Boosting High-Voltage Practical Lithium Metal Batteries with Tailored Additives.

The lithium (Li) metal anode is widely regarded as an ideal anode material for high-energy-density batteries. However, uncontrolled Li dendrite growth often leads to unfavorable interfaces and low Coulombic efficiency (CE), limiting its broader application. Herein, an ether-based electrolyte (termed FGN-182) is formulated, exhibiting ultra-stable Li metal anodes through the incorporation of LiFSI and LiNO3 as dual salts. The synergistic effect of the dual salts facilitates the formation of a highly robust SEI film with fast Li+ transport kinetics. Notably, Li||Cu half cells exhibit an average CE reaching up to 99.56%. In particular, pouch cells equipped with high-loading lithium cobalt oxide (LCO, 3 mAh cm-2) cathodes, ultrathin Li chips (25 µm), and lean electrolytes (5 g Ah-1) demonstrate outstanding cycling performance, retaining 80% capacity after 125 cycles. To address the gas issue in the cathode under high voltage, cathode additives 1,3,6-tricyanohexane is incorporated with FGN-182; the resulting high-voltage LCO||Li (4.4 V) pouch cells can cycle steadily over 93 cycles. This study demonstrates that, even with the use of ether-based electrolytes, it is possible to simultaneously achieve significant improvements in both high Li utilization and electrolyte tolerance to high voltage by exploring appropriate functional additives for both the cathode and anode.

Achieving the High Capacity and High Stability of Li-Rich Oxide Cathode in Garnet-Based Solid-State Battery.

Solid-state batteries (SSBs) based on Li-rich Mn-based oxide (LRMO) cathodes attract much attention because of their high energy density as well as high safety. But their development was seriously hindered by the interfacial instability and inferior electrochemical performance. Herein, we design a three-dimensional foam-structured GaN-Li composite anode and successfully construct a high-performance SSB based on Co-free Li1.2 Ni0.2 Mn0.6 O2 cathode and Li6.5 La3 Zr1.5 Ta0.5 O12 (LLZTO) solid electrolyte. The interfacial resistance is considerably reduced to only 1.53â€…Ω cm2 and the assembled Li symmetric cell is stably cycled more than 10,000 h at 0.1-0.2 mA cm-2 . The full battery shows a high initial capacity of 245 mAh g-1 at 0.1 C and does not show any capacity degradation after 200 cycles at 0.2 C (≈100 %). The voltage decay is well suppressed and it is significantly decreased from 2.96 mV/cycle to only 0.66 mV/cycle. The SSB also shows a very high rate capability (≈170 mAh g-1 at 1 C) comparable to a liquid electrolyte-based battery. Moreover, the oxygen anion redox (OAR) reversibility of LRMO in SSB is much higher than that in liquid electrolyte-based cells. This study offers a distinct strategy for constructing high-performance LRMO-based SSBs and sheds light on the development and application of high-energy density SSBs.

Universal F4-Modified Strategy on Metal-Organic Framework to Chemical Stabilize PVDF-HFP as Quasi-Solid-State Electrolyte.

Solid-state electrolytes (SSEs) based on metal organic framework (MOF) and polymer mixed matrix membranes (MMMs) have shown great promotions in both lithium-ion conduction and interfacial resistance in lithium metal batteries (LMBs). However, the unwanted structural evolution and the and the obscure electrochemical reaction mechanism among two phases limit their further optimization and commercial application. Herein, fluorine-modified zirconium MOF with diverse F-quantities is synthesized, denoted as Zr-BDC-Fx (x = 0, 2, 4), to assemble high performance quais-solid-state electrolytes (QSSEs) with PVDF-HFP. The chemical complexation of F-sites in Zr-BDC-F4 stabilized PVDF-HFP chains in ß-phase and disordered oscillation with enhanced charge transfer and Li transmit property. Besides, the porous confinement and electronegativity of F-groups enhanced the capture and dissociation of TFSI- anions and the homogeneous deposition of LiF solid electrolyte interphase (SEI), promoting the high-efficient transport of Li+ ions and inhibiting the growth of Li dendrites. The superb specific capacities in high-loaded Li.

Combined Stabilizing of the Solid-Electrolyte Interphase with Suppression of Graphite Exfoliation via Additive-Solvent Optimization in Li-Ion Batteries.

Propylene carbonate (PC) is a promising solvent for extending the operating temperature range for lithium-ion batteries (LIBs) because of its high dielectric constant and wide temperature range stability. However, PC can cause graphite exfoliation through cointercalation, leading to electrolyte decomposition and subsequent irreversible capacity loss. This work reports the formulation of a ternary electrolyte with the introduction of an inorganic salt additive, potassium hexafluorophosphate (KPF6), to address the aforementioned concerns. We demonstrate the cumulative effect of solvent and additive on delivering multiple performance benefits and safety of the battery. The faster diffusion rate of K + solvation shell decreases the rate of PC decomposition, thereby reducing its cointercalation. Additionally, the optimum concentration of KPF6, i.e., 0.1 M constructs a robust and insoluble LiF-rich electrode/electrolyte interphase, further suppressing graphite exfoliation and Li dendrite formation. The stable cyclability is achieved by enhanced Li + transportation through the LiF-rich interphase, enabling an exfoliation-free and dendrite-free graphite anode in the ternary electrolyte.

Solid Electrolyte Interphase Architecture for a Stable Li-electrolyte Interface.

Li metal anode has attracted extensive attention as the state-of-the-art anode material for rechargeable batteries. It is defined as the ultimate anode material for the high theoretical specific capacity (3860 mAh g-1 ) and the lowest negative electrochemical potential (-3.04 V vs. Standard Hydrogen Electrode). However, the uncontrolled Li dendrites and the spontaneous side reactions between Li and electrolytes hinder its commercialization. To overcome these obstacles, the optimized solid electrolyte interphase (SEI) with excellent performance was proposed by the artificial method. The improved performance includes high stability, ionic conductivity, compactness, and flexibility. In this review, the strategies for artificial SEI engineering in liquid and solid electrolytes are summarized. To fabricate an ideal artificial SEI, the component, distribution, and structure should be fully and reasonably considered. This review will also provide perspectives for the SEI design and lay a foundation for the future research and development of Li metal batteries.

Lithiophilic Zn3N2-Modified Cu Current Collectors by a Novel FCVA Technology for Stable Anode-Free Lithium Metal Batteries.

Anode-free lithium metal batteries (AFLMBs) offer high-energy-density battery systems, but their commercial viability is hindered by irregular lithium dendrite growth and "dead Li" formation caused by current collector defects. This study employed filtered cathode vacuum arc (FCVA) technology to fabricate Cu current collectors (CCs) with a lithiophilic Zn3N2 film. This advanced preparation process ensures an evenly distributed film that reduces the nucleation overpotential, homogenizes the interfacial electric field during plating/stripping processes, inhibits lithium dendrite growth, and forms a stable solid-electrolyte interphase (SEI). Our results show that the advanced Zn3N2@Cu CCs exhibit superior performance with a high CE of above 99.3% after 230 cycles at a current density of 0.5 mA cm-2 and an area capacity of 1 mAh cm-2. Additionally, Li-Zn3N2@Cu||Li-Zn3N2@Cu symmetrical cells had a longer stable cycle time of over 1000 h than that of Li||Li and Li-Cu||Li-Cu symmetrical cells at a current density of 1 mA cm-2 and an area capacity of 2 mAh cm-2. Compared with bare Cu CCs, the capacity retention rate is increased from 14.9 to 63.1% after 100 cycles with a 0.5C rate in the AFLMBs with LFP as the cathode. This work provides a pioneering, eco-friendly, and effective solution for the fabrication of anode CCs in AFLMBs, addressing a significant challenge in their commercial application.

Functional Separator Enabled by Covalent Organic Frameworks for High-Performance Li Metal Batteries.

Uncontrolled ion transport and susceptible SEI films are the key factors that induce lithium dendrite growth, which hinders the development of lithium metal batteries (LMBs). Herein, a TpPa-2SO3 H covalent organic framework (COF) nanosheet adhered cellulose nanofibers (CNF) on the polypropylene separator (COF@PP) is successfully designed as a battery separator to respond to the aforementioned issues. The COF@PP displays dual-functional characteristics with the aligned nanochannels and abundant functional groups of COFs, which can simultaneously modulate ion transport and SEI film components to build robust lithium metal anodes. The Li//COF@PP//Li symmetric cell exhibits stable cycling over 800 h with low ion diffusion activation energy and fast lithium ion transport kinetics, which effectively suppresses the dendrite growth and improves the stability of Li+ plating/stripping. Moreover, The LiFePO4//Li cells with COF@PP separator deliver a high discharge capacity of 109.6 mAh g-1 even at a high current density of 3 C. And it exhibits excellent cycle stability and high capacity retention due to the robust LiF-rich SEI film induced by COFs. This COFs-based dual-functional separator promotes the practical application of lithium metal batteries.

The Inducement and "Rejuvenation" of Li Dendrites by Space Confinement and Positive Fe/Co-Sites.

The high reactivity of Li metal and the inhomogeneous Li deposition leads to the formation of Li dendrites and "dead" Li, which impedes the performance of Li metal batteries (LMBs) with high energy density. The regulating and guiding the Li dendrite nucleation is a desirable tactic to realize concentrated distribution of Li dendrites instead of completely inhibiting dendrite formation. Here, a Fe-Co-based Prussian blue analog with hollow and open framework (H-PBA) is employed to modify the commercial polypropylene separator (PP@H-PBA). This functional PP@H-PBA can guide the lithium dendrite growth to form uniform lithium deposition and activate the inactive Li. In details, the H-PBA with macroporous structure and open framework can induce the growth of lithium dendrites via space confinement, while the positive Fe/Co-sites lowered by polar cyanide (-CN) of PBA can reactivate the inactive Li. Thus, the Li|PP@H-PBA|Li symmetric cells exhibit long-term stability at 1 mA cm-2 for 1 mAh cm-2 over 500 h. And the Li-S batteries with PP@H-PBA deliver favorable cycling performance at 500 mA g-1 for 200 cycles.

Directing Highly Ordered and Dense Li Deposition to Achieve Stable Li Metal Batteries.

Li metal anode is promising to achieve high-energy-density battery. However, it has rapid capacity fading due to the generation of inactive Li (dead Li), especially at high current density. This study reveals that the random distribution of Li nuclei leads to large uncertainty for the further growth behavior on Cu foil. Here, periodical regulation of Li nucleation sites on Cu foil by ordered lithiophilic micro-grooves is proposed to precisely manipulate the Li deposition morphology. The management of Li deposits in the lithiophilic grooves can induce high pressure on the Li particles, leading to the formation of dense Li structure and smooth surface without dendrite growth. Li deposits comprising tightly packed large Li particles largely reduce the side reaction and the generation of isolated metallic Li at high current density. Less dead Li accumulating on the substrate significantly prolongs the cycling life of full cells with limited Li inventory. The precise manipulation of the Li deposition on Cu is promising for high-energy and stable Li metal batteries.

Bifunctional Separator with Ultra-Lightweight MnO2 Coating for Highly Stable Lithium-Sulfur Batteries.

The severe shuttling behavior in the discharging-charging process largely hampers the commercialization of lithium-sulfur (Li-S) batteries. Herein, we design a bifunctional separator with an ultra-lightweight MnO2 coating to establish strong chemical adsorption barriers for shuttling effect alleviation. The double-sided polar MnO2 layers not only trap the lithium polysulfides through extraordinary chemical bonding but also ensure the uniform Li+ flux on the lithium anode and inhibit the side reaction, resulting in homogeneous plating and stripping to avoid corrosion of the Li anode. Consequently, the assembled Li-S battery with the MnO2-modified separator retains a capacity of 665 mA h g-1 at 1 C after 1000 cycles at the areal sulfur loading of 2.5 mg cm-2, corresponding to only 0.028% capacity decay per cycle. Notably, the areal loading of ultra-lightweight MnO2 coating is as low as 0.007 mg cm-2, facilitating the achievement of a high energy density of Li-S batteries. This work reveals that the polar metal oxide-modified separator can effectively inhibit the shuttle effect and protect the Li anode for high-performance Li-S batteries.

Carbonized Polymer Dots with Controllable N, O Functional Groups as Electrolyte Additives to Achieve Stable Li Metal Batteries.

Electrolyte additive is an effective strategy to inhibit the uncontrolled growth of Li dendrites for lithium metal batteries (LMBs). However, most of the additives are complex synthesis and prone to decompose in cycling. Herein, in order to guide the homogeneous deposition of Li+ , carbonized polymer dots (CPDs) as electrolyte additives are successfully designed and synthesized by microwave (M-CPDs) and hydrothermal (H-CPDs) approaches. The controllable functional groups containing N or O (especially pyridinic-N, pyrrolic-N, and carboxyl group) enable CPDs to keep stable in electrolytes for at least 3 months. Meanwhile, the clusters formed between CPDs and Li+ through electrostatic interaction effectively guide the uniform Li dispersion and limit the "tip effect" and dendrite formation. Moreover, as lithiophilic groups increase, the strong electrostatic interference for the solvation effect of Li+ in the electrolyte is formed, which induces faster Li+ diffusion/transfer. As expected, H-CPDs achieve the ultra-even Li+ transfer. The corresponding Li//LiFePO4 full cell delivers a high capacity retention rate of 93.8% after 200 cycles, which is much higher than that of the cells without additives (61.2%) and with M-CPDs (83.7%) as additives. The strategy in this work provides a theoretical direction for CPDs as electrolyte additives used in energy storage devices.

Hexachloro-1,3-butadiene as a Functional Additive for Constructing an Efficient Solid Electrolyte Interface Layer for Long-Life Stable Li Anodes.

Lithium (Li) metal is considered as one of the attractive anodes for next-generation high-energy-density batteries due to its ultrahigh theoretical specific capacity and low potential. However, many great challenges including uncontrolled dendrite growth and undesired side reactions during repeated cycling still seriously hinder its practical application in Li metal secondary batteries. Herein, we report the hexachloro-1,3-butadiene (HCBD) molecule as a functional additive to stabilize the Li anode by forming a stable solid electrolyte interface (SEI) layer with high Li ion conductivity via in situ surface and electrochemical reactions. Density functional theory calculations demonstrate that HCBD can preferentially react with the Li anode, which generates an ionic conducting species (LiCl) into an SEI layer. The LiCl-rich SEI layer effectively regulates Li+ deposition/stripping kinetics and then induces uniform nucleation of Li+ and reduces the side reactions between the Li anode and electrolyte. With an optimal amount of HCBD in an ether-based electrolyte, an excellent cycling lifespan (7000 h) was achieved with a low hysteresis voltage of ∼10 mV at 1.0 mA cm-2 in a Li||Li symmetrical cell. Furthermore, the LiFePO4-based cell with the additive-functionalized Li anode displays obviously improved cycling stability (with a high specific capacity of 141.1 mAh g-1 after 350 cycles at 1 C).

Modulating Electron Conducting Properties at Lithium Anode Interfaces for Durable Lithium-Sulfur Batteries.

The lithium (Li) ion and electron diffusion behaviors across the actual solid electrolyte interphase (SEI) play a critical role in regulating the Li nucleation and growth and improving the performance of lithium-sulfur (Li-S) batteries. To date, a number of researchers have pursued an SEI with high Li-ion conductivity while ignoring the Li dendrite growth caused by electron tunneling in the SEI. Herein, an artificial anti-electron tunneling layer with enriched lithium fluoride (LiF) and sodium fluoride (NaF) nanocrystals is constructed using a facile solution-soaking method. As evidenced theoretically and experimentally, the LiF/NaF artificial SEI exhibits an outstanding electron-blocking capability that can reduce electron tunneling, resulting in dendrite-free and dense Li deposition beneath the SEI, even with an ultrahigh areal capacity. In addition, the artificial anti-electron tunneling layer exhibits improved ionic conductivity and mechanical strength, compared to those of routine SEI. The symmetric cells with protected Li electrodes achieve a stable cycling of 1500 h. The LiF/NaF artificial SEI endows the Li-S full cells with long-term cyclability under conditions of high sulfur loading, lean electrolyte, and limited Li excess. This study provides a perspective on the design of the SEI for highly safe and practical Li-S batteries.

Li2Se: A High Ionic Conductivity Interface to Inhibit the Growth of Lithium Dendrites in Garnet Solid Electrolytes.

All-solid-state Li metal batteries (ASSLBs) are currently regarded as one of the most promising next-generation energy storage technologies because of their great potential in realizing both high energy density and safety. However, the development of high performance ASSLBs is still restricted by the large interfacial resistance and Li dendrite propagation within solid electrolytes. Herein, a simple and efficient interfacial modification strategy is proposed to improve the interfacial contact between Li and Li6.4La3Zr1.4Ta0.6O12 (LLZTO) by introducing a uniform and thin Li2Se buffer layer. The Li2Se buffer layer formed by an in situ conversion reaction can not only enhance the wettability of lithium metal toward LLZTO electrolyte but also facilitate uniform lithium plating/stripping. As a result, the interfacial resistance of Li/LLZTO decreased from 270.5 to 5.1 Ω cm2, and the lithium symmetric cell can cycle stably for 350 h at a current density of 0.5 mA cm-2. Meanwhile, the Li|LLZTO-Li2Se|LiNi0.8Co0.1Mn0.1O2 full cells exhibit a high initial capacity of 162.3 mAh g-1 and good cycling stability with a capacity retention of 84.3% after 100 cycles at 0.2 C. These results prove the effectiveness of this modification method and provide new design strategies for the development of high performance ASSLBs.

Gel Electrolyte for Li Metal Battery.

The pursuit of high energy density enables lithium metal batteries (LMBs) to become the research hotpot again. However, the safety concerns including easy leakage and inflammability of the liquid electrolyte and the performance deterioration due to the uncontrollable Li dendrites growth in liquid electrolyte limit the further development of LMBs. Gel electrolyte, the most promising alternative for the commercial liquid electrolyte, is expected to solve the dilemma faced by the liquid electrolyte because of its higher safety, good flexibility and adaptability to the electrode and high ionic conductivity comparable to that of liquid electrolyte. Deeply understanding the characteristics and the role of the gel electrolyte in LMBs is of great importance to achieve superior electrochemical performance of LMBs. In this review, we comprehensively introduce the chemical fundamental of the gel electrolyte. On this basis, the modification strategies and the recent progress of the gel electrolyte for LMBs are systematically reviewed and particularly highlighted, which are categorized based on composition regulation, structural design and functional design. We endeavor to provide guidance for the rational design of the gel electrolyte with superior properties for LMBs.

Graphene in Solid-State Batteries: An Overview.

Solid-state batteries (SSBs) have emerged as a potential alternative to conventional Li-ion batteries (LIBs) since they are safer and offer higher energy density. Despite the hype, SSBs are yet to surpass their liquid counterparts in terms of electrochemical performance. This is mainly due to challenges at both the materials and cell integration levels. Various strategies have been devised to address the issue of SSBs. In this review, we have explored the role of graphene-based materials (GBM) in enhancing the electrochemical performance of SSBs. We have covered each individual component of an SSB (electrolyte, cathode, anode, and interface) and highlighted the approaches using GBMs to achieve stable and better performance. The recent literature shows that GBMs impart stability to SSBs by improving Li+ ion kinetics in the electrodes, electrolyte and at the interfaces. Furthermore, they improve the mechanical and thermal properties of the polymer and ceramic solid-state electrolytes (SSEs). Overall, the enhancements endowed by GBMs will address the challenges that are stunting the proliferation of SSBs.

Stable Lithium Plating and Stripping Enabled by a LiPON Nanolayer on PP Separator.

The practical application of the Li metal anode (LMA) is hindered by its low coulombic efficiency and dendrite formation. Although solid-state electrolytes hold promise as ideal partners for LMA, their effectiveness is limited by the poor workability and ionic conductivity. Herein, a modified separator combining the rapid Li+ transport of a liquid electrolyte and the interfacial stability of a solid-state electrolyte is explored to realize stable cycling of the LMA. A conformal nanolayer of LiPON is coated on a polypropylene separator by a scalable magnetron sputtering method, which is compatible with current Li-ion battery production lines and promising for the practical applications. The resulting LMA-electrolyte/separator interface is Li+ -conductive, electron-insulating, mechanically and chemically stable. Consequently, Li|Li cells maintain stable dendrite-free cycling with overpotentials of 10 and 40 mV over 2000 h at 1 and 5 mA cm-2 , respectively. Additionally, the Li|LiFePO4 full cells achieve a capacity retention of 92% after 550 cycles, confirming its application potential.

Additive-Assisted Hydrophobic Li+ -Solvated Structure for Stabilizing Dual Electrode Electrolyte Interphases through Suppressing LiPF6 Hydrolysis.

Lithium-metal batteries have attracted much attention due to their high energy density. However, the hydrolysis of LiPF6 leads to uncontrollable Li dendrites growth and fast capacity fading. Herein, a hydrophobic Li+ -solvated structure is designed by inducing the hexafluoroisopropyl acrylate into the electrolyte system. Due to the alkene groups and non-polar perfluorocarbon (-CF2 CF2 CF3 ) chain, a hydrophobic surface around Li-ion solvated aggregates can be obtained to protect the LiPF6 against the attack from trace H2 O. Moreover, the additive could also help to form an organic solid electrolyte interphase with rich polar C-F bonds, which can capture Li ions to restrain the dendrite growth. Therefore, the Li||Li symmetric cells show a stable cycling performance up to 500 h at a current density of 1 mA cm-2 . The Li||LiNi0.6 Co0.2 Mn0.2 O2 cells show good cycling stability, exhibiting a specific capacity of 111 mAh g-1 at 1 C with a capacity retention of 74 % after 200 cycles.

Single-Ion versus Dual-Ion Conducting Electrolytes: The Relevance of Concentration Polarization in Solid-State Batteries.

Lithium batteries with solid polymer electrolytes (SPEs) and mobile ions are prone to mass transport limitations, that is, concentration polarization, creating a concentration gradient with Li+-ion (and counter-anion) depletion toward the respective electrode, as can be electrochemically observed in, for example, symmetric Li||Li cells and confirmed by Sand and diffusion equations. The effect of immobile anions is systematically investigated in this work. Therefore, network-based SPEs are synthesized with either mobile (dual-ion conduction) or immobile anions (single-ion conduction) and proved via solvation tests and nuclear magnetic resonance spectroscopy. It is shown that the SPE with immobile anions does not suffer from concentration polarization, thus disagreeing with Sand and diffusion assumptions, consequently suggesting single-ion (Li+) transport via migration instead. Nevertheless, the practical relevance of single-ion conduction can be debated. Under practical conditions, that is, below the limiting current, the concentration polarization is generally not pronounced with DIC-based electrolytes, rendering the beneficial effect of SIC redundant and DIC a better choice due to better kinetical aspects under these conditions. Also, the observed dendritic Li in both electrolytes questions a relevant impact of mass transport on its formation, at least in SPEs.

Efficient Anion Fluoride-Doping Strategy to Enhance the Performance in Garnet-Type Solid Electrolyte Li7La3Zr2O12.

Garnet-type solid-state electrolyte Li7La3Zr2O12 (LLZO) is expected to realize the next generation of high-energy-density lithium-ion batteries. However, the severe dendrite penetration at the pores and grain boundaries inside the solid electrolyte hinders the practical application of LLZO. Here, it is reported that the desirable quality and dense garnet Li6.8Al0.2La3Zr2O11.80F0.20 can be obtained by fluoride anion doping, which can effectively facilitate grain nucleation and refine the grain; thereby, the ionic conductivity increased to 7.45 × 10-4 at 30 °C and the relative density reached to 95.4%. At the same time, we introduced a transition layer to build the Li6.8Al0.2La3Zr2O11.80F0.20-t electrolyte in order to supply a stable contact; as a result, the interface resistance of Li|Li6.8Al0.2La3Zr2O11.80F0.20-t decreases to 12.8 Ω cm2. The Li|Li6.8Al0.2La3Zr2O11.80F0.20-t|Li symmetric cell achieved a critical current density of 1.0 mA cm-2 at 25 °C, which could run stably for 1000 h without a short circuit at 0.3 mA cm-2 and 25 °C. Moreover, the Li|LiFePO4 battery exhibited a high Coulombic efficiency (>99.5%), an excellent rate capability, and a great capacity retention (123.7 mA h g-1, ≈80%) over 500 cycles at 0.3C and 25 °C. The Li|LiNi0.8Co0.1Mn0.1O2 cell operated well at 0.2C and 25 °C and delivered a high initial discharge capacity of 151.4 mA h g-1 with a good capacity retention (70%) after 195 cycles. This work demonstrates that the anion doping in LLZO is an effective method to prepare a dense garnet ceramic for the high-performance lithium batteries.