Interface Regulation of Electrochemical Potential in NASICON-type Ceramic Solid-state Batteries

doi:10.15541/jim20240518

Abstract

Abstract:

Li_1.3Al_0.3Ti_1.7(PO₄)₃ (LATP), one of the NASICON-type solid-state electrolytes, possesses a high ionic conductivity, excellent chemical stability, and high shear modulus (40-60 GPa). However, the tetravalent titanium ion in LATP is particularly prone to undergo reduction reaction with lithium metal during cycling, leading to the structure degradation and electron introduction in LATP electrolyte. In order to maintain the chemical and electrochemical stability of LATP, this work modified the surface of LATP solid electrolyte with a Prussian blue (PB) interfacial layer to optimize the contact between electrolyte and anode. Using PB with abundant open-frame lithium ion diffusion channels as the mixed conductive modification layer has several advantages. (1) Intrinsic conductivity of PB layer is enhanced after lithiation, accelerating homogenized transmission of electrons from the interfacial layer to the negative electrode. (2) Lithiation process is accompanied by enhancing lithium affinity of PB intermediate layer, which enables the interface contact between LATP and lithium metal to be closer during the electrochemical process. (3) Lithiated PB still maintains a three-dimensional skeleton structure, which is conducive to the homogenization effect of lithium ion flux at interface, thereby promoting stabilization of lithium deposition/stripping process. (4) The PB with metal-organic framework (MOF) structure is conducive to ensuring the mechanical stability of interface during cycling and reducing volume change of lithium negative electrode. (5) The PB structure does not collapse after lithiation, not easy to cause phase separation and additional phase boundaries or phase gaps, which is conducive to the integration of lithium ion flow and electron flow. (6) More uniquely, redox potential of PB is higher than those of lithium metal and LATP on both sides of the PB interface, conducive to the formation of an electron transport barrier between Li and LATP, and prevents the reduction and degradation of LATP. The improved solid-state battery has good cycling stability and kinetic performance. At a current density of 0.025 mA·cm^-2, the PB-modified Li/Li symmetric solid-state cell can achieve a stable cycle of 800 h. After 160 cycles at a current density of 0.025 mA·cm^-2, the capacity of PB-modified Li/LiFePO₄ solid-state battery is still close to 200 mAh·g^-1. The modified Li/FeF₃ solid-state battery can be operated at 0.025 mA·cm^-2 with the preservation of a high Coulombic efficiency, indicating that the PB modification has good tolerance to the volume change generated during electrochemical cycling.

Key words: solid-state electrolyte, interface modification, NASICON-type ceramic, Prussian blue, solid-state lithium battery

CLC Number:

O614

LI Yongfeng, GU Yuping, SHI Guangzhao, HU Jiulin, LEI Meng, PENG Hui, ZENG Yuping, LI Chilin. Interface Regulation of Electrochemical Potential in NASICON-type Ceramic Solid-state Batteries[J]. Journal of Inorganic Materials, 2025, 40(11): 1201-1211.

Figures/Tables 10

Fig. 1 Basic characteristics of LATP (a) XRD pattern of LATP; (b, c) Cross-sectional SEM images of LATP electrolyte; (d) AC impedance spectra of LATP at different temperatures and corresponding equivalent circuit; (e) Arrhenius plots based on LATP ionic conductivities

Fig. 2 Basic characteristics of PB and its modification mechanism (a) Schematic diagram of LATP interface reaction and corresponding products; (b) Schematic diagram of PB structure; (c) XRD pattern of PB; (d) Modulation mechanism of PB interface on Li-ion and electron flux

Fig. 3 Schematic and electrochemical performance of symmetric cells (a) Schematic diagram of assembly of Li-Li symmetric cell; (b, c) Li plating and stripping voltage curves of symmetric cells of Li/LATP/Li, Li/IL@LATP/Li, and Li/IL@PB@LATP/Li at current densities of (b) 0.05 and (c) 0.1 mA·cm-2; (d) Li plating and stripping voltage curves of symmetric cell of Li/IL@PB@LATP/Li at different current densities

Fig. 4 Arrhenius curves based on interface resistances at different temperatures for symmetric cells of (a) Li/LATP/Li, (b) Li/IL@LATP/Li, and (c) Li/IL@PB@LATP/Li after different cycling time

Fig. 5 Schematic diagram of structure and electrochemical performance of Li//LFP and Li//FeF3 full cells under different conditions (a) Schematic diagram of Li//LFP or Li//FeF3 full cell; (b-d) Charging-discharging curves of (b) Li/LATP/LFP, (c) Li/IL@LATP/LFP, and (d) Li/IL@PB@LATP/LFP full cells at different cycle stages under a current density of 0.025 mA·cm-2; (e) Cycling performance of Li/IL@PB@LATP/LFP full cell at a current density of 0.025 mA·cm-2; (f) Cycling performance of Li/IL@LATP/LFP and Li/IL@PB@LATP/LFP full cells at a current density of 0.1 mA·cm-2, and Coulombic efficiency of Li/IL@PB@LATP/LFP; (g) Initial charging-discharging curves of Li/IL@PB@LATP/LFP cell at different current densities; (h) Cycling performance of Li/IL@PB@LATP/FeF3 full cell at 0.025 mA·cm-2

Fig. 6 SEM images of PB@LATP under different conditions (a) Cross-sectional SEM image of PB-modified solid electrolyte LATP; (b) Surface and (c) cross-sectional SEM images of LATP for Li/IL@PB@LATP/LFP full cell after 50 cycles at a current density of 0.05 mA·cm-2; (d) SEM image of LATP surface from Li/IL@LATP/LFP full cell after 50 cycles at a current density of 0.05 mA·cm-2

Fig. 7 XPS spectra of LATP surface of symmetric cell Li/IL@PB@LATP/Li after 50 cycles at 0.05 mA·cm-2 (a) C1s; (b) F1s; (c) Li1s; (d) N1s; (e) O1s

Fig. S1 Li plating and stripping voltage curves of symmetric cell of Li/IL@PB@LATP/Li at a current density of 0.05 mA·cm-2

Fig. S2 Li plating and stripping voltage curves of symmetric cell of Li/IL@PB@LATP/Li at a current density of 0.1 mA·cm-2

Fig. S3 Photo comparison of LATP ceramic electrolyte surface before (a) and after (b) coating with PB

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