In Situ Lithiated ALD Niobium Oxide for Improved Long Term Cycling of Layered Oxide Cathodes: A Thin-Film Model Study

Aribia, Abdessalem; Sastre, Jordi; Chen, Xubin; Gilshtein, Evgeniia; Futscher, Moritz H.; Tiwari, Ayodhya N.; Romanyuk, Yaroslav E.

doi:10.1149/1945-7111/abf215

“…While the voltage window increased from 3–4.3 V to 1.5–4.7 V, the impedance rose only from 300 Ω cm 2 to below 500 Ω cm 2 .These results suggest that the LiPON solid‐state electrolyte helps to stabilize the cathode electrolyte interface and to mitigate the impedance increase during cell operation. This effect is reminiscent of those reported for a Li‐Nb‐O or LiPON coating of active cathode material in bulk cells [ 27,30,40 ] or coated multi‐electron vanadium‐based cathodes. [ 37 ]…”

Section: Resultssupporting

confidence: 61%

Unlocking Stable Multi‐Electron Cycling in NMC811 Thin‐Films between 1.5 – 4.7 V

Aribia

¹

,

Sastre

²

,

Chen

³

et al. 2022

Advanced Energy Materials

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reversible capacity of current cathodes is lower than that of conventional graphite anodes (372 mAh g -1 ) and far behind that of high-capacity anodes such as lithium metal (3860 mAh g -1 ) and silicon (4200 mAh g -1 ). [2,3] Simultaneously, the cathode is the main contributor to the material cost at the cell level. [4] Currently, LiNi 0.8 Mn 0.1 Co 0.1 O 2 (NMC811) is gaining commercial adoption due to its capacity of ≈200 mAh g -1 assuming one Li-ion per formula unit and low content of expensive cobalt. [5] Two intriguing research questions stand out: i) Is it possible to increase the cathodic discharge capacity by introducing additional lithium into the host NMC811 structure? ii) Can we control the reactivity of Ni-rich cathode material with the electrolyte and prevent the formation of a solid electrolyte interphase (SEI) layer and consequent low capacity retention? [6,7] NMC cathodes can actually store more than one lithium ion per formula unit. This phenomenon is by no means a recent discovery, and the first reports of Li-rich NMC-type layered oxide cathodes date back to 2003. [8] When discussing Li-rich layered cathode materials, it is important to differentiate between Mn-based and Ni-based compositions. Most of the investigated Li-rich NMC compounds are based on Mn as main redox-active transition metal. [9,10] This allows for excess lithium to be stored in a Li 2 MnO 3 composite structure embedded in Li(Ni, Mn, Co)O 2 , where oxygen atoms are involved in the redox process above 4.5 V. [11] Such Among cathode materials, LiNi 0.8 Mn 0.1 Co 0.1 O 2 (NMC811) is the most discussed for high performance Li-ion batteries, thanks to its capacity of ≈200 mAh g -1 and low Co content. Here, it is demonstrated that NMC811 can reversibly accommodate more than one Li-ion per formula unit when coupled with a solid-state electrolyte, thus significantly increasing its capacity. Sputtered Li-rich NMC811 cathodes are tested with lithium-phosphorus-oxynitride as a solidstate electrolyte in a thin-film architecture, which is a simplified 2D model with direct access to the cathode-electrolyte interface. The solid-state electrolyte helps to stabilize the interface and prevents capacity fading, voltage decay, and interface resistance growth, thus allowing cycling at extended voltage ranges of 1.5-4.7 V. While the liquid electrolyte cells suffer from rapid capacity decay, the Li-rich NMC811 cells with the solid-state electrolyte can cycle at a fast rate and an initial capacity of 149 mAh g -1 from 1.5 to 4.3 V for 1000 cycles. The all-solidstate thin-film cells with a lithium metal anode yield a discharge capacity of up to 350 mAh g -1 at C/10 because of multi-electron cycling with a coulombic efficiency of 90.1%. The results demonstrate how solid-state electrolytes that are stable against NMC811 cathodes can unlock the full potential of this Li-rich and Ni-rich cathode class.

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“…While the voltage window increased from 3-4.3 V to 1.5-4.7 V, the impedance rose only from 300 Ω cm 2 to below 500 Ω cm 2 .These results suggest that the LiPON solid-state electrolyte helps to stabilize the cathode electrolyte interface and to mitigate the impedance increase during cell operation. This effect is reminiscent of those reported for a Li-Nb-O or LiPON coating of active cathode material in bulk cells [27,30,40] or coated multielectron vanadium-based cathodes. [37] In a next step, prolonged cycling of thin-film Li-rich NMC811 cathodes in liquid-and solid electrolyte cells was attempted.…”

Section: Resultssupporting

confidence: 59%

Unlocking Stable Multi-Electron Cycling in NMC811 Thin-Films between 1.5 – 4.7 V

Aribia

¹

,

Futscher

²

,

Sastre

³

et al. 2022

Proceedings of the Materials for Sustainable Development Conference (MAT-SUS)

0

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reversible capacity of current cathodes is lower than that of conventional graphite anodes (372 mAh g -1 ) and far behind that of high-capacity anodes such as lithium metal (3860 mAh g -1 ) and silicon (4200 mAh g -1 ). [2,3] Simultaneously, the cathode is the main contributor to the material cost at the cell level. [4] Currently, LiNi 0.8 Mn 0.1 Co 0.1 O 2 (NMC811) is gaining commercial adoption due to its capacity of ≈200 mAh g -1 assuming one Li-ion per formula unit and low content of expensive cobalt. [5] Two intriguing research questions stand out: i) Is it possible to increase the cathodic discharge capacity by introducing additional lithium into the host NMC811 structure? ii) Can we control the reactivity of Ni-rich cathode material with the electrolyte and prevent the formation of a solid electrolyte interphase (SEI) layer and consequent low capacity retention? [6,7] NMC cathodes can actually store more than one lithium ion per formula unit. This phenomenon is by no means a recent discovery, and the first reports of Li-rich NMC-type layered oxide cathodes date back to 2003. [8] When discussing Li-rich layered cathode materials, it is important to differentiate between Mn-based and Ni-based compositions. Most of the investigated Li-rich NMC compounds are based on Mn as main redox-active transition metal. [9,10] This allows for excess lithium to be stored in a Li 2 MnO 3 composite structure embedded in Li(Ni, Mn, Co)O 2 , where oxygen atoms are involved in the redox process above 4.5 V. [11] Such Among cathode materials, LiNi 0.8 Mn 0.1 Co 0.1 O 2 (NMC811) is the most discussed for high performance Li-ion batteries, thanks to its capacity of ≈200 mAh g -1 and low Co content. Here, it is demonstrated that NMC811 can reversibly accommodate more than one Li-ion per formula unit when coupled with a solid-state electrolyte, thus significantly increasing its capacity. Sputtered Li-rich NMC811 cathodes are tested with lithium-phosphorus-oxynitride as a solidstate electrolyte in a thin-film architecture, which is a simplified 2D model with direct access to the cathode-electrolyte interface. The solid-state electrolyte helps to stabilize the interface and prevents capacity fading, voltage decay, and interface resistance growth, thus allowing cycling at extended voltage ranges of 1.5-4.7 V. While the liquid electrolyte cells suffer from rapid capacity decay, the Li-rich NMC811 cells with the solid-state electrolyte can cycle at a fast rate and an initial capacity of 149 mAh g -1 from 1.5 to 4.3 V for 1000 cycles. The all-solidstate thin-film cells with a lithium metal anode yield a discharge capacity of up to 350 mAh g -1 at C/10 because of multi-electron cycling with a coulombic efficiency of 90.1%. The results demonstrate how solid-state electrolytes that are stable against NMC811 cathodes can unlock the full potential of this Li-rich and Ni-rich cathode class.

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“…Given the amorphous nature of these coatings, it is unlikely that ALD NbO or ALD LiNbO have any propensity to lithiate further, as evidenced in other studies utilizing high annealing or calcination temperatures to obtain a favorable crystal structure and lattice parameters for lithium intercalation or release. 33,34 To demonstrate the realistic application of these protective coatings, the protected copper foils were used in full coin cells. As shown in Figure 6A, the bare copper foils remained unable to adequately cycle beyond the first 15-20 cycles and quickly lost any usable capacity due to an extremely low Coulombic efficiency.…”

Section: Resultsmentioning

confidence: 99%

Atomic layer deposition niobium oxide and lithium niobium oxide as a protection technique for anode‐free batteries

Doyle‐Davis,

Adair,

Wang

et al. 2023

Battery Energy

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As demand for extended range in electric vehicles and longer battery lifetimes in consumer electronics has grown, so have the requirements for higher energy densities and longer cycle lifetimes of the cells that power them. One solution to this is the implementation of an “anode‐free” battery. By removing the anode and plating lithium directly onto the current collector, it is possible to access the same capacities and voltage windows as traditional lithium metal batteries, with the entirety of the lithium source coming from the cathode. Herein, a copper foil current collector coated with niobium oxide or lithium niobium oxide through atomic layer deposition (ALD) is applied to extend the cycling life of the anode‐free batteries by reducing dendrite formation and improving the stability of the lithium metal surface throughout cycling. The ALD coatings are able to extend the cycle lifetime in full coin cells from 20 cycles to 80% capacity retained in the bare copper controls to 50 and 115 cycles for the NbO and LiNbO coatings, respectively. Over the lifetime of the cells, the ALD‐LiNbO is able to cumulatively offer a staggering improvement of an additional 100 kWh L−1 compared to the bare copper control.

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In Situ Lithiated ALD Niobium Oxide for Improved Long Term Cycling of Layered Oxide Cathodes: A Thin-Film Model Study

Cited by 9 publications

References 36 publications

Unlocking Stable Multi‐Electron Cycling in NMC811 Thin‐Films between 1.5 – 4.7 V

Unlocking Stable Multi‐Electron Cycling in NMC811 Thin‐Films between 1.5 – 4.7 V

Unlocking Stable Multi-Electron Cycling in NMC811 Thin-Films between 1.5 – 4.7 V

Atomic layer deposition niobium oxide and lithium niobium oxide as a protection technique for anode‐free batteries

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