Silicon is considered an important anode material for solid-state batteries (SSBs) because of its unique properties in addressing key challenges associated with Li metal anodes such as dendrite formation and morphological instability. Despite many exciting results from previous reports on solid-state Si anodes, the initial Coulombic efficiency (ICE), a critical parameter that characterizes the electrochemical reversibility for the first cycle and directly influences the energy density of the battery, has not been well considered. Here we study the electrochemical stability between Si and three representative solid electrolytes (SEs), including a typical sulfide (75Li 2 S-25P 2 S 5 , LPS), an iodide-substituted sulfide (70(0.75Li 2 S-0.25P 2 S 5 )-60LiI, LPSI), and a hydride-based SE (3LiBH 4 -LiI, LBHI), to improve the ICE of solid-state Si anodes. Combining first-principles computations, electrochemical measurements, ex situ XPS characterizations, and mechanical measurements, we report that LBHI demonstrates superior electrochemical and chemical stability with Si anodes compared with sulfide-based SEs, enabling a high-performance solid-state Si anode with a record high ICE of 96.2% among all Si anodes reported to date. The excellent stability of LBHI with Si anode was also demonstrated in solid-state full cells with nickel-rich layered oxide cathodes. The research provides novel insights into developing high-performance Si anodes for practical applications.
more »
« less
Unveiling the Mechanical and Electrochemical Evolution of Nanosilicon Composite Anodes in Sulfide‐Based All‐Solid‐State Batteries
The utilization of silicon anodes in all‐solid‐state lithium batteries provides good prospects for facilitating high energy density. However, the compatibility of sulfide solid‐state electrolytes (SEs) with Si and carbon is often questioned due to potential decomposition. Herein, operando X‐ray absorption near‐edge structure (XANES) spectroscopy, ex situ scanning electron microscopy (SEM), and ex situ X‐ray nanotomography (XnT) are utilized to investigate the chemistry and structure evolution of nano‐Si composite anodes. Results from XANES demonstrate a partial decomposition of SEs during the first lithiation stage, which is intensified by the presence of carbon. Nevertheless, the performances of first three cycles in Si–SE–C are stable, which proves that the generated media is ionically conductive. XnT and SEM results show that the addition of SEs and carbon improves the structural stability of the anode, with fewer pores and voids. A chemo‐elasto‐plastic model reveals that SEs and carbon buffer the volume expansion of Si, thus enhancing mechanical stability. The balance between the pros and cons of SEs and carbon in enhancing reaction kinetics and structural stability enables the Si composite anode to demonstrate the highest Si utilization with higher specific capacities and a better rate than pure Si and Si composite anodes with only SEs.
more » « less- Award ID(s):
- 1924534
- NSF-PAR ID:
- 10406687
- Publisher / Repository:
- Wiley Blackwell (John Wiley & Sons)
- Date Published:
- Journal Name:
- Advanced Energy Materials
- Volume:
- 13
- Issue:
- 14
- ISSN:
- 1614-6832
- Format(s):
- Medium: X
- Sponsoring Org:
- National Science Foundation
More Like this
-
-
more » « less
Abstract Si‐based anodes with a stiff diamond structure usually suffer from sluggish lithiation/delithiation reaction due to low Li‐ion and electronic conductivity. Here, a novel ternary compound ZnSi2P3with a cation‐disordered sphalerite structure, prepared by a facile mechanochemical method, is reported, demonstrating faster Li‐ion and electron transport and greater tolerance to volume change during cycling than the existing Si‐based anodes. A composite electrode consisting of ZnSi2P3and carbon achieves a high initial Coulombic efficiency (92%) and excellent rate capability (950 mAh g−1at 10 A g−1) while maintaining superior cycling stability (1955 mAh g−1after 500 cycles at 300 mA g−1), surpassing the performance of most Si‐ and P‐based anodes ever reported. The remarkable electrochemical performance is attributed to the sphalerite structure that allows fast ion and electron transport and the reversible Li‐storage mechanism involving intercalation and conversion reactions. Moreover, the cation‐disordered sphalerite structure is flexible to ionic substitutions, allowing extension to a family of Zn(Cu)Si2+
x P3solid solution anodes (x = 0, 2, 5, 10) with large capacity, high initial Coulombic efficiency, and tunable working potentials, representing attractive anode candidates for next‐generation, high‐performance, and low‐cost Li‐ion batteries. -
Among anode materials for Li-ion batteries, Si is known for high theoretical capacity, low cost, large volume change, relatively fast capacity fade and significant stress-potential coupling. This article shows that a Li(Ni0.5Co0.2Mn0.3)O2-Si battery can store energy, actuate with Si volume change and sense with stress-potential coupling. Experiments are conducted in an electrolyte-filled chamber with a glass window with Li(Ni0:5Co0:2Mn0:3)O2 cathodes and Si composite anodes. The Si anodes are single-side coated on Cu current collector with Si nanoparticles, polyacrylic acid binder and conductive carbon black in a porous composite structure. During charging, the battery stores energy, Li inserts in the cantilevered Si anodes and the cantilevers bend laterally. Discharging the battery releases the stored energy and straightens the Si cantilevers. Imposing deformation on the Si cantilevers at a fixed state of charge causes bending stress in the composite coating and a change in the open circuit potential. Testing at 1Hz confirms that the Si composite responds to dynamic stress variations and with almost no phase lag, indicating the bandwidth of the stress-potential coupling in Si composite anodes is at least 1Hz.more » « less
-
more » « less
Abstract Prelithiation as a facile and effective method to compensate the lithium inventory loss in the initial cycle has progressed considerably both on anode and cathode sides. However, much less research has been devoted to the prelithiation effect on the interface stabilization for long‐term cycling of Si‐based anodes. An in‐depth quantitative analysis of the interface that forms during the prelithiation of SiOxis presented here and the results are compared with prelithiaton of Si anodes. Local structure probe combined with detailed electrochemical analysis reveals that a characteristic mosaic interface is formed on both prelithiated SiOxand Si anodes. This mosaic interface containing multiple lithium silicates phases, is fundamentally different from the solid electrolyte interface (SEI) formed without prelithiation. The ideal conductivity and mechanical properties of lithium silicates enable improved cycling stability of both prelithiated anodes. With a higher ratio of lithium silicates due to the oxygen participation, prelithiated SiO1.3anode improves the initial coulombic efficiency to 94% in full cell and delivers good cycling retention (77%) after 200 cycles. The insights provided in this work can be used to further optimize high Si loading (>70% by weight) based anodes in future high energy density batteries.
-
more » « less
Abstract The anode plays a critical role relating to the energy density in all‐solid‐state lithium batteries (ASLBs). Silicon (Si) and lithium (Li) metal are two of the most attractive anodes because of their ultrahigh theoretical capacities. However, most investigations focus on Li metal, leaving the great potential of Si underrated. This work investigates the stability, processability, and cost of Si anodes in ASLBs and compares them with Li metal. Moreover, single‐crystal LiNi0.8Mn0.1Co0.1O2is stabilized with lithium silicate (Li2SiO
x ) through a scalable sol–gel method. ASLBs with a cell‐level energy density of 285 Wh kg−1are obtained by sandwiching the Si anode, the thin sulfide solid‐state electrolyte membrane, and the interface stabilized LiNi0.8Mn0.1Co0.1O2. The full cell delivers a high capacity of 145 mAh g−1at C/3 and maintains stability for 1000 cycles. This work inspires commercialization of ASLBs on a large scale with exciting manufacturing lines for large‐scale, safe, and economical energy storage.
