Fluoroethylene Carbonate Research Articles

Terminally fluorinated glycol ether electrolyte for lithium metal batteries

Despite being an excellent candidate for lithium metal batteries due to its stability towards lithium metal, ethereal solvent suffers from relatively low anodic stability, rendering it incompatible with high voltage cathode. Although the anodic stability of ethereal solvent can be enhanced by fluorination, the lithium solvating ability of fluorinated ethers is largely reduced. As a result, common hydrofluoroethers, such as 1,1,2,2-tetrafluoroethyl-2,2,3,3-tetrafluoropropylether (TTE) and bis(2,2,2-trifluoroethyl) ether (BTFE) are not able to dissolve any lithium salt, albeit enhanced oxidation potential. Therefore, new fluorinated glycol ethers were synthesized in this research. The diglyme analog, which was terminally fluorinated, demonstrated high anodic stability and excellent capability to facilitate lithium plating/stripping. Unlike its non-fluorinated counterpart, the fluorinated diglyme analog displayed outstanding compatibility with lithium hexafluorophosphate, which is an essential salt in lithium-ion batteries. It was shown that the electrolyte based on fluorinated diglyme analog with fluoroethylene carbonate as co-solvent enabled highly stable cycling of Li-metal batteries pairing with layered oxide cathode.

First-Principles Examination of Multiple Criteria of Organic Solvent Oxidative Stability in Batteries

Oxidative instability of the liquid electrolyte at or near battery cathode oxide surfaces has significant detrimental effects on batteries. Organic solvent molecules are often the fuel and precursors of such degradation processes, releasing electrons and protons that react with cathode oxides and electrolyte anions. These reactions contribute to cathode–electrolyte interphase (CEI) film formation, transition-metal ion dissolution, and phase transformation of the surface regions of the cathode. Here we apply density functional theory calculations to examine four criteria of oxidative stability (oxidation potential, hydrogen removal energies, and initial reactivity on two types of oxide facets) using four different solvent/additive molecules (ethylene carbonate, fluoroethylene carbonate, 1,3-dioxolane, and dimethyl ether). The ranking of molecular stability differs with each criterion. Surprisingly, the all-oxygen-terminated basal planes of layered oxides exhibit lower reaction barriers than spinel surface facets with exposed transition-metal cations, especially for ether solvents; the calculations also suggest basal planes contribute to the dissolution of transition-metal ions. The structure–degradation relation complexity underscores the challenge of understanding the function of the CEI but also offers a guide to future degradation-mitigation strategies including facet engineering. Our predictions and models help establish a framework for future studies relevant to high-voltage conditions.

Perfluoro Macrocyclic Ether as an Ambifunctional Additive for High‐Performance SiO and Nickel 88%‐Based High‐Energy Li‐ion Battery

AbstractState‐of‐the‐art lithium (Li)‐ion batteries employ silicon anode active material at a limited fraction while strongly relying on fluoroethylene carbonate (FEC) electrolyte additive exceeding 10 wt.% to enable stable cycling. The swelling issue of silicon in the aspect of solid electrolyte interphase (SEI) instability and a risk of safety hazards and high manufacturing cost due to FEC has motivated the authors to design a well‐working fluorinated additive substitute. High‐capacity cells employing nickel‐rich oxide cathode are pursued by operating at > 4.2 V versus Li/Li+, for which anodic stability of electrolyte is required. Herein, a highly effective new ambifunctional additive of icosafluoro‐15‐crown 5‐ether is proposed at a little fraction of 0.4 wt.% for the stabilized interfaces and reduced swelling of high capacity (3.5 mAh cm−2) 5 wt.% SiO‐graphite anode and LiNi0.88Co0.08Mn0.04O2 cathode. Utilizing together with a lowered fraction of FEC, reversible long 300 cycles at 4.35 V and 1 C (225 mA g−1) are achieved. Material characterization results reveal that such stabilization is derived from the surface passivation of both anode and cathode with perfluoro ether, LiF, and LixPFy species. The present study gives insight into electrolyte formulation design with lower cost and both‐side stabilization strategies for silicon and nickel‐rich active materials and their interfaces.

Solid–Electrolyte Interface Formation on Si Nanowires in Li-Ion Batteries: The Impact of Electrolyte Additives

The morphological changes of Si nanowires (Si NWs) cycled in 1:1 ethylene–carbonate (EC)/diethyl–carbonate (DEC) with or without different additives, fluoroethylene carbonate (FEC) or vinylene carbonate (VC), as well as the composition of the deposited solid–electrolyte interphase layer, are investigated by a combination of experimental microscopic and spectroscopic techniques. Scanning electron microscopy and optical spectroscopy highlight that the NW morphology is better preserved in samples cycled in the presence of FEC and VC additives compared to the additive-free electrolyte. However, only the use of FEC is capable of slightly mitigating the amorphization of silicon upon cycling. The solid electrolyte interphase (SEI) formed over the Si NWs cycled in the additive-free electrolyte is richer in organic and inorganic carbonates compared to the SEI grown in the presence of the VC and FEC additives. Furthermore, both additives are able to remarkably limit the degradation of the LiPF6 salt. Overall, the use of the FEC-additive in the carbonate-based electrolyte promotes both morphological and structural resilience of the Si NWs upon cycling thanks to the optimal composition of the SEI layer.

Anion-enrichment interface enables high-voltage anode-free lithium metal batteries

Aggressive chemistry involving Li metal anode (LMA) and high-voltage LiNi0.8Mn0.1Co0.1O2 (NCM811) cathode is deemed as a pragmatic approach to pursue the desperate 400 Wh kg−1. Yet, their implementation is plagued by low Coulombic efficiency and inferior cycling stability. Herein, we propose an optimally fluorinated linear carboxylic ester (ethyl 3,3,3-trifluoropropanoate, FEP) paired with weakly solvating fluoroethylene carbonate and dissociated lithium salts (LiBF4 and LiDFOB) to prepare a weakly solvating and dissociated electrolyte. An anion-enrichment interface prompts more anions’ decomposition in the inner Helmholtz plane and higher reduction potential of anions. Consequently, the anion-derived interface chemistry contributes to the compact and columnar-structure Li deposits with a high CE of 98.7% and stable cycling of 4.6 V NCM811 and LiCoO2 cathode. Accordingly, industrial anode-free pouch cells under harsh testing conditions deliver a high energy of 442.5 Wh kg−1 with 80% capacity retention after 100 cycles.

Phosphate-Rich Interface for a Highly Stable and Safe 4.6V LiCoO2 Cathode.

Increasing the upper cut-off voltage of LiCoO2 (LCO) is one of the most efficient strategies to gain high-energy density for current lithium-ion batteries. However, surface instability is expected to be exaggerated with increasing voltage arising from the high reactivity between the delithiated LCO and electrolytes, leading to serious safety concerns. This work is aimed to construct a physically and chemically stable phosphate-rich cathode-electrolyte interface (CEI) on the LCO particles to mitigate this issue. This phosphate-rich CEI is generated during the electrochemical activation by using fluoroethylene carbonate and 1,1,2,2-tetrafluoroethyl-2,2,3,3-tetrafluoropropyletherare as the solvents. Both solvents also demonstrate high thermal stability, reducing the intrinsic flammability of the commercial organic electrolyte, thereby eliminating the safety concern in the LCO-based systems upon high-voltage operation. This stable CEI layer on the particle surface can also enhance the surface structure by blocking direct contact between LCO and electrolyte, improving the cycling stability. Therefore, by using the proposed electrolyte, the LCO cathode exhibits a high-capacity retention of 76.1% after 200 cycles at a high cut-off voltage of 4.6V. This work provides a novel insight into the rational design of high-voltage and safe battery systems by adopting the flame-retardant electrolyte.

Achieving stable interface for lithium metal batteries using fluoroethylene carbonate-modified garnet-type Li6.4La3Zr1.4Ta0.6O12 composite electrolyte

Composite polymer electrolytes (CPEs) with Li6.4La3Zr1.4Ta0.6O12 (LLZTO) ceramic oxide electrolytes are attracting significant interest because of the merits of LLZTO. However, inadequate solid-solid contact between electrolytes and electrodes invariably results in high interfacial impedance, which is harmful to CPEs' performance. Herein, fluoroethylene carbonate (FEC) additive which possesses excellent ability in guiding uniform Li+ deposition and suppressing Li dendrite growth was introduced into the electrolyte, and novel CPEs were successfully prepared. It shows a broad electrochemical window of 5.2 V (vs. Li+/Li), low interface impedance, and a high lithium ion migration number of 0.62. As a result, the assembled symmetrical Li/PHTL-FEC-LLZTO/Li cells can run stably for over 500 h at 0.2 mA cm–2. Moreover, the Li metal battery with LiFePO4 (LFP) cathode shows superior cyclic stability with a high initial capacity of 132.9 mAh g–1, and a large retention of 88.5% after 200 cycles at 0.5 C. This excellent electrochemical performance of the battery can be attributed to the employment of FEC additives, which endows promising potential in reducing the interface impedance, promoting lithium uniform deposition, and stabling interface performance in the electrolyte.

A localized high concentration carboxylic ester-based electrolyte for high-voltage and low temperature lithium batteries

In this work, a methyl propionate (MP)/fluoroethylene carbonate (FEC)-based localized high concentration electrolyte with lithium difluoro(oxalato)borate (LiDFOB) as the additive is reported. The tuned solvation structure and the addition of LiDFOB enable fast desolvation process of Li+ and good formation of cathode/electrolyte interphase. This optimized electrolyte shows good compatibility with both lithium cobaltate (LCO) cathode and lithium metal anode, enabling 4.5 V Li/LCO cell to cycle 300 cycles at 1C (180 mAh g−1) rate with 87.7 % capacity retention. Even at 10C high-rate cycling, around 75.0 % of initial capacity is also achieved. In addition, it possesses decent conductivity and viscosity at low temperature, demonstrating the great low-temperature performance. It enables the high-loading Li/LCO cell to deliver 136.9 mAh g−1capacity at −70 °C, showing the great discharge performance and application potential at such low temperature. In addition, the cell with this electrolyte could even be cycled at −40 °C with 77.8 % capacity retention after 100 cycles. This work implements the high-voltage, high-rate and low-temperature functions of battery by choosing appropriate electrolyte component and tuning its formulation. This work provides an effective method for designing a multifunctional lithium battery electrolyte.

Investigation of SnS2 -rGO Sandwich Structures as Negative Electrode for Sodium-Ion and Potassium-Ion Batteries.

Sodium-ion and potassium-ion batteries (NIBs and KIBs) are considered promising alternatives to replace lithium-ion batteries (LIBs) in energy storage applications due to the natural abundance and low cost of Na and K. Nevertheless, a critical challenge is that the large size of Na+ /K+ leads to a huge volume change of the hosting material during electrochemical cycling, resulting in rapid capacity decay. Among negative candidates for alkali-metal-ion batteries, SnS2 is attractive due to the competitively high specific capacity, low redox potential and high abundance. Porous few-layer SnS2 nanosheets are in situ grown on reduced graphene oxide, forming a SnS2 -rGO sandwich structure via strong C-O-Sn bonds. This nano-scaled sandwich structure not only shortens Na+ /K+ and electron transport pathways but also accommodates volume expansion, thereby enabling high and stable electrochemical cycling performance of SnS2 -rGO. This work explores the influence of different conductive carbons (Super P and C65) on the SnS2 -rGO electrode. In addition, the effects of the electrolyte additive fluoroethylene carbonate (FEC) on the electrochemical performance in NIBs and KIBs is evaluated. This work provides guidelines for optimized electrode structure design, electrolyte additives and carbon additives for the realization of better NIBs and KIBs.

Enhancement of the Na2FePO4F@gC3N4 electrochemical performance in view of its implementation in sodium-ion batteries

Na2FePO4F fluorophosphate has long been regarded as potential cathode material for sodium-ion batteries (SIBs) due to its undeniable economic and environmental advantages. Herein, the preparation of Na2FePO4F powder using an easier and cost-effective technique is reported. The prepared compound, using phosphoric acid as P-source, crystallizes in an orthorhombic structure with the Pbcn space group as confirmed by X-Ray Diffraction (XRD) analysis. The pristine material (refers to as PM) is combined with different percentages of graphitic carbon nitride g-C3N4 as a carbon source (15% and 20%), to build large specific surfaces, boost electronic conductivity, and achieve the optimal carbon content. Raman spectrum reveals the existence of residual carbon denoting that the in-situ carbon coating process is successful. Thermogravimetric analysis (TGA) confirmed the stability of iron fluorophosphate at temperatures of 750 °C. Scanning electron microscope (SEM), and energy-dispersive X-ray spectroscopy (EDS) are used to investigate the materials' surface morphology and particle size. The performance of 15% and 20% g-C3N4 coated materials are tested as cathodes in both pure 1 M NaClO4 in polycarbonate electrolyte and in added 5% fluoroethylene carbonate electrolyte. High cycling properties and improved electrochemical performance were revealed when compared to the additive-free electrolyte.

Non‐Flammable Electrolyte with Lithium Nitrate as the Only Lithium Salt for Boosting Ultra‐Stable Cycling and Fire‐Safety Lithium Metal Batteries

AbstractLithium metal batteries (LMBs) attract considerable attention for their incomparable energy density. However, safety issues caused by uncontrollable lithium dendrites and highly flammable electrolyte limit large‐scale LMBs applications. Herein, a low‐cost, thermally stable, and low environmentally‐sensitive lithium nitrate (LiNO3) is proposed as the only lithium salt to incorporate with nonflammable triethyl phosphate and fluoroethylene carbonate (FEC) co‐solvent as the electrolyte anticipated to enhance the performance of LMBs. Benefiting from the presence of NO3− and FEC with strong solvation effect and easily reduced ability, a Li3N–LiF‐rich stable solid electrolyte interphase is constructed. Compared to commercial electrolytes, the proposed electrolyte has a high Coulombic efficiency of 98.31% in Li‐Cu test at 1 mA cm−2 of 1.0 mAh cm−2 with dendrite‐free morphology. Additionally, the electrolyte system shows high voltage stability and cathode electrolyte interphase film‐forming properties with stable cycling performances, which exhibit outstanding capacity retention rates of 96.39% and 83.74% after 1000 cycles for LFP//Li and NCM811//Li, respectively. Importantly, the non‐flammable electrolyte delays the onset of combustion in lithium metal soft pack batteries by 255 s and reduces the peak heat release by 21.02% under the continuous external high‐temperature heating condition. The novel electrolyte can contribute immensely to developing high‐electrochemical‐performance and high‐safety LMBs.

High Performance Low-Temperature Lithium Metal Batteries Enabled by Tailored Electrolyte Solvation Structure.

The electrochemical performances of lithium metal batteries are determined by the kinetics of interfacial de-solvation and ion transport, especially at low-temperature environments. Here, a novel electrolyte that easily de-solvated and conducive to interfacial film formation is designed for low-temperature lithium metal batteries. A fluorinated carboxylic ester, diethyl fluoromalonate (DEFM), and a fluorinated carbonate, fluoroethylene carbonate (FEC) are used as solvents, while high concentrated lithium bis(trifluoromethanesulfonyl)imide (LiTFSI) is served as the solute. Through tailoring the electrolyte formulation, the lithium ions in the high concentrated fluorinated carboxylic ester electrolyte are mainly combined with anions, which weakens the bonding strength of lithium ions and solvent molecules in the solvation structure, beneficial to the de-solvation process at low temperature. The fluorinated carboxylic ester (FCE) electrolyte enables the LiFePO4 (LFP) | Li half-cell achieves a high capacity of 91.9 mAh g-1 at -30 °C, with high F content in the interface. With optimized de-solvation kinetics, the LFP | Li full cell remains over 100 mAh g-1 at 0 °C after cycling 100 cycles. Building new solvents with outstanding low-temperature properties and weaker solvation to match with Li metal anode, this work brings new possibilities of realizing high energy density and low temperature energy storage batteries.

Implications of the Thermal Stability of FEC-Based Electrolytes for Li-Ion Batteries

Fluoroethylene-carbonate (FEC) is a common co-solvent for high-voltage cathodes and for silicon-based anodes in lithium-ion batteries. However, FEC has a limited thermal stability when used with LiPF6 as conductive salt, and its decomposition can trigger detrimental side reactions. Here, we will examine the reaction mechanism of FEC with LiPF6, confirming that vinylene-carbonate (VC) and HF are produced at elevated temperatures. By full-cell cycling at 45 °C in a T-cell setup with a micro-reference electrode (μ-RE), we can show by electrochemical impedance spectroscopy that these side reactions not only lead to an impedance increase of the anode and the cathode, but also trigger transition metal dissolution. By comparison of FEC and ethylene-carbonate (EC) as cyclic carbonate, we demonstrate that FEC has no advantage at high-voltage operation compared to EC, when employing cathode materials or cathode potentials for which no lattice oxygen is evolved. Finally, we use multi-layer pouch-cells to analyze the gassing of an EC- and FEC-based electrolyte upon extended charge/discharge cycling at 45 °C, showing that the latter leads to cell bulging upon extended charge/discharge cycling at 45 °C due to the oxidation of the VC formed by the thermal decomposition of FEC above ≈4.4 − 4.5 V vs. Li+/Li.

Inhibition of transition-metal dissolution with advanced electrolytes in batteries with silicon-graphite anodes and high-nickel cathodes

Transition-metal (TM) ion dissolution from high-nickel cathodes and the subsequent deposition on Silicon-based anodes impose significant detrimental influence on the cell stability, hindering the application of high-energy-density lithium-ion batteries. Here, we demonstrate an effective approach to inhibit the dissolution of TM ions by using medium concentrated lithium bis(fluorosulfonyl)imide (LiFSI)-based electrolytes with an optimized fluoroethylene carbonate content. The advanced LiFSI-based electrolyte not only stabilizes the surface lattice structure of high-Ni cathodes but also effectively suppress the TM ion dissolution, which benefit from the formation of a LiF-rich solid-electrolyte interphase (SEI) layer on the LiNi0.90Mn0.05Co0.05O2 cathode surface. A robust and protective SEI layer on the SiOx/Gr anode surface is also realized with the newly developed electrolyte, which effectively alleviates anode deterioration caused by the deposited TM ions. The SiOx/Gr||LiNi0.90Mn0.05Co0.05O2 cells with such an advanced electrolyte exhibit remarkably improved cycling stability compared to those with conventional LiPF6-based electrolyte. This study provides insights towards the development of next-generation high-energy-density batteries with high-Ni cathodes and Si-based anodes.

Nonflammable Electrolyte Based on Fluoroethylene Carbonate for High-Voltage LiCoO2/Si–Graphite Lithium-Ion Batteries

An electrolyte for high-voltage LiCoO2/Si–graphite pouch cells is proposed in this work, which is composed of LiPF6 salt and fluoroethylene carbonate solvent as well as tris(trimethylsilyl) phosphate and (ethoxy)pentafluorocyclotriphosphazene additives. Tris(trimethylsilyl) phosphate additive plays a role in improving the interfacial properties of electrodes, and (ethoxy)pentafluorocyclotriphosphazene additive makes this electrolyte nonflammable. Its conductivity is as high as 5.48 mS cm–1 at 25 °C. This safe electrolyte also enables the high-voltage LiCoO2/Si–graphite pouch cells to obtain the ideal electrochemical performances. At room temperature, the capacity retention reaches 81.7% after 200 cycles at 1C, and the discharge capacity at 3C still retains about 77% of the capacity at 1C. Furthermore, the interfacial properties of electrodes are analyzed by scanning electron microscopy and X-ray photoelectron spectroscopy measurements.

Effect of the Electric Double Layer (EDL) in Multicomponent Electrolyte Reduction and Solid Electrolyte Interphase (SEI) Formation in Lithium Batteries.

Electrolytes, consisting of salts, solvents, and additives, must form a stable solid electrolyte interphase (SEI) to ensure the performance and durability of lithium(Li)-ion batteries. However, the electric double layer (EDL) structure near charged surfaces is still unsolved, despite its importance in dictating the species being reduced for SEI formation near a negative electrode. In this work, a newly developed model was used to illustrate the effect of EDL on SEI formation in two essential electrolytes, the carbonate-based electrolyte for Li-ion batteries and the ether-based electrolyte for batteries with Li-metal anodes. Both electrolytes have fluoroethylene carbonate (FEC) as a common additive to form the beneficial F-containing SEI component (e.g., LiF). However, the role of FEC drastically differs in these electrolytes. FEC is an effective SEI modifier for the carbonate-based electrolyte by being the only F-containing species entering the EDL and being reduced, as the anion (PF6-) will not enter the EDL. For the ether-based electrolyte, both the anion (TFSI-) and FEC can enter the EDL and be reduced. The competition of the two species within the EDL due to the surface charge and temperature leads to a unique temperature effect observed in prior experiments: the FEC additive is more effective in modulating SEI components at a low temperature (-40 °C) than at room temperature (20 °C) in the ether-based electrolyte. These collective quantitative agreements with experiments emphasize the importance of incorporating the effect of the EDL in multicomponent electrolyte reduction reactions in simulations/experiments to predict/control the formation of the SEI layer.

Lithium Difluorophosphate: A Boon for High Voltage Li Ion Batteries and a Bane for High Thermal Stability/Low Toxicity: Towards Synergistic Dual Additives to Circumvent this Dilemma.

The specific energy/energy density of state-of-the-art (SOTA) Li-ion batteries can be increased by raising the upper charge voltage. However, instability of SOTA cathodes (i. e., LiNiy Cox Mny O2 ; x+y+z=1; NCM) triggers electrode crosstalk through enhanced transition metal (TM) dissolution and contributes to severe capacity fade; in the worst case, to a sudden death ("roll-over failure"). Lithium difluorophosphate (LiDFP) as electrolyte additive is able to boost high voltage performance by scavenging dissolved TMs. However, LiDFP is chemically unstable and rapidly decomposes to toxic (oligo)organofluorophosphates (OFPs) at elevated temperatures; a process that can be precisely analyzed by means of high-performance liquid chromatography-high resolution mass spectroscopy. The toxicity of LiDFP can be proven by the well-known acetylcholinesterase inhibition test. Interestingly, although fluoroethylene carbonate (FEC) is inappropriate for high voltage applications as a single electrolyte additive due to rollover failure, it is able to suppress formation of toxic OFPs. Based on this, a synergistic LiDFP/FEC dual-additive approach is suggested in this work, showing characteristic benefits of both individual additives (good capacity retention at high voltage in the presence of LiDFP and decreased OFP formation/toxicity induced by FEC).

Optimal Blend between Carbonate Solvents and Fluoroethylene Carbonate for High-Voltage and High-Safety Li(Ni0.8Mn0.1Co0.1)O2 Lithium-Ion Cells

Optimal Blend between Carbonate Solvents and Fluoroethylene Carbonate for High-Voltage and High-Safety Li(Ni_0.8Mn_0.1Co_0.1)O₂ Lithium-Ion Cells

Synergistic effect of cathode and electrolyte additives on stabilizing the anodic interface for sodium-based dual-carbon batteries

Sodium-based dual-carbon batteries (SDCBs), as a novel energy storage device, have aroused increasing interest due to their low cost and the natural abundance of sodium. However, the application of such devices is currently limited by the low specific capacity and inferior cyclic stability, which is caused by the formation of an unstable anodic interface and significant crosstalk between anions and cations in the electrolyte. Here, we propose a dual-additive strategy employing Na2C2O4 as a cathode additive and fluoroethylene carbonate (FEC) as an electrolyte additive that effectively creates a stable anodic interface and suppresses anion-cation crosstalk. The as-constructed SDCBs with dual additives deliver good rate capability (30.9 mAh g−1 at 0.5 A g−1), excellent cyclic stability (∼81.9 % retention at 0.1 A g−1 after 280 cycles), and a high energy density of 192.6 Wh kg−1, which is superior to the performance of SDCBs with only one of the additives or without either additive. The anodic interface on the cycled anode becomes stable and uniform after the addition of the dual additives, and contains more Na-rich inorganic species and fewer organic species. The proposed strategy can improve the electrochemical performances of SDCBs and promote the commercial application of such devices thanks to the low cost, ease of operation, high safety, and environmental friendliness.

Synergistic Approach toward Developing Highly Compatible Garnet‐Liquid Electrolyte Interphase in Hybrid Solid‐State Lithium‐Metal Batteries

AbstractThe hybrid solid‐liquid electrolyte concept is one of the best approaches for counteracting the interface problems between solid electrolytes and Li anodes/cathodes. However, a solid‐liquid electrolyte layer forming at the interfaces degrades battery capacity and power during a longer cycle due to highly reactive chemical and electrochemical reactions. To solve this problem in the present study, a synthetic approach is demonstrated by combining AlCl3 Lewis acid and fluoroethylene carbonate as additives in a conventional LiPF6‐containing carbonate‐based electrolyte. This electrolyte design triggers the fluoroethylene carbonate polymerization by AlCl3 addition and can also form a mechanically robust and ionically conductive Al‐rich interphase on the surface of Li7La2.75Ba0.25Zr1.75Ta0.25O12 garnet‐type structured solid electrolytes, Li anodes and LiNi0.6Mn0.2Co0.2O2 cathodes. Benefitting from this approach, the assembled Li symmetric cell exhibits a remarkably high critical current density of 4.2 mA cm−2, and stable long‐term cycling over 3000 h at 0.5 mA cm−2 at 25 °C. The assembled hybrid full cell shows an impressive specific capacity retention of 92.2% at 1 C till 200 cycles. This work opens a new direction in developing safe, long‐lasting, and high‐energy hybrid solid‐state lithium‐metal batteries.