Rechargeable Batteries: Grasping for the Limits of Chemistry

Berg, Erik J.; Villevieille, Claire; Streich, Daniel; Trabesinger, Sigita; Novák, Petr

doi:10.1149/2.0081514jes

Cited by 219 publications

(273 citation statements)

References 70 publications

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“…53 Assuming all electrodes used here have the same initial porosity of 35%, the specific volume of electrode (including voids) per gram LNMO increases from 0.44 cm 3 /g LNMO to 0.46 cm 3 /g LNMO or 0.48 cm 3 /g LNMO by adding 2.5 wt% or 5 wt% lithium oxalate, respectively (calculated from electrode compositions given in Table I and bulk densities of 4.4 g/cm 3 for LNMO, 1.8 g/cm 3 for PVDF, 2.2 g/cm 3 for C65 and 2.1 g/cm 3 for lithium oxalate). 55 Accordingly, the oxidation of lithium oxalate leads to a porosity increase from 35% to 38% in the electrodes with 2.5 wt% and to 40% in the electrodes with 5 wt% lithium oxalate. The resulting volumetric energy density, here defined as energy per entire electrode volume including voids, is around 1272 Wh/L electrode at cycle 5 for cells without lithium oxalate and rises about 3% to 1315 Wh/L electrode for cells containing 2.5 wt% lithium oxalate.…”

Section: Discussionmentioning

confidence: 99%

Lithium Oxalate as Capacity and Cycle-Life Enhancer in LNMO/Graphite and LNMO/SiG Full Cells

Solchenbach

Wetjen

Pritzl

et al. 2018

J. Electrochem. Soc.

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In the present study, we explore the use of lithium oxalate as a "sacrificial salt" in combination with lithium nickel manganese spinel (LNMO) cathodes. By online electrochemical mass spectrometry (OEMS), we demonstrate that the oxidation of lithium oxalate to CO 2 (corresponding to 525 mAh/g) occurs quantitatively around 4.7 V vs. Li/Li + . LNMO/graphite cells containing 2.5 or 5 wt% lithium oxalate show an up to ∼11% higher initial discharge capacity and less capacity fade over 300 cycles (12% and 8% vs. 19%) compared to cells without lithium oxalate. In LNMO/SiG full-cells with an FEC-containing electrolyte solution, lithium oxalate leads to a better capacity retention (45% vs 20% after 250 cycles) and a higher coulombic efficiency throughout cycling (∼1%) compared to cells without lithium oxalate. When CO 2 from lithium oxalate oxidation is removed after formation, a similar capacity fading as in LNMO/SiG cells without lithium oxalate is observed. Hence, we attribute the improved cycling performance to the presence of CO 2 in the cells. Further analysis (e.g., FEC consumption by 19 F-NMR) indicate that CO 2 is an effective SEI-forming additive for SiG anodes, and that a combination of FEC and CO 2 has a synergistic effect on the lifetime of full-cells with SiG anodes. Lithium nickel manganese spinel (LiNi 0.5 Mn 1.5 O 4 , LNMO) is a promising cathode material for high energy lithium ion batteries due to its high operating potential around 4.7 V vs. Li/Li + , its high rate capability, structural stability and the absence of cobalt. However, its lower specific capacity (146 mAh/g LNMO ) compared to layered oxide materials (e.g. lithium nickel manganese cobalt oxide (NMC), specific capacity 150-250 mAh/g NMC ) 1 is regarded as a major drawback. In full-cells, the practically achievable capacity of LNMO is even lower, as the formation of the solid-electrolyte interphase (SEI) on the graphite anode consumes active lithium. For many layered oxide cathodes, however, the first cycle irreversible capacity of the cathode is similar to the capacity needed for SEI formation (∼20 mAh/g NMC ), and hence the practical discharge capacity of the cathode and the remaining active lithium are more or less balanced again. 2,3 In contrast, the first cycle irreversible capacity of LNMO (∼6 mAh/g LNMO ) is much lower than the capacity needed for SEI formation. This leads to a mismatch between active lithium and practical cathode capacity, i.e., there is not enough active lithium available to fully discharge the LNMO cathode during subsequent cycling.In cells with silicon-based anodes, active lithium losses on the anode are even higher compared to graphite, as the expansion of the silicon particles during the first lithiation leads to a continuous exposure of fresh, unpassivated silicon surface. 4 On this new surface, electrolyte reduction occurs instantaneously, which reduces the total lithium reservoir in the cell. Therefore, different ideas to increase the amount of active lithium in lithium ion full-cells have been suggested, ...

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Section: Discussionmentioning

confidence: 99%

Lithium Oxalate as Capacity and Cycle-Life Enhancer in LNMO/Graphite and LNMO/SiG Full Cells

Solchenbach

Wetjen

Pritzl

et al. 2018

J. Electrochem. Soc.

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“…This is due, first of all, to their high energy density and good cyclability [1][2][3][4]. Important materials for cathodes (or positive electrodes) of LIBs are lithium and manganese-rich layered composites from the xLi 2 MnO 3 ·(1 − x)Li[Ni a Co b Mn c ]O 2 (a + b + c = 1) family that are normally described as comprising two layered structure phases, Li 2 MnO 3 (C/2m space group) and Li[Ni a Co b Mn c ]O 2 (a + b + c = 1) (R3m space group), integrated on the atomic level [5][6][7][8]. These two The TM migration to the Li-layer during later stages of charging, that causes the large charge/discharge voltage hysteresis, is also the main reason for the large capacity fades during the cycling of the Li-and Mn-rich materials [37][38][39][40].…”

Section: Introductionmentioning

confidence: 99%

Study of Cathode Materials for Lithium-Ion Batteries: Recent Progress and New Challenges

et al. 2017

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Amongst a number of different cathode materials, the layered nickel-rich LiNi y Co x Mn 1−y−x O 2 and the integrated lithium-rich xLi 2 MnO 3 ·(1 − x)Li[Ni a Co b Mn c ]O 2 (a + b + c = 1) have received considerable attention over the last decade due to their high capacities of~195 and~250 mAh·g −1 , respectively. Both materials are believed to play a vital role in the development of future electric vehicles, which makes them highly attractive for researchers from academia and industry alike. The review at hand deals with both cathode materials and highlights recent achievements to enhance capacity stability, voltage stability, and rate capability, etc. The focus of this paper is on novel strategies and established methods such as coatings and dopings.

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“…The resultant pack-level mean-cost per unit energy ($/kWh) of these chemistries was 280 for LMO, 257 for LFP, 224 for NCA, and 241 for NMC. Studies 73 on prismatic cells estimate the cell cost ($/kWh) to be slightly over 200 for LMO, NCA, and NMC, and over 280 for LFP. Another study 32 reports cell costs of 290 $/kWh for LMO, 310 for LFP, 260 for NCA, and 250 for NMC, for slightly different electrode design parameters with cathode thickness of 80 μm.…”

Section: Resultsmentioning

confidence: 99%

“…But other studies 52 have used a 1:1 ratio in their analysis. For LMO cathodes, certain studies use active material weight fractions of as low as 73.5% 53 and others use values as high as 90%. 54 All electrodes in our study are designed with Polyvinylidene difluoride (PVDF) as the binder and Carbon black (CB) as the conductive additive, the active material fraction of the cathode is maintained at approximately 85% by weight, and the binder and conductive additive ratio is decided on the basis of the values used by other studies.…”

Section: Methodsmentioning

confidence: 99%

Evaluation of Current, Future, and Beyond Li-Ion Batteries for the Electrification of Light Commercial Vehicles: Challenges and Opportunities

Sripad

Viswanathan

2017

J. Electrochem. Soc.

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While the electrification of the transportation sector is underway with a consistently increasing market share, segments like light commercial vehicles (LCVs) have not seen any significant market penetration. The major barriers are primarily in the shortcomings in specific energy, power, and cost associated with Li-ion batteries. With an initiative from several automakers to electrify other segments, there is a need to critically examine the performance requirements and to understand the factors governing such a transition in the near-term and long-term. In this study, we develop a systematic methodological framework to analyze the performance demands for electrification through an approach that couples considerations for battery chemistries, load profiles based on a set of vehiclespecific drive cycles, and finally applying these loads to a battery pack that solves a 1-D thermally coupled battery model within the AutoLion-ST framework. Using this framework, we analyze the performance of a fully electric LCV over its lifetime under various driving conditions and explore the trade-offs between battery metrics and vehicle design parameters. We find that in order to enable a driving range of over 400-miles for LCVs at a realistic battery pack weight, specific energies of over 400 Wh/kg at the cell-level and 200 Wh/kg at the pack-level needs to be achieved. A crucial factor that could bring down both the energy requirements and cost is through a vehicle re-design that lowers the drag coefficient to about 0. The complete electrification of the transportation sector is essential to reduce CO 2 emissions and improve air quality in densely populated cities.1 There has been remarkable progress toward electrification in the passenger sedan market, with a market share of more than a few hundred thousand vehicles, and reaching as high as 23% in Norway and 10% Netherlands.2 Light commercial vehicles (LCVs) form nearly one-tenth of the global market share 3 and about 30% in the United States where they account for approximately 30% of the greenhouse gas emissions of the transportation sector.4 Yet, the electrification of this segment is very limited, primarily due to the shortcomings of the current state of battery technology. [5][6][7][8] The average fuel economy for this segment has remained largely stagnant since 1985, while the engine fuel efficiency has been increasing continuously. 9 This is in large part due to automakers increasing the performance of the vehicles at the expense of fuel economy, thus, maintaining sustained demand for high-performance LCVs.Prior work has explored the implementation of hybrid electric pickup trucks 10 with the drivetrains utilizing internal combustion engines (ICEs) for longer distances. A few other studies 11,12 have discussed the potential use of a battery pack by retrofitting conventional pickup trucks with electric drivetrains. With major electric automakers such as Tesla Inc., announcing their work toward fully electric LCVs, 13 there is an urgent need to understand systematically th...

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Rechargeable Batteries: Grasping for the Limits of Chemistry

Cited by 219 publications

References 70 publications

Lithium Oxalate as Capacity and Cycle-Life Enhancer in LNMO/Graphite and LNMO/SiG Full Cells

Lithium Oxalate as Capacity and Cycle-Life Enhancer in LNMO/Graphite and LNMO/SiG Full Cells

Study of Cathode Materials for Lithium-Ion Batteries: Recent Progress and New Challenges

Evaluation of Current, Future, and Beyond Li-Ion Batteries for the Electrification of Light Commercial Vehicles: Challenges and Opportunities

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