Philosophiae Doctor - PhD / Aqueous ion-intercalation batteries (AIB’s) have the potential to provide both high power for hybrid-electric transport, and low cost bulk energy storage for electric grid supply. However, a major setback to AIB development is the instability of suitable ionintercalation anode material in aqueous electrolyte. To counter this problem, the use of activated carbon (AC) (a supercapacitor anode) paired against the low cost ionintercalation cathode spinel LiMn2O4 (LMO) provides a stable alternative. This thesis comprises two novel areas of investigation concerning: (1) the development of the AC/LMO cell for high power applications, and (2) the introduction of PbSO4 as a high capacity alternative anode material paired against LMO for low cost bulk energy storage. The study on AC/LMO explores the electrode combination’s practical specific energy and power capability at high P/E (power to energy ratio) of 50:1 suitable for hybrid electric vehicle batteries. To study the relationship between electrode material loading density, active material performance, and current collector mass contribution, a specially designed cell was constructed for galvanic cycling of different thicknesses of electrode. Between a loading density range of 25 – 100 mg, ~50 mg of total active material between two 1 cm2 current collectors produced the highest 50:1 P/E ratio values of 4 Wh/kg and 200 W/kg, constituting a 4-fold reduction of the active material values of thin films at 50:1 P/E. The cycling potentials of the individual electrodes revealed that doublings of electrode film loading density increased the LMO electrode’s polarization and voltage drop to similar levels as doublings in applied current density. However, by increasing the charging voltage from 1.8 V to 2.2 V, 6 Wh/kg and 300 W/kg was obtainable with minimal loss of energy efficiency. Finally a large-format cell of a calculated 3 Ah capacity at 50:1 P/E was constructed and tested. The cell produced ~60% of the anticipated capacity due to a suspected high level of resistance in the electrode contact points. The overall conclusion to the study was that AC/LMO holds promise for high power applications, and that future use of higher rate capability forms of LMO offers a promising avenue for further research. v The second part of this thesis presents the development of a novel cell chemistry, PbSO4/LMO, that has yet to be reported elsewhere in existing literature. The cell uses aqueous pH 7, 1 M, Li2SO4 electrolyte, and forms an electrode coupling where the PbSO4 anode charge/discharge is analogous to that in Pb-acid batteries. The average discharge voltage of the cell was 1.4 V and formed a flat charge/discharge plateau. The use of a low cost carbon coating method to encapsulate PbSO4 microparticles had a marked improvement on cell performance, and compared to uncoated PbSO4 improved both rate capability and specific capacity of the material. The active materials of the carbon-coated PbSO4/LMO cell produced a specific energy 51.1 Wh/kg, which, if a 65% yield is possible for a practical cell format, equals 38.4 Wh/kg, which is 15 Wh/kg higher than AC/LMO bulk storage cells at 23 Wh/kg, but lower than Pb-acid batteries at ~25-50 Wh/kg. Interestingly, the specific capacity of PbSO4 was 76 mAh/g compared to 100 mAh/g in Pb-acid cells. The predicted cost of the cell, providing a 65% value of the active material specific energy for a practical cell can be realized, is on par with Pb-acid battery technology and, importantly, uses 2.3 × less Pb/kWh. The cycling stability achieved thus far is promising, but will require testing over comparable cycle life periods to commercial batteries, which could be anywhere between 5 – 15 years.

A Comprehensive review of literature on electrode materials for lithium-ion batteries is provided in Chapter 1 of the thesis. Chapter 2 deals with the studies on porous, sub-micrometer size LiNi1/3Co1/3O2 as a positive electrode material for Li-ion cells synthesized by inverse microemulsion route and polymer template route. The electromechanical characterization studies show that carbon-coated LiNi1/3Co1/3O2 samples exhibit improved rate capability and cycling performance. Furthermore, it is anticipated that porous LiNi1/3Co1/3O2 could be useful for high rates of charge-discharge cycling. Synthesis of sub-micrometer size, porous particles of LiNi1/3Co1/3O2 using a tri-block copolymer as a soft template is carried out. LiNi1/3Co1/3O2 sample prepared at 900ºC exhibits a high rate capability and stable capacity retention of cycling. The electrochemical performance of LiNi1/3Co1/3O2 prepared in the absence of the polymer template is inferior to that of the sample prepared in the presence of the polymer template. Chapter 4 involves the synthesis of sub-micrometer size particles of LiMn2O4 in quaternary microemulsion medium. The electrochemical characterization studies provide discharge capacity values of about 100 mAh g-1 at C/5 rate and there is moderate decrease in capacity by increasing the rate of charge-discharge cycling. Studies also include charge-discharge cycling as well as ac impedance studies in temperature range from -10 to 40º C. Chapter 5 reports the synthesis of nano-plate LiFePO4 by polyol route starting from two reactants, namely, FePO42H2O and LiOH.2H2O. The electrodes fabricated out of nano-plate of LiFePO4 exhibit a high electrochemical activity. A stable capacity of about 155 mAh g-1 is measured at 0.2 C over 50 charge-discharge cycles. Mesoporous LiFePO4/C composite with two sizes of pores is prepared for the first time via solution-based polymer template technique. The precursor of LiFePO4/C composite is heated at different temperatures in the range from 600 to 800ºC to study the effect of crystalllinity, porosity and morphology on the electrochemical performance. The compound obtained at 700ºC exhibits a high rate capability and stable capacity retention on cycling with pore size distribution around 4 and 46nm. In Chapter 6, the electrochemical characterization of LiMn2O4 in an aqueous solution of 5 M LiNO3 is reported. A typical cell employing LiMn2O4 as the positive electrode and V2O5 as the negative electrode was assembled and the characterized by charge-discharge cycling in 5 M LiNO3 aqueous electrolyte. Furthermore, it is shown that Li+-ion in LiMn2O4 can be replaced by other divalent ions resulting in the formation of MMn2O4 (M = Ca, Mg, Ba and Sr) in aqueous M(NO3)2 electrolytes by subjecting LiMn2O4 electrodes to cyclic voltametry. Cyclic voltammetry and chronopotentiometry studies suggest that MMn2O4 can undergo reversible redox reaction by intercalation/deintercalation of M2+-ions in aqueous M(NO3)2 electrolytes.

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<p>Recently, energy storage systems have become more focused towards sustainable energy sources like LIBs due to attractive attributes like high energy density and volumetric density which make them extremely competitive compared to other energy sources for many portable and non-portable applications (smartphones, eVTOLs, stationary storage systems, electric vehicle and so on). Longer cycling stability, capacitance retentive power, lower self-discharge rate and high voltage window are qualitative features in LIB. Even though LIBs are rechargeable energy storage systems, all cells decay and degrade over time causing capacity and power fade due to a number of factors such as manufacturing defects, usage outside the normal operating conditions, and other abuse conditions like overcharge, over-discharge and indentation. This work presents a systematic investigation of several off-nominal conditions which are typically observed in LIBs such as overcharge, over-discharge, nail indentation, periodic overcharge, and over-discharge in order to form a comparative analysis on the effect of each of these conditions on cycle life aging, morphological changes on the cell components and also to evaluate potential internal short circuit (ISC) mechanisms. The cell failure mechanism induced by each condition and its negative impact on the electrochemical performance has been rigorously analyzed in this work based on the proper protocols. The correlation of the galvanostatic performance with the morphological change of the individual electrodes was also scrutinized under SEM and EDS to demarcate the severity of the defect into Li-ion cells. The practical off-nominal condition analysis of LIB will pave the way for more reliable cell functioning and recommendations to be considered to effectively analyze these off-nominal conditions. The analysis was divided into two parts; 1) curve-based analysis which included capacity fade, internal resistance, Incremental & Differential capacity analysis and EIS analysis 2) disassembly-based analysis which consisted of post-mortem visual inspection, morphology-based analysis using electron microscopy and composition analysis. From the capacity fade and IR evolution study, it was observed that periodic off-nominal conditions exhibited the highest rate of capacity fade and the greatest increase in DC internal resistance consistently. The least rate of capacity loss was shown by overcharged and no defect cells and a similar trend for DCIR values as well indicating that there was a positive correlation between capacity fade and internal resistance evolution. From the EIS study a slightly different trend was observed with the overcharged cell exhibiting the highest ohmic resistance and the no defect cell XV </p> <p>the least indicating ORI as an aging mechanism in overcharged and periodic overcharge/over-discharged cells. Another interesting observation was that the highest change in change transfer resistance was shown by over-discharged cell followed by nail-indented and overcharged cells and the least for cells subjected to periodic off-nominal conditions. This was attributed to a large amount of delamination caused by particle cracking in no defect cells causing LAM in these cells, lithium plating in Overcharged, copper current collector dissolution in over-discharged cells which resulted in LLI as the primary aging mechanism in these cells. This was further confirmed by ICA-DVA curve analysis at various capacity fades, postmortem inspection and SEM-EDS analysis. The periodic overcharged cells underwent a combination of degradation mechanisms including LAM from delamination, LLI through lithium deposition on the separators and Contact loss due to electrolyte vaporization causing active material adhesion on the separator and vice versa. The last degradation mechanism exacerbated the rate of increase of internal resistance by blocking pathways for Li+ ion diffusion. To summarize, while no defect and nail-indented cells exhibited primarily one aging mechanism (ORI) other cells exhibited a combination of degradation modes and the decoupling of these modes became increasingly indistinguishable for the cells subjected to periodic off-nominal conditions. Interestingly, no manifestation of soft or hard Internal short circuits was observed in the tested cells. However, it should be noted that for the periodic overcharged cells which underwent excessive lithium plating on the separators and charring of electrodes, dendrite formation could potentially have caused ISC upon further cycling. This cements the fact that periodic off-nominal conditions exacerbate the possibility of sudden failures and accelerate degradation in Li-ion cells. </p>

<p>Energy storage devices have become an integral part of the digital infrastructure of the 21st century. Li-ion batteries are a widely used chemical form of energy storage devices comprising components with varied chemical, mechanical and electrochemical properties. Over long-term usage, the anode and cathode experience spatially heterogeneous Li reaction, mechanical degradation, and reversible capacity loss. The small particle size and environmental sensitivity of materials used in Li-ion battery materials make investigating electrodes' electrochemical and mechanical properties an arduous task. Nevertheless, understanding the effect of electrochemical fatigue load (during the battery's charging and discharging process) on composite electrodes' mechanical stability is imperative to design and manufacture long-lasting energy storage devices.</p><p>Due to the low-symmetry lattice, Lithium Nickel Manganese Cobalt Oxide (NMC) cathode materials exhibit direction-dependent (anisotropic) mechanical properties. In this Dissertation, we first measure the anisotropic elastic stiffness of NMC cathode material using nano-indentation. We also determine the effect of Ni stoichiometry on the indentation modulus, hardness, and fracture toughness of NMC materials. The complete information on the mechanical properties of cathode materials will enable accurate computational results and the design of robust cathodes.</p><p>Further, using operando optical experiments, we report that NMC porous composite cathode experiences asynchronous reactions only during the 1st charging process. Non-uniform carbon binder network coverage across the cathode and Li concentration-dependent material properties of NMC results in the initial asynchronous phenomenon. The information on the degree of electrochemical conditioning of Li-ion battery cathode obtained from optical microscopy can test the consistency of product quality in the industrial manufacturing process. We also investigate the effects of non-uniform reactions on active material’s local morphology change and study the evolution of particle network over long-term cycling. Reported data from experiments depicts that in the early cycles, individual particles’ characteristics significantly influence the degree of damage across the cathode.</p><p>However, the interaction with neighboring particles becomes more influential in later cycles. Computational modeling uses a multiphysics-based theoretical framework to explain the interplay between electrochemical activity and mechanical damage. The methodology, theoretical framework, and experimental procedure detailed here will enable the design of efficient composite electrodes for long-lasting batteries.</p>

<p dir="ltr">Li-ion batteries are ubiquitous in today’s world with portable electronics, EVs making inroads into daily lives, and electric aircraft at the cusp of becoming reality. These and many more applications revolutionize the world with improvements in batteries at scales from materials, manufacturing, electrode architectures, cell design, and protocols. The various challenges associated with the current generation of batteries include the fast-charging capabilities, economic return of the longevity of the battery, and thermal safety characteristics. The aging and degradation of LIBs appears to be a key pain point particularly when exposed to harsh operating temperature and fast charging conditions. LIBs undergo aging due to numerous chemical and physical degradation processes throughout their lifetime owing to their operation. These challenges are exacerbated by the presence of stringent operating conditions including extreme fast charging, and sub-zero temperature resulting in severe degradation and short cycle life. The LIBs also face challenges in their thermal stability characteristics, failing catastrophically when exposed to high temperature or mechanical abuse conditions. The onset and intensity of these thermal runaway behaviors are further modified when batteries undergo varied aging leading to increased heat and gas generation potentially causing fire or explosions. Overall, a comprehensive characterization to delineate the interconnected role and implications of operating extremes and electrode design on electrochemical performance, cell aging, and thermal runaway behavior is critical for better batteries. </p><p dir="ltr">To this end, the role of electrode microstructure in mitigating lithium plating behavior under various operating conditions, including extreme fast charging has been examined. Further, these multi-length scale characteristics of the electrode microstructure are explored via data-driven approaches to study the complex interaction of transport and kinetic limitations on the microstructure designs. A third study is undertaken for in-operando characterization of the LIB degradation, probing the multi-length scale degradation using pulse voltammetry. Here an accurate degradation descriptors dataset is identified and accurately parametrized, throughout its cycling lifespan. These aging behaviors are translated to physio-chemical degradation mechanisms via a reduced-order coupled electrochemical-thermal-aging interactions model. Lastly, the implication of aging behavior on thermal-safety interactions is delineated. Overall the dissertation is focused on developing a fundamental understanding of the LIB performance, degradation, and safety interactions.</p>

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LIBs have become an ideal choice in the EVs batteries and stationary storage applications due to their invaluable advantages. The demand for LIBs is projected to increase due to the growth in the sale of EVs. But an average lifespan of LIBs is expected to be around 8 years, thus resulting in the generation of a huge pile of spent batteries after their end of life. The disposal of spent LIBs has several environmental impacts and also results in the loss of valuable metals as a waste. So, efficient, and sustainable recycling methods should also grow at the same pace as of the EVs industries. Li is one of the vital elements for the modern energy revolution and there is a growing demand for its usage in the battery applications. High demand for Li along with supply risks due to its uneven distribution in different geographical locations will increase the Li price. Also, Li was added to the list of EUs critical materials. Currently, only 1% of Li from the end of life products is being recovered. The hydrometallurgy processes based on acid leaching followed by recovery steps are found to be efficient in the recovery of a considerable amount of Li yet there are many drawbacks. Therefore, a combined method such as a thermal treatment followed by water leaching is found to be a promising route to first selectively separate Li from the other valuable metals. The purpose of this research is to investigate the selective leaching of Li from thermally pretreated waste LIBs (by pyrolysis and incineration processes between 400 – 700 ºC for 30, 60, 90min) with water as a leaching agent at high temperature and low L/S ratio. Al salts were also leached along with Li with an efficiency not higher than 3.5%. The finding showed that the time of thermal pretreatment did not have a significant change in Li leaching efficiency. The effect of the S/L ratio showed that the leaching efficiency of Li was higher with an increase in liquid content, keeping the mass of solid constant. At a higher leaching temperature, the leaching efficiency of Li was higher due to an increase in the solubility of Li salts. The highest Li leaching efficiency of nearly 60% was observed from the sample pyrolyzed at 700 ºC for 60 min with the leaching condition S/L ratio = 1:20 g/mL, 80 ºC, 300 rpm, 3 hrs. Furthermore, the tests such as addition of 10% excess carbon during thermal treatment or use of carbonated water during leaching were carried out to enhance the leaching efficiency of Li. However, the test results did not have a significant increase in the leaching efficiency of Li. / LIB har blivit ett idealiskt val i EV-batterier och stationära lagringsapplikationer på grund av deras ovärderliga fördelar. Efterfrågan på LIB bedöms öka på grund av tillväxten i försäljningen av elbilar. Men en genomsnittlig livslängd på LIB förväntas vara cirka 8 år, vilket resulterar i att en enorm hög med förbrukade batterier genereras efter deras livslängd. Bortskaffande av förbrukade LIB har flera miljöpåverkan och resulterar också i förlust av värdefulla metaller som avfall. Så effektiva och hållbara återvinningsmetoder borde också växa i samma takt som inom elbranschen. Li är ett av de viktigaste elementen för den moderna energirevolutionen och det finns en växande efterfrågan på dess användning i batteritillämpningarna. Hög efterfrågan på Li tillsammans med utbudsrisker på grund av dess ojämna fördelning på olika geografiska platser kommer att öka Li-priset. Li läggs också till i listan över EU: s kritiska material. För närvarande återvinns endast 1% av Li från uttjänta produkter. Hydrometallurgiprocesserna baserade på syraläckning följt av återvinningssteg har visat sig vara effektiva vid utvinningen av en betydande mängd Li men det finns många nackdelar. Därför har en kombinerad metod, såsom en termisk behandling följt av vattenlakning, visat sig vara en lovande väg att först selektivt separera Li från de andra värdefulla metallerna. Syftet med denna forskning är att undersöka den selektiva urlakningen av Li från termiskt förbehandlade avfall LIB (genom pyrolys och förbränningsprocesser mellan 400 - 700 ºC under 30, 60, 90 minuter) med vatten som läckmedel vid hög temperatur och låg L / S förhållande. Al-salter lakades också ut tillsammans med Li med en verkningsgrad som inte var högre än 3,5%. Resultatet visade att tiden för termisk förbehandling inte hade någon signifikant förändring av Li-utlakningseffektiviteten. Effekten av S / L-förhållandet visade att urlakningseffektiviteten för Li var högre med en ökning av vätskeinnehållet, vilket höll massan av fast ämne konstant. Vid en högre urlakningstemperatur var urlakningseffektiviteten för Li högre på grund av en ökning av lösligheten av Li-salter. Den högsta Li-lakningseffektiviteten på nästan 60% observerades från provet pyrolyserat vid 700 ° C under 60 minuter med läckningsförhållandet S / L-förhållande = 1:20 g / ml, 80 ° C, 300 rpm, 3 timmar. Vidare utfördes testerna såsom tillsats av 10% överskott av kol under termisk behandling eller användning av kolsyrat vatten under lakning för att förbättra lakningseffektiviteten för Li. Emellertid hade testresultaten ingen signifikant ökning av utlakningseffektiviteten för Li.