Sulfide solid electrolytes (SEs) show promise for Li metal solid-state batteries due to their high ionic conductivities and relative ease of manufacturing. However, many sulfide SEs suffer from limited electrochemical stability against Li metal electrodes. In this work, we use a suite of
While much of the current research on glassy solid electrolytes (GSEs) has focused on the binary Li2S+P2S5system, compositions with Si are of interest because Si promotes stronger glass formation and allows low‐cost melt‐quenching (MQ) synthesis under ambient pressure. Another advantage is that they can be formed in homogeneous and continuous glass forms, as a result they are free of grain boundaries. In this work, we have examined the structures and electrochemical properties of bulk glass pieces of sulfide and oxy‐sulfide GSE compositions and have also expanded the study by using LiPON glass as a dopant to produce an entirely new class of nitrogen doped mixed oxy‐sulfide nitride (MOSN) GSEs. Upon doping with oxygen and nitrogen, the solid electrolyte interface (SEI) is stabilized and the doped MOSN GSE exhibits a critical current density (CCD) of 1.8 mA cm−2at 100 °C. We also report on improving the glass quality, the SEI engineering and its limitations, and future plans of improving the electrochemical performance of these homogeneous MQ MOSN GSEs. These fundamental results can help to understand the structures and doping effects of the bulk GSEs, and as such can provide a guide to design improved homogeneous grain‐boundary‐free GSEs.
more » « less- Award ID(s):
- 1936913
- PAR ID:
- 10444537
- Publisher / Repository:
- Wiley Blackwell (John Wiley & Sons)
- Date Published:
- Journal Name:
- Batteries & Supercaps
- Volume:
- 5
- Issue:
- 11
- ISSN:
- 2566-6223
- Format(s):
- Medium: X
- Sponsoring Org:
- National Science Foundation
More Like this
-
operando analytical techniques to investigate the dynamics of solid electrolyte interphase (SEI) formation and the associated effects on Li plating. We contrast a sulfide SE that forms an electrically insulating SEI (Li6PS5Cl) with an SE that forms an SEI with electrically conducting phases present (Li10GeP2S12). Using anode-free cell configurations, where the Li/SE interface is formed against a current collector, we perform complimentaryoperando video microscopy andoperando X-ray photoelectron spectroscopy (XPS) experiments. The combination of these techniques allows for the interpretation of electrochemical voltage traces during Li plating. The electrically insulating nature of the SEI in Li6PS5Cl facilitates Li metal nucleation and plating after the initial SEI formation. In contrast, in cells that form an electronically conducting SEI, the onset of Li plating is suppressed, which is attributed to a low Faradaic efficiency from continuous SE decomposition. The insights in this study reveal how interphase dynamics control the transition from SEI formation to plating in anode-free solid-state batteries. -
Abstract In this report, a facile wet chemical method using acetonitrile combined with thermal annealing was used to prepare Li2S‐P2S5(LPS) based glass‐ceramic electrolytes with (1 wt%, 3 wt%, and 5 wt% Ce2S3) and without Ce2S3doping. The crystal structure, ionic conductivity, and chemical stability of Li7P3S11glass‐ceramic electrolytes were examined at varying temperatures (250–350°C). The results indicated that the highest ionic conductivity of 3.15 × 10−4S cm−1for pure Li7P3S11was observed at a temperature of 325°C. By incorporating 1 wt% Ce2S3and subjecting it to a heat treatment at 250°C, the glass ceramic electrolyte attained a remarkable ionic conductivity of 7.7 × 10−4(S cm−1) at 25°C. Furthermore, it exhibited a stable and extensive electrochemical potential range, reaching up to 5 volts when compared to the Li/Li+reference electrode. By tuning the glass transition and crystallization temperature, cerium doping seems to make Li7P3S11more chemically stable, compared to its original 70Li2S‐30P2S5counterpart. According to Raman and X‐ray photoelectron spectroscopy analyses, cerium doping inhibits the decomposition of highly conductive P2S74‐(pyro‐thiophosphate) to PS43−and P2S64−. Doped LPS has a greater crystallinity and more uniform microstructure than pure LPS, according to XRD, Raman spectroscopy, and scanning electron microscopy analysis. Consequently, Li7P2.9Ce0.1S11electrolyte shows great potential as a solid‐state electrolyte for constructing high‐performance sulfide‐based all‐solid‐state batteries.
-
Li2S is one of the most promising cathode materials for Li‐ion batteries because of its high theoretical capacity and compatibility with Li‐metal‐free anode materials. However, the poor conductivity and electrochemical reactivity lead to low initial capacity and severe capacity decay. In this communication, a nitrogen and phosphorus codoped carbon (N,P–C) framework derived from phytic acid doped polyaniline hydrogel is designed to support Li2S nanoparticles as a binder‐free cathode for Li–S battery. The porous 3D architecture of N and P codoped carbon provides continuous electron pathways and hierarchically porous channels for Li ion transport. Phosphorus doping can also suppress the shuttle effect through strong interaction between sulfur and the carbon framework, resulting in high Coulombic efficiency. Meanwhile, P doping in the carbon framework plays an important role in improving the reaction kinetics, as it may help catalyze the redox reactions of sulfur species to reduce electrochemical polarization, and enhance the ionic conductivity of Li2S. As a result, the Li2S/N,P–C composite electrode delivers a stable capacity of 700 mA h g−1with average Coulombic efficiency of 99.4% over 100 cycles at 0.1C and an areal capacity as high as 2 mA h cm−2at 0.5C.
-
Abstract Nitrogen‐doped carbon nanofibers (CNFs) were synthesized using a facile electrospinning technique with the addition of urea as a nitrogen‐doping agent. The amount of urea was selectively adjusted to control the degree and effectiveness of N‐doping. The morphology of N‐doped CNFs was investigated by scanning electron microscopy, transmission electron microscopy, and X‐ray diffraction, whereas their electrochemical performance was studied using cyclic voltammetry and galvanostatic charge–discharge experiments. The nitrogen content of N‐doped CNFs increased significantly from 11.31 % to 19.06 % when the doping amount of urea increased from 0 % to 30 %. N‐doping also played an important role in improving the electrochemical performance of the CNFs by introducing more defects in the carbon structure. Results showed that N‐doped CNFs with the highest nitrogen content (19.06 %) exhibited the largest reversible capacity of 354 mAh g−1under a current density of 50 mA g−1; and when the current density was increased to 1 A g−1, a capacity of 193 mAh g−1was still maintained. It is, therefore, demonstrated that N‐doped CNFs have great potential as suitable sodium‐ion battery anode material.
-
Abstract A dual‐layer interphase that consists of an in‐situ‐formed lithium carboxylate organic layer and a thin BF3‐doped monolayer Ti3C2MXene on Li metal is reported. The honeycomb‐structured organic layer increases the wetting of electrolyte, leading to a thin solid electrolyte interface (SEI). While the BF3‐doped monolayer MXene provides abundant active sites for lithium homogeneous nucleation and growth, resulting in about 50% reduced thickness of inorganic‐rich components among the SEI layer. A low overpotential of less than 30 mV over 1000 h cycling in symmetric cells is received. The functional BF3 groups, along with the excellent electronic conductivity and smooth surface of the MXene, greatly reduce the lithium plating/stripping energy barrier, enabling a dendrite‐free lithium‐metal anode. The battery with this dual‐layer coated lithium metal as the anode displays greatly improved electrochemical performance. A high capacity‐retention of 175.4 mAh g−1at 1.0 C is achieved after 350 cycles. In a pouch cell with a capacity of 475 mAh, the battery still exhibits a high discharge capacity of 165.6 mAh g−1with a capacity retention of 90.2% after 200 cycles. In contrast to the fast capacity decay of pure Li metal, the battery using NCA as the cathode also displays excellent capacity retention in both coin and pouch cells. The dual‐layer modified surface provides an effective approach in stabilizing the Li‐metal anode.