No abstract

Currently, concentrated electrolyte solutions are attracting special attention because of their unique characteristics such as unusually improved oxidative stability on both the cathode and anode sides, the absence of free solvent, the presence of more anion content, and the improved availability of Li + ions. Most of the concentrated electrolytes reported are lithium bis(fluorosulfonyl)imide (LiFSI) salt with ether-based solvents because of the high solubility of salts in ether-based solvents. However, their poor anti-oxidation capability hindered their application especially with high potential cathode materials (>4.0 V). In addition, the salt is very costly, so it is not feasible from the cost analysis point of view. Therefore, here we report a locally concentrated electrolyte, 2 M LiPF 6 , in ethylene carbonate/diethyl carbonate (1:1 v/v ratio) diluted with fluoroethylene carbonate (FEC), which is stable within a wide potential range (2.5−4.5 V). It shows significant improvement in cycling stability of lithium with an average Coulombic efficiency (ACE) of ∼98% and small voltage hysteresis (∼30 mV) with a current density of 0.2 mA/cm 2 for over 1066 h in Li||Cu cells. Furthermore, we ascertained the compatibility of the electrolyte for anode-free Li−metal batteries (AFLMBs) using Cu||LiNi 1/3 Mn 1/3 Co 1/3 O 2 (NMC, ∼2 mA h/ cm 2 ) with a current density of 0.2 mA/cm 2 . It shows stable cyclic performance with ACE of 97.8 and 40% retention capacity at the 50th cycle, which is the best result reported for carbonate-based solvents with AFLMBs. However, the commercial carbonate-based electrolyte has <90% ACE and even cannot proceed more than 15 cycles with retention capacity >40%. The enhanced cycle life and well retained in capacity of the locally concentrated electrolyte is mainly because of the synergetic effect of FEC as the diluent to increase the ionic conductivity and form stable anion-derived solid electrolyte interphase. The locally concentrated electrolyte also shows high robustness to the effect of upper limit cutoff voltage.

Anode-free batteries (AFBs) are impressive and recent phenomena in the era of energy storage devices due to their high energy density and relative ease of production compared to the traditional Lithium metal batteries (LMBs). However, dendrite formation during plating and stripping and low coulombic efficiency (CE) are the main challenges that impede practical implementation of these batteries. Here we report an extremely stable dual-salt electrolyte, 2M LiFSI+1M LiTFSI (2FSI+1TFSI)) in DME/DOL (1:1, v/v), system in comparison to the single salt 3M LiTFSI (3TFSI) in DME/DOL (1:1, v/v), to effectively stabilize AFB composed of LiFePO 4 cathode and bare Cu-foil anode for the first time. The electrolyte stabilized anode-free cell with the configuration Cu||LiFePO 4 via reductive decomposition of its anions and enabled the cell to be cycled with CE of 98.9% for 100 cycles. This results from the formation of stable, ion conductive and electrically insulating inorganic components rich Solid Electrolyte Interface (SEI) layer on the surface of in-situ deposited Li-metal that blocks the undesirable parasitic reaction between the deposited Li and the electrolyte. Thus, aforesaid SEI mitigates formation of dead lithium and dissolution of the in-situ deposited Li surface during repeated cycling and prolongs cycle life of the battery.

Li7La3Zr2O12 (LLZO) garnet is one kind of solid electrolyte drawing extensive attention due to its good ionic conductivity, safety, and stability toward lithium metal anodes. However, the stability problem during synthesis and storage results in high interfacial resistance and prevents it from practical applications. We synthesized air-stable dual-doped Li6.05La3Ga0.3Zr1.95Nb0.05O12 ((Ga, Nb)-LLZO) cubic-phase garnets with ionic conductivity of 9.28 × 10–3 S cm–1. The impurity-phase species formation on the garnet pellets after air exposure was investigated. LiOH and Li2CO3 can be observed on the garnet pellets by Raman spectroscopy, X-ray diffraction (XRD), and X-ray photoelectron spectroscopy (XPS) once the garnets are exposed to humid air or come in contact with water. The (Ga, Nb)-LLZO garnet is found to form less LiOH and Li2CO3, which can be further reduced or removed after drying treatment. To confirm the stability of the garnet, an electrochemical test of the Li//Li symmetric cell was also performed in comparison with previously reported garnets (Li7La2.75Ca0.25Zr1.75Nb0.25O12, (Ca, Nb)-LLZO). The dual-doped (Ga, Nb)-LLZO showed less polarized and stable plating/stripping behavior than (Ca, Nb)-LLZO. Through Rietveld refinement of XRD patterns of prepared materials, dopant Ga was found to preferably occupy the Li site and Nb takes the Zr site, while dopant Ca mainly substituted La in the reference sample. The inherited properties of the dopants in (Ga, Nb)-LLZO and their structural synergy explain the greatly improved air stability and reduced interfacial resistance. This may open a new direction to realize garnet-based solid electrolytes with lower interfacial resistance and superior air stability.

No abstract

A cell with doped LPS – Li1.5Al0.33Sc0.17Ge1.5(PO4)3 shows improved conductivity and a capacity retention of 83.6% for more than 80 cycles.

No abstract

No abstract