New Use of LiMn2O4 Batteries Under Renewable Overvoltage as Thermal Power Generators: Energy and Exergy Analysis

New use of Li/MnO2 batteries under renewable overvoltage as thermal power generators: energy and exergy analysis Juan Carlos Ríos-Fernández 1*, Celestino González Nicieza2, M. Inmaculada Álvarez Fernández2 1 University of Oviedo, Department of Energy, Polytechnic School of Engineering of Gijón, 33203 Gijón (Asturias). Spain 2 University of Oviedo, Department of Exploitation and Prospecting Mines, Polytechnic School of Mieres, 33600 Mieres (Asturias). Spain * Corresponding author E-mail address: [email protected] (Juan Carlos Ríos-Fernández) This preprint research paper has not been peer reviewed. Electronic copy available at: https://ssrn.com/abstract=4592752 Preprint not peer reviewed Abstract Lithium-ion batteries are widely used to store electrical energy for applications such as solar power, consumer electronics or automotive. However, once their electrical energy storage capacity is exhausted, they constitute hazardous waste that also has a high environmental impact and whose recycling process consumes large amounts of energy. In this study, a thermodynamic and heat transfer study was conducted on lithium-ion batteries subjected to electrical overvoltage to quantify the thermal energy generated. Thus, a detailed mathematical model of a renewable electric power surge process applied to a lithium manganese oxide cathode battery was developed for use as a renewable thermal energy source. Furthermore, the model was evaluated using experimental data under various overvoltage and battery charging conditions. As a result, energy and exergy analysis was used to determine the configuration that provides the highest energy and exergy efficiency or performance for both new and used batteries. Thus, the maximum energy efficiency value was 81% for new batteries and 4% for used batteries, whereas the exergy efficiency reached a maximum value of 5% for new batteries and 1.6% for used batteries. These results allow lithium-ion batteries to be considered as thermal energy sources, opening the possibility of new uses, valorising the waste generated at the end of the current useful life of these devices, and reducing their carbon footprint. Keywords Energy and exergetic analysis; lithium-ion batteries; MnO2 cathode; energy storage; resource saving; SDG 12. Highlights Energy and exergetic analysis with experimental validation of a lithium-ion battery subjected to overvoltage. Calculation of energy and exergy efficiency as well as the maximum available work of a lithium-ion battery used as a thermal energy source. Thermal power generation in a lithium-ion battery using electrical energy from a renewable source. Reuse of spent lithium-ion batteries as sources of thermal energy. Abbreviations BTMS: Battery thermal management system. COP: Coefficient of performance. EVs: Electric vehicles. HEVs: Hybrid electric vehicles. PCM: Phase change materials. SDG: Sustainable development goal. This preprint research paper has not been peer reviewed. Electronic copy available at: https://ssrn.com/abstract=4592752 Preprint not peer reviewed 1. Introduction Lithium-ion batteries have become an essential element of life today, storing energy and providing portable and rechargeable power to electronic devices as well as pure electric vehicles (EVs) and hybrid electric vehicles (HEVs). The configuration of lithium-ion batteries is typical of more classical electrochemical batteries [1]. They are made up of a container, two electrodes (anode and cathode), a liquid or solid electrolyte material, and a permeable membrane that allows ionic movement between the electrodes and prevents short circuits between them. They constitute the basic components of a cell. Thus, current is produced by the oxidation and reduction reactions between the electrolyte and the electrodes of the cell. The electrolyte next to the electrode releases electrons (it is oxidised) when the battery is connected to a load. While this occurs, the process is completed when the ions next to the other electrode accept the electrons (it is reduced). On the other hand, this procedure is reversed when the batteries are charged. There are several lithiumion batteries on the market that vary in the material used for their cathode, with iron phosphate, cobalt oxide, and manganese oxide being the most common materials [2]. Iron phosphate batteries have lower energy densities than those using other cathode materials. This results in lower voltages, making them unsuitable for certain applications such as high-performance automotive [3]. Cobalt oxide cathodes have several drawbacks, including toxicity and high cost due to the scarcity of cobalt [4]. However, manganese oxide cathode batteries are very interesting due to their non-toxic, safe, low cost due to the abundance of manganese, good high-rate capability as well as low-rate capability, high performance, and excellent shelf life [5], [6]. Thus, one of the most popular cathode materials in primary Li-ion batteries is MnO2, and its usage in secondary Li-ion batteries has also been researched [7], [8], [9], [10], [11]. Therefore, the analysis performed in this study will focus on a primary Li/MnO2 battery. Figure 1 shows the operating diagram of a Li/MnO2 battery, where the direction of circulation of electrons (direction of the electric current) and lithium ions is represented in the charging and discharging process of the battery. Fig. 1. Scheme of Li/MnO2 battery operation During battery discharge, which is the process that allows the battery to supply power to an external device, electrons flow from the anode to the cathode through an external circuit, thus generating electrical current. Lithium ions also flow from anode to cathode through the electrolyte. During the charging process, the direction of the cycle is reversed. That is, the circulation of electrons and Li+ ions occurs from the cathode to the anode, and the chemical reactions also occur in the opposite direction. During the charging process, the lithium ions migrate to the negative electrode, where they react with the electrons to intercalate in the solid particles of manganese oxide, forming LiMn2O4 molecules. Furthermore, during this process, each LiC6 molecule on the anode breaks down into pure carbon, a Li+ ion, and an electron (e-). Thus, the reactions that take place inside a Li/MnO2 cell or battery are as follows [12]: This preprint research paper has not been peer reviewed. Electronic copy available at: https://ssrn.com/abstract=4592752 Preprint not peer reviewed Reaction at the positive electrode (cathode) LiC6 (s) ↔ 6C (graphite) + Li+ + e- (1) Reaction at the negative electrode (anode) Mn2O4 (s) + Li+ + e- ↔ LiMn2O4 (s) (2) Considering the sense of the reactions during the charge and discharge of the battery the following: ← Charge → Discharge Despite all the advantages that lithium batteries have, at the end of their useful life, they become a waste that generates a large amount of energy and economic investment to recover part of its components [13], [14]. To assess this potential waste and reduce the carbon footprint of these batteries, this research was conducted to study the thermal behaviour of lithium batteries and to describe the mathematical and physicochemical models for the use of the thermal energy generated in these devices. With the increasing use of renewable energies and other technologies that use storage batteries [15], [16], [17], it is necessary to develop new efficient technological processes that reduce their environmental impact. Likewise, achieving sustainable development based on the use of renewable energy and the development of energy efficiency is a necessity within the economic model of the European Union (EU) [18], [19]. This growing global concern about climate change caused by greenhouse gases (GHG) has recently translated into increasing regulations regarding polluting emissions and waste generation [20], [21]. Thus, the new European Regulation [22] aims to promote a circular economy by regulating cells and batteries throughout their entire life cycle. In this context, this research showed that lithium batteries could be used to store energy in the form of heat, to be used later or directly, by converting electrical energy into thermal energy. The generation of thermal energy in these devices is based on the principle of conversion of the chemical energy released in the chemical reactions caused in the battery when it is subjected to an electric current. To achieve this goal, the batteries were subjected to power overvoltage that activated the chemical processes of oxidation and reduction and generated heating of the material from which the battery was made up by the Joule effect. Therefore, diagnosing the amount of thermal energy available in these batteries, to be used later and generate work, and quantifying the maximum useful work available, was of great interest. This interest was increased by using a photovoltaic solar energy installation as a source of electrical energy. Energy of a totally renewable nature and without associated polluting emissions. As a result, with the combination of electrical energy from a renewable source and lithium batteries, it was possible to generate clean thermal energy. This process was especially interesting when the batteries used ended their useful life as electrical energy stores, going from being a waste product to an energetically and economically recoverable product. Figure 2 represents the process of harnessing electrical energy from a renewable source to obtain thermal energy and useful work through lithium batteries. This preprint research paper has not been peer reviewed. Electronic copy available at: https://ssrn.com/abstract=4592752 Preprint not peer reviewed Fig. 2. Scheme of the thermal energy generation process in lithium batteries and its use to generate useful work According to the analysis of the thermal energy generated by lithium batteries, various studies have been conducted, but all of them minimize the impact of this energy on the operation of the battery as an electrical energy store. Thus, in 2020, Lamrani et al. presented a thermal model of lithium battery simulating phase transition processes in battery materials using a heat source [23]. Following a similar line of research, in 2022 Wang et al. developed another numerical model based on the comparison of phase change materials for thermal management of hybrid batteries [24]. Using nanomaterials, Anqi et al. [25] and de Bais et al. developed a battery thermal management system (BTMS) [26]. In 2015, Ling et al. studied heat buildup in lithium batteries by analysing a combined system of phase change materials (PCM) and forced air convection [27]. In this last case, the investigation was not interested in the use of this thermal energy generated in the batteries, but rather tried to find a solution to the overheating of batteries. In 2018, Hussain et al. analysed the thermal management of these batteries using different materials to avoid heating during use [28]. In addition, the thermal energy generated was studied in 2016 and 2022 to extend the life of lithium batteries in EVs and HEVs [29], [30]. The study performed in this article focused on lithium batteries with a manganese oxide cathode, which is currently one of the most widely used cathodes. However, it allows us to define the process of calculating the thermodynamic characteristics of any other type of lithium battery cathode chemistry. Thus, a mathematical model was created to quantify the amount of thermal energy that can be obtained from a lithium battery subjected to overvoltage. In addition, a mathematical model was developed to calculate the amount of entropy, the destroyed exergy or irreversibility, and the maximum or reversible work that can be obtained during the process. The uses of these thermal energy generators into which lithium batteries are converted were not analysed in this research but are expected to be very diverse. Among others, lithium batteries could be used as heat sources or to use the generated thermal energy for mechanical work. The novelties and main contributions of this work are as follows: 1. For the first time, a thermodynamic and heat transfer study was conducted on lithium-ion batteries subjected to power overvoltage to quantify the thermal energy generated. 2. A detailed mathematical model of an overvoltage process using renewable electrical energy in a lithium manganese oxide cathode battery as a thermal energy source was developed. In addition, the model was evaluated using experimental data under various conditions of temperature, battery combinations, thermal insulation, and overvoltage. This preprint research paper has not been peer reviewed. Electronic copy available at: https://ssrn.com/abstract=4592752 Preprint not peer reviewed 3. Exergy and energy analysis was used to determine the configuration that provided the highest energy and exergy efficiency or performance in both new and used batteries. For this purpose, different electrical and thermal configurations of the battery groups were analysed. 4. An effective energy and exergetic calculation method was provided for the consideration of lithium-ion batteries as sources of thermal energy to increase the energy efficiency of these energy storage devices and reduce the polluting emissions generated by the used batteries. 2. Dynamic model and experimental installation 2.1. Description of model and experimental installation The battery model used in the tests was a lithium battery with a manganese oxide cathode, a charge capacity of 800 mAh and a voltage of 3 V. To supply electrical overvoltage to the battery, its poles or terminals were connected to a power source. Electrical energy was obtained from a photovoltaic solar installation located on the roof of the laboratory. Subsequently, this energy from a renewable source was used to supply, through an electrical power source, different overvoltage to the lithium battery. For the measurements, thermocouple K-type temperature measuring devices with protective metal sheath (0° to +1100°C / -180° to -1300°C) were connected to the battery surface, data were recorded using a Cometsystem datalogger model MS6D and downloaded via the Monitoring Systems MS series software. In this way, the surface temperatures of the battery under overvoltage for 290 minutes were obtained. Ambient temperatures and atmospheric pressures were also recorded in the different tests. Figure 3 shows the experimental facility. The mathematical model obtained for a single battery was applied to different tests with different battery arrangements as follows. Fig. 3 Experimental facility 2.2. Model validation When the battery was subjected to an electric current, its surface heated steadily over time until it reached a maximum value. Simultaneously, heat transfer from the battery to the surroundings was generated. This consideration was used to validate the proposed model by calculating the heat released by the battery during this period of temperature loss. The heat was calculated in two ways, and the results were compared. The first way is through an energy balance of the overvoltage process in the battery. The second method involves applying a formula that relates the amount of heat exchanged by a substance of a given mass and specific heat and generates a given temperature variation. The energy model is detailed in point 4, and the formula relating the heat given off to the specific heat of the substance, which is a known and validated equation in classical thermodynamics, is as follows: 𝑄 = 𝑚 · 𝑐 · ∆ 𝑇 (3) This preprint research paper has not been peer reviewed. Electronic copy available at: https://ssrn.com/abstract=4592752 Preprint not peer reviewed Where: Q is the heat exchanged in J. m is the mass of the substance in kg. c is the specific heat of the substance in 𝐽 𝑘𝑔 · 𝐾 . ∆ 𝑇 is the temperature variation experienced in the substance in K or ºC. 2.3. Dynamic tests description 2.3.1. Test 1 by applying a voltage of 5 V to a charged battery A single charged lithium battery (3.28 V) was tested at a constant voltage of 5 V for 100 min. Under these conditions, and keeping the ambient temperature constant at 20 ºC, the outside temperature of the battery was measured. The maximum temperature was obtained at 9.1 min and was 82.20 ºC. This temperature was reached rapidly by heat transfer from the interior of the battery to the surface. Once this maximum peak was reached, there was a rapid decrease in the surface temperature. This was due to the temperature loss caused by a constant flow of heat to the environment and the end of the chemical reactions that occurred during the loading process, as reflected in point 1. With a small temperature rise reached shortly after 20 min of testing, the temperature starts to slowly decrease to a constant value between 50 and 60 degrees Celsius. On the other hand, two gas leaks occurred at the cathode. The first leak occurred after less than 1 minute and the second one after 9 minutes of testing. 2.3.2. Test 2 by applying a voltage of 10 V to a charged battery Once test 1 was completed, and without interruption in the supply of electrical current to the battery, a constant voltage of 10 V was applied for 190 min. As in the previous case, the ambient temperature was maintained at 20 °C, and the outside temperature of the battery was measured. The maximum temperature was obtained at 2.03 min and was 85.21 ºC. As in test 1, heat transfer from the inside of the battery to the surface rapidly reached this temperature. The temperature drops after reaching this maximum peak were also rapid, and on this occasion, there was no temperature recovery during this process of temperature decrease. During the process of temperature increase, the current intensity also increased, reaching a maximum peak of 1.29 A at 0.92 min after starting with a 10 V overvoltage. Figures 4 and 5 represent the data obtained from tests 1 and 2. The blue curve indicates the variations in the intensity of the electrical current as a function of time, and the orange curve shows the variation in the temperature on the surface of the battery as a function of time. This preprint research paper has not been peer reviewed. Electronic copy available at: https://ssrn.com/abstract=4592752 Preprint not peer reviewed Fig. 4. Effect of a 5 V overvoltage applied to a Li/MnO2 charged battery for 100 minutes. Diagram Temperature vs. Time Fig. 5. Effect of a 10 V overvoltage applied to a Li/MnO2 charged battery for 190 minutes. Diagram Temperature vs. Time 2.3.3. Test 3 by applying a voltage of 5 V to a discharged battery The same lithium battery used in the previous tests was tested at a constant voltage of 5 V for 144 minutes. In this test, the battery was discharged at a polymer voltage of 1.85 V. Under these conditions and keeping the ambient temperature constant at 20 ºC, the outside temperature of the battery was measured. During the test, practically no current flowed through the battery. The surface temperature of the battery barely increased by 2 °C and subsequently stabilized, and the current dropped to 0 A, as shown in Figure 6. This preprint research paper has not been peer reviewed. Electronic copy available at: https://ssrn.com/abstract=4592752 Preprint not peer reviewed Fig. 6. Effect of a 5 V overvoltage applied to a Li/MnO2 discharged battery for 144 minutes. Diagram Temperature vs. Time 2.3.4. Test 4 by applying a voltage of 10 V to a discharged battery At minute 144 of test 3, the source voltage was increased to 10 V. No current continued to flow through the battery despite the source voltage being increased. However, at minute 151, a current of 0.01 A started to flow and the battery temperature slowly increased to a maximum of 47.72 °C. It is shown in Figure 7. Fig. 7. Effect of a 10 V overvoltage applied to a Li/MnO2 discharged battery for 460 minutes. Diagram Temperature vs. Time This preprint research paper has not been peer reviewed. Electronic copy available at: https://ssrn.com/abstract=4592752 Preprint not peer reviewed 8. Conclusion The feasibility of a method for calculating the thermal energy, entropy generated, exergy destroyed, and maximum work generated by a Li/MnO2 battery when subjected to an electric current was demonstrated and experimentally validated. Two different configurations were analysed (new or charged battery and discharged battery) under two overvoltage conditions (5 V and 10 V) generated on the battery using electrical energy from a renewable source. The calculation method could be applied to different types of batteries with different cathode materials, provided that the thermal characteristics of the different chemical reactions taking place in the overvoltage processes were considered. Furthermore, it was found that doubling the electrical voltage applied to the battery (from 5 V to 10 V) increased the maximum work generated by 110.4%, the exergy destroyed by 109.7%, the entropy generated by 99.5% and the thermal energy generated by 56.5%. Therefore, this voltage increase can be considered useful in the case of trying to achieve the maximum work that the battery can provide or in the case of needing higher thermal energies than those achieved with lower current voltages. However, the heat gain generated was reduced to just over 50% compared to that achieved with 5 V and was therefore not as interesting. On the other hand, after a short period of time and once the maximum temperatures had been reached, the temperature on the outside of the new battery subjected to an external electric current was approximately 50-60 °C for both 5 V and 10 V. In the case of the used battery, the temperature increase was negligible at 5 V overvoltage and reached values below 50 °C at 10 V. The energy and exergetic efficiency of the process in the new battery were lower at 10 V than at 5 V. Both values decreased significantly in the case of the discharged battery. This situation makes it uninteresting to subject the battery to higher voltages. However, in the discharged battery, the 10 V voltage was necessary to generate thermal energy increases with temperature rises up to 28 °C, while 5 V was not sufficient. Thus, the maximum energy efficiency value was 81% for new batteries and 4% for used batteries, whereas the exergy efficiency reached a maximum value of 5% for new batteries and 1.6% for used batteries. These results would meet the Sustainable Development Goal (SDG) 12 of the 2030 Agenda for Sustainable Development adopted by the United Nations. SDG 12 targets sustainable production and consumption. This goal can be achieved by reducing waste generation through recycling and reuse. Thus, the feasibility of recycling and reuse of used or new lithium batteries was demonstrated through the thermal recovery discussed in this article. Consequently, and according to the 2030 Agenda, the pollutant emissions associated with lithium batteries would be reduced. Declaration of Competing Interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper. References [1] Scrosati, B. (2011). History of lithium batteries. J. of Solid State Electrochem., 15(7-8), 16231630. [2] Wu, J., Shen, L., Zhang, Z., Liu, G., Wang, Z., Zhou, D., Wan, H. & Yao, X. (2021). Allsolid-state lithium batteries with sulfide electrolytes and oxide cathodes. Electrochem. Energy Rev., 4, 101-135. This preprint research paper has not been peer reviewed. 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Electronic copy available at: https://ssrn.com/abstract=4592752 Preprint not peer reviewed