Low concentration electrolyte with non-solvating cosolvent enabling high-voltage lithium metal batteries.
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ABSTRACT:
SUBMITTER: Jiang Z
PROVIDER: S-EPMC8715189 | biostudies-literature |
REPOSITORIES: biostudies-literature
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Project description:The growth of dendrites on lithium metal electrodes is problematic because it causes irreversible capacity loss and safety hazards. Localised high-concentration electrolytes (LHCEs) can form a mechanically stable solid-electrolyte interphase and prevent uneven growth of lithium metal. However, the optimal physicochemical properties of LHCEs have not been clearly determined which limits the choice to fluorinated non-solvating cosolvents (FNSCs). Also, FNSCs in LHCEs raise environmental concerns, are costly, and may cause low cathodic stability owing to their low lowest unoccupied molecular orbital level, leading to unsatisfactory cycle life. Here, we spectroscopically measured the Li+ solvation ability and miscibility of candidate non-fluorinated non-solvating cosolvents (NFNSCs) and identified the suitable physicochemical properties for non-solvating cosolvents. Using our design principle, we proposed NFNSCs that deliver a coulombic efficiency up to 99.0% over 1400 cycles. NMR spectra revealed that the designed NFNSCs were highly stable in electrolytes during extended cycles. In addition, solvation structure analysis by Raman spectroscopy and theoretical calculation of Li+ binding energy suggested that the low ability of these NFNSCs to solvate Li+ originates from the aromatic ring that allows delocalisation of electron pairs on the oxygen atom.
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Project description:The development of new solvents is imperative in lithium metal batteries due to the incompatibility of conventional carbonate and narrow electrochemical windows of ether-based electrolytes. Whereas the fluorinated ethers showed improved electrochemical stabilities, they can hardly solvate lithium ions. Thus, the challenge in electrolyte chemistry is to combine the high voltage stability of fluorinated ethers with high lithium ion solvation ability of ethers in a single molecule. Herein, we report a new solvent, 2,2-dimethoxy-4-(trifluoromethyl)-1,3-dioxolane (DTDL), combining a cyclic fluorinated ether with a linear ether segment to simultaneously achieve high voltage stability and tune lithium ion solvation ability and structure. High oxidation stability up to 5.5 V, large lithium ion transference number of 0.75 and stable Coulombic efficiency of 99.2% after 500 cycles proved the potential of DTDL in high-voltage lithium metal batteries. Furthermore, 20 μm thick lithium paired LiNi0.8Co0.1Mn0.1O2 full cell incorporating 2 M LiFSI-DTDL electrolyte retained 84% of the original capacity after 200 cycles at 0.5 C.
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Project description:High-voltage lithium metal batteries suffer from poor cycling stability caused by the detrimental effect on the cathode of the water moisture present in the non-aqueous liquid electrolyte solution, especially at high operating temperatures (e.g., ≥60 °C). To circumvent this issue, here we report lithium hexamethyldisilazide (LiHMDS) as an electrolyte additive. We demonstrate that the addition of a 0.6 wt% of LiHMDS in a typical fluorine-containing carbonate-based non-aqueous electrolyte solution enables a stable Li||LiNi0.8Co0.1Mn0.1O2 (NCM811) coin cell operation up to 1000 or 500 cycles applying a high cut-off cell voltage of 4.5 V in the 25 °C-60 °C temperature range. The LiHMDS acts as a scavenger for hydrofluoric acid and water and facilitates the formation of an (electro)chemical robust cathode|electrolyte interphase (CEI). The LiHMDS-derived CEI prevents the Ni dissolution of NCM811, mitigates the irreversible phase transformation from layered structure to rock-salt phase and suppresses the side reactions with the electrolyte solution.
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Project description:Nowadays, lithium (Li) metal batteries arouse widespread concerns due to its ultrahigh specific capacity (3,860 mAh g-1). However, the growth of Li dendrites has always limited their industrial development. In this paper, the use of concentrated electrolyte with lithium difluoro(oxalate)borate (LiODFB) salt in 1, 2-dimethoxyethane (DME) enables the good cycling of a Li metal anode at high Coulombic efficiency (up to 98.1%) without dendrite growth. Furthermore, a Li/Li cell can be cycled at 1 mA cm-2 for over 3,000 h. Besides, compared to conventional LiPF6-carbonate electrolyte, Li/LiFePO4 cells with 4 M LiODFB-DME exhibit superior electrochemical performances, especially at high temperature (65°C). These outstanding performances can be certified to the increased availability of Li+ concentration and the merits of LiODFB salt. We believe that the concentrated LiODFB electrolyte is help to enable practical applications for Li metal anode in rechargeable batteries.
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Project description:The electrochemical instability of ether-based electrolyte solutions hinders their practical applications in high-voltage Li metal batteries. To circumvent this issue, here, we propose a dilution strategy to lose the Li+/solvent interaction and use the dilute non-aqueous electrolyte solution in high-voltage lithium metal batteries. We demonstrate that in a non-polar dipropyl ether (DPE)-based electrolyte solution with lithium bis(fluorosulfonyl) imide salt, the decomposition order of solvated species can be adjusted to promote the Li+/salt-derived anion clusters decomposition over free ether solvent molecules. This selective mechanism favors the formation of a robust cathode electrolyte interphase (CEI) and a solvent-deficient electric double-layer structure at the positive electrode interface. When the DPE-based electrolyte is tested in combination with a Li metal negative electrode (50 μm thick) and a LiNi0.8Co0.1Mn0.1O2-based positive electrode (3.3 mAh/cm2) in pouch cell configuration at 25 °C, a specific discharge capacity retention of about 74% after 150 cycles (0.33 and 1 mA/cm2 charge and discharge, respectively) is obtained.
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Project description:There is a critical need to evaluate lithium-sulfur (Li-S) batteries with practically relevant high sulfur loadings and minimal electrolyte. Under such conditions, the concentration of soluble polysulfide intermediates in the electrolyte drastically increases, which can alter the fundamental nature of the solution-mediated discharge and thereby the total sulfur utilization. In this work, we present an investigation into various high donor number (DN) electrolytes that allow for increased polysulfide dissolution, and demonstrate how this property may in fact be necessary for increasing sulfur utilization at low electrolyte and high loading conditions. The solvents dimethylacetamide, dimethyl sulfoxide, and 1-methylimidazole are holistically evaluated against dimethoxyethane as electrolyte co-solvents in Li-S cells, and they are used to investigate chemical and electrochemical properties of polysulfide species at both dilute and practically relevant conditions. The nature of speciation exhibited by lithium polysulfides is found to vary significantly between these concentrations, particularly in regards to the S3•- species. Furthermore, the extent of the instability in conventional electrolyte solvents and high DN solvents with both lithium metal and polysulfides is thoroughly investigated. These studies establish a basis for future efforts into rationally designing an optimal electrolyte for a lean electrolyte, high energy density Li-S battery.
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Project description:Safety and high-voltage operation are key metrics for advanced, solid-state energy storage devices to power low- or zero-emission HEV or EV vehicles. In this study, we propose the modification of single-ion conducting polyelectrolytes by designing novel block copolymers, which combine one block responsible for high ionic conductivity and the second block for improved mechanical properties and outstanding electrochemical stability. To synthesize such block copolymers, the ring opening polymerization (ROP) of trimethylene carbonate (TMC) monomer by the RAFT-agent having a terminal hydroxyl group is used. It allows for the preparation of a poly(carbonate) macro-RAFT precursor that is subsequently applied in RAFT copolymerization of lithium 1-[3-(methacryloyloxy)propylsulfonyl]-1-(trifluoromethylsulfonyl)imide and poly(ethylene glycol) methyl ether methacrylate. The resulting single-ion conducting block copolymers show improved viscoelastic properties, good thermal stability (T onset up to 155 °C), sufficient ionic conductivity (up to 3.7 × 10-6 S cm-1 at 70 °C), and high lithium-ion transference number (0.91) to enable high power. Excellent plating/stripping ability with resistance to dendrite growth and outstanding electrochemical stability window (exceeding 4.8 V vs Li+/Li at 70 °C) are also achieved, along with enhanced compatibility with composite cathodes, both LiNiMnCoO2 - NMC and LiFePO4 - LFP, as well as the lithium metal anode. Lab-scale truly solid-state Li/LFP and Li/NMC lithium-metal cells assembled with the single-ion copolymer electrolyte demonstrate reversible and very stable cycling at 70 °C delivering high specific capacity (up to 145 and 118 mAh g-1, respectively, at a C/20 rate) and proper operation even at a higher current regime. Remarkably, the addition of a little amount of propylene carbonate (∼8 wt %) allows for stable, highly reversible cycling at a higher C-rate. These results represent an excellent achievement for a truly single-ion conducting solid-state polymer electrolyte, placing the obtained ionic block copolymers on top of polyelectrolytes with highest electrochemical stability and potentially enabling safe, practical Li-metal cells operating at high-voltage.
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Project description:The development of solid-state electrolytes (SSEs) for high energy density lithium metal batteries (LMBs) usually needs to take into account of the interfacial compatibility against lithium metal and the electrolyte stability suitable for a high-potential cathode. In this study, through a facile two-step coating process, novel double-layer solid composite electrolytes (SCEs) with Janus characteristics are customized for the high-voltage LMBs with improved room-temperature cycling performance. Among which, high-voltage resistant poly(vinylidene fluoride) (PVDF) is adopted here for the construction of an electrolyte layer facing the cathode, while the other layer against the lithium anode is composed of the polymer matrix of poly(ethylene oxide) (PEO) blended with PVDF to obtain a lithium metal-friendly interface. With the further incorporation of Laponite clay, the PVDF/(PEO+PVDF)-L SCEs not only exhibit improved mechanical properties, but also achieve a highly increased ionic conductivity (5.2 × 10-4 S cm-1) and lithium ion migration number (0.471) at room temperature. The assembled NCM523|PVDF/(PEO+PVDF)-L SCEs|Li cells thus are able to deliver the initial discharge capacity of 153.9 mAh g-1 with 80.8% capacity retention after 200 cycles at 0.3 C. Such easily manufactured double-layer SCEs capable of operating steadily at room temperature provide a competitive electrolyte option for high-voltage solid-state LMBs.
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Project description:Rechargeable lithium batteries with high-voltage/capacity cathodes are regarded as promising high-energy-density energy-storage systems. Nevertheless, these systems are restricted by some critical challenges, such as flammable electrolyte, lithium dendrite formation and rapid capacity fade at high voltage and elevated temperature. In this work, we report a quasi-solid-state composite electrolyte (QCE) prepared by in situ polymerization reactions. The electrolyte consists of polymer matrix, inorganic filler, nonflammable plasticizers and Li salt, and shows a good thermal stability, a moderate ionic conductivity of 2.8 × 10-4 S cm-1 at 25 °C, and a wide electrochemical window up to 6.7 V. The batteries with the QCE show good electrochemical performance when coupled with lithium metal anode and LiCoO2 or LiNi0.8Mn0.1Co0.1O2 cathodes. Pouch-type batteries with the QCE also exhibit stable cycling, and can tolerate abuse testes such as folding, cutting and nail penetration. The in situ formed fluorides and phosphides from the plasticizers stabilize the interfaces between the QCE and electrodes, which enables stable cycling of Li metal batteries.
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