Unraveling the Voltage-Fade Mechanism in High-Energy-Density Lithium-Ion Batteries: Origin of the Tetrahedral Cations for Spinel Conversion

Mohanty, Debasish; Li, Jianlin; Abraham, Daniel P.; Huq, Ashfia; Payzant, E. Andrew; Wood, David L.; Daniel, Claus

doi:10.1021/cm5031415

Cited by 268 publications

(235 citation statements)

References 29 publications

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“…16,21 Their in operando X-ray diffraction measurements reveal an increase in c-and decrease in a-lattice parameters leading to a gradual non-monotonic decrease in unit cell volume during the first charge to 4.8 V. The observed crystal structure changes do not correlate exactly with the measured stress, which indicates that the supposedly 'inactive' electrode components such as the carbons and the binder also contribute to stress evolution. For instance, intercalation of PF 6 − anions at voltages >4.45 V vs. Li/Li + leads to lattice expansion and structure disordering of graphite contained in the positive electrode. 22 In addition, the maximum stress, between 1.2 and 1.5 MPa, displayed by the positive electrode could also be due to the finite tensile strength of the PVdF binder.…”

Section: Resultsmentioning

confidence: 99%

Stress Evolution in Lithium-Ion Composite Electrodes during Electrochemical Cycling and Resulting Internal Pressures on the Cell Casing

Nadimpalli¹,

Sethuraman²,

Abraham³

et al. 2015

J. Electrochem. Soc.

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Composite cathode coatings made of a high energy density layered oxide (Li 1.2 Ni 0.15 Mn 0.55 Co 0.1 O 2 , theoretical capacity ∼377 mAh-g −1 ), polyvinylidene fluoride (PVdF) binder, and electron-conduction additives, were bonded to an elastic substrate. An electrochemical cell, built by pairing the cathode with a capacity-matched graphite anode, was electrochemically cycled and the real-time average stress evolution in the cathode coating was measured using a substrate-curvature technique. Features in the stress evolution profile showed correlations with phase changes in the oxide, thus yielding data complementary to in situ XRD studies on this material. The stress evolution showed a complex variation with lithium concentration suggesting that the volume changes associated with phase transformations in the oxide are not monotonically varying functions of lithium concentration. The peak tensile stress in the cathode during oxide delithiation was approximately 1.5 MPa and the peak compressive stress during oxide lithiation was about 6 MPa. Stress evolution in the anode coating was also measured separately using the same technique. The measured stresses are used to estimate the internal pressures that develop in a cylindrical lithium-ion cell with jelly-roll electrodes. Lithium-ion cells are the primary choice for portable energy storage devices because of their high energy densities. Presently, lithiumion cells typically contain carbon-based materials, such as graphite, in the negative electrode (anode) and transition metal oxides in the positive electrode (cathode). State-of-the-art lithium-ion batteries have a specific capacity of ∼ 150 Wh-kg −1 ; energy densities, two to five times higher, are needed to meet the performance and range requirements of hybrid and all-electric vehicles for transportation applications. The energy densities can be increased by using anode and cathode materials with higher capacities and/or higher voltages. For example, anode materials Sn and Si can accommodate several lithium atoms per metal/metalloid unit yielding theoretical capacities of 960 (Li 4.25 Sn) and 4009 mAh-g −1 (Li 4.2 Si), respectively. Cathode materials from the xLi 2 MnO 3 · (1-x)LiMO 2 family of compounds have been reported to display capacities approaching 300 mAh-g −1 , significantly larger than the 140-170 mAh-g −1 useable capacities exhibited by commercial materials.Several recent investigations have focused on exploring the structure-property relationships of the xLi 2 MnO 3 · (1-x)LiMO 2 compounds. Multiple experimental techniques including electron microscopy, 2,3 X-ray and neutron diffraction, 4-6 X-ray absorption spectroscopy, 7 and nuclear magnetic resonance 8,9 have been used to characterize the structural changes in these oxides resulting from electrochemical cycling. In addition to structural changes, variation in lithium concentrations during electrochemical cycling can result in complex stress fields within (and between) the oxide secondary particles resulting in mechanical degradation, 10 which ca...

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Section: Resultsmentioning

confidence: 99%

Stress Evolution in Lithium-Ion Composite Electrodes during Electrochemical Cycling and Resulting Internal Pressures on the Cell Casing

Nadimpalli¹,

Sethuraman²,

Abraham³

et al. 2015

J. Electrochem. Soc.

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“…122 The voltage fade has been attributed to chemical and structural changes including oxygen evolution, Ni and Co migration from the surface into the bulk, reduction of Mn 4+ to Mn 3+ , and formation of a spinel-like phase. [123][124][125][126][127][128][129] The spinel-like phase is formed by the migration of lithium ion from octahedral lithium site to tetrahedral lithium site and migration of TM ions from octahedral M site to octahedral lithium site via oxygen vacancies. Therefore, strategies to mitigate phase change are to restrict the cation migration.…”

Section: High-voltage Cathode Materialsmentioning

confidence: 99%

“…The phase change also results in a somewhat more complex CEI formation mechanism than that of Ni-rich NMC. 130,131 Strategies to stabilize the surface of Li-rich NMCs include coatings, [132][133][134][135] surface treatments, 126 cycling protocols, 136 synthesis routes, 137,138 and electrolyte additives. 135 Most of these efforts have failed to stop the underlying mechanisms responsible for voltage fade, 135 although compositions that incorporate small amounts of spinel domains into the layered structure show some promise.…”

Section: High-voltage Cathode Materialsmentioning

confidence: 99%

Toward Low-Cost, High-Energy Density, and High-Power Density Lithium-Ion Batteries

Ruther

et al. 2017

JOM

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232

159

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Reducing cost and increasing energy density are two barriers for widespread application of lithium-ion batteries in electric vehicles. Although the cost of electric vehicle batteries has been reduced by $70% from 2008 to 2015, the current battery pack cost ($268/kWh in 2015) is still >2 times what the USABC targets ($125/kWh). Even though many advancements in cell chemistry have been realized since the lithium-ion battery was first commercialized in 1991, few major breakthroughs have occurred in the past decade. Therefore, future cost reduction will rely on cell manufacturing and broader market acceptance. This article discusses three major aspects for cost reduction: (1) quality control to minimize scrap rate in cell manufacturing; (2) novel electrode processing and engineering to reduce processing cost and increase energy density and throughputs; and (3) material development and optimization for lithium-ion batteries with high-energy density. Insights on increasing energy and power densities of lithium-ion batteries are also addressed.

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“…10 Further studies have also been widely done to unravel the mechanism underlying the intrinsic voltage decay upon subsequent cycling of Li-rich manganese layered oxide. [11][12][13][14] Recently, we first reported that the solid solution of Li 2 Mn 1¹x Ru x O 3 exhibit high capacity of about 200 mAh g ¹1 and lower electrical resistivity five order of magnitude than Li 2 MnO 3 , indicating that the substitution of Ru is effective to enhance the electrochemical as well as electrical properties. 15 Li 2 RuO 3 is isostructural with Li 2 MnO 3 , composed of lithium and lithium-transition metal layer except for a minor stacking difference.…”

Section: Introductionmentioning

confidence: 99%

Relationship between Cyclic Properties and Charge-discharge Condition for Li2Mn0.4Ru0.6O3 and Li2RuO3

et al. 2015

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Capacity and voltage retentions upon subsequent cycles for Li 2 RuO 3 and Li 2 Mn 0.4 Ru 0.6 O 3 (LMR) under various cutoff voltages have been investigated. The change in average and local structures upon electrochemical cycling were examined by ex-situ XRD and Ru L 3 -edge XANES measurements, and the relationship between the cyclic capabilities and the structural changes is discussed. The deteriorations of discharge capacity and average discharge voltage in the subsequent cycles of LMR with a charge cut-off voltage of 4.8 V vs. Li/Li + are remarkably smaller than that with the voltage of 4.2 V. Moreover, LMR exhibits higher average discharge voltage than Li 2 RuO 3 under a charge cut-off voltage of 4.8 V. The phase transition behavior of LMR was not similar to Li 2 RuO 3 upon electrochemical cycling. Ru L 3 -edge XANES spectra measurements reveal that RuO 6 octahedra in LMR charged at 4.2 V are much distorted. The local structure of RuO 6 octahedra is associated with the cyclic capability of LMR and Li 2 RuO 3 .

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Unraveling the Voltage-Fade Mechanism in High-Energy-Density Lithium-Ion Batteries: Origin of the Tetrahedral Cations for Spinel Conversion

Cited by 268 publications

References 29 publications

Stress Evolution in Lithium-Ion Composite Electrodes during Electrochemical Cycling and Resulting Internal Pressures on the Cell Casing

Stress Evolution in Lithium-Ion Composite Electrodes during Electrochemical Cycling and Resulting Internal Pressures on the Cell Casing

Toward Low-Cost, High-Energy Density, and High-Power Density Lithium-Ion Batteries

Relationship between Cyclic Properties and Charge-discharge Condition for Li<sub>2</sub>Mn<sub>0.4</sub>Ru<sub>0.6</sub>O<sub>3</sub> and Li<sub>2</sub>RuO<sub>3</sub>

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