surface with the electrolyte and thus minimized the hydrogen evolution reaction, which led to an increased discharge capacity. Additionally, bismuth doping enhanced conductivity within the silica coating and increased zinc utilization. Those coated zinc particles inhibited corrosion, i.e., corrosion efficiency reached 87.9% compared to uncoated zinc. Additionally, the coating achieved a capacity retention of 90.9% (670 mAh g−1) after 48 h dwell time in 6 M KOH. The coatings were prepared by sol-gel technology and characterized by Fourier transform infrared spectroscopy (FTIR), X-ray diffractometry (XRD), X-ray photoelectron spectroscopy (XPS), scanning electron microscopy (SEM), and Brunauer-Emmett-Teller (BET) surface determination. Full article
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Open AccessArticle
An Electrical Equivalent Circuit Model of a Lithium Titanate Oxide Battery
Received: 29 January 2019 / Revised: 6 March 2019 / Accepted: 7 March 2019 / Published: 13 March 2019
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Abstract
A precise lithium-ion battery model is required to specify their appropriateness for different applications and to study their dynamic behavior. In addition, it is important to design an efficient battery system for power applications. In this investigation, a second-order equivalent electrical circuit battery [...] Read more.
A precise lithium-ion battery model is required to specify their appropriateness for different applications and to study their dynamic behavior. In addition, it is important to design an efficient battery system for power applications. In this investigation, a second-order equivalent electrical circuit battery model, which is the most conventional method of characterizing the behavior of a lithium-ion battery, was developed. The current pulse procedure was employed for parameterization of the model. The construction of the model was described in detail, and a battery model for a 13 Ah lithium titanate oxide battery cell was demonstrated. Comprehensive characterization experiments were accomplished for an extensive range of operating situations. The outcomes were employed to parameterize the suggested dynamic model of the lithium titanate oxide battery cell. The simulation outcomes were compared to the laboratory measurements. In addition, the proposed lithium-ion battery model was validated. The recommended model was assessed, and the proposed model was able to anticipate precisely the current and voltage performance. Full article
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Open AccessArticle
Refractive Index Measurement of Lithium Ion Battery Electrolyte with Etched Surface Cladding Waveguide Bragg Gratings and Cell Electrode State Monitoring by Optical Strain Sensors
Received: 30 January 2019 / Revised: 5 March 2019 / Accepted: 6 March 2019 / Published: 12 March 2019
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Abstract
In this scientific publication, a new sensor approach for status monitoring, such as state of charge and state of health, of lithium ion batteries by using special Bragg gratings inscribed into standard optical glass fibers is presented. In addition to well-known core gratings, [...] Read more.
In this scientific publication, a new sensor approach for status monitoring, such as state of charge and state of health, of lithium ion batteries by using special Bragg gratings inscribed into standard optical glass fibers is presented. In addition to well-known core gratings, embedded into the anode of 5 Ah lithium ion pouch cells as a strain monitoring unit, the manufacturing of a surface cladding waveguide Bragg grating sensor incorporated into the cell’s separator, that is sensitive to changes of the refractive index of the surrounding medium, is demonstrated. On the basis of the experiments carried out, characteristics of the cell behavior during standard cyclization and recognizable marks in subsequent post-mortem analyses of the cell components are shown. No negative influence on the cell performance due to the integrated sensors have been observed; however, the results show a clear correlation between fading cell capacity and changes of the interior optical signals. Additionally, with the novel photonic sensor, variations in the electrolyte characteristics are determinable as the refractive index of the solution changes at different molar compositions. Furthermore, with the manufactured battery cells, abuse tests by overcharging were conducted, and it was thereby demonstrated how internal battery sensors can derive additional information beyond conventional battery management systems to feasibly prevent catastrophic cell failures. The result of the research work is an early stage photonic sensor that combines chemical, mechanical and thermal information from inside the cell for an enhanced battery status analysis. Full article
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Open AccessArticle
A Suggested Improvement for Small Autonomous Energy System Reliability by Reducing Heat and Excess Charges
Received: 30 January 2019 / Revised: 19 February 2019 / Accepted: 6 March 2019 / Published: 11 March 2019
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Abstract
Devices operating in complete energy autonomy are multiplying: small fixed signaling applications or sensors often operating in a network. To ensure operation for a substantial period, for applications with difficult physical access, a means of storing electrical energy must be included in the [...] Read more.
Devices operating in complete energy autonomy are multiplying: small fixed signaling applications or sensors often operating in a network. To ensure operation for a substantial period, for applications with difficult physical access, a means of storing electrical energy must be included in the system. The battery remains the most deployed solution. Lead-acid batteries still have a significant share of this market due to the maturity of their technology. However, even by sizing all the system elements according to the needs and the available renewable energy, some failure occurs. The battery is the weak element. It can be quickly discharged when the renewable energy source is no longer present for a while. It can also be overloaded or subjected to high temperatures, which affects its longevity. This paper presents a suggested improvement for these systems, systematically adding extra devices to reduce excess charges and heat and allowing the battery use at lower charges. The interest of this strategy is presented by comparing the number of days of system failure and the consequences for battery aging. To demonstrate the interest of the proposed improvement track, a colored Petri net is deployed to model the battery degradation parameters evolution, in order to compare them. Full article
(This article belongs to the Special Issue Batteries and Supercapacitors Aging)
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Open AccessArticle
Lifetime Prediction of Lithium-Ion Capacitors Based on Accelerated Aging Tests
Received: 18 December 2018 / Revised: 12 February 2019 / Accepted: 26 February 2019 / Published: 5 March 2019
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Abstract
Lithium-ion Capacitors (LiCs) that have intermediate properties between lithium-ion batteries and supercapacitors are still considered as a new technology whose aging is not well studied in the literature. This paper presents the results of accelerated aging tests applied on 12 samples of LiCs. [...] Read more.
Lithium-ion Capacitors (LiCs) that have intermediate properties between lithium-ion batteries and supercapacitors are still considered as a new technology whose aging is not well studied in the literature. This paper presents the results of accelerated aging tests applied on 12 samples of LiCs. Two high temperatures (60 °C and 70 °C) and two voltage values were used for aging acceleration for 20 months. The maximum and the minimum voltages (3.8 V and 2.2 V respectively) had different effects on capacitance fade. Cells aging at 2.2 V encountered extreme decrease of the capacitance. After storing them for only one month at 60 °C, they lost around 22% of their initial capacitance. For this reason, an aging model was developed for cells aging at the lowest voltage value to emphasize the huge decrease of the lifetime at this voltage condition. Moreover, two measurement tools of the capacitance were compared to find the optimal method for following the evolution of the aging process. It was proved that electrochemical impedance spectroscopy is the most accurate measurement technique that can reveal the actual level of degradation inside a LiC cell. Full article
(This article belongs to the Special Issue Batteries and Supercapacitors Aging)
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Open AccessArticle
Fabrication of Porous [email protected] Composites with Core-Shell Structure and Their Electrochemical Performance for Li-ion Batteries
Received: 17 January 2019 / Revised: 23 February 2019 / Accepted: 25 February 2019 / Published: 27 February 2019
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Abstract
The pores in silicon particles can accommodate the volume expansion of silicon during the charging–discharging process. However, pores in silicon particles are easily occupied by carbon during the preparation of silicon/carbon composites. In this paper, sulfur was adsorbed in the pores of porous [...] Read more.
The pores in silicon particles can accommodate the volume expansion of silicon during the charging–discharging process. However, pores in silicon particles are easily occupied by carbon during the preparation of silicon/carbon composites. In this paper, sulfur was adsorbed in the pores of porous silicon particles before polyaniline (PANI) coating by in-situ polymerization, so that the pores were preserved in porous [email protected] (p-Si/@C) composites after the sublimation of sulfur during carbonization. The microstructure and the electrochemical performances of the obtained p-Si/@C composites were investigated. The results indicate that p-Si/@C composites prepared with a sulfur-melting process show a better high-rate performance than those without a sulfur-melting process. Remarkably, the former show a better capacity retention when returning to a low current density. The reversible capacities of the former were 1178 mAh·g−1, 1055 mAh·g−1, 944 mAh·g−1, and 751 mAh·g−1 at 0.2 A·g−1, 0.3 A·g−1, 0.5 A·g−1, and 1.0 A·g−1, respectively. Moreover, the reversible capacities could return to 870 mAh·g−1, 996 mAh·g−1, and 1027 mAh·g−1 when current densities returned to 0.5, 0.3, and 0.2 A·g−1, respectively. Full article
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Open AccessArticle
Correlation of Mechanical and Electrical Behavior of Polyethylene Oxide-Based Solid Electrolytes for All-Solid State Lithium-Ion Batteries
Received: 29 December 2018 / Revised: 15 February 2019 / Accepted: 18 February 2019 / Published: 24 February 2019
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Abstract
Mechanical and electrochemical stability are key issues for large-scale production of solid state Li-ion batteries. Polymer electrolytes can provide good ionic conductivity, but mechanical strength needs to be improved. In this study, we investigate the correlation of mechanical and electrical properties of poly [...] Read more.
Mechanical and electrochemical stability are key issues for large-scale production of solid state Li-ion batteries. Polymer electrolytes can provide good ionic conductivity, but mechanical strength needs to be improved. In this study, we investigate the correlation of mechanical and electrical properties of poly (ethylene oxide) (PEO)-based solid electrolytes for Li-ion batteries. The influence of alumina and LiClO4 addition are investigated. Differential scanning calorimetry (DSC) is used to study the thermal behavior of salt-free and salt-containing samples and to identify the melting temperature. Dynamic mechanical analysis reveals the elastic properties as a function of temperature. Electrochemical properties are investigated using impedance spectroscopy. It is found that addition of alumina increases mechanical strength, while LiClO4 decreases it. Addition of LiClO4 and Al2O3 increases ionic conductivity and improves mechanical properties. However, there is no overlapping window of high mechanical strength and high ionic conductivity. Full article
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Open AccessArticle
A One-Dimensional Stack Model for Redox Flow Battery Analysis and Operation
Received: 1 January 2019 / Revised: 6 February 2019 / Accepted: 12 February 2019 / Published: 22 February 2019
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Abstract
Current redox flow battery (RFB) stack models are not particularly conducive to accurate yet high-throughput studies of stack operation and design. To facilitate system-level analysis, we have developed a one-dimensional RFB stack model through the combination of a one-dimensional Newman-type cell model and [...] Read more.
Current redox flow battery (RFB) stack models are not particularly conducive to accurate yet high-throughput studies of stack operation and design. To facilitate system-level analysis, we have developed a one-dimensional RFB stack model through the combination of a one-dimensional Newman-type cell model and a resistor-network to evaluate contributions from shunt currents within the stack. Inclusion of hydraulic losses and membrane crossover enables constrained optimization of system performance and allows users to make recommendations for operating flow rate, current densities, and cell design given a subset of electrolyte and electrode properties. Over the range of experimental conditions explored, shunt current losses remain small, but mass-transfer losses quickly become prohibitive at high current densities. Attempting to offset mass-transfer losses with high flow rates reduces system efficiency due to the increase in pressure drop through the porous electrode. The development of this stack model application, along with the availability of the source MATLAB code, allows for facile approximation of the upper limits of performance with limited empiricism. This work primarily presents a readily adaptable tool to enable researchers to perform either front-end performance estimates based on fundamental material properties or to benchmark their experimental results. Full article
(This article belongs to the Special Issue Vanadium Redox Flow Battery and Its Applications)
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Open AccessArticle
Vanadium Oxygen Fuel Cell Utilising High Concentration Electrolyte
Received: 20 December 2018 / Revised: 8 February 2019 / Accepted: 12 February 2019 / Published: 19 February 2019
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Abstract
A vanadium oxygen fuel cell is a modified form of a conventional vanadium redox flow battery (VRFB) where the positive electrolyte (VO2+/VO2+ couple) is replaced by the oxygen reduction (ORR) process. This potentially allows for a significant improvement in [...] Read more.
A vanadium oxygen fuel cell is a modified form of a conventional vanadium redox flow battery (VRFB) where the positive electrolyte (VO2+/VO2+ couple) is replaced by the oxygen reduction (ORR) process. This potentially allows for a significant improvement in energy density and has the added benefit of overcoming the solubility limits of V (V) at elevated temperatures, while also allowing the vanadium negative electrolyte concentration to increase above 3 M. In this paper, a vanadium oxygen fuel cell with vanadium electrolytes with a concentration of up to 3.6 M is reported with preliminary results presented for different electrodes over a range of current densities. Using precipitation inhibitors, the concentration of vanadium can be increased considerably above the commonly used 2 M limit, leading to improved energy density. Full article
(This article belongs to the Special Issue Vanadium Redox Flow Battery and Its Applications)
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Open AccessArticle
Eco-Efficiency of a Lithium-Ion Battery for Electric Vehicles: Influence of Manufacturing Country and Commodity Prices on GHG Emissions and Costs
Received: 14 January 2019 / Revised: 11 February 2019 / Accepted: 14 February 2019 / Published: 19 February 2019
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Abstract
Lithium-ion battery packs inside electric vehicles represents a high share of the final price. Nevertheless, with technology advances and the growth of the market, the price of the battery is getting more competitive. The greenhouse gas emissions and the battery cost have been [...] Read more.
Lithium-ion battery packs inside electric vehicles represents a high share of the final price. Nevertheless, with technology advances and the growth of the market, the price of the battery is getting more competitive. The greenhouse gas emissions and the battery cost have been studied previously, but coherent boundaries between environmental and economic assessments are needed to assess the eco-efficiency of batteries. In this research, a detailed study is presented, providing an environmental and economic assessment of the manufacturing of one specific lithium-ion battery chemistry. The relevance of parameters is pointed out, including the manufacturing place, the production volume, the commodity prices, and the energy density. The inventory is obtained by dismantling commercial cells. The correlation between the battery cost and the commodity price is much lower than the correlation between the battery cost and the production volume. The developed life cycle assessment concludes that the electricity mix that is used to power the battery factory is a key parameter for the impact of the battery manufacturing on climate change. To improve the battery manufacturing eco-efficiency, a high production capacity and an electricity mix with low carbon intensity are suggested. Optimizing the process by reducing the electricity consumption during the manufacturing is also suggested, and combined with higher pack energy density, the impact on climate change of the pack manufacturing is as low as 39.5 kg CO2 eq/kWh. Full article
(This article belongs to the Special Issue Sustainable Lithium Ion Batteries: From Production to Recycling)
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Open AccessArticle
Comparative Life Cycle Environmental Impact Analysis of Lithium-Ion (LiIo) and Nickel-Metal Hydride (NiMH) Batteries
Received: 31 December 2018 / Revised: 30 January 2019 / Accepted: 13 February 2019 / Published: 18 February 2019
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Abstract
Batteries have been extensively used in many applications; however, very little is explored regarding the possible environmental impacts for their whole life cycle, even though a lot of studies have been carried out for augmenting performance in many ways. This research paper addresses [...] Read more.
Batteries have been extensively used in many applications; however, very little is explored regarding the possible environmental impacts for their whole life cycle, even though a lot of studies have been carried out for augmenting performance in many ways. This research paper addresses the environmental effects of two different types of batteries, lithium-ion (LiIo) and nickel-metal hydride (NiMH) batteries, in terms of their chemical constituents. Life cycle impact analysis has been carried out by the CML, ReCiPe, EcoPoints 97, IPCC, and CED methods. The impacts are considered in categories such as global warming, eutrophication, freshwater aquatic ecotoxicity, human toxicity, marine aquatic ecotoxicity and terrestrial ecotoxicity. The results reveal that there is a significant environmental impact caused by nickel-metal hydride batteries in comparison with lithium-ion batteries. The reason behind these impacts is the relatively large amount of toxic chemical elements which are present as constituents of NiMH batteries. It can be anticipated that a better environmental performance can be achieved through optimization, especially by cautiously picking the constituents, taking into account the toxicity aspects, and by minimizing the impacts related to these chemicals. Full article
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Open AccessArticle
Electrochemical Performance of a Lithium Ion Battery with Different Nanoporous Current Collectors
Received: 26 November 2018 / Revised: 15 January 2019 / Accepted: 31 January 2019 / Published: 12 February 2019
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Abstract
In this work, we use ultrasonication and chemical etching agents to assist preparation of metal current collectors with nano-scale pores on the surface. Four different current collectors (copper foil, copper foam, aluminum foil, and aluminum foam) are prepared. The preparation parameters, ultrasonic time [...] Read more.
In this work, we use ultrasonication and chemical etching agents to assist preparation of metal current collectors with nano-scale pores on the surface. Four different current collectors (copper foil, copper foam, aluminum foil, and aluminum foam) are prepared. The preparation parameters, ultrasonic time and etching agent concentration, are investigated and optimized accordingly. The morphologies of the as-prepared current collectors are observed under a scanning electronic microscope. Soft-packed lithium ion batteries with various current collectors are fabricated and tested. The prepared lithium ion batteries show good long-term cycle stability. The nanoporous structure of the current collector has little impact on the improvement of battery capacity under slow charging/discharging rates but has a positive impact on capacity retention under fast charging/discharging rates. Full article
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Open AccessArticle
Optimal Charging of Vanadium Redox Flow Battery with Time-Varying Input Power
Received: 14 November 2018 / Revised: 19 January 2019 / Accepted: 31 January 2019 / Published: 10 February 2019
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Abstract
The battery energy storage system has become an indispensable part of the current electricity network due to the vast integration of renewable energy sources (RESs). This paper proposes an optimal charging method of a vanadium redox flow battery (VRB)-based energy storage system, which [...] Read more.
The battery energy storage system has become an indispensable part of the current electricity network due to the vast integration of renewable energy sources (RESs). This paper proposes an optimal charging method of a vanadium redox flow battery (VRB)-based energy storage system, which ensures the maximum harvesting of the free energy from RESs by maintaining safe operations of the battery. The VRB has a deep discharging capability, long cycle life, and high energy efficiency with no issues of cell-balancing, which make it suitable for large-scale energy storage systems. The proposed approach determines the appropriate charging current and the optimal electrolyte flow rate based on the available time-varying input power. Moreover, the charging current is bounded by the limiting current, which prevents the gassing side-reactions and protects the VRB from overcharging. The proposed optimal charging method is investigated by simulation studies using MATLAB/Simulink. Full article
(This article belongs to the Special Issue Vanadium Redox Flow Battery and Its Applications)
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Open AccessReview
Recent Advances in Non-Flammable Electrolytes for Safer Lithium-Ion Batteries
Received: 19 December 2018 / Revised: 13 January 2019 / Accepted: 17 January 2019 / Published: 1 February 2019
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Abstract
Lithium-ion batteries are the most commonly used source of power for modern electronic devices. However, their safety became a topic of concern after reports of the devices catching fire due to battery failure. Making safer batteries is of utmost importance, and several researchers [...] Read more.
Lithium-ion batteries are the most commonly used source of power for modern electronic devices. However, their safety became a topic of concern after reports of the devices catching fire due to battery failure. Making safer batteries is of utmost importance, and several researchers are trying to modify various aspects in the battery to make it safer without affecting the performance of the battery. Electrolytes are one of the most important parts of the battery since they are responsible for the conduction of ions between the electrodes. In this paper, we discuss the different non-flammable electrolytes that were developed recently for safer lithium-ion battery applications. Full article
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Open AccessArticle
Discharge by Short Circuit Currents of Parallel-Connected Lithium-Ion Cells in Thermal Propagation
Received: 28 December 2018 / Revised: 17 January 2019 / Accepted: 19 January 2019 / Published: 29 January 2019
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Abstract
The increasing need for high capacity batteries in plug-in hybrids and all-electric vehicles gives rise to the question of whether these batteries should be equipped with a few large capacity cells or rather many low capacity cells in parallel. This article demonstrates the [...] Read more.
The increasing need for high capacity batteries in plug-in hybrids and all-electric vehicles gives rise to the question of whether these batteries should be equipped with a few large capacity cells or rather many low capacity cells in parallel. This article demonstrates the possible benefits of smaller cells connected in parallel because of discharge effects. Measurements have been conducted proving the beneficial influence of a lower SoC on the thermal runaway behaviour of lithium-ion cells. A second test series examines the short circuit currents during an ongoing thermal propagation in parallel-connected cells. With the help of a developed equivalent circuit model and the results of the test series two major system parameters, the ohmic resistance of a cell during thermal runaway R tr and the resistance post thermal runaway R ptr are extracted for the test set-up. A further developed equivalent circuit model and its analytical description are presented and illustrate the great impact of R ptr on the overall discharged capacity. According to the model, cells with a capacity of no more than C cell = 10–15 Ah and a parallel-connection of 24 cells show the most potential to discharge a significant amount. Full article
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Open AccessArticle
Low Reversible Capacity of Nitridated Titanium Electrical Terminals
Received: 29 November 2018 / Revised: 13 January 2019 / Accepted: 22 January 2019 / Published: 29 January 2019
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Abstract
The currently preferred manufacturing method for Lithium-ion battery (LIB) electrodes is via the slurry route. While such an approach is appealing, the complexity of the electrode layers containing the active materials, conductivity helpers, and binders, has hampered detailed investigations of the active materials. [...] Read more.
The currently preferred manufacturing method for Lithium-ion battery (LIB) electrodes is via the slurry route. While such an approach is appealing, the complexity of the electrode layers containing the active materials, conductivity helpers, and binders, has hampered detailed investigations of the active materials. As an alternative, an active material can be deposited as a thin film on a planar substrate, which enables a more robust and detailed analysis. However, due to the small areal capacity of nanometric thin films, the electrochemical activity of the cell casing must be negligible or at least well determined. We reported on the capacity and the differential capacity metrics of several materials used in the construction of the electrical terminals in LIBs. Among these materials, Ti was revealed to have the minimum reversible capacity for lithium-ion storage. The mechanical and electrochemical properties of the Ti–based materials were further improved through surface nitridation with thermal treatment in an ammonia-rich atmosphere. The nitridated Ti electrical terminal achieved a reversible capacity that was at least fifteen times lower than that of stainless steel, with a featureless differential capacity representation creating quasi-ideal experimental conditions for a detailed investigation of electroactive thin films. Full article
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Open AccessArticle
Degradation Phenomena of Bismuth-Modified Felt Electrodes in VRFB Studied by Electrochemical Impedance Spectroscopy
Received: 13 November 2018 / Revised: 9 December 2018 / Accepted: 17 January 2019 / Published: 23 January 2019
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Abstract
The performance of all-V redox flow batteries (VRFB) will decrease when they are exposed to dynamic electrochemical cycling, but also when they are in prolonged contact with the acidic electrolyte. These phenomena are especially severe at the negative side, where the parasitic hydrogen [...] Read more.
The performance of all-V redox flow batteries (VRFB) will decrease when they are exposed to dynamic electrochemical cycling, but also when they are in prolonged contact with the acidic electrolyte. These phenomena are especially severe at the negative side, where the parasitic hydrogen evolution reaction (HER) will be increasingly favored over the reduction of V(III) with ongoing degradation of the carbon felt electrode. Bismuth, either added to the electrolyte or deposited onto the felt, has been reported to suppress the HER and therefore to enhance the kinetics of the V(II)/V(III) redox reaction. This study is the first to investigate degradation effects on bismuth-modified electrodes in the negative half-cell of a VRFB. By means of a simple impregnation method, a commercially available carbon felt was decorated with Bi 2 O 3 , which is supposedly present as Bi(0) under the working conditions at the negative side. Modified and unmodified felts were characterized electrochemically using cyclic voltammetry (CV) and electrochemical impedance spectroscopy (EIS) in a three-electrode setup. Surface morphology of the electrodes and composition of the negative half-cell electrolyte were probed using scanning electron microscopy (SEM) and X-ray fluorescence spectroscopy (TXRF), respectively. This was done before and after the electrodes were subjected to 50 charge-discharge cycles in a battery test bench. Our results suggest that not only the bismuth catalyst is dissolved from the electrode during battery operation, but also that the presence of bismuth in the system has a strong accelerating effect on electrode degradation. Full article
(This article belongs to the Special Issue Vanadium Redox Flow Battery and Its Applications)
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Open AccessArticle
Mechanism of Ionic Impedance Growth for Palladium-Containing CNT Electrodes in Lithium-Oxygen Battery Electrodes and Its Contribution to Battery Failure
Received: 30 November 2018 / Revised: 7 January 2019 / Accepted: 22 January 2019 / Published: 23 January 2019
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Abstract
The electrochemical oxygen evolution reaction (OER) and oxygen reduction reaction (ORR) and on CNT (carbon nanotube) cathode with a palladium catalyst, palladium-coated CNT (PC-CNT), and palladium-filled CNT (PF-CNT) are assessed in an ether-based electrolyte solution in order to fabricate a lithium-oxygen battery with [...] Read more.
The electrochemical oxygen evolution reaction (OER) and oxygen reduction reaction (ORR) and on CNT (carbon nanotube) cathode with a palladium catalyst, palladium-coated CNT (PC-CNT), and palladium-filled CNT (PF-CNT) are assessed in an ether-based electrolyte solution in order to fabricate a lithium-oxygen battery with high specific energy. The electrochemical properties of the CNT cathodes were studied using electrochemical impedance spectroscopy (EIS). Palladium-filled cathodes displayed better performance as compared to the palladium-coated ones due to the shielding of the catalysts. The mechanism of the improvement was associated to the reduction of the rate of resistances growth in the batteries, especially the ionic resistances in the electrolyte and electrodes. The scanning electron microscopy (SEM) and spectroscopy were used to analyze the products of the reaction that were adsorbed on the electrode surface of the battery, which was fabricated using palladium-coated and palladium-filled CNTs as cathodes and an ether-based electrolyte. Full article
(This article belongs to the Special Issue Recent Advances in Post-Lithium Ion Batteries)
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Open AccessArticle
Design and Analysis of the Use of Re-Purposed Electric Vehicle Batteries for Stationary Energy Storage in Canada
Received: 5 December 2018 / Revised: 10 January 2019 / Accepted: 15 January 2019 / Published: 19 January 2019
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Abstract
Vehicle electrification increases the fuel efficiency of the transportation sector while lowering emissions. Eventually, however, electric vehicle batteries will reach their end-of-life (EOL) point, when the capacity of the battery is insufficient for operating a motor vehicle. At this point, the battery is [...] Read more.
Vehicle electrification increases the fuel efficiency of the transportation sector while lowering emissions. Eventually, however, electric vehicle batteries will reach their end-of-life (EOL) point, when the capacity of the battery is insufficient for operating a motor vehicle. At this point, the battery is typically removed for recycling. This treatment of the electric vehicle battery is not efficient, as there is still a high enough storage capacity that they can be used in various non-vehicular uses. Unfortunately, there are numerous barriers limiting the adoption of re-used electric vehicle batteries. Herein, the authors analyze the limitations and current codes and standards that affect re-purposed battery pack designs. Utilizing these requirements, a bench test setup is designed and built, to determine feasibility of a repurposed electric vehicle (EV) battery for stationary energy storage in Canada. Full article
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Open AccessArticle
Vanadium Electrolyte for All-Vanadium Redox-Flow Batteries: The Effect of the Counter Ion
Received: 17 December 2018 / Revised: 8 January 2019 / Accepted: 13 January 2019 / Published: 18 January 2019
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Abstract
In this study, 1.6 M vanadium electrolytes in the oxidation forms V(III) and V(V) were prepared from V(IV) in sulfuric (4.7 M total sulphate), V(IV) in hydrochloric (6.1 M total chloride) acids, as well as from 1:1 mol mixture of V(III) and V(IV) [...] Read more.
In this study, 1.6 M vanadium electrolytes in the oxidation forms V(III) and V(V) were prepared from V(IV) in sulfuric (4.7 M total sulphate), V(IV) in hydrochloric (6.1 M total chloride) acids, as well as from 1:1 mol mixture of V(III) and V(IV) (denoted as V3.5+) in hydrochloric (7.6 M total chloride) acid. These electrolyte solutions were investigated in terms of performance in vanadium redox flow battery (VRFB). The half-wave potentials of the V(III)/V(II) and V(V)/V(IV) couples, determined by cyclic voltammetry, and the electronic spectra of V(III) and V(IV) electrolyte samples, are discussed to reveal the effect of electrolyte matrix on charge-discharge behavior of a 40 cm2 cell operated with 1.6 M V3.5+ electrolytes in sulfuric and hydrochloric acids. Provided that the total vanadium concentration and the conductivity of electrolytes are comparable for both acids, respective energy efficiencies of 77% and 72–75% were attained at a current density of 50 mA∙cm−2. All electrolytes in the oxidation state V(V) were examined for chemical stability at room temperature and +45 °C by titrimetric determination of the molar ratio V(V):V(IV) and total vanadium concentration. Full article
(This article belongs to the Special Issue Redox Flow Batteries for Large-Scale Energy Storage)
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Open AccessReview
Critical Review of the Use of Reference Electrodes in Li-Ion Batteries: A Diagnostic Perspective
Received: 26 November 2018 / Revised: 9 January 2019 / Accepted: 14 January 2019 / Published: 18 January 2019
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Abstract
Use of a reference electrode (RE) in Li-ion batteries (LIBs) aims to enable quantitative evaluation of various electrochemical aspects of operation such as: (i) the distinct contribution of each cell component to the overall battery performance, (ii) correct interpretation of current and voltage [...] Read more.
Use of a reference electrode (RE) in Li-ion batteries (LIBs) aims to enable quantitative evaluation of various electrochemical aspects of operation such as: (i) the distinct contribution of each cell component to the overall battery performance, (ii) correct interpretation of current and voltage data with respect to the components, and (iii) the study of reaction mechanisms of individual electrodes. However, care needs to be taken to ensure the presence of the RE does not perturb the normal operation of the cell. Furthermore, if not properly controlled, geometrical and chemical features of the RE can have a significant influence on the measured response. Here, we present a comprehensive review of the range of RE types and configurations reported in the literature, with a focus on critical aspects such as electrochemical methods of analysis, cell geometry, and chemical composition of the RE and influence of the electrolyte. Some of the more controversial issues reported in the literature are highlighted and the benefits and drawbacks of the use of REs as an in situ diagnostic tool in LIBs are discussed. Full article
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Open AccessArticle
Silicon/Mesoporous Carbon (Si/MC) Derived from Phenolic Resin for High Energy Anode Materials for Li-ion Batteries: Role of HF Etching and Vinylene Carbonate (VC) Additive
Received: 30 November 2018 / Revised: 7 January 2019 / Accepted: 14 January 2019 / Published: 16 January 2019
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Abstract
Silicon/mesoporous carbon (Si/MC) composites with optimum Si content, in which the volumetric energy density would be maximized, while volume changes would be minimized, have been developed. The composites were prepared by dispersing Si nanoparticles in a phenolic resin as a carbon source, subsequent [...] Read more.
Silicon/mesoporous carbon (Si/MC) composites with optimum Si content, in which the volumetric energy density would be maximized, while volume changes would be minimized, have been developed. The composites were prepared by dispersing Si nanoparticles in a phenolic resin as a carbon source, subsequent carbonization, and etching with hydrofluoric acid (HF). Special attention was paid to understanding the role of HF etching as post-treatment to provide additional void spaces in the composites. The etching process was shown to reduce the SiO2 native layer on the Si nanoparticles, resulting in increased porosity in comparison to the non-etched composite material. For cell optimization, vinylene carbonate (VC) was employed as an electrolyte additive to build a stable solid electrolyte interphase (SEI) layer on the electrode. The composition of the SEI layer on Si/MC electrodes, cycled with and without VC-containing electrolytes for several cycles, was then comprehensively investigated by using ex-situ XPS. The SEI layers on the electrodes working with VC-containing electrolyte were more stable than those in configurations without VC; this explains why our sample with VC exhibits lower irreversible capacity losses after several cycles. The optimized Si/MC composites exhibit a reversible capacity of ~800 mAhg−1 with an average coulombic efficiency of ~99 % over 400 cycles at C/10. Full article
(This article belongs to the Special Issue Silicon for High-Energy Lithium Ion Batteries)
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Open AccessArticle
Exploring the Economic Potential of Sodium-Ion Batteries
Received: 30 November 2018 / Revised: 4 January 2019 / Accepted: 9 January 2019 / Published: 16 January 2019
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Abstract
Sodium-ion batteries (SIBs) are a recent development being promoted repeatedly as an economically promising alternative to lithium-ion batteries (LIBs). However, only one detailed study about material costs has yet been published for this battery type. This paper presents the first detailed economic assessment [...] Read more.
Sodium-ion batteries (SIBs) are a recent development being promoted repeatedly as an economically promising alternative to lithium-ion batteries (LIBs). However, only one detailed study about material costs has yet been published for this battery type. This paper presents the first detailed economic assessment of 18,650-type SIB cells with a layered oxide cathode and a hard carbon anode, based on existing datasheets for pre-commercial battery cells. The results are compared with those of competing LIB cells, that is, with lithium-nickel-manganese-cobalt-oxide cathodes (NMC) and with lithium-iron-phosphate cathodes (LFP). A sensitivity analysis further evaluates the influence of varying raw material prices on the results. For the SIB, a cell price of 223 €/kWh is obtained, compared to 229 €/kWh for the LFP and 168 €/kWh for the NMC batteries. The main contributor to the price of the SIB cells are the material costs, above all the cathode and anode active materials. For this reason, the amount of cathode active material (e.g., coating thickness) in addition to potential fluctuations in the raw material prices have a considerable effect on the price per kWh of storage capacity. Regarding the anode, the precursor material costs have a significant influence on the hard carbon cost, and thus on the final price of the SIB cell. Organic wastes and fossil coke precursor materials have the potential of yielding hard carbon at very competitive costs. In addition, cost reductions in comparison with LIBs are achieved for the current collectors, since SIBs also allow the use of aluminum instead of copper on the anode side. For the electrolyte, the substitution of lithium with sodium leads to only a marginal cost decrease from 16.1 to 15.8 €/L, hardly noticeable in the final cell price. On the other hand, the achievable energy density is fundamental. While it seems difficult to achieve the same price per kWh as high energy density NMC LIBs, the SIB could be a promising substitute for LFP cells in stationary applications, if it also becomes competitive with LFP cells in terms of safety and cycle life. Full article
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Open AccessArticle
Real-Time Performance Optimization and Diagnostics during Long-Term Operation of a Solid Anolyte Microbial Fuel Cell Biobattery
Received: 15 August 2018 / Revised: 12 December 2018 / Accepted: 25 December 2018 / Published: 15 January 2019
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Abstract
This study describes a novel approach for real-time energy harvesting and performance diagnostics of a solid anolyte microbial fuel cell (SA-MFC) representing a prototype smart biobattery. The biobattery power output was maximized in real time by combining intermittent power generation with a Perturbation-and-Observation [...] Read more.
This study describes a novel approach for real-time energy harvesting and performance diagnostics of a solid anolyte microbial fuel cell (SA-MFC) representing a prototype smart biobattery. The biobattery power output was maximized in real time by combining intermittent power generation with a Perturbation-and-Observation algorithm for maximum power point tracking. The proposed approach was validated by operating the biobattery under a broad range of environmental conditions affecting power production, such as temperature (4–25 °C), NaCl concentration (up to 2 g L−1), and carbon source concentration. Real-time biobattery performance diagnostics was achieved by estimating key internal parameters (resistance, capacitance, open circuit voltage) using an equivalent electrical circuit model. The real time optimization approach ensured maximum power production during 388 days of biobattery operation under varying environmental conditions, thus confirming the feasibility of biobattery application for powering small electronic devices in field applications. Full article
(This article belongs to the Special Issue Bio-Batteries)
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Open AccessArticle
Characterizing Large-Scale, Electric-Vehicle Lithium Ion Transportation Batteries for Secondary Uses in Grid Applications
Received: 28 November 2018 / Revised: 14 December 2018 / Accepted: 9 January 2019 / Published: 12 January 2019
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Abstract
Lithium ion battery modules have significant capacity left after their useful life in transportation applications. This empirical study successfully tested the used modules in secondary grid applications in laboratory conditions. The selection of the secondary application was based on the construction features of [...] Read more.
Lithium ion battery modules have significant capacity left after their useful life in transportation applications. This empirical study successfully tested the used modules in secondary grid applications in laboratory conditions. The selection of the secondary application was based on the construction features of the modules and the growing need for storage in grid operations. Description of the laboratory setup is provided in the context of a critical practical constraint where the battery management system and the usage and health history are not available to the secondary battery integrator. Charge and discharge profiles were developed based upon applications for peak shaving and firming renewables. Techno-economic analysis was focused on peak shaving at the utility level, considering a growing need for an affordable and environmentally friendly replacement to the traditional solutions based on environmentally costly peaker plants. The analysis showed strong evidence that near-term and future storage markets will be characterized by a large mismatch between the demand and supply of reused batteries from automotive primary applications for peak-shaving purposes in the generation side. The paper includes a discussion on successful adoption of cascaded use of batteries and their potential to reduce both economic and environmental cost of peak shaving. Full article
(This article belongs to the Special Issue Sustainable Lithium Ion Batteries: From Production to Recycling)
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Open AccessEditorial
Acknowledgement to Reviewers of Batteries in 2018
Published: 11 January 2019
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Abstract
Rigorous peer-review is the corner-stone of high-quality academic publishing [...] Full article
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