Lithium Batteries for Electric Vehicles: From Economy to Research

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Lithium Batteries for Electric Vehicles: From Economy to Research Strategy Ali Eftekhari ACS Sustainable Chem. Eng., Just Accepted Manuscript • DOI: 10.1021/ acssuschemeng.8b01494 • Publication Date (Web): 20 Feb 2019 Downloaded from http://pubs.acs.org on February 22, 2019

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ACS Sustainable Chemistry & Engineering

Lithium Batteries for Electric Vehicles: From Economy to Research Strategy Dedicated to Stanley Whittingham who built the foundation of not only lithium batteries but also intercalation chemistry Ali Eftekhari Belfast Academy, 2 Queens Road, Belfast BT3 9FG, United Kingdom Email: [email protected] Abstract Environmental concerns and governmental policies have paved the path for a rapid shift from petrol-powered to electric vehicles (EVs). The prime technological requirement is the advancement of lithium-ion batteries (LIBs) to satisfy the everyday habits of the society for relinquishing the well-established petrol-powered vehicles. Despite the generously increased research funds to facilitate breakthroughs to the next generation of renewable power sources for EVs, the available strategies of research are not satisfactorily practical. On the other hand, recent reports stressing the scarcity of lithium have raised the concern about a possible lithium deficit or increasing cost. These all have caused a sentiment for moving beyond LIBs. Although the emerging hype is the result of a misconception about the scarcity of lithium again, there is no practical research strategy to make this breakthrough within the present critical timeframe of transition to EVs. This article attempts to answer some common questions. Are there sufficient lithium resources? Can a lithium deficient halt the EV industry? Is it necessary to move beyond LIBs? Is the research on the right track? Is the taxpayers' money efficiently invested for the targeted purpose? Keywords: Lithium supply; Electric vehicles; Lithium-ion batteries; Energy storage; Energy economy; Market research

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Innovative technologies find their way into our everyday life much faster than what is initially anticipated. Take mobile phones, for example; when gaining the popularity in the 1990s, the target was to facilitate the old-fashioned telephone calling, but within two decades, they become a vital element in everyday life. There is no doubt that the advancement of electronic technology paved the path, but it was the commercialisation of lithium-ion batteries (LIBs) in 1991 which made this quick progress possible. The mobility of mobile phones relies on the high energy LIBs to power high-resolution large screens and intensive CPU tasks. However, the story of electric vehicles (EVs) is slightly different. The idea of EVs was around for over a century, but it was still a fancy idea in the 1990s. Tesla Motors was founded in 2003 with an ambitious idea of commercial production of EVs.1 In the mid-2010s, shifting towards EVs was strategically planned by the policymakers in many countries. Norway ambitiously ruled to ban petrol-powered cars by 2025, Germany and India by 2030, and France and the UK by 2040.2-5 As a matter of fact, a recent analysis reported that Europe must end the sale of petrol-only cars by 2030 to meet the Paris Accord targets.6 Despite an unprecedented fortune of these enforcing policies, the emanating question is whether we are technologically prepared to provide the market need. The performance of available EVs is quite promising, but still, far behind the petrol-powered rivals. The annoying aspect of driving an EV is the long charging time. Battery research should make a breakthrough in this matter within a few years, but are we on the right track? On the other hand, a recent deficit in battery-grade lithium supply raised the question if the lithium industry can be impacted by the emerging supply issues. This paper attempts to inspect the industry from different angles to provide reasonable answers to these questions and build an overall picture of the evolving technology. The next 10 years or so are of strategic importance during the transition from petrol-powered vehicles to EVs.2,4 In addition to the governmental policies, some automakers have also followed the trending market to change their strategies. Volvo has announced to stop the production of petrol-only cars by 2019.7 Jaguar Land Rover, which has not produced an EV yet, decided to quickly jump into this emerging market by announcing that all the productions after 2020 will be electric or hybrid.8 Therefore, it is evidently a critical period in the automotive industry, but many factors have been neglected, and some exaggerated as will be discussed here. The discussion is specifically about the critical aspects of this particular period of time. Figure 1 represents a representative estimation of the number of EV sales in the forthcoming years. Page 2 of 33 ACS Paragon Plus Environment

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Figure 1. An estimate of the EV sales in the next years. Data obtained from Ref.9

Electric Vehicles In the nineteenth century, there was an engineering competition between different engines in the emerging automotive industry. Electric engines were powered by lead-acid batteries whose specific energy was low. The internal combustion engine gained the high specific energy of fuels such as kerosene and petrol, but the price of fossil fuels was too high at the time. With the advancement of the oil industry, the price of oil was massively dropped (Figure 2), and thus, the combustion engine predominately won the competition. Among many reasons, the abundance of oil in the United States paved the path for a rapidly growing market and automotive industry there. Before the Great Depression in 1929, 90% of the world's cars were in the US where there were 4.87 cars per person.11 In the 1990s, the idea of EVs was revisited for three reasons: (i) Novel battery options particularly LIB and nickel metal hydride (NiMH) came into play. (ii) The direct pollution of big cities and the climate change raised environmental concerns about petrol-powered cars. (iii) The price of renewable energy become competitive to move beyond the dominant option of oil.



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Figure 2. Changes in the price of oil in time. Data obtained from Ref.10

Motives: Environmental Reasons The first action was taken by the California Air Resources Board (CARB) to introduce the Zero Emission Vehicles (ZEVs) regulatory mandating that at least 2% of the vehicle sales in the state of California should be ZEVs by 1990s, 5% by 2001, and 10% by 2003. This motivated the automakers to produce EVs. The first response was EV1 by General Motors (GM). The production of EV1 had a short lifespan between 1996-1999. In 1997, Toyota introduced a hybrid car, Prius, utilising a NiMH battery. The CARB incentive was a good motive for automakers to pursue the development of EVs, but the Board eased the regulations under a pressure from the federal government. On the other hand, the Bush administration heavily invested in the idea of fuel cell vehicles (FCVs). In both NiMH batteries and fuel cells, the key element is hydrogen, but they work with quite different mechanisms for energy storage and conversion, respectively.12 In practice, neither of them could support the mass production of EVs. There are some FCVs available on the market, but the fuel cell technology is far behind the potentials of LIBs for powering the EVs in the near future. A key advantage of EVs was that they could be charged with home outlets, but FCVs necessarily needed an advanced infrastructure for the fuel stations. Although commercially available, large-scale application of LIBs was just an idea at the time. In the 2010s, the price of LIBs was low enough to be reasonable for EVs, and its high energy density paved the way for close competition with petrol-powered vehicles. Therefore, as mentioned earlier, Page 4 of 33 ACS Paragon Plus Environment

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many countries imposed strict regulations for shifting to EVs for environmental reasons. In line with the global agreement on the climate change, the so-called Paris Accord, almost any country has some tax incentives for supporting the EVs. Although modern EVs are as powerful as the petrol-powered counterparts, the main motive of the consumers is the zero-emission feature of EVs. In practice, EVs are not as green as consumers may think it is since the electricity is produced mainly by fossil fuel power plants. The problem is that though these power plants are about to be replaced by renewable sources, EVs will progressively impose a huge demand from the grid.13-14 One of the most practical approaches for shifting towards renewable energy is the roof solar panels by individual households, which has been successfully implemented in various countries. Because of the discontinuity of energy conversion by solar panels, households sell the electricity generation to the grid and buy it when needed. The better solution is to store the generated electricity locally to be independent of the grid. Tesla produces the household energy storage batteries as well as EVs, but the market is much smaller than EVs (Figure 3). The reason is that it takes about ten years to pay back the battery cost, and there is no meaningful government subsidy for this purpose (except for recent political plans such as that of Victoria state in Australia15). According to the electricity consumption pattern of EVs, power plants should change their supply pattern. Since the supply of electricity from available renewable resources such as solar and wind is not fully adjustable, fossil fuel power plants will be the justified choices. Household energy storage, on the other hand, can reduce the number of grid subscribers, but this increases the dependency on the lithium supply.

Figure 3. Various markets of the lithium-ion batteries. Data obtained from Ref.22

Motives: Economic Reasons and Oil Competition Perhaps, the main reason for the failure of the GM EV1 production was inappropriate timing since Page 5 of 33 ACS Paragon Plus Environment


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it was introduced during a declining period of the oil price reaching $10 per barrel. The increasing oil price during the 2000s again motivated the development of EVs. Surprisingly, new players came into the market such as Tesla Motors, which were EV manufacturers rather than automakers intrinsically preferring petrol cars to EVs. On the other hand, the global concerns about the climate change persuade governments to reduce the CO2 emission. The alarming air pollution makes the necessity of EVs inevitable. This is the reason why countries like China, which are critically struggling with the pollution in their big cities, are committed to the idea of EVs (Figure 1). This suggests that the rapid pace of the EV growth will not be slowed down as happened before. Therefore, the hindering factor is not predominately the oil price or oil companies at the moment, and other factors such as technological obstacles may cause a halt in the projected future of EVs. The dependency of renewable energy on the oil price is not unprecedented. In the 1960s, there was a hike in the oil price following a conflict between the Arab states and Israel (Figure 2). The high price of oil made renewable energy economical, and thus, a massive amount of research funds was allocated to explore possible alternatives. Even Iran as a major oil supplier, who was the main winner of that price hike, established a research centre for the industrial development of solar panels. The research centre was able to gather ambitious scientists who later become the leading pioneers of solar panels and batteries (such as John B. Goodenough who is partially credited for the development of LIBs). The current popularity of solar panels is, in part, because of the sudden attention paid that time. Of course, this attention was reduced by the subsequent drop in the oil price but again restored in the 2000s. Overall, today's competitive price of solar electricity is the result of the oil price hike and subsequent governmental subsidies to reduce the energy dependence on unpredictable oil price. The point is that the EV industry is already facing a major threat to the declining oil price, and cannot survive a sudden increase in the battery price or technological halt. One of the key motives for the mass production of electric vehicles was the price of oil. From mid2003 to mid-2008, the price of oil was increased by 5-fold to reach the record high of over $150 per barrel and remained around $100 per barrel from 2011 to late 2015. The average price of oil has been about $50 per barrel during the last two years, and the emerging market of electric vehicles will probably push it even lower. Oil companies such as British Petroleum (BP) have predicted that the price of oil will remain at this level because of new development projects in the developing countries.16 Nonetheless, the rapid decline of the oil demand in the developed countries can be even faster.


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Lithium-ion Batteries Although LIBs were commercially available in the 1990s, they were considered too expensive for EVs. The early model of GM EV1 was based on lead-acid battery, which was indeed the idea backed to the nineteenth century. NiMH batteries were then considered for a short period of time. The increased price of LIBs as a result of the economy of scale facilitated the birth of high-energy EVs of today. Lithium is technically an excellent charge career. While its negative potential on the anode side guarantees a high cell voltage, transport of 1g of Li from the cathode to the anode can store 3,842 mAh of electricity. This is roughly the capacity of a 45-g 18650 cell17, which is used in various devices from laptops to Tesla cars. However, everything is not about the charge career, as the roles of the cathode and anode materials in reversibly hosting the charge career is much more important. The prime reason for sticking to LIBs is not the lightweight charge carrier but the availability of host materials. Lithium Resources Despite being a light element, the natural abundance of lithium is exceptionally lower than its heavier group members (1/1000 of sodium or potassium). Since the commercial success of LIBs, there has always been a concern about the supply of lithium as the lightest metal. In 2010, Wanger predicted that the occurrence of lithium deficient by 2025 is inevitable even if recycling all LIBs.18 However, this concern was never considered a serious threat to the industry until 2015 when a deficient in the supply-demand of lithium happened. This made a potential lithium crisis a hot topic in the mainstream media.19-21 As a result, several investment banks and consultant firms prepared extensive reports about potential lithium crisis and its consequences on the production of EVs.22-23 These reports are of particular importance since they are considered as comprehensive resources for planning the foreseeable technological advancements; instead of being advising reports for potential investors, which is indeed the prime purpose of these reports. On the other hand, quite recently, a possible lithium crisis has frequently been addressed in the scientific literature too.24-25 The primary market of LIBs during the 1990s and 2000s was small portable electronic devices such as cell phones and laptops. Therefore, the supply grew slowly with the demand. However, sudden growth in the market for large-scale batteries in electric vehicles (EVs) and household energy storage made the supply lag behind the growing demand. On the other hand, a significant part of Page 7 of 33 ACS Paragon Plus Environment


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brine-based natural resources of lithium is located in the so-called lithium triangle (brines from salt lakes) shared between Bolivia, Chile, and Argentina. Although the brine evaporation process is somewhat time-consuming (about a year), the exploitation process is still easier and cheaper. Thus, the future of lithium supply may suffer an uncertainty because of the political instabilities in these Latin American countries, as will be discussed later. The 2015 deficit resulted in a price hike. This raised the concern that there might not be enough lithium resources for the growing market of LIBs on which the EV industry depends. Following the recent lithium deficit, many reports predicted a significant lithium deficit would occur in the forthcoming years. However, there are massive differences between these estimations. Figure 4 compares the supply-demand of lithium over the next years by two major market research reports.22-23 Not only the predictions are significantly different but also the current situations are not identical in the reports. The reason is that the lithium market is conducted by a few major companies and the key proprietary data are not accurately available. Currently, about 39% of lithium is consumed in the battery industry.22 The second important application is the glass industry. The latter is also a growing consumption because of its technological importance in new electronic devices particularly cameras.


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Figure 4. Estimations of the lithium supply-demand over the forthcoming years by Deutsche Bank (solid lines) and Macquarie Research (dashed lines). (a) The supply-demand in the world, and (b) supply by each country. Data obtained from Refs.22 and 23.

The cheapest resource of lithium is the brine lakes26-28 in Latin America (Figure 5). Bolivia, which owns the largest lithium reserve in the world, has not yet exploited its natural resources due to a nationalistic policy. The sentiment about the case of lithium is entangled with nationalism in Bolivia29; a country with a long history of providing natural resources to the industrial world free of charge.30 In the era of independence, Bolivia believes it is the time to take control of the natural resources.30-31 However, the idea is too ambitious to be practical. Bolivia does not have sufficient technology to independently exploit lithium, and it is unlikely to convince foreign investors to build mining facilities when they cannot gain the exploitation. The ambitious plan does not stop here, and Bolivia plans to build the final product, LIB, inside the country. The problem is that other foreign tech companies should invest to build a manufacturer for making the battery grade lithium out of the extracted lithium. Although lithium is a key ingredient of LIBs, having lithium is a trivial privilege for the technological production of LIBs32, which are currently produced in a few Page 9 of 33 ACS Paragon Plus Environment


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countries only.33 Because of the popularity of LIBs, they are commonly a topic of academic research even in the developing countries. Despite the national interest, a quick search of the scholarly databases reveals that LIBs have not be considered in Bolivia even at the academic level. In any case, Bolivia decided to reinvent the wheel by developing a native technology for the lithium exploitation. There has been a trivial supply so far but Bolivia has a plan to export 10,000 tonnes of lithium carbonate.20 All these factors plus the strong political and nationalistic reactions suggest that the largest natural resource of lithium will not be available in the near future to supply the growing demand.

Figure 5. Map of lithium natural resources indicating the available reserves and resources. Countries with brine resources are coloured blue and those with mineral ores red. Those with both resources are coloured purple. Data obtained from Ref.36

Meanwhile, Chile is known as a business-friendly country in Latin America, and thus, well facilitated the exploitation of lithium during the last years (Chile is the largest supplier of lithium).34 However, the increase in the lithium price since 2015 has tempted its policymakers to move towards nationalisation of lithium, similar to Bolivia.35 Argentina had an opposite direction. Until 2015, the lithium industry was somehow nationalised, but the new government has insisted on the international collaboration. Therefore, Argentina expands its lithium exploitation as fast as possible. However, the opposition party is fighting for the next election, and utilising the motivation of increasing lithium price. The situation in all these three Latin American countries indicates that the supply of lithium for the rapidly growing demand is not fully reliable. Lithium Crisis? The impact of a possible lithium crisis is not as severe as portrayed in the public media. Overall, the lithium crisis as a result of an unexpected change in the supply from the "lithium triangle" may temporarily affect the EV industry, but in long-term, the lithium supply will probably satisfy the growing market. Figure 6 shows the changes in the estimation of the world's lithium resources by the United States Geological Surveys over the last eight years.36 On the other hand, the exploitation Page 10 of 33 ACS Paragon Plus Environment

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of lithium from other resources might be more difficult but possible.37 The increasing price of lithium makes the exploitation of other resources economical. Market research by Martin et al. also suggested that the lithium crisis is mostly due to the strategic reasons rather than natural scarcity.38

Figure 6. The estimated resources of lithium by the United States Geological Survey during the past 8 years. Data obtained from Ref.36

On the other hand, Latin American countries should consider that a lithium crisis is not necessarily in their favour, as the price hikes have never been in favour of the oil-supplying countries. The emerging lithium crisis will make the conservative industries determined to move beyond the lithium option faster. It is unlikely to find a universally better option since lithium is an excellent charge carrier because of its lightweight, but if this happens, even the dominant market of small batteries will be lost. The price of mineral commodities quickly changes by the shifting demand. Ten years ago, platinum was the only choice in various catalytic systems including fuel cells, which were considered as a promising option for the electric vehicles. The price of platinum was two times higher than gold and four times higher than palladium, but now it is the cheapest of the three precious metals. Despite the current low natural resources of lithium, there will be enough lithium for all the growing market of LIBs in long-term. Christmann et al. provided a detailed analysis of lithium resources globally.26 On the other hand, lithium as the lightest metal most likely preserves its superiority as a light charge carrier. Therefore, there is a short-term requirement for new alternatives. This defines the research strategy that these alternatives should be commercialised in the near future, and thus, more practical research is required. As a result of the economy of scale, the cost of LIBs has been massively reduced during the last Page 11 of 33 ACS Paragon Plus Environment


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years (Figure 7). Similar estimations have been made by others.39 Nevertheless, the battery component is still responsible for over 20% of the cost of EVs on average. Although lithium is the main materials in these batteries, its cost is not dominant as compared with other materials used. Like any other commercial products, the price of electric vehicles should fall by increasing the production. The concern is that this increase in the production results in an increase in the lithium at the danger of deficit.

Figure 7. The decreasing cost of lithium-ion batteries in various applications as a result of the economy of scale. Data obtained from Ref.9

As mentioned before, a 45-g 18650 cell has 1 g of Li charge carrier. Since only half of the Li atoms in LiCoO2 can be extracted, an additional 1 g remains in the cathode. Considering the excess Li in the electrolyte, the Li content of a LIB is around 5%. Thus, an increase in the Li price does not massively affect the price of LIB. On the other hand, a recent analysis by Morgan Stanley suggested that the price of lithium will drop by 45% until 2021.40 It is worth noting that the whole crisis panic is due to a misconception. The massive price hike frequently quoted by both mainstream media and scientific literature was not of lithium but batterygrade lithium on the Chinese market. In fact, the lithium problem was a matter of quality rather than quantity. Materials and Recycling Although LIBs specifically carry the name of lithium, it is not the only key element in the battery structure. In the current design, the largest portion of LIBs is mainly made of graphite as the anode material. The battery application makes only 2% of the graphite demand, and thus, the growth of EVs does not have a huge impact on the graphite demand.41 Nevertheless, the supply of spherical Page 12 of 33 ACS Paragon Plus Environment

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natural graphite, which is the best choice for LIBs, is limited and may not cope with the growing demand. However, alternative forms of graphite including synthetic graphite can satisfy the growing demand. The most critical element in LIBs is cobalt. According to almost all estimations, the cobalt supply is not enough for the rapidly growing market of LIBs (Figure 8).

Figure 8. Supply-demand of cobalt. Data obtained from Ref.23

Again, the cost and scarcity of cobalt were not a sufficient motive for shifting from the safe choice of LiCoO2 in small LIBs for portable electronic devices. New alternatives should come into play not only because of cost but also the desire for better performance. This shift has already been started, as nickel has acutely replaced cobalt to a great degree.42 These two transition metals are similar (in both cost and natural abundance), but the nickel supply/demand is ten times more than that of cobalt, and thus, will not be affected by the sudden growth of large-scale LIBs. In fact, cobalt is usually a by-product of nickel exploitation. In the case of lead-acid batteries, recycling has been conducted quintessentially following strict regulations because of the lead toxicity. Cobalt in LIBs is of environmental concern but not as toxic as lead. The majority of the lithium-ion batteries are not recycled, particularly because of the size of available LIBs used in portable electronic devices. In any case, recycling has not targeted the restoration of lithium so far, because the cost of recycling is more than the value of comprised lithium.43-46 The main target of recycling is currently more expensive metals such as cobalt.47 If shifting towards cheaper transition metals in the cathode, the incentive for recycling becomes even less significant.



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Research Strategy Asking the right question is much more difficult than finding the answer. Similarly, the research idea is much more important than the research itself. Having an imperative and reasonable question, finding the answer just needs technical skills and research funds. Thanks to mass higher education and increasing national R&D budget in almost all countries, the latter requirements are already available. The inceptive idea should be well adapted within the research strategy. Not only research strategies are highly discipline-dependent but also every researcher has a unique strategy for doing the research. This is indeed the triumph of research as pushing the boundaries of science needs to look at known issues from new perspectives. The problem, as will be discussed in this section, is that research approaches have become less innovative, partially because of institutional financial burdens and inappropriate funding strategies which have persuaded researchers to stay in the safe zone. Since the critical aspect of LIBs is still the development of active materials, most of the research endeavours are devoted to this matter. Roughly speaking, the common research strategies in the realm of materials science can be categorised into three types: Fundamental research: in which the intention is not directly the application but understanding the system under consideration. In the 1970s, Stanley Whittingham investigated the intercalation of Li into MoS2, which not only was the groundbreaking foundation of LIBs but also formed the entire area of intercalation chemistry.48 A series of fundamental studies built our understanding of the underlying electrochemical systems. Michel Armand was among the first who theoretically explained LIBs.49 John Newman, who is often credited as the father of electrochemical engineering, proposed fundamental theories of LIB which still account for the intercalation systems. Peter Bruce developed a subtle outlook of the solid-state chemistry of electrode materials to shed light on the underlying phenomena of Li intercalation. Unfortunately, this is not a long list (probably 10-20 scientists who shaped our understanding of LIBs during the 1980s and 1990s), but the groundbreaking contributions are too long to be summarised here. Innovation: aiming at new opportunities or novel possibilities for the targeted applications. When the practical potential of LIBs was established, the trending research strategy was to devise new designs to satisfy the practical requirements. This innovative ideas may result in an immediate practical breakthrough or emerging a long-term opportunity. For instance, Jeff Dahn examined the Page 14 of 33 ACS Paragon Plus Environment

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possibility of aqueous electrolytes for LIB, but he soon gave up the idea due to low voltage resulting in a significantly lower energy density. After two decades, the idea has attracted massive attention for a new type of LIBs while a 4-voltage performance is now achievable.50 Some of these innovations were too early and at the boundary of the first category somewhat. The early commercial prototypes of LIBs back to the late 1970s based on the cell devised by Whittingham, but safety concerns soon hindered the practical development. A key issue was the absence of solid electrolyte interphase (SEI) in the early architecture. Armand demonstrated the possibility of solve-free polymer electrolytes.49 Except for a few examples, this idea did not attract the attention deserved until recently when solid-state and quasi-solid-state batteries have become practical choices because of safety and energy storage capacity. The practical birth of LIBs can be portrayed (albeit, too simplified): John Goodenough investigated the extraction of Li from LiCoO2 as an alternative to the MoS2 electrode introduced by Whittingham. At the same time, Yazami reported the possibility of accommodating Li ions within graphite interlayers. The practical innovation was made by Akira Yoshino who put all the available ideas to build a modern LIB in 1985. Improvement: to empirically examine various combinations for finding the best performance. There is a long road from the innovative discovery of the second categories to the practical development. From the cell design to the electrode materials, there are many aspects which should be gradually improved to make the battery performance satisfactory. This strategy is usually based on 'trial and error', though ideally, fundamental knowledge should guide us to pick the most promising choices. For instance, the role of a conductive agent in the electrode architecture is vital to satisfactorily enhance the electrical conductivity of the active material. Since there is an unlimited number of carbonaceous materials, there will be unlimited choices for building nanocomposites, which can improve the battery performance of an electrode material. These works pave the path for optimising the cell architecture in long-term but rarely lead to a breakthrough. In general, during the 1980s, many works on LIBs were in the first category. Upon the commercial success, the majority of works (or at least the goals) moved to the second category to devise new types of LIBs during the 1990s and early 2000s. Since then, the dominant research strategy became the third one because most of the possible options had already been tested; it is unlikely (or at least quite difficult) to propose a new electrode material for Li intercalation, which has not been tested Page 15 of 33 ACS Paragon Plus Environment


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before. From the practical perspective, the rapidly growing market of LIBs for portable electronic devices needed an eventual improvement along with the electronic technology development. The desirable improvement was obviously in the direction of the market demand, which was a higher capacity. It is inconvenient to wait 1-2 hours to charge an electronic device but not annoying since this is the minimum time the customers have experienced. They do not have an experience of fueling their mobile phones with petrol within a few minutes to get annoyed by the long charging time. However, this is indeed the key competition point of EVs. Therefore, we need a new strategy of research to address the requirement of LIBs for new sets of applications rather than their old ones. The huge investment of the taxpayers' money in energy storage whether in the form of research funds or government subsidies to support the industry directly aims at short-term outcomes since this is what the emerging industry desperately needs. Hence, the classic strategy of research is not appropriate at this particular time because the current funding is not merely for the technology advancement but to facilitate the transition from petrol cars to EVs to ease the burden of government subsidies. Lessons Learned from Fuel Cells By 2009, the US had invested over $1bn of research funds in fuel cells, but in the absence of any tangible outcome, the Obama administration cut the budget.51 Although this change in policy was officially limited to the United States, its impact on the overall publications of the field was obvious (Figure 9). However, this does not mean that fuel cells do not have a potential to power the future electric vehicles. The problem is that they are lagging behind scientifically. It is frequently discussed that the overpotential required for oxygen evolution reaction (OER) is still too high for the practical energy conversion.52 Figure 9 indicates that the focus was not on this key issue during the hype of FCVs, and it has recently attracted the attention of researchers to systematically deal with. Note that OER was not a new concept whatsoever, and its history backs to the classic electrochemistry.


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Figure 9. Number of publications devoted to fuel cells and oxygen evolution reaction (OER) according to the database Scopus.

Therefore, the failure of the idea of FCVs (or at least with respect to the claimed prospect) is not related to the incapability of fuel cells to convert the energy required by modern vehicles, but the inappropriate strategy of research. Morrison et al. estimated that the cost of fuel cells would be lower than its battery counterpart for powering vehicles by 2040.53 The common misconception is that sufficient research fund can tackle any scientific problem. Strange as it may seem, well-funded scheme ruined the prospect of FCVs. This can be explained by the non-cooperative game theory proposed by John Nash (1994 Nobel laureate in Economics), but it is beyond the scope of this article. After the hype of FCVs when the funding was more reasonable, the scientific community found its way on the right track (Figure 9). The same story is about to happen (or it has already been started in a sense) about batteries. The research funds have been massively increased during the last years, and new schemes are now introduced to address the need of the rapidly expanding market of EVs. For instance, the UK government has committed £246m to Faraday battery challenge.54 Directly quoting Nick Cliffe, the Interim Head of Innovative UK, "There is so much expertise on batteries in the UK. Faraday is about translating it"; it seems the strategy is very similar to the US investment on FCVs when President Bush said, "a child born today will be driving hydrogen, pollution-free vehicle as his or her first car". Not only, there is no evidence that the UK is ahead of other countries in this field, but also the problem is to claim we already have the answer and need to translate it into industrial action. With a realistic outlook of the market demand, the first step is to admit what we are lacking. Even at the lab scale, the current status of batteries is not sufficient to reasonably replace the petrolpowered vehicles. Page 17 of 33 ACS Paragon Plus Environment


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Evidently, there are more outstanding works as a result of more research funds but have we ever considered the efficiency of such investments? Almost any working idea in the current battery industry has a history of older than 15 years. However, with the pace of technology advancement in the 1980s, it took only ten years to commercialise LIBs from its raw idea. Lithium-ion Batteries With Tesla superchargers, the battery can be charged to 80% within 30min. The resulting millage is comparable with the petrol-powered counterparts, but the charging time is still much longer than fueling a petrol car. Therefore, the immediate need for EVs to widely replace the petrol-powered vehicles as mandated by the aforementioned policies is fast charging capability.55-56 A recent paper comprehensively reviewed the rate capability of various LIB electrode materials.57 Although rate capability has been a critical factor since the early days of LIBs, there has been no appropriate attention to this matter in accordance with the practical requirement. It was clarified that there is no standard for the definition of a fast-charging performance of LIB since there is no direct comparison with the current status to move beyond the available possibilities.57 Figure 10 compares the percentage of papers focused on the capacity of LIBs versus those on the rate capability. This is a rough and naive calculation but can clearly provide a comparative outlook. On the other hand, scientific achievements are often exaggerated in the mainstream media by highlighting an aspect and ignoring the whole picture. For example, it was reflected in the public media that the next generation of batteries can be charged within one minute following a report of an aluminium battery.58 Notwithstanding, the specific energy with respect to the weight of electrodes and electrolyte was about 40 Wh kg–1, which is still much lower than that of commercial LIBs. Theoretically, aluminium batteries are excellent choices, but controlling the electrochemical behaviour of trivalent Al ions needs decades of research.59


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Figure 10. Percentage of scientific publications on LIBs devoted to capacity or fast charging. The keywords searched in the Scopus database are annotated on the curves.

The hype of fast charging is indeed an attractive point in the marketing strategy. A technology startup with over $60m fund claimed the commercial development of a battery to be charged within 30 seconds in 201460, 1 minute in 201561, and 5 minutes in 2017.62 Fisker has recently claimed the development of a new battery of EVs, which can be charged within 1 minute for 500 miles of range.63 Whether the scientific research as reflected in the literature is years behind the industrial R&D counterparts or the common strategy of business is to convince the investors with mesmerising claims and then look for a solution (though money cannot guarantee a scientific discovery). Even if these claims are correct, they do not lead us very far. Battery development is not merely an engineering matter and requires scientific perspectives. Can an R&D group develop a battery without reading the scientific literature? For the same reason, an idea which has not been examined by other scientists does not have a guaranteed prospect. R&D developments are based on new ideas to implement the available knowledge in practical cases, not jumping far ahead of the literature with no trace. Linus's law in computer engineering states, "given a large enough beta-tester and codeveloper base, almost every problem will be characterised quickly, and the fix obvious to someone". The underlying electrochemical system of a battery is controlled by many factors, and in the best case scenario, the predicted performance is just an estimation. In any case, the problem is not limited to the overemphasis on capacity over rate capability, but the lack of a practical perspective. For example, neglecting the critical importance of the energy Page 19 of 33 ACS Paragon Plus Environment


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efficiency in the studies of electrode materials can shift the attention towards the materials with no practical potential.64 It has been analysed that a majority of the works reported in the literature have focused on materials with low energy efficiencies down to the level of 50%. Such materials are unlikely to find a potential for energy storage in neither short-term nor long-term. Under no circumstance, it is reasonable to waste the storing energy, and it should be kept in mind that wasted energy is normally transformed to heat, which is a major concern in batteries. Note that reducing this level of overpotentials needs much more work than reducing the overpotential of the available OER electrocatalysts for fuel cells (as quoted above). Roughly speaking, just in this typical example, millions of dollars of taxpayers' money have been (and are still being) wasted in the absence of an appropriate strategy of research. As another example, a majority of works on anode materials is the quest for high-capacity materials to replace the graphitic anode, which was the dominant anode materials for three decades and has reached its theoretical capacity. These new anode materials usually have a pseudocapacitive nature, and thus, cannot deliver a constant voltage close to that of Li/Li+ redox as graphite does. The higher capacities (as compared with graphite) reported in the literature are the result of performance over a potential window of 3-V with an average voltage of 1.5 V vs Li/Li+. This means even if the specific capacity is twice of graphite, the specific energy is still the same as that of graphite because of low cell voltage.65 These materials will probably have some applications in long-term but cannot contribute any meaningful possibility to the highly demanding energy storage within the next 10-20 years. Another example is the focus on nanocomposites, which are normally aimed at improvement rather than a breakthrough. Conductive additives such as carbonaceous materials are an essential part of electrode casting. Nanocomposites can improve the battery performance, but they are not usually practical choices due to low tapped density resulting in low energy density. Owing to the hype of nanotechnology since the 2000s, it is reasonable to witness the increased attention. However, the percentage of nano-related works on LIBs (Figure 11) reveals that the strategy of research has been massively shifted towards a direction, which is neither practical nor what the emerging EV industry currently needs. A better case for inspecting this shift is the popularity of graphene since the 2010 Nobel Prize in Physics, as a significant percentage of LIB research is devoted to this material, though no practical potential has yet offered (the tapped density of graphene is among the worst nanomaterials).


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Figure 11. Percentage of scientific publications devoted to specific cases of LIB and NIB as searched in the Scopus database. Nano refers to the papers having a nano-related keywords (mostly a sort of nanocomposite).

Beyond Lithium-ion Batteries LIBs are backed by a 50-year history. This is both advantage and disadvantage; while our knowledge about the Li systems is quite profound, there are fewer rooms for breakthroughs. We have to move beyond LIBs, not because of Li scarcity or cost, but for new opportunities which can substantially change the energy storage systems. It is the beginning of alternative batteries (though they officially have longer histories), and one may anticipate the rational strategy of research is to follow the footsteps of LIBs but for the emerging applications (i.e., EV and household batteries). The number of research publications on lithium batteries has increased by about 20% during the last four years, but those focused on sodium batteries have been doubled in the same period (Figure 12). However, still, the number of research works on lithium batteries is at least seven times more than those dealing with sodium batteries. This indicates that the battery researchers are rapidly shifting towards lithium alternatives, but this shift might not be fast enough to introduce practical choices for the emerging EV industry.



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Figure 12. Number of research publications focused on lithium, sodium, and other (potassium/magnesium/calcium/aluminum) batteries as searched in the Scopus database. For the sake of visualisation, the latter two have been multiplied.

Nevertheless, the trend depicted in Figure 11 suggests that the immature shift to the third type of research strategy is even more severe for the case of NIB as compared with LIB. In the case of LIB, the focus is on the 'improvement' strategy is due to the low prospect of discovering new materials and the satisfactory performance of commercial LIBs. Obviously, these are not the case for NIB, and the focus should be at least similar to the fundamental and innovation strategy of the 1980s and 1990s in the LIB research. While any NIB prototype even at lab scale is still far behind the LIB counterparts in spite of competitive potentials from the theoretical perspective17, the research efforts are paid to improving the systems, which may never be commercialised. In other words, while the main challenge of NIB is still the lack of appropriate electroactive materials for hosting Na charge carrier on both sides (anode and cathode), 60% of the current research is focused on improving the electrode casting by devising nanocomposites.

Concluding Remarks Transition to EVs is indeed a must. Not only because of the CO2 emission but also for the reason of technological advancement. The old-fashioned internal combustion engine is inefficient in terms of energy conversion. It is not ideal that the electricity of EV might be partially supplied from nongreen resources, but it is not an excuse to undermine the importance of EVs. However, all these reasons are not enough to force the consumers to sacrifice their comfort in this transition. In other words, EVs should be able to compete with petrol-powered vehicles in every aspect. Page 22 of 33 ACS Paragon Plus Environment

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LIB is now the safest choice for powering EVs, but this does not mean we have to stick to this idea forever. Nonetheless, the lithium scarcity is not the reason for moving beyond LIBs but the desire for new technological opportunities. The recent lithium deficit was the result of an unexpected increase in the demand and failure to foresee the rising demand, not the lack of natural resources. Therefore, the supply will be smoothly increased by the growing demand. The strategic problem is that the current LIB technology may satisfy the EV enthusiasts but not the expectation of general consumers. For massively replacing the petrol-powered vehicles with their electric counterparts (including hybrids), the current battery technology is not sufficient. Hence, it is of critical importance to develop new battery systems within a short period of time (ca. 5 years). To this aim, the strategy of research in this particular time should be different from the standard one. Simply investing more money does not lead us very far. It is difficult to judge the scientific significance of a research work, as the real potential may emerge in the future. Notwithstanding, it is not difficult to tell a promising strategy. If the research strategy aims at improving the performance of available battery systems, whether the performance should be better than commercial batteries or the underlying mechanism should explain the how we can take the next step. Otherwise, a tiny improvement in a typical system with no strategical outlook is not worthy of the research funds invested. The short history of Tesla Motors well represents the sudden shift toward EVs when an ambitious idea (and impractical to many including the Bush administration) turned into reality within 15 years. However, the battery technology has not been advanced as it should be despite sufficient research funds. The problem is that there is no measure (and unfortunately no attempt) to monitor the efficiency of research funds. Funding agencies has no practical mechanism for this purpose, universities prefer extravagant scholars (due to the overheads), and taxpayers are promised that their money is in safe hands. Surely, a higher level of funding has resulted in outstanding outcomes, but it is not discussed what we could ideally achieve to realise our pitfalls. Latin American silver spoiled Spain, oil is ruining the Middle East, and political funding destroyed the true potential of fuel cells; this is the same old story. There are evidently groundbreaking advancements in the realm of lithium batteries and their counterparts, but what percentage of research endeavour actually contributed to this progress? One may argue that the same situation Page 23 of 33 ACS Paragon Plus Environment


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exists in every field more or less. The aim of this paper is to emphasise that the future 5-10 years are of strategical importance in the realm of energy storage, and thus, there is no time for going astray for finding the way.


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(http://www.bbc.co.uk/news/technology-39895898), 2017. [63] Fisker Patents Car Battery with 500-Mile Range on a Minute’s Charge (https://www.foxbusiness.com/features/fisker-patents-car-battery-with-500-mile-range-on-aminutescharge), 2017. [64] Eftekhari, A. Energy Efficiency: a Critically Important but Neglected Factor in Battery Research. Sustainable Energy Fuels, 2017, 1, DOI 10.1039/c7se00350a [65] Eftekhari, A. Metrics for Fast Supercapacitors as Energy Storage Devices. ACS Sustainable Chem. Eng., 2018, 6, DOI 10.1021/acssuschemeng.7b04532


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Figure Captions

Figure 1. An estimate of the EV sales in the next years. Data obtained from Ref.9

Figure 2. Changes in the price of oil in time. Data obtained from Ref.10

Figure 3. Various markets of the lithium-ion batteries. Data obtained from Ref.22

Figure 4. Estimations of the lithium supply-demand over the forthcoming years by Deutsche Bank (solid lines) and Macquarie Research (dashed lines). (a) The supply-demand in the world, and (b) supply by each country. Data obtained from Ref.36

Figure 5. Map of lithium natural resources indicating the available reserves and resources. Countries with brine resources are coloured blue and those with mineral ores red. Those with both resources are coloured purple. Data obtained from Ref.36

Figure 6. The estimated resources of lithium by the United States Geological Survey during the past 8 years. Data obtained from Ref.36

Figure 7. The decreasing cost of lithium-ion batteries in various applications as a result of the economy of scale. Data obtained from Ref.9

Figure 8. Supply-demand of cobalt. Data obtained from Ref.23

Figure 9. Number of publications devoted to fuel cells and oxygen evolution reaction (OER) according to the database Scopus.

Figure 10. Percentage of scientific publications on LIBs devoted to capacity or fast charging. The keywords search in the Scopus database are annotated on the curves.



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Figure 11. Percentage of scientific publications devoted to specific cases of LIB and NIB as searched in the Scopus database. Nano refers to the papers having a nano-related keywords (mostly a sort of nanocomposite).

Figure 12. Number of research publications focused on lithium, sodium, and other (potassium/magnesium/calcium/aluminum) batteries as searched in the Scopus database. For the sake of visualisation, the latter two have been multiplied.

For Table of Contents Only


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The prospect of EVs depends on an appropriate strategy of research from a comprehensive perspective far from emerging sentiments and marketing hypes.



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Graphical Abstract


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Lithium Batteries for Electric Vehicles: From Economy to Research

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