Lithium-ion battery

What lies ahead for the future of LIBs and what can we do?

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Having discussed so much about the negative impacts and pollution lithium-ion batteries (LIBs) cause, can we really just do away with LIBs altogether? And what do we replace it if we were ever to get rid of LIBs altogether? To what extent can we blame the increasing pollution by LIBs on the decreasing cost of LIBs? These are all unanswered questions that remain difficult to answer. 

While LIB and the process of manufacturing and disposing of them can be very polluting, we continue relying heavily on them. Their close relationship with renewable energy makes them even more sticky issue. The decreasing cost of LIBs has also undeniably played an important role in allowing the implementation of renewable green energy to become more economically feasible than ever by reducing their margins between fossil fuel-produced energy (Gielen et al., 2019). Global greenhouse gas emissions can potentially decrease significantly once renewables reach grid parity. 

Do we attempt to reduce global greenhouse gas (GHG) emissions by moving towards renewables instead while knowingly producing more LIBs or reduce LIB-related pollution by continue sticking with fossil fuels? For now, as global warming and climate change is the most pressing environmental issue globally discussed, reducing GHGs will take priority (United Nations, n.d.). However, what will happen when LIB-related pollution starts impacting the global environment negatively we will never know. Will it become the next plastic? It has brought us so much convenience by allowing us to store energy efficiently. Yet we still do not have a perfect way of discarding them when they are no longer deemed useful to us. 

Moreover, will there be a new energy storage technology that will emerge as economically competitive and greener than LIBs? Even if there is, constructing such an energy storage system will require minerals and resources which are polluting in their own ways.

Nevertheless, these blogs are not here to reject LIBs altogether. I still do believe that they are important for the future of clean energy. The main message I hope to get across is that as long as our demand for energy continues to rise, no matter how ‘clean’ our energy becomes, it will never become completely ‘green’. While we cannot stop using energy and electricity altogether, we should be aware of the impacts these ‘clean’ energy has and never stop looking for ways to reduce their impacts (United Nations, n.d.).

What will happen to the future of LIBs, only time will tell. For now, reducing our energy use is a simple way to start protecting our environment. 

Reference List

Gielen, D., Boshell, F., Saygin, D., Bazilian, M., Wagner, N. L., & Gorini, R. (2019). The role of renewable energy in the global energy transformation. Energy Strategy Reviews, 24, 38–50. https://doi.org/10.1016/j.esr.2019.01.006 

United Nations. (n.d.). Li-ion batteries – powering the fossil-fuel-free economy | United Nations. https://www.un.org/en/Frontier-Technologies-Issues

Lithium, Lithium Pollution, Lithium-ion battery

Problems associated with recycling of LIBs

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Despite having discussed all the environmental and social impacts of lithium-ion batteries (LIBs), we cannot ignore the fact that the demand for LIBs will continue to rise due to their importance in the clean energy sector. To reduce pollution in a trend that cannot be reversed, many would think of the 3Rs, reduce, reuse and recycle. However, as briefly mentioned in the first few blogs, implementing the 3Rs have its own set of problems. As the demand for LIBs is expected to grow exponentially, reducing the use of LIBs is not very feasible now. Hence, this blog will mainly explore the challenges related to reusing and recycling LIBs. 

Reusing LIBs:

Reusing refurbished or repurposed LIBs is not a new practice. LIBs have long been reused for less demanding purposes at the end of their first end-of-life (Beaudet et al., 2020). This is because most batteries will still have a charge capacity of up to 80% at their first end of life (Beaudet et al., 2020).Through reusing these LIBs, demand for new LIBs which are much more polluting due to pollution related to production decreases. 

However, the decreasing production cost of LIBs especially in recent years has made reusing LIBs increasingly less economically viable (Beaudet et al., 2020; Ziegler et al., 2021; Mauler et al., 2021). According to Ziegler et al. (2021), LIB technology has decreased by up to 97% since they were first commercially used 30 years ago. This exponential decrease in the cost of LIBs is closely tied to the emergence of Chinese LIB producers (Figure 1) (Wakabayashi & Fu, 2022). Along with the stagnation of the high restoration cost of LIBs, it is becoming increasingly attractive for manufacturers to choose new LIBs rather than refurbish old ones. 

Figure 1: Decrease in LIB technology over the years (Mauler et al., 2021)

Recycling LIBs: 

The recycling process of LIBs remains tedious due to the cumbersome collection and recycling process (Spector, 2022; Beaudet et al., 2020). Although governments such as the Chinese government have encouraged manufacturers to choose recycled materials for manufacturing (Wei et al., 2022), the success of these efforts is put into question. It is costly, time-consuming and troublesome for manufacturers to collect the LIBs back for disassembling and recycling (Spector, 2022; Beaudet et al., 2020). LIBs that are exported overseas will need to be shipped back to manufacturers if manufacturers do not have factories overseas which are more often than not the case. 

What about engaging a recycling firm?

While engaging a third part recycling firm may sound feasible, it is often difficult for manufacturers and recycling firms to reach an agreement due to a variety of reasons. Due to intellectual property rights and industrial secrets, manufacturers are often unwilling to share the chemical formulas of batteries with third-party recycling firms making the safe discharging of batteries an extremely difficult one (Sachan et al., 2020). Disassembling a battery without discharging often leads to explosions and fires making LIB recycling facilities particularly expensive to protect the safety of workers and ensure a safe disassembling process. 

Reference List

Beaudet, A., Larouche, F., Amouzegar, K., Bouchard, P., & Zaghib, K. (2020). Key Challenges and Opportunities for Recycling Electric Vehicle Battery Materials. Sustainability, 12(14), 5837. https://doi.org/10.3390/su12145837 

Mauler, L., Duffner, F., Zeier, W. G., & Leker, J. (2021). Battery cost forecasting: a review of methods and results with an outlook to 2050. Energy and Environmental Science, 14(9), 4712–4739. https://doi.org/10.1039/d1ee01530c 

Sachan, S., Deb, S., & Singh, S. N. (2020). Different charging infrastructures along with smart charging strategies for electric vehicles. Sustainable Cities and Society, 60, 102238. https://doi.org/10.1016/j.scs.2020.102238 

Spector, J. (2022, June 13). EV battery recycling is costly. These 5 startups could change that. Canary Media. https://www.canarymedia.com/articles/electric-vehicles/ev-battery-recycling-is-costly-these-five-startups-could-change-that 

Wakabayashi, D., & Fu, C. (2022, September 27). For China’s Auto Market, Electric Isn’t the Future. It’s the Present. The New York Times. https://www.nytimes.com/2022/09/26/business/china-electric-vehicles.html 

Wei, L., Wang, C., & Li, Y. (2022). Governance strategies for end-of-life electric vehicle battery recycling in China: A tripartite evolutionary game analysis. Frontiers in Environmental Science, 10. https://doi.org/10.3389/fenvs.2022.1071688 

Ziegler, M. S., Song, J., & Trancik, J. E. (2021). Determinants of lithium-ion battery technology cost decline. Energy and Environmental Science, 14(12), 6074–6098. https://doi.org/10.1039/d1ee01313k 

Environmental pollution, Lithium-ion battery

Carbon footprint of lithium-ion battery production

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Despite the problems lithium-ion batteries (LIBs) pose, their demand is still increasing. With the mass production of LIBs increasing globally, total greenhouse gas (GHGs) emissions from the production of LIBs are also rising rapidly. The mining of raw materials, production process and recycling process at the battery’s end-of-life release substantial amounts of GHGs. 

As the demand for LIBs is expected to rise by over 500% by 2030 (Kaunda, 2020), it is no surprise that the demand for minerals to produce LIBs such as lithium and nickel is expected to rise exponentially as well. Beaudet et al., 2020 (2020) estimate that the demand for lithium and nickel is expected to rise by over 575% and 1237% respectively in the decade. Besides the adverse environmental impact mining brings to the environment and local population as mentioned in the earlier blogs, mining itself is an emitter of GHGs. Today, global mining accounts for 4-7% of GHG emissions and this percentage is expected to increase further when global mass production of LIBs gains momentum (Henderson, 2020) (Figure 1). 

Figure 1: Lithium mine (Battery Industry, 2022)

Moving from raw materials to factories, the processes involved in the manufacturing of LIBs are also great emitters of GHGs. The production of a LIB is not a simple one, lasting from weeks to months depending on the type of batteries produced (EPEC, n.d.; Liu et al., 2021). The highly specific conditions during each phase of the production process also require high amounts of energy to sustain. Dry rooms, high temperatures and high-pressure equipment are all large electricity consumers (Liu et al., 2021) (Figure 2, 3).

Figure 2: General manufacturing process of LIBs (Liu et al., 2021)

Figure 3: Energy consumption of LIB manufacturing processes (Liu et al., 2021)

From Figure 3, we need 13.28 kWh of energy to produce a cell after summing the total energy consumption per cell of all the processes. Depending on the source of this energy comes from, the carbon dioxide emitted differs significantly (EIA, n.d.) (Figure 4). 

Figure 4: U.S. electricity net generation and resulting CO2 emissions by fuel in 2021 (EIA, n.d.)

Carbon emissions from LIB production will be significantly reduced should the majority of electricity be generated from renewable sources of energy. However, the global energy grid is still dominated by fossil fuels and coal, the most polluting fossil fuel (ClientEarth Communications, 2022). The largest GHG emitters today, China, the USA and India still rely heavily on fossil fuels particularly coal for China and India (World Population Review, 2023). In the US, fossil fuels are still responsible for over 60% of electricity generated (EIA, 2023), while coal alone still accounts for over 75% of electricity generated in India (Ministry of Coal, 2023). Despite the rapid development of renewables in China in recent years, coal still accounts for 55% of the energy generated in China (EIA, 2022). Therefore, without a significant change in the energy mix allowing renewables to dominate electricity production, the production of LIBs will without question become a great contributor to GHG emissions. 

 

Reference List

Battery Industry. (2022, June 3). Advance Lithium provides an update on mining law changes. BatteryIndustry.tech. https://batteryindustry.tech/advance-lithium-provides-an-update-on-mining-law-changes/ 

Beaudet, A., Larouche, F., Amouzegar, K., Bouchard, P., & Zaghib, K. (2020). Key Challenges and Opportunities for Recycling Electric Vehicle Battery Materials. Sustainability, 12(14), 5837. https://doi.org/10.3390/su12145837 

ClientEarth Communications. (2022, February 18). Fossil fuels and climate change: the facts. ClientEarth. https://www.clientearth.org/latest/latest-updates/stories/fossil-fuels-and-climate-change-the-facts/#:~:text=Coal%20is%20a%20fossil%20fuel,the%20world%27s%20total%20carbon%20emissions 

EIA. (n.d.). Frequently Asked Questions (FAQs) – U.S. Energy Information Administration (EIA). US Energy Information Administration. https://www.eia.gov/tools/faqs/faq.php?id=74&t=11 

EIA. (2022, August 8). International – U.S. Energy Information Administration (EIA). US Energy Information Administration. https://www.eia.gov/international/analysis/country/CHN 

EIA. (2023). Frequently Asked Questions (FAQs) – U.S. Energy Information Administration (EIA). US Energy Information Administration. https://www.eia.gov/tools/faqs/faq.php?id=427&t=3 

EPEC. (n.d.). Battery Pack Development Timeline – Prototypes to Product Production. EPEC Engineered Technologies. https://www.epectec.com/batteries/development-timeline.html#:~:text=This%20process%20can%20range%20from,material%20and%20battery%20cell%20availability 

Henderson, K. (2020, August 27). Here’s how the mining industry can respond to climate change. McKinsey & Company. https://www.mckinsey.com/capabilities/sustainability/our-insights/sustainability-blog/here-is-how-the-mining-industry-can-respond-to-climate-change 

Kaunda, R. B. (2020). Potential environmental impacts of lithium mining. Journal of Energy and Natural Resources Law, 38(3), 237–244. https://doi.org/10.1080/02646811.2020.1754596 

Liu, Y., Zhang, R., Wang, J., & Wang, Y. (2021). Current and future lithium-ion battery manufacturing. IScience, 24(4), 102332. https://doi.org/10.1016/j.isci.2021.102332 

Ministry of Coal. (2023). Generation of Thermal Power from Raw Coal. https://coal.nic.in/en/major-statistics/generation-of-thermal-power-from-raw-coal 

World Population Review. (2023). Greenhouse Gas Emissions by Country 2023. https://worldpopulationreview.com/country-rankings/greenhouse-gas-emissions-by-country 

Environmental pollution, Lithium Pollution, Pollution, SO2, Toxic Gases

Toxic gases released during the burning of Lithium-ion batteries (SO2)

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The third toxic gas I will be discussing is sulfur dioxide (SO2), a colourless but odorous gas that is highly toxic (United States Environmental Protection Agency, 2023). It is most commonly produced from the burning of fossil fuels and by the smelting of sulfur-containing mineral ores (Queensland Government, 2017). Naturally, erupting volcanoes are a significant source of SO2 emissions (Queensland Government, 2017). Similar to HF discussed in blog 11, SO2 is much more toxic compared to other gases released during the burning of lithium-ion batteries (LIBs) (Peng et al., 2020). 

Within batteries, SO2 is produced from burning sulfur-based compounds which are commonly used as reduction-type additives (Peng et al., 2020; Zhang, 2006). Similar to other toxic gases released during the burning of LIBs, the concentration of SO2 released depends on the state of charge (SOC) of the battery (Peng et al., 2020). The higher the SOC, the higher the concentration of SO2 released (Peng et al., 2020) (Figure 1). Despite, a lower concentration at lower SOCs, SO2 continues to make up a large part of all the toxic gases released regardless of SOC (Peng et al., 2020). While the maximum concentration of SO2 released, 115 mg/m3 (around 43.89 ppm), does not pose an immediate threat to the survival of a person, this concentration is more than enough to cause, mucositis, irritation to mucous membranes (Peng et al., 2020; Cleveland Clinic, 2022 ). 

According to Queensland Government (2017), the recommended air quality standards for sulfur dioxide are:

  • 0.20 ppm for a 1-hour exposure period
  • 0.08ppm for a 24-hour exposure period
  • 0.02ppm for an annual exposure period.

Health impacts of high concentrations of SO2:

  1. Respiratory problems
  • Difficulty to breath, people with existing respiratory problems such as asthma, and young children are particularly sensitive to the impacts of inhaling SO2. 
  • People with existing heart problems and diseases are also much more sensitive to the effects of SO2. 

2. Painful sores in the mouth/ gastrointestinal symptoms

  • High concentrations of SO2 will result in soreness in the mouth due to mucositis. Coughing and throat irritation are common symptoms related to high exposure to SO2 as well. 

(United States Environmental Protection Agency, 2023; Queensland Government, 2017)

Besides the direct impacts of SO2, SO2 can react with other chemicals in the atmosphere to form small particles that can easily enter the lungs of a person causing adverse health impacts (Queensland Government, 2017). For instance, reactions between SO2 and NOx form sulfates, which form fine particles (He et al., 2015). These fine particles are often the main culprit behind haze in parts of the world (He et al., 2015). They were also the main cause of the major haze events in Beijing-Tianjin-Hebei regions in China in 2013 (He et al., 2015). 

Figure 1: Haze event in Beijing in 2013 (Branigan, 2013)

Reference List

Branigan, T. (2013, January 14). Beijing smog continues as Chinese state media urge more action. The Guardian. https://www.theguardian.com/world/2013/jan/14/beijing-smog-continues-media-action 

Cleveland Clinic. (2022). Mucositis: Types, Symptoms & Treatment. https://my.clevelandclinic.org/health/diseases/24181-mucositis#:~:text=Mucositis%20is%20inflammation%20of%20the,painful%20and%20carries%20certain%20risks 

He, H., Wang, X., Ma, Q., Ma, J., Chu, B., Ji, D., Tang, G., Liu, C., Zhang, H., & Hao, J. (2015). Mineral dust and NOx promote the conversion of SO2 to sulfate in heavy pollution days. Scientific Reports, 4(1). https://doi.org/10.1038/srep04172 

Peng, Y., Yang, L., Ju, X., Liao, B., Ye, K., Li, L., Cao, B., & Ni, Y. (2020). A comprehensive investigation on the thermal and toxic hazards of large format lithium-ion batteries with LiFePO4 cathode. Journal of Hazardous Materials, 381, 120916. https://doi.org/10.1016/j.jhazmat.2019.120916 

Queensland Government. (2017, March 27). Sulfur dioxide. Environment, Land and Water | Queensland Government. https://www.qld.gov.au/environment/management/monitoring/air/air-pollution/pollutants/sulfur-dioxide#:~:text=Sulfur%20dioxide%20affects%20the%20respiratory,as%20asthma%20and%20chronic%20bronchitis 

United States Environmental Protection Agency. (2023, February 16). Sulfur Dioxide Basics | US EPA. US EPA. https://www.epa.gov/so2-pollution/sulfur-dioxide-basics 

Zhang, S. (2006). A review on electrolyte additives for lithium-ion batteries. Journal of Power Sources, 162(2), 1379–1394. https://doi.org/10.1016/j.jpowsour.2006.07.074

CO and CO2, Electric Vehicles, Environmental pollution, Lithium-ion battery, Toxic gases

Toxic gases released during the burning of Lithium-ion batteries (CO and CO2)

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Similar to hydrogen fluoride (HF), carbon monoxide (CO) and carbon dioxide (CO2) are common toxic gases that are released in the burning of LIB (Peng et al., 2020 ). CO is one of the two asphyxiant gas in ISO 13571 (Peng et al., 2020). 

ISO 13571:2012 establishes procedures to evaluate the life-threatening components of fire hazard analysis in terms of the status of exposed human subjects at discrete time intervals. – (International Organization for Standardization, 2020)

What is an asphyxiant gas?

Asphyxiant gas is a gas that results in hypoxia, the decrease of oxygen level in body tissue (Cleveland Clinic, 2022), by disarranging oxygen in the respiratory system (Gold, 2022). Besides hypoxia, asphyxiant gases will also cause ischaemia and metabolic acidosis (Gold, 2022; Cowled, 2011). Ischaemia causes deficiencies in blood oxygen, glucose and other substances (Cowled, 2011). When the supply of blood is lower than the demand, the body is no longer able to support essential normal functions (Cowled, 2011). The decrease in blood oxygen and other key substances deranges metabolic function which plays a crucial role in converting food and water into energy in the body (Cowled, 2011; Schoeller & Fjeld, 1991). On the other hand, metabolic acidosis is the buildup of acid in the body when the kidney is unable to remove enough acid in time due to failure (Gold, 2022). 

Symptoms:

  • Headaches, vomiting, lethargy, confusion
  • Loss of appetite 
  • Chest pain
  • Shortness of breath 
  • Fast heart rate
  • Loss of consciousness
  • Cardiac arrest

(Gold, 2022)

The symptoms a person suffers from by inhaling CO vary according to the concentration of CO and the duration they are exposed to. Furthermore, the deleterious effects of CO can be amplified when CO2 is breathed in with CO (Peng et al., 2020). As both of these gases are produced in conjunction with the burning of batteries, the effects of CO will be intensified. 

According to CO2 Meter (2023), the duration before CO takes effect significantly reduces when the concentration of CO exceeds 200 ppm (Figure 1). 

Figure 1: Carbon monoxide levels chart (CO2 Meter, 2023)

Burning behaviours of a 68 Ah battery (Figure 2) was studied by Peng et al. (2020) at different state of charge (SOC) and the concentration of CO and CO2 released over time was studied (Figure 3). 

Figure 2: 68 Ah lithium iron phosphate battery (Peng et al., 2020)

Figure 3: Experimental setup (Peng et al., 2020)

Batteries at a higher SOC produced the maximum CO and CO2 in the shortest duration after the battery started burning (Peng et al., 2020) (Figure 4). CO production reached a maximum of 258 ppm for 100% SOC albeit for a very short duration (Peng et al., 2020). 

Figure 4: Graphs of CO and CO2 production (Peng et al., 2020)

Although this concentration of CO will not have immediate health impacts when exposed to such a short period of time (Figure 1), we must bear in mind that this experiment used a 68 Ah battery with a nominal voltage of 3.22 V (Peng et al., 2020). According to E.ON, (n.d.), the battery capacity of an electric car (EV) is around 40 kWh with some going as high as 100 kWh and the common voltage of the batteries are 280 V and 360 V (Matsusada Precision Inc., 2019). A battery with a capacity of  40 kWh and voltage of 280 V will have a current of 143 Ah, more than double the current of the battery used in the experiment. Burning this battery will most likely increase the concentration of CO and CO2 produced to a lethal concentration that is fatal within minutes of exposure (Figure 1). 

 

Reference List

Cleveland Clinic. (2022). Hypoxia: Causes, Symptoms, Tests, Diagnosis & Treatment. https://my.clevelandclinic.org/health/diseases/23063-hypoxia#:~:text=Hypoxia%20is%20low%20levels%20of,Hypoxia%20can%20be%20life%2Dthreatening 

CO2 Meter. (2023, January 23). Carbon Monoxide Levels Chart. https://www.co2meter.com/blogs/news/carbon-monoxide-levels-chart 

Cowled, P. (2011). Pathophysiology of Reperfusion Injury. Mechanisms of Vascular Disease – NCBI Bookshelf. https://www.ncbi.nlm.nih.gov/books/NBK534267/#:~:text=Ischaemia%20occurs%20when%20the%20blood,begin%20during%20this%20ischaemic%20phase 

E.ON. (n.d.). Electric vehicles | Battery | Capacity and Lifespan. https://www.eonenergy.com/electric-vehicle-charging/costs-and-benefits/battery-capacity-and-lifespan.html#:~:text=The%20average%20capacity%20is%20around,higher%20the%20kWh%20the%20better 

Gold, A. (2022, September 26). EMS Asphyxiation And Other Gas And Fire Hazards. StatPearls – NCBI Bookshelf. https://www.ncbi.nlm.nih.gov/books/NBK519487/ 

International Organization for Standardization. (2020). ISO 13571:2012. ISO. https://www.iso.org/standard/56172.html 

Matsusada Precision Inc. (2019, June 4). Power Supply and Voltage of EV Motor | Tech | Matsusada Precision. Matsusada Precision. https://www.matsusada.com/column/ev-power.html#:~:text=Lithium%2Dion%20batteries%20are%20the,connected%20in%20series%20and%20parallel 

Peng, Y., Yang, L., Ju, X., Liao, B., Ye, K., Li, L., Cao, B., & Ni, Y. (2020). A comprehensive investigation on the thermal and toxic hazards of large format lithium-ion batteries with LiFePO4 cathode. Journal of Hazardous Materials, 381, 120916. https://doi.org/10.1016/j.jhazmat.2019.120916 

Schoeller, D. A., & Fjeld, C. R. (1991). Human Energy Metabolism: What Have We Learned from the Doubly Labeled Water Method? Annual Review of Nutrition, 11(1), 355–373. https://doi.org/10.1146/annurev.nu.11.070191.002035 

Environmental pollution, HF, Pollution, Toxic Gases

Toxic gases released during the burning of Lithium-ion batteries (HF)

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The first gas that we will be discussing in detail is hydrogen fluoride (HF). HF is a colourless gas which readily dissolves in water to form hydrofluoric acid (HFA) (Marx et al., 2005; Gad & Sullivan, 2014). HF is an extremely toxic gas and HFA is one of the strongest existing acids (Marx et al., 2005). 

Ingestions of more than 20 mg/kg body weight are considered a lethal dose. – Marx et al., 2005

Adverse health impacts will arise when exposed to it either in gaseous or liquid form (Centers for Disease Control and Prevention, 2018). 

Immediate signs and symptoms of exposure to HF/HFA:

  • Exposure to HFA: severe pain on exposed skin immediately or more often several hours after exposure despite no physical burns observed.
  • Ingestion of HFA: small amount of highly concentrated HF can severely damage internal organs and may even be fatal.
  • Exposure to HF gas: at low concentrations will result in eye, nose and respiratory irritation. At high concentrations, it may be fatal due to the accumulation of fluid in the lungs or cardiac arrhythmia.

Long-term impacts of short contact with HF/HFA: 

  • Survivors of inhalation of HF often suffer from chronic lung disease.
  • Survivors may suffer from permanent visual problems and damage.

(Centers for Disease Control and Prevention, 2018)

Immediate intensive care treatment is required when exposed to HF/HFA. The damage of HF/HFA to the body can continue for weeks and will have lasting impacts on the person’s health (Centers for Disease Control and Prevention, 2018; Gad & Sullivan, 2014). 

HF is one of the main toxic gas released from the combustion of batteries (refer to chemical equations in the previous blog). Although many studies about the combustion of batteries and toxic gas release have been done, few have released exact amounts of HF gases produced when a battery burns (Larsson et al., 2017). Additionally, as the different battery manufacturers and battery types contain different variations of chemical compositions, it is difficult to specify the exact amount of HF gas released for a battery with a certain capacity (Larsson et al., 2017) (Figure 1). Generally, pouch cells tend to produce the highest concentrations of HF (Larsson et al., 2017). 

[A] possible explanation would be that hard prismatic and cylindrical cells can build a higher pressure before bursting, rapidly releasing a high amount of gases/vapours from the electrolyte. Due to the high velocity of the release and thus the short reaction time, combustion reactions might be incomplete and less reaction products might be produced. – Larsson et al., 2017

Figure 1: HF released during the burning of 7 different types of batteries at different SOC (Larsson et al., 2017)

From the experiments conducted by Larsson et al. (2017), they also found that the state of charge (SOC) of a battery will also affect the rate of HF released when the battery burns. Batteries at 100% SOC tend to have more extreme heat release and flames (Larsson et al., 2017). Experiments conducted on the same type of battery also found a clear correlation between the SOC of the battery and the rate of HF produced over time (Larsson et al., 2017; Zhang et al., 2022) (Figure 2). Similar experiments on different types of cells conducted showed similar results (Larsson et al., 2017). 

Figure 2: Correlation between the rate of heat release and concentration of HF over time at different SOC (Larsson et al., 2017)

 

Reference List

Centers for Disease Control and Prevention. (2018, April 4). CDC | Facts About Hydrogen Fluoride (Hydrofluoric Acid). CDC. https://emergency.cdc.gov/agent/hydrofluoricacid/basics/facts.asp 

Gad, S., & Sullivan, D. (2014). Hydrofluoric Acid. Encyclopedia of Toxicology, 964–966. https://doi.org/10.1016/b978-0-12-386454-3.00853-8 

Larsson, F., Andersson, P., Blomqvist, P., & Mellander, B. E. (2017). Toxic fluoride gas emissions from lithium-ion battery fires. Scientific Reports, 7(1). https://doi.org/10.1038/s41598-017-09784-z 

Marx, C., Trautmann, S., Halank, M., & Weise, M. (2005). Lethal intoxication with hydrofluoric acid. Critical Care, 9(Suppl 1), P407 (2005). https://doi.org/10.1186/cc3470 

Zhang, L., Duan, Q., Meng, X., Jin, K., Xu, J., Sun, J., & Wang, Q. (2022). Experimental investigation on intermittent spray cooling and toxic hazards of lithium-ion battery thermal runaway. Energy Conversion and Management, 252, 115091. https://doi.org/10.1016/j.enconman.2021.115091 

Electric Vehicles, Environmental pollution, Lithium-ion battery, Pollution, Toxic gases

Toxic gases released during the burning of Lithium-ion batteries

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Today, lithium-ion batteries (LIB)/ grid-scale battery storage is one of the fastest-growing energy storage systems globally with China, US and Europe leading the market (Schoenfisch & Dasgupta, 2022) (Figure 1). Although the global economy plunged in 2020 due to the COVID pandemic, the battery market continued to grow exponentially. Between 2020 and 2021, the grid-scale battery storage market saw an annual increase of over 60% in global storage capacity (Schoenfisch & Dasgupta, 2022). 

Figure 1: Annual grid-scale battery storage additions and distribution (Schoenfisch & Dasgupta, 2022)

In spite of the rapid growth in grid-scale battery storage, the global capacity remains undesirably low should we want to reach a net zero scenario. To meet the goal, Schoenfisch & Dasgupta (2022) estimate that the global grid-scale battery storage capacity will have to increase to 680 GW by 2030 (Figure 2). 

Figure 2: Required annual increase of gird-scale battery storage to meet the net zero scenario (Schoenfisch & Dasgupta, 2022)

Although LIB is an excellent alternative and direction towards a low-carbon future, the gaps and problems these batteries continue to plague the industry. The most pressing problem these batteries have today is their sensitivity to high temperatures and susceptibility to burn (Ghiji et al., 2020) (Figure 3). There are a few ways a LIB can be ignited, they include short-circuit, overcharging, exposure to high temperature, mechanical stress and more (Larsson et al., 2017). The hazardous nature of these batteries is particularly risky when used in vehicles such as electrical vehicles and aeroplanes (Ghiji et al., 2020). 

Figure 3: Electric car on fire (Ghoshal, 2021)

According to Larsson et al. (2017), the electrolyte of LIBs often contains lithium hexafluorophosphate (LiPF6) or other Li-salts containing fluorine, which are highly flammable and reactive compounds (Guo et al., 2020). Furthermore, fluorine is commonly found in other parts of the LIB in components such as fire retardants and electrodes (Larsson et al., 2017). Being one of the lightest and most reactive metals, this makes LIBs extremely vulnerable to high temperatures and combustion. 

Besides the immediate thermal damage from burning, LIBs also release toxic gases such as carbon monoxide (CO) and hydrogen fluoride (HF) (Zhang et al., 2022). The decomposition of LiPF6 is further exacerbated when water is used as an extinguisher (Larsson et al., 2017). 

LiPF6  → LiF + PF5 – (1)

PF5 + H2O + → POF3 + 2HF – (2)

LiPF6 + H2O → LiF + POF3 + 2HF – (3)

Additionally, the composition of toxic gases released between different batteries varies according to the particular chemical composition and state of charge (SOC) of each battery (Larsson et al., 2017). The volume and threat of toxic gases released are also larger for bigger cell packs (Larsson et al., 2017). When a large amount of electrolyte evaporates when batteries are heated, this gas may not ignite immediately when released but may accumulate and result in gas explosions at later stages (Larsson et al., 2017). 

In the coming blogs, I will explore the toxic gases produced from the combustion of LIBs in detail so stay tuned for more!

 

Reference List

Ghiji, M., Novozhilov, V., Moinuddin, K., Joseph, P., Burch, I. A., Suendermann, B., & Gamble, G. (2020). A Review of Lithium-Ion Battery Fire Suppression. Energies, 13(19), 5117. https://doi.org/10.3390/en13195117 

Ghoshal, A. (2021, December 15). How Lithium Ion batteries in EVs catch fire – Adreesh Ghoshal – Medium. Medium. https://adreesh-ghoshal.medium.com/how-lithium-ion-batteries-in-evs-catch-fire-9d166c5b3af1 

Guo, F., Ozaki, Y., Nishimura, K., Hashimoto, N., & Fujita, O. (2020). Influence of lithium salts on the combustion characteristics of dimethyl carbonate-based electrolytes using a wick combustion method. Combustion and Flame, 213, 314–321. https://doi.org/10.1016/j.combustflame.2019.12.001 

Larsson, F., Andersson, P., Blomqvist, P., & Mellander, B. (2017). Toxic fluoride gas emissions from lithium-ion battery fires. Scientific Reports, 7(1). https://doi.org/10.1038/s41598-017-09784-z 

Schoenfisch, M., & Dasgupta, A. (2022, September). Grid-Scale Storage – Analysis – IEA. IEA. https://www.iea.org/reports/grid-scale-storage 

Zhang, L., Duan, Q., Meng, X., Jin, K., Xu, J., Sun, J., & Wang, Q. (2022). Experimental investigation on intermittent spray cooling and toxic hazards of lithium-ion battery thermal runaway. Energy Conversion and Management, 252, 115091. https://doi.org/10.1016/j.enconman.2021.115091

Impact on Humans and Animals, Lithium

Benefits of naturally occurring Lithium in water

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Having discussed the negative impact Li pollution has on biodiversity, I would like to explore the benefits natural Li, Li in small amounts can have for biodiversity in this blog. Like most naturally occurring things (e.g. greenhouse effect), Li plays an important role in the healthy growth and development of humans and animals in small amounts. Li occurs naturally in small amounts in groundwater and soil (Memon et al., 2020). Although only found in small concentrations averaging between 3.8 and 46.3 μg/L (0.0005–0.0067 mmol/L) (Araya et al., 2022), Li positively impacts the health of people. 

Figure 1

The benefits of naturally occurring Li include:

1. Reduces rates of suicide

Drinking water with naturally occurring Li has been found to improve the mental health of people (Memon et al., 2020). Over the years, many studies have been conducted to find the relationship between different concentrations of Li and suicide rates (Memon et al., 2020; Araya et al., 2022). Although little correlation has been found in concentrations below 30.7 μg/L (0.0044 mmol/L) in drinking water, a much stronger correlation was found between Li and suicide rate at a higher concentration from 32.9 μg/L (0.0047 mmol/L) (Araya et al., 2022). Generally, among the areas studied, areas with a higher natural concentration of Li also recorded lower rates of suicide (Forlenza et al., 2012) (Figure 2). 

Figure 2: Reduce suicide levels with an increase in Li levels (Ohgami et al., 2009)

2. Mood stabilising effects

Apart from reducing rates of suicide, Li have mood stabilisation effects, independent of its anti-suicidal effect (Memon et al., 2020). This is also why despite having negative health impacts when taken in at above natural concentrations, Li continues to be used in bipolar treatment and medicine to stabilise the mood swings of patients (Forlenza et al., 2012). 

3. Neuroprotective effects

Additionally, Li can improve a person’s cognitive function (Neves et al., 2020). Despite only being present naturally, in small amounts, Kessing et al. (2017) found that water with higher concentrations of Li significantly reduced dementia in Denmark. However, when used in the treatment of neurological diseases such as Alzheimer’s disease often requires a higher than the natural concentration of Li of up to 300 µg/day (Neves et al., 2020).

4. Reduces inflammation

Finally, Li is also able to reduce inflammation thanks to its ability to inhibit glycogen synthase kinase-3 (GSK3) (Beurel & Jope, 2014).

GSK3 promotes the production of inflammatory molecules and cell migration, which together make GSK3 a powerful regulator of inflammation. – Jope et al., 2007

While naturally occurring Li benefits humans, the rapid increase in Li pollution can result in Li concentration soaring exponentially in coming years if few related regulations and policies are passed and enforced. The impacts of Li in nature at a much higher concentration will no longer be just beneficial and adverse health impacts discussed in previous blogs will arise, further straining the global health system. 

 

Reference List

Araya, P. E., Martínez, C., & Barros, J. (2022). Lithium in Drinking Water as a Public Policy for Suicide Prevention: Relevance and Considerations. Frontiers in Public Health, 10. https://doi.org/10.3389/fpubh.2022.805774 

Beurel, E., & Jope, R. S. (2014). Inflammation and lithium: clues to mechanisms contributing to suicide-linked traits. Translational Psychiatry, 4(12), e488. https://doi.org/10.1038/tp.2014.129 

Forlenza, O. V., De Paula, V. S., Machado-Vieira, R., Diniz, B. S., & Gattaz, W. F. (2012). Does Lithium Prevent Alzheimerʼs Disease? Drugs & Aging, 29(5), 335–342. https://doi.org/10.2165/11599180-000000000-00000 

Jope, R. S., Yuskaitis, C. J., & Beurel, E. (2007). Glycogen Synthase Kinase-3 (GSK3): Inflammation, Diseases, and Therapeutics. Neurochemical Research, 32(4–5), 577–595. https://doi.org/10.1007/s11064-006-9128-5 

Kessing, L. V., Gerds, T. A., Knudsen, N. N., Jørgensen, L., Kristiansen, S., Voutchkova, D. D., Ernstsen, V., Hansen, B., Andersen, P. K., & Ersbøll, A. K. (2017). Association of Lithium in Drinking Water With the Incidence of Dementia. JAMA Psychiatry, 74(10), 1005. https://doi.org/10.1001/jamapsychiatry.2017.2362 

Memon, A., Rogers, I., Fitzsimmons, S. M. D. D., Carter, B., Strawbridge, R., Hidalgo-Mazzei, D., & Young, A. H. (2020). Association between naturally occurring lithium in drinking water and suicide rates: systematic review and meta-analysis of ecological studies. British Journal of Psychiatry, 217(6), 667–678. https://doi.org/10.1192/bjp.2020.128 

Neves, M. G. P. M. S., Marques, J. C., & Eggenkamp, H. G. (2020). Lithium in Portuguese Bottled Natural Mineral Waters—Potential for Health Benefits? International Journal of Environmental Research and Public Health, 17(22), 8369. https://doi.org/10.3390/ijerph17228369 

Ohgami, H., Terao, T., Shiotsuki, I., Ishii, N., & Iwata, N. (2009). Lithium levels in drinking water and risk of suicide. British Journal of Psychiatry, 194(5), 464–465. https://doi.org/10.1192/bjp.bp.108.055798

Electric Vehicles, Environmental pollution, Lithium Pollution, Lithium-ion battery

Lithium-ion batteries and Regulations in Singapore

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As Li pollution is a relatively new pollution that has only appeared in the past 2 to 3 decades, the attention it receives remains limited. Today, only a few countries such as Australia (Shen et al., 2020), have identified and listed Li as a pollutant in water. Li is also missing from the list of pollutants tested to qualify water as safe drinking water published by PUB, Singapore’s National Water Agency (Public Utilities Board, n.d.) (Figure 1). With the growing concentration of Li to levels no longer negligible in the environment, it is necessary to include Li as a pollutant in indicators (Shen et al., 2020).

Figure 1: Singapore Drinking Water Quality (Jul 2021 – Jun 2022) (Public Utilities Board, n.d.)

Besides the lack of Li indicators, there is also a lack of standards and regulations imposed on lithium-ion battery producers. Despite having over a decade of production history in China, China’s Ministry of Ecology and Environment only issued the Technical Specification of Pollution Control for Treatment of Waste Power Lithium-ion Battery at the end of 2021 (AOKI, 2021). On the other hand, places where the lithium-ion battery industry is still very young such as Australia does not have related regulations and standards for new battery factories yet (ERAC, n.d.). Very often, places that lack a national standard for battery manufacturing will refer to overseas standards such as CE standards required by the European Union (EU, 2022) (Figure 2).

Figure 2: CE sign (American Society for Quality, n.d.)

However, as these are just references, factories are not legally required to abide by these standards. Without proper enforcement, Li waste material can easily escape into the environment polluting water sources consumed and used for agriculture. Drinking Li-polluted water for prolonged periods can have detrimental health impacts. 

 

Moving back to Singapore, although Singapore does not currently have a lithium-ion battery of its own, Singapore continues to rely heavily on lithium-ion battery-powered devices and machines. In an effort to reduce carbon emissions, The Singapore Green Plan 2030 campaigns to raise awareness and promote electric vehicles to the public (LTA, 2022) (Figure 3). 

The Singapore Green Plan 2030 includes a strong push to electrify our vehicle population, which would help Singapore achieve our vision of 100% cleaner energy vehicles by 2040. – LTA, 2022

Figure 3: Power EVery Move campaign logo (LTA, 2022)

This move towards EVs will no doubt significantly increase the use and disposal of lithium-ion batteries. Currently, little information can be found online about the recycling and management of these lithium-ion batteries in Singapore. To promote the use of these batteries, Tan (2020), Director of the Waste and Resource Management Department National Environment Agency (NEA), has even gone on to state that 

Lithium-ion batteries are not hazardous, while nickel metal hydride batteries are hermetically sealed to prevent materials within the batteries from escaping into the environment. 

However, Li does have impacts on the environment and humans when consumed and lithium-ion batteries do contain nickel and other heavy metals in its cathode etc. (Yan et al., 2020). Given the increase in the concentration of Li in rivers in Shanghai and other major cities due to the increase in lithium-ion batteries (Shen et al., 2020), Singapore must ensure that proper regulations are set in place to ensure that these batteries are properly recycled and disposed of. 

 

Reference List

 

American Society for Quality. (n.d.). What is CE Marking? – CE Mark Certification vs. Self Declaration | ASQ. https://asq.org/quality-resources/ce-marking 

AOKI, K. (2021, September 17). China issues technical standards to control pollution from treatment of EVs’ waste lithium-ion batteries | Enviliance ASIA. Enviliacne ASIA. https://enviliance.com/regions/east-asia/cn/report_4282 

ERAC. (n.d.). Standards – ERAC. https://www.erac.gov.au/standards/

EU. (2022). CE marking – obtaining the certificate, EU requirements. Your Europe. https://europa.eu/youreurope/business/product-requirements/labels-markings/ce-marking/index_en.htm

LTA. (2022, April). LTA | Electric Vehicles. https://www.lta.gov.sg/content/ltagov/en/industry_innovations/technologies/electric_vehicles.html 

Public Utilities Board. (n.d.). Singapore Drinking Water Quality. In Public Utilities Board. https://www.pub.gov.sg/Documents/Singapore_Drinking_Water_Quality.pdf 

Shen, J., Li, X., Shi, X., Wang, W., Zhou, H., Wu, J., Wang, X., & Li, J. (2020). The toxicity of lithium to human cardiomyocytes. Environmental Sciences Europe, 32(1). https://doi.org/10.1186/s12302-020-00333-6 

Tan, D. (2020, April). Readers’ Letters. National Environment Agency. https://www.nea.gov.sg/media/readers-letters/index/nea-ensures-that-all-e-waste-recyclers-have-the-necessary-pollution-control-equipment-to-meet-nea-s-emissions-and-discharge-standards 

Yan, W., Yang, S., Huang, Y., Yang, Y., & Guohui Yuan. (2020). A review on doping/coating of nickel-rich cathode materials for lithium-ion batteries. Journal of Alloys and Compounds, 819, 153048. https://doi.org/10.1016/j.jallcom.2019.153048 

 

Environmental pollution, Impact on Humans and Animals, Lithium Pollution, Pollution

Impacts of Lithium Pollution on Humans and Animals Part 3

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Albeit having negative impacts on human health, Li is not an uncommon component of many medicines including treatment for bipolar disorder (Gitlin, 2016; Duvall & Gallicchio, 2017). Side effects of patients taking these medicine include kidney problems and dizziness similar to those discussed in the previous blogs, further proving the impacts Li have on human health (Gitlin, 2016; Duvall & Gallicchio, 2017). 

However, currently, most studies about the negative impacts Li has on humans revolve around the kidney and little is known about its impacts on the cardiovascular system (Shen et al., 2020). Besides cardiovascular diseases caused by kidney diseases, Shen et al. (2020) found that Li significantly constrained the proliferation of cardiomyocytes, the ‘cell responsible for the contraction of the heart’ (Keepers et al., 2020). Li was also found to encourage cell apoptosis (Shen et al., 2020) (Figure 1). 

Apoptosis: A type of cell death in which a series of molecular steps in a cell lead to its death. This is one method the body uses to get rid of unneeded or abnormal cells. The process of apoptosis may be blocked in cancer cells. Also called programmed cell death. – National Cancer Institute, n.d. 

Figure 1: Apoptosis VS Necrosis, ways a cell dies (CUSABIO TECHNOLOGY LLC, n.d.)

Shen et al. (2020) tested the impact of Li on AC16 Human Cardiomyocyte Cell Line propagated using DMEM High Glucose (Dulbecco’s Modified Eagle Medium) at different concentrations. 

AC16 is a proliferating human cardiomyocyte cell line that was derived from the fusion of primary cells from adult human ventricular heart tissues with SV40 transformed, uridine auxotroph human fibroblasts, devoid of mitochondrial DNA… AC-16 can be used to address questions of cardiac biology at the cellular and molecular levels. – Merck KGaA, n.d.

Cell Proliferation

LiCl/Li2SO4 at 0.2  mmol/L, 1  mmol/L, 5 mmol/L or 25 mmol/L were used over a period of 2 days on the AC16 Human Cardiomyocyte cells (Shen et al., 2020). After 2 days, Shen et al. (2020) discovered that the growth of cells that were exposed to 5 mmol/L and 25 mmol/L of LiCl was notably inhibited (Figure 2).   

Figure 2: Proliferation of AC16 cells measured in luminescent assay and CCK-8 assay (Shen et al., 2020)

To determine if growth inhibition was due to Cl instead of Li, Shen et al. (2020) added NaCl to the study and found no significant change when NaCl was added. Additionally, the growth of cells that were exposed to 2.5 mmol/L and 12.5 mmol/L of Li2SO4 was also evidently inhibited (Shen et al., 2020).   

Cell Apoptosis

To study cell apoptosis, Annexin V‐FITC/PI apoptosis assay is used(Shen et al., 2020; Rieger et al., 2011). 

The Annexin V/PI protocol is a commonly used approach for studying apoptotic cells. PI is used more often than other nuclear stains because it is economical, stable and a good indicator of cell viability, based on its capacity to exclude dye in living cells. – Rieger et al., 2011

After 2 days, cells treated with 5 mmol/L LiCl and 2.5  mmol/L Li2SO4 observed a significant increase in cell apoptosis compared to uncontaminated cells (Shen et al., 2020) (Figure 3). 

Figure 3: Cell apoptosis of AC16 cells (Shen et al., 2020)

Therefore, besides the known effects Li has on the kidney and liver, exposure and intake of high concentrations of Li can potentially have a deadly effect on the heart and the cardiovascular system. In the next blog, I will explore how we may be more vulnerable to taking in high concentrations of Li today as compared to the past. 

 

Reference List:

CUSABIO TECHNOLOGY LLC. (n.d.). Get an Overview of Cell Death- CUSABIO. https://www.cusabio.com/cytokines/Cell-Death.html 

Duvall, A. E., & Gallicchio, V. S. (2017). Lithium Treatment in Clinical Medicine: History, Current Status and Future Use. Journal of Cell Science &Amp; Therapy, 08(03). https://doi.org/10.4172/2157-7013.1000270 

Gitlin, M. (2016). Lithium side effects and toxicity: prevalence and management strategies. International Journal of Bipolar Disorders, 4(1). https://doi.org/10.1186/s40345-016-0068-y 

Keepers, B., Liu, J., & Qian, L. (2020). What’s in a cardiomyocyte – And how do we make one through reprogramming? Biochimica Et Biophysica Acta (BBA) – Molecular Cell Research, 1867(3), 118464. https://doi.org/10.1016/j.bbamcr.2019.03.011 

Merck KGaA. (n.d.). AC16 Human Cardiomyocyte Cell Line. In Merck KGaA. https://www.sigmaaldrich.com/deepweb/assets/sigmaaldrich/product/documents/150/525/20228073-scc109.pdf 

National Cancer Institute. (n.d.). NCI Dictionary of Cancer Terms. https://www.cancer.gov/publications/dictionaries/cancer-terms/def/apoptosis 

Rieger, A. M., Nelson, K. L., Konowalchuk, J. D., & Barreda, D. R. (2011). Modified Annexin V/Propidium Iodide Apoptosis Assay For Accurate Assessment of Cell Death. Journal of Visualized Experiments, 50. https://doi.org/10.3791/2597 

Shen, J., Li, X., Shi, X., Wang, W., Zhou, H., Wu, J., Wang, X., & Li, J. (2020). The toxicity of lithium to human cardiomyocytes. Environmental Sciences Europe, 32(1). https://doi.org/10.1186/s12302-020-00333-6