The rapidly expanding field of nonaqueous multivalent intercalation batteries offers a promising way to overcome safety, cost, and energy density limitations of state-of-the-art Li-ion battery technology. We present a critical and rigorous analysis of the increasing volume of multivalent battery research, focusing on a wide range of intercalation cathode materials and the mechanisms of multivalent ion insertion and migration within those frameworks. The present analysis covers a wide variety of material chemistries, including chalcogenides, oxides, and polyanions, highlighting merits and challenges of each class of materials as multivalent cathodes. The review underscores the overlap of experiments and theory, ranging from charting the design metrics useful for developing the next generation of MV-cathodes to targeted in-depth studies rationalizing complex experimental results. On the basis of our critical review of the literature, we provide suggestions for future multivalent cathode studies, including a strong emphasis on the unambiguous characterization of the intercalation mechanisms.
Energy storage is increasingly seen as a valuable asset for electricity grids composed of high fractions of intermittent sources, such as wind power or, in developing economies, unreliable generation and transmission services. However, the potential of batteries to meet the stringent cost and durability requirements for grid applications is largely unquantified. We investigate electrochemical systems capable of economically storing energy for hours and present an analysis of the relationships among technological performance characteristics, component cost factors, and system price for established and conceptual aqueous and nonaqueous batteries. We identified potential advantages of nonaqueous flow batteries over those based on aqueous electrolytes; however, new challenging constraints burden the nonaqueous approach, including the solubility of the active material in the electrolyte. Requirements in harmony with economically effective energy storage are derived for aqueous and nonaqueous systems. The attributes of flow batteries are compared to those of aqueous and nonaqueous enclosed and hybrid (semi-flow) batteries. Flow batteries are a promising technology for reaching these challenging energy storage targets owing to their independent power and energy scaling, reliance on facile and reversible reactants, and potentially simpler manufacture as compared to established enclosed batteries such as lead-acid or lithium-ion. Broader context Cost-effective electrochemical energy storage has the potential to dramatically change how society generates and delivers electricity. A few key market opportunities include supporting high fractions of intermittent renewable energy sources and deferring upgrades of existing electricity grid infrastructure. Unfortunately, present state-of-the-art technologies are too expensive for broad deployment. Reductions in manufacturing costs and associated overheads are identied as the single largest cost-savings opportunity for today's battery-based storage options. In addition, increasing production volume and market competition will lead to lower material costs. Both aqueous and nonaqueous ow batteries are promising technology platforms capable of achieving the low costs required for widespread implementation. Non-aqueous systems enable higher cell voltages than their aqueous counterparts but also require higher active material solubility to offset higher electrolyte costs. For both battery types, a key enabling development will be the discovery of tailored molecules that are long lived, provide large cell voltages, and have costs similar to existing commodity chemicals.
Increasing the areal capacity or electrode thickness in lithium ion batteries is one possible means to increase pack level energy density while simultaneously lowering cost. The physics that limit use of high areal capacity as a function of battery power to energy ratio are poorly understood and thus most currently produced automotive lithium ion cells utilize modest loadings to ensure long life over the vehicle battery operation. Here we show electrolyte transport limits the utilization of the positive electrode at critical C-rates during discharge; whereas, a combination of electrolyte transport and polarization lead to lithium plating in the graphite electrode during charge. Experimental measurements are compared with theoretical predictions based on concentrated solution and porous electrode theories. An analytical expression is derived to provide design criteria for long lived operation based on the physical properties of the electrode and electrolyte. Finally, a guideline is proposed that graphite cells should avoid charge current densities near or above 4 mA/cm 2 unless additional precautions have been made to avoid deleterious side reaction. Lithium-ion (Li-ion) batteries are currently being used as the primary energy storage device in hybrid, plug-in, and all electric vehicles. This commercialization has been possible only by leveraging decades of previous scientific and engineering advances on materials, electrodes, and cell development. However, interactions in this complex system are still not fully understood. Automotive grade battery cells are required to fulfill a variety of optimization criteria in order to meet customer expectations and enable highly functional, robust and competitive products. In Fig. 1, key cell level criteria are shown for available technology as well as future development goals. Many of these values are highly influential on each other. In order to optimize one of the criteria it is always necessary to critically evaluate the impact on others. Key goals are to increase vehicle range and decrease cost at the same time. Minimizing the fraction of non-active material is an intuitive path to achieve these goals; however, the cell power and rate capability must simultaneously be maintained. [1][2][3] To derive clear development goals, the high level targets can be broken down to specific component requirements on the different levels of a storage system. 1,4 In Fig. 2, an analysis is shown for a state of the art prismatic hard-case automotive cell format. A battery level specific energy of ∼225 Wh/kg is widely accepted to be a critical value for sustainable implementation of long range electric vehicles. It represents a useful ratio between vehicle weight and range. In order to achieve this high specific energy, all subcomponents of the storage system have to meet demanding requirements as well. On the cell level, large format cells are favorable as they reduce the amount of cell housing needed per cell volume. Prismatic cell formats have a positive influence on the packing densi...
Researchers worldwide view the high theoretical specific energy of the lithium-air or lithium-oxygen battery as a promising path to a transformational energy-storage system for electric vehicles. Here, we present a self-consistent material-to-system analysis of the best-case mass, volume, and cost values for the nonaqueous lithium-oxygen battery and compare them with current and advanced lithium-based batteries using metal-oxide positive electrodes. Surprisingly, despite their high theoretical specific energy, lithium-oxygen systems were projected to achieve parity with other candidate chemistries as a result of the requirement to deliver and purify or to enclose the gaseous oxygen reactant. The theoretical specific energy, which leads to predictions of an order of magnitude improvement over a traditional lithium-ion battery, is shown to be an inadequate predictor of systems-level cost, volume, and mass. This analysis reveals the importance of system-level considerations and identifies the reversible lithium-metal negative electrode as a common, critical high-risk technology needed for batteries to reach long-term automotive objectives. Additionally, advanced lithium-ion technology was found to be a moderate risk pathway to achieve the majority of volume and cost reductions. Broader contextThe commercialization of battery electric vehicles has provided a glimpse of one potential future paradigm of the transportation sector. Moving to an electricitybased transportation system could enable a domestically produced, potentially near-zero emission energy source if coupled to clean, domestic sources of electricity production. However, the batteries used in electric vehicles in 2013 are too expensive, large, and heavy for mass market adoption; signicant progress is needed. The lithium-air or lithium-oxygen battery is a high visibility archetype for the "best-case" possible electrochemical energy-storage system for electric vehicles. We present a material-to-systems analysis of the lithium-oxygen chemistry with comparison to current and future lithium-based chemistries to identify scientic challenges and technological possibilities. Through translation of materials-level science to the systems-level engineering, we show that a lithiumoxygen battery system for automotive applications has comparable cost, volume, and mass to other advanced chemistries that are in more mature states of development and have less technical risk. This result demonstrates that system-level analysis is necessary and may contradict trends predicted from active materials based specic energy and energy density calculations that are the basis for many research investment decisions.
A materials-to-system analysis for the lithium-sulfur (Li-S) electric vehicle battery is presented that identifies the key electrode and cell design considerations from reports of materials chemistry. The resulting systems-level energy density, specific energy and battery price as a function of these parameters is projected. Excess lithium metal amount at the anode and useable specific capacity, electrolyte volume fraction, sulfur to carbon ratio and reaction kinetics at the cathode are all shown to be critical for the high energy density and low cost requirements. Electrode loading is determined as a key parameter to relate the battery price for useable energy to the investigated design considerations. The presented analysis proposes that electrode loadings higher than 8 mAh/cm 2 (∼7 mg S/cm 2 ) are necessary for Li-S systems to exhibit the high energy density and low cost required for transportation applications. Stabilizing the interface of lithium metal at the required current densities and areal capacities while simultaneously maintaining cell capacity with high sulfur loading in an electrolyte starved cathode are identified as the key barriers for ongoing research and development efforts to address. In the search for high energy density and inexpensive rechargeable batteries for the electric vehicles, Li-S batteries have gained significant attention due to the high specific capacity (1675 mAh/g), low cost, natural abundance and non-toxicity of elemental sulfur.1-6 Compared to the state-of-art Li-ion batteries, Li-S batteries have very high theoretical specific energy of 2567 Wh/kg.1-6 The Li-S battery is commonly composed of a sulfur-carbon composite cathode, an organic electrolyte and a lithium anode.1-6 The overall Li-S redox reaction is given in equation 1.with a standard potential of U 0 = 2.2 V (vs Li/Li + ). 1,2Despite these attractive features of the Li-S battery, multiple formidable challenges limit the cycle life significantly. [1][2][3][4][5][6] Firstly, precipitation of insulating reactants, sulfur and Li 2 S, in the cathode leads to poor electronic conductivity and passivation that could limit the active material utilization.1-6 Secondly, the soluble polysulfide reaction intermediates produced during charging can migrate to the anode where they react with Li to either precipitate on the anode surface or migrate back to the cathode causing infinite charging.1-6 This polysulfide shuttle mechanism leads to poor coulombic efficiency and significant self-discharge as well as corrosion of the Li-anode.1-6 Finally, the instability of the Li-anode is a major concern.2,4,5,7 Li surface area can increase significantly with cycling due to morphological changes, which accelerate Li and electrolyte depletion owing to the absence of a stable interphase. 2,4,5,7 While polysulfide migration may lead to the corrosion of dendritic or high surface area lithium reducing the risk of short circuiting, the resulting reactions typically result in a reduction in inventory of cyclable lithium. 4 All of these mechanisms ...
This paper reports the results of an initial investigation into the phenomenon of hysteresis in the charge−discharge profile of high-capacity, lithiumand manganese-rich "layered−layered" xLi 2 MnO 3 •(1−x)LiMO 2 composite cathode structures (M = Mn, Ni, Co) and "layered−layered-spinel" derivatives that are of interest for Li-ion battery applications. In this study, electrochemical measurements, combined with in situ and ex situ X-ray characterization, are used to examine and compare electrochemical and structural processes that occur during charge (lithium extraction) and discharge (lithium insertion) of preconditioned cathodes. Electrochemical measurements of the open-circuit voltage versus lithium content demonstrate a ∼1 V hysteresis in site energy for approximately 12% of the total lithium content during the early cycles, which is markedly different from the hysteresis commonly observed in other intercalation materials. X-ray absorption data indicate structural differences in the cathode at the same state of charge (i.e., the same lithium content) during lithium insertion and extraction reactions. The data support an intercalation mechanism whereby the total number of lithium ions extracted at the top of charge is not reaccommodated in the structure until low states of charge are reached. The hysteresis in this class of materials is attributed predominantly to an inherent structural reorganization after an electrochemical activation of the Li 2 MnO 3 component that alters the crystallographic site energies.
This article examines three key questions in environmental analysis of EVs and their batteries that influence EV-to-ICV comparative environmental performance.
A new approach to synthesizing high capacity lithium-metal-oxide cathodes for lithium-ion batteries from a Li 2 MnO 3 precursor is described. The technique, which is simple and versatile, can be used to prepare a variety of integrated 'composite' electrode structures, such as 'layered-layered' xLi 2 MnO 3 •(1-x)LiMO 2 , 'layered-spinel' xLi 2 MnO 3 •(1-x)LiM 2 O 4 , 'layered-rocksalt' xLi 2 MnO 3 • (1-x)MO and more complex arrangements, in which M is typically Mn, Ni, and/or Co. Early indications are that electrodes prepared by this method are effective in 1) countering the voltage decay that occurs on cycling 'layered-layered' xLi 2 MnO 3 •(1-x)LiMO 2 electrodes without compromising capacity, and 2) reducing the extent of electrochemical activation required above 4.5 V on the initial charge. In particular, a 0.5Li 2 MnO 3 •0.5LiMn 0.5 Ni 0.5 O 2 electrode, after activation at 4.6 V, delivers a steady capacity of 245 mAh/g between 4.4 and 2.5 V at 15 mA/g (∼C/15 rate) with little change to the voltage profile; a first cycle capacity loss of 12%, which is significantly less than usually observed for 'layered-layered' electrodes, has been achieved with a manganese-rich 0.1Li 2 MnO 3 •0.9LiMn 0.50 Ni 0.37 Co 0.13 O 2 electrode. These results have implications for enhancing the performance of the next generation of high-energy lithium-ion batteries. The flexibility of the method and the variation in electrochemical properties of various composite electrode structures and compositions are demonstrated.
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