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. 2021 Aug 11;13(31):37809-37815.
doi: 10.1021/acsami.1c07952. Epub 2021 Jul 29.

High Energy Density Single-Crystal NMC/Li6PS5Cl Cathodes for All-Solid-State Lithium-Metal Batteries

Christopher Doerrer  1 , Isaac Capone  1 , Sudarshan Narayanan  1 , Junliang Liu  1 , Chris R M Grovenor  1   2 , Mauro Pasta  1   2 , Patrick S Grant  1   2
Affiliations

High Energy Density Single-Crystal NMC/Li6PS5Cl Cathodes for All-Solid-State Lithium-Metal Batteries

Christopher Doerrer et al. ACS Appl Mater Interfaces. .

Abstract

To match the high capacity of metallic anodes, all-solid-state batteries require high energy density, long-lasting composite cathodes such as Ni-Mn-Co (NMC)-based lithium oxides mixed with a solid-state electrolyte (SSE). However in practice, cathode capacity typically fades due to NMC cracking and increasing NMC/SSE interface debonding because of NMC pulverization, which is only partially mitigated by the application of a high cell pressure during cycling. Using smart processing protocols, we report a single-crystal particulate LiNi0.83Mn0.06Co0.11O2 and Li6PS5Cl SSE composite cathode with outstanding discharge capacity of 210 mA h g-1 at 30 °C. A first cycle coulombic efficiency of >85, and >99% thereafter, was achieved despite a 5.5% volume change during cycling. A near-practical discharge capacity at a high areal capacity of 8.7 mA h cm-2 was obtained using an asymmetric anode/cathode cycling pressure of only 2.5 MPa/0.2 MPa.

Keywords: composite cathode; interfacial contact; pressure dependence; single-crystal NMC; solid-state battery; stack pressure; sulfide electrolyte; volume expansion.

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Conflict of interest statement

The authors declare no competing financial interest.

Figures

Figure 1
Figure 1
(a) SEM micrograph of the as-supplied SC-NMC powder and (b) corresponding particle size distribution. SEM micrograph of the (c) in-house LPSCl-SP used in the composite cathode and (d) as-supplied LPSCl-LP used in the SSE separator. (e) Ionic conductivity of LPSCl powders as a function of pressure, and (f) XRD spectra of the LPSCl powders.
Figure 2
Figure 2
(a) Schematic of the cell manufacturing steps, (b) cross-section of a SC-NMC/LPSCl composite cathode after cell assembly and before cycling, and (c) EDX element maps for carbon, sulfur, and nickel.
Figure 3
Figure 3
(a) Initial charge/discharge curves (with average voltages UC and UDC) of a SC-NMC/LPSCl composite cathode (14 mg cm–2, 3 mA h cm–2) cycled at 2.5 MPa, 0.2 mA cm–2, 30 °C and the (b) differential capacity. (c) Ex situ XRD spectra before cycling, after charge and discharge. (d) Cathode cross-section after charging with some loss of contact at the SC-NMC/LPSCl interface and particle separation of previously agglomerated crystals.
Figure 4
Figure 4
Charge/discharge curves of a SC-NMC/LPSCl composite cathode (14 mg cm–2, 3 mA h cm–2) with a Li anode, and capacity fade (inset) at (a) 2.5 and (b) 10 MPa. (c) Discharge capacity at different current densities and higher cycle numbers of the same SC-NMC/LPSCl cathode with a LTO/LPSCl composite anode cycled at 10 MPa.
Figure 5
Figure 5
(a) Asymmetric load cell setup used to lower the cathode stack pressure while maintaining anode pressure. Corresponding voltage capacity curves for a cell cycled at 0.2 mA cm–2 and an anode/cathode pressure of 2.5 MPa/0.2 MPa for a (b) SC-NMC/LPSCl composite cathode of 14 mg cm–2 (3 mA h cm–2), and capacity fade compared to different pressures and a (c) SC-NMC/LPSCl composite cathode of 43 mg cm–2 (8.7 mA h cm–2). (d) Discharge capacity comparison for Ni-rich composite cathodes pressed at RT as a function of the stack pressure during cycling.
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