Surface Structure of LiMn[sub 2]O[sub 4] Electrodes

Eriksson, Therése; Gustafsson, Torbjörn; Thomas, Josh

doi:10.1149/1.1432782

Cited by 42 publications

(29 citation statements)

References 32 publications

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“…[4][5][6][7][8][9][10] Considerable efforts have been devoted to alleviating these deficiencies by coating the LNMO surface using metal oxides, [11][12][13] phosphates, [14][15][16][17] fluorides, [18,19] and so forth. diffuse into the surface lattices and help improve the performance of the electrode materials by: (1) eliminating the onset of Jahn-Teller distortion of transition metals such as Mn 3+ ; (2) suppressing the transition metals dissolution; (3) preventing severe electrolyte oxidative decomposition; (4) combating second phase formation; (5) strengthening the metal-oxygen bonds on the surface; and (6) changing the surface basicity. Bulk doping during materials preparation is another strategy aimed at suppressing the phase transition in LNMO, [20][21][22][23][24][25][26] but the excessive and uncontrollable doping will block the Li ions transportation channels in its bulk structure, leading to active capacity loss.…”

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confidence: 99%

“…[2,3] Nevertheless, such high operating voltage of LNMO involves surface chemistry issues such as irreversible surface phase transition, transition metal dissolution, Jahn-Teller distortion of Mn 3+ , electrolyte oxidation, etc. [4][5][6][7][8][9][10] Considerable efforts have been devoted to alleviating these deficiencies by coating the LNMO surface using metal oxides, [11][12][13] phosphates, [14][15][16][17] fluorides, [18,19] and so forth. These coating materials can tackle the metal dissolution, electrolyte decomposition, and Mn 3+ Jahn-Teller distortion problems by simply shielding the cathode material from direct exposure to the electrolyte.…”

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confidence: 99%

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Nanoscale Manipulation of Spinel Lithium Nickel Manganese Oxide Surface by Multisite Ti Occupation as High‐Performance Cathode

et al. 2017

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A novel two-step surface modification method that includes atomic layer deposition (ALD) of TiO followed by post-annealing treatment on spinel LiNi Mn O (LNMO) cathode material is developed to optimize the performance. The performance improvement can be attributed to the formation of a TiMn O (TMO)-like spinel phase resulting from the reaction of TiO with the surface LNMO. The Ti incorporation into the tetrahedral sites helps to combat the impedance growth that stems from continuous irreversible structural transition. The TMO-like spinel phase also alleviates the electrolyte decomposition during electrochemical cycling. 25 ALD cycles of TiO growth are found to be the optimized parameter toward capacity, Coulombic efficiency, stability, and rate capability enhancement. A detailed understanding of this surface modification mechanism has been demonstrated. This work provides a new insight into the atomic-scale surface structural modification using ALD and post-treatment, which is of great importance for the future design of cathode materials.

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confidence: 99%

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confidence: 99%

Nanoscale Manipulation of Spinel Lithium Nickel Manganese Oxide Surface by Multisite Ti Occupation as High‐Performance Cathode

et al. 2017

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“…Particle sizes were determined with a Beckman Coulter particle size analyzer ͑model LS 230, with small volume module͒, and a scanning electron microscope ͑ISI-DS 130C dual stage͒ with an attached X-ray energy-dispersive spectrometer ͑EDAX model DS130 144-10, with amplifier model 184͒ was used to determine the approximate composition and to observe the particle morphologies. 7 Li magic angle spinning ͑MAS͒ nuclear magnetic resonance ͑NMR͒ experiments were performed at 38.95 MHz on a Bruker AMX-100 spectrometer with a Doty probe equipped with a 7 mm rotor. To prevent the loss of data in the beginning of the free induction decay ͑FID͒ due to the probe recovery time, a Hahn echo sequence (90°Ϫ Ϫ 180°Ϫ Ϫ acq.)…”

Section: Methodsmentioning

confidence: 99%

Sulfur-Doped Aluminum-Substituted Manganese Oxide Spinels for Lithium-Ion Battery Applications

Doeff

Hollingsworth

Shim

et al. 2003

J. Electrochem. Soc.

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Spinels with nominal composition Li 1.02 Al 0.25 Mn 1.75 O 3.97 S 0.03 , Li 1.02 Al 0.25 Mn 1.75 O 4 , and Li 1.02 Al 0.15 Mn 1.85 O 3.96 S 0.04 have been evaluated for their suitability as positive electrode materials in rechargeable lithium-ion batteries for electric ͑EV͒ and hybrid electric vehicle ͑HEV͒ applications. 7 Li magic angle spinning, nuclear magnetic resonance, X-ray diffraction, ͑XRD͒ and energydispersive spectroscopy experiments indicate that sulfur is most likely present as a trace impurity on the surface of the spinel particles rather than substituting for oxygen ions in the bulk, so it is unlikely to account for the previously reported enhanced cyclability of this material. Rather, the unusual particle morphology produced during calcination of some samples in the presence of sulfur compounds appears to impede ͑but does not completely prevent͒ conversion to the tetragonal phase that occurs at 3 V vs. Li and ameliorates the capacity fading associated with it. These materials exhibit reduced rate capability and capacity at 4 V, making them unsuitable for high energy density EV, or high power density applications.The synthesis and electrochemical behavior of LiAl 0.25 Mn 1.75 O 3.97 S 0.03 , a novel sulfur-doped spinel, have recently been described. 1,2 In contrast to other manganese oxide spinels, it has been reported to show excellent reversibility even when cycled at 3 V vs. Li or at elevated temperatures. Although power management considerations preclude utilization of capacity on both the 3 and 4 V plateaus in batteries for vehicular applications, stable electrode materials that can withstand overdischarge and other abusive conditions are necessary to obtain the desired long cycle life of the cell stacks. Because of severe cost constraints 3 associated with devices intended for electric vehicles ͑EVs͒ and hybrid electric vehicles ͑HEVs͒, less expensive manganese oxide spinels would make particularly attractive replacements for cobalt and cobalt nickel oxides currently used in lithium-ion batteries, provided that cycling problems can be overcome. Spinels may be particularly well suited for HEV batteries, because high energy density is not required, but high power density is.Capacity fading upon cycling of Li/LiMn 2 O 4 cells has been attributed to irreversible oxidation of electrolyte, 4,5 dissolution of manganese ions in acidic electrolyte solutions, and formation of defect spinel near the end of charge ͑particularly above 55°C͒, 6,7 and disconnection of particles associated with the tetragonal phase conversion that occurs at 3 V vs. Li. 8 The latter may also occur at 4 V during high-rate discharges. 9 Development of new electrolytes, 10 partial substitution of manganese with lithium 11 or other transition metals, 12 and protective coating of particles with lithium carbonate, 13 zinc oxide, 14 or LiCoO 2 15 have substantially improved cyclability in recent years. The severe capacity loss associated with reduction of spinels past an average Mn oxidation state of 3.5 and transformation to a tetr...

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“…The positive electrode contains LMO and LCO active material, which both have been investigated regarding ageing mechanisms in earlier studies [11][12][13][14]. The negative electrode active material LTO has a flat discharge curve over almost the complete State of Charge (SOC) range [15,16] resulting in that the differential voltage (dV/dQ) curve of the cell will mirror the differential voltage curve of the positive electrode.…”

Section: Differential Voltage Analysismentioning

confidence: 99%

Lithium-Ion Battery Cell Cycling and Usage Analysis in a Heavy-Duty Truck Field Study

2015

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This paper presents results from a field test performed on commercial power-optimized lithium-ion battery cells cycled on three heavy-duty trucks. The goal with this study was to age battery cells in a hybrid electric vehicle (HEV) environment and find suitable methods for identifying cell ageing. The battery cells were cycled on in-house developed equipment intended for testing on conventional vehicles by emulating an HEV environment. A hybrid strategy that allows battery usage to vary within certain limits depending on driving patterns was used. This concept allows unobtrusive and low-cost testing of battery cells under realistic conditions. Each truck was equipped with one cell cycling equipment and two battery cells. One cell per vehicle was cycled during the test period while a reference cell on each vehicle experienced the same environmental conditions without being cycled. Differential voltage analysis and electrochemical impedance spectroscopy were used to identify ageing of the tested battery cells. Analysis of driving patterns and battery usage was performed from collected vehicle data and battery cell data.

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Surface Structure of LiMn[sub 2]O[sub 4] Electrodes

Cited by 42 publications

References 32 publications

Nanoscale Manipulation of Spinel Lithium Nickel Manganese Oxide Surface by Multisite Ti Occupation as High‐Performance Cathode

Nanoscale Manipulation of Spinel Lithium Nickel Manganese Oxide Surface by Multisite Ti Occupation as High‐Performance Cathode

Sulfur-Doped Aluminum-Substituted Manganese Oxide Spinels for Lithium-Ion Battery Applications

Lithium-Ion Battery Cell Cycling and Usage Analysis in a Heavy-Duty Truck Field Study

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