Chemical Tuning of NaSICON Surfaces for Fast-Charging Na Metal Solid-State Batteries

Solid-state batteries (SSBs) with alkali metal anodes hold great promise as energetically dense and safe alternatives to conventional Li-ion cells. Whilst, in principle, SSBs have the additional advantage of offering virtually unlimited plating current densities, fast charges have so far only been achieved through sophisticated interface engineering strategies. Here, we reveal that such interface engineering can be easily achieved by tuning the chemistry of NaSICON solid electrolytes (Na3.4Zr2Si2.4P0.6O12) and taking advantage of the thermodynamic stabilization of a Na3PO4 layer on their surface upon thermal activation. The optimized planar Na|NZSP interfaces are characterized by their exceptionally low interface resistances (down to 0.1 Ω cm2 at room temperature) and, more importantly, by their tolerance to large plating current densities (up to 10 mA cm-2) even for extended cycling periods of 30 minutes (corresponding to an areal capacity 5 mAh cm-2).

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The Role of Areal Capacity in Determining Short Circuiting of Sulfide-Based Solid-State Batteries

10.33774/chemrxiv-2021-q0vbw ◽

2021 ◽

Author(s):

John Lewis ◽

Chanhee Lee ◽

Yuhgene Liu ◽

Sang Yun Han ◽

Dhruv Prakash ◽

...

Keyword(s):

Solid State ◽

Current Density ◽

Specific Energy ◽

Research Effort ◽

Short Circuit ◽

Lithium Ion ◽

Solid State Batteries ◽

Current Densities ◽

High Specific Energy ◽

Areal Capacity

Solid-state batteries (SSBs) with lithium metal anodes offer higher specific energy than conventional lithium-ion batteries, but they must utilize areal capacities >3 mAh cm-2 and cycle at current densities >3 mA cm-2 to achieve commercial viability. Substantial research effort has focused on increasing rate capabilities of SSBs by mitigating detrimental processes such as lithium filament penetration. Less attention has been paid to understanding how areal capacity impacts plating/stripping behavior, despite the importance of areal capacity for achieving high specific energy. Here, we investigate and quantify the relationships among areal capacity, current density, and plating/stripping stability using both symmetric and full-cell configurations with a sulfide solid-state electrolyte (Li6PS5Cl). We show that unstable deposition and short circuiting readily occur at rates much lower than the measured critical current density when a sufficient areal capacity is passed. A systematic study of continuous plating under different electrochemical conditions reveals average “threshold capacity” values at different current densities, beyond which short circuiting occurs. Cycling cells below this threshold capacity significantly enhances cell lifetime, enabling stable symmetric cell cycling at 2.2 mA cm-2 without short circuiting. Finally, we show that full cells also exhibit threshold capacity behavior, but they tend to short circuit at lower current densities and areal capacities. Our results quantify the effects of transferred capacity and demonstrate the importance of using realistic areal capacities in experiments to develop viable solid-state batteries.

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On the Feasibility of All-solid-state Batteries with LLZO as a Single Electrolyte

10.21203/rs.3.rs-1020785/v1 ◽

2021 ◽

Author(s):

Kostiantyn V. Kravchyk ◽

Dogan Tarik Karabay ◽

Maksym V. Kovalenko

Keyword(s):

Solid State ◽

Electronic Conductivity ◽

Lithium Ion ◽

Metal Anode ◽

Solid State Batteries ◽

Li Ion ◽

All Solid State Batteries ◽

Battery Discharge ◽

Power Densities ◽

Areal Capacity

Abstract Replacement of Li-ion liquid-state electrolytes by solid-state counterparts in a Li-ion battery (LIB) is a major research objective as well as an urgent priority for the industry, as it enables the use of a Li metal anode and provides new opportunities to realize safe, non-flammable, and temperature-resilient batteries. Among the plethora of solid-state electrolytes (SSEs) investigated, garnet-type Li-ion electrolytes based on cubic Li7La3Zr2O12 (LLZO) are considered the most appealing candidates for the development of future solid-state batteries because of their low electronic conductivity of ca. 10−8 S cm−1 (RT) and a wide electrochemical operation window of 0 ‒ 6 V vs. Li+/Li. However, high LLZO density (5.1 g cm-3) and its lower level of Li-ion conductivity (up to 1 mS cm−1 at RT) compared to liquid electrolytes (1.28 g cm-3; ca. 10 mS cm−1 at RT) still raise the question as to the feasibility of using solely LLZO as an electrolyte for achieving competitive energy and power densities. In this work, we analyzed the energy densities of Li-garnet all-solid-state batteries based solely on LLZO SSE by modeling their Ragone plots using LiCoO2 as the model cathode material. This assessment allowed us to identify values of the LLZO thickness, cathode areal capacity, and LLZO content in the solid-state cathode required to match the energy density of conventional lithium-ion batteries (ca. 180 Wh kg-1 and 497 Wh L-1) at the power densities of 200 W kg-1 and 600 W L-1, corresponding to ca. 1h of battery discharge time (1C). We then discuss key challenges in the practical deployment of LLZO SSE in the fabrication of Li-garnet all-solid-state batteries.

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Li2(BH4)(NH2) Nanoconfined in SBA-15 as Solid-State Electrolyte for Lithium Batteries

Nanomaterials ◽

10.3390/nano11040946 ◽

2021 ◽

Vol 11 (4) ◽

pp. 946

Author(s):

Qianyi Yang ◽

Fuqiang Lu ◽

Yulin Liu ◽

Yijie Zhang ◽

Xiujuan Wang ◽

...

Keyword(s):

Solid State ◽

High Performance ◽

Coulombic Efficiency ◽

Specific Capacity ◽

Transference Number ◽

Electrochemical Stability ◽

Ion Conductivity ◽

Solid State Batteries ◽

Li Ion ◽

Conduction Properties

Solid electrolytes with high Li-ion conductivity and electrochemical stability are very important for developing high-performance all-solid-state batteries. In this work, Li2(BH4)(NH2) is nanoconfined in the mesoporous silica molecule sieve (SBA-15) using a melting–infiltration approach. This electrolyte exhibits excellent Li-ion conduction properties, achieving a Li-ion conductivity of 5.0 × 10−3 S cm−1 at 55 °C, an electrochemical stability window of 0 to 3.2 V and a Li-ion transference number of 0.97. In addition, this electrolyte can enable the stable cycling of Li|Li2(BH4)(NH2)@SBA-15|TiS2 cells, which exhibit a reversible specific capacity of 150 mAh g−1 with a Coulombic efficiency of 96% after 55 cycles.

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Recycling of Li-Ion and Li-Solid State Batteries: The Role of Hydrometallurgy

The Minerals, Metals & Materials Series - Extraction 2018 ◽

10.1007/978-3-319-95022-8_214 ◽

2018 ◽

pp. 2541-2553 ◽

Cited By ~ 1

Author(s):

François Larouche ◽

George P. Demopoulos ◽

Kamyab Amouzegar ◽

Patrick Bouchard ◽

Karim Zaghib

Keyword(s):

Solid State ◽

Solid State Batteries ◽

Li Ion

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Quantifying the impact of disorder on Li-ion and Na-ion transport in perovskite titanate solid electrolytes for solid-state batteries

Journal of Materials Chemistry A ◽

10.1039/d0ta05343k ◽

2020 ◽

Vol 8 (37) ◽

pp. 19603-19611

Author(s):

Adam R. Symington ◽

John Purton ◽

Joel Statham ◽

Marco Molinari ◽

M. Saiful Islam ◽

...

Keyword(s):

Solid State ◽

Ion Transport ◽

Solid Electrolytes ◽

Research Interest ◽

Considerable Research ◽

Solid State Batteries ◽

Li Ion ◽

All Solid State Batteries ◽

And Performance ◽

The Impact

Solid electrolytes for all-solid-state batteries are generating considerable research interest as a means to improving their safety, stability and performance.

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(Invited) In Operando and in Situ techniques for Intercalation Compounds in Li-Ion and All-Solid-State Batteries

ECS Meeting Abstracts ◽

10.1149/ma2020-02116mtgabs ◽

2020 ◽

Vol MA2020-02 (1) ◽

pp. 16-16

Author(s):

Karim Zaghib ◽

Wen Zhu ◽

Shirin Kaboli ◽

Hendrix Demers ◽

Michel Trudeau ◽

...

Keyword(s):

Solid State ◽

Intercalation Compounds ◽

In Situ Techniques ◽

Solid State Batteries ◽

Li Ion ◽

All Solid State Batteries ◽

In Operando

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SnO2 nanowire anchored graphene nanosheet matrix for the superior performance of Li-ion thin film battery anode

Journal of Materials Chemistry A ◽

10.1039/c4ta04836a ◽

2015 ◽

Vol 3 (1) ◽

pp. 274-280 ◽

Cited By ~ 44

Author(s):

Rajesh Thomas ◽

G. Mohan Rao

Keyword(s):

Thin Film ◽

Solid State ◽

Superior Performance ◽

Graphene Nanosheet ◽

Thin Film Battery ◽

Portable Electronics ◽

Solid State Batteries ◽

Li Ion ◽

All Solid State Batteries ◽

Battery Anode

All solid state batteries are essential candidate for miniaturizing the portable electronics devices.

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Garnet-Type Fast Li-Ion Conductors with High Ionic Conductivities for All-Solid-State Batteries

ACS Applied Materials & Interfaces ◽

10.1021/acsami.7b00614 ◽

2017 ◽

Vol 9 (14) ◽

pp. 12461-12468 ◽

Cited By ~ 77

Author(s):

Jian-Fang Wu ◽

Wei Kong Pang ◽

Vanessa K. Peterson ◽

Lu Wei ◽

Xin Guo

Keyword(s):

Solid State ◽

Ionic Conductivities ◽

Solid State Batteries ◽

Li Ion ◽

All Solid State Batteries ◽

Li Ion Conductors ◽

Ion Conductors

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Correction to “Atomic-Scale Influence of Grain Boundaries on Li-Ion Conduction in Solid Electrolytes for All-Solid-State Batteries”

Journal of the American Chemical Society ◽

10.1021/jacs.8b04915 ◽

2018 ◽

Vol 140 (22) ◽

pp. 7044-7044 ◽

Cited By ~ 2

Author(s):

James A. Dawson ◽

Pieremanuele Canepa ◽

Theodosios Famprikis ◽

Christian Masquelier ◽

M. Saiful Islam

Keyword(s):

Solid State ◽

Grain Boundaries ◽

Solid Electrolytes ◽

Atomic Scale ◽

Ion Conduction ◽

Solid State Batteries ◽

Li Ion ◽

All Solid State Batteries

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Blocking Lithium Dendrite Growth in Solid-State Batteries with an Ultrathin Amorphous Li-La-Zr-O Solid Electrolyte

10.26434/chemrxiv.13331084.v1 ◽

2020 ◽

Author(s):

Jordi Sastre ◽

Moritz H. Futscher ◽

Lea Pompizi ◽

Abdessalem Aribia ◽

Agnieszka Priebe ◽

...

Keyword(s):

Solid State ◽

Electronic Conductivity ◽

High Capacity ◽

Dendrite Growth ◽

Potential Candidate ◽

Sputtering Deposition ◽

Lithium Garnet ◽

Solid State Batteries ◽

Current Densities ◽

Lithium Dendrite

Lithium garnet Li7La3Zr2O12 (LLZO) electrolyte is a potential candidate for the development of solid-state batteries with lithium metal as high-capacity anode. But ceramic LLZO in the form of pellets or polycrystalline films can still suffer from lithium dendrite penetration because of surface and bulk inhomogeneities and grain boundaries with non-negligible electronic conductivity. In contrast, the amorphous phase of LLZO (aLLZO) possesses a grain-boundary-free microstructure with moderate ionic conductivity (10-7 S cm-1) and high electronic insulation (10-14 S cm-1), which in the form of thin coatings can offer resistance to lithium dendrite growth. We explore the electrochemical properties and applications of aLLZO ultrathin films prepared by sputtering deposition. The defect-free and conformal nature of the films enables microbatteries with an electrolyte thickness as low as 70 nm, which withstand charge-discharge at 0.2 mA cm-2 for over 500 cycles. In Li/aLLZO/Li symmetric cells, plating-stripping at current densities up to 3.2 mA cm-2 shows no signs of lithium penetration. Finally, we show that the application of aLLZO as a coating on LLZO ceramic pellets significantly impedes the formation of Li dendrites.

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