Cooperative Proton and Li-ion Conduction in a 2D-Layered MOF via Mechanical Insertion of Lithium Halides

Ionic conduction in highly designable and porous metal–organic frameworks has been explored through the introduction of various ionic species (H⁺, OH⁻, Li⁺, etc.) using post-synthetic modification such as acid, salt, or ionic liquid incorporation. Here, we report on high ionic conductivity (σ>10⁻² S cm⁻¹) in a two-dimensionally (2D)-layered Ti-dobdc (Ti₂(Hdobdc)₂(H₂dobdc), H₄dobdc: 2,5-dihydroxyterephthalic acid) via LiX (X=Cl, Br, I) intercalation using mechanical mixing. The anionic species in lithium halide strongly affect the ionic conductivity and durability of conductivity. Solid-state pulsed-field gradient nuclear magnetic resonance (PFG NMR ) verified the high mobility of H⁺ and Li⁺ ions in the temperature range of 300–400 K. In particular, the insertion of Li salts improved the H⁺ mobility above 373 K owing to strong binding with H₂O. Furthermore, the continuous increase in Li⁺ mobility with temperature contributed to the retention of the overall high ionic conductivity at high temperatures.     

Ordered and Fast Ion Transport of Quasi-solid-state Electrolyte with Regulated Coordination Strength for Lithium Metal Batteries

Polymer based quasi-solid-state electrolyte (QSE) has attracted great attention due to its assurance for high safety of rechargeable batteries including lithium metal batteries (LMB). However, it faces the issue of low ionic conductivity of electrolyte and solid-electrolyte-interface (SEI) layer between QSE and lithium anode. Herein, we firstly demonstrate that the ordered and fast transport of lithium ion (Li⁺) can be realized in QSE. Due to the higher coordination strength of Li⁺ on tertiary amine (−NR₃) group of polymer network than that on carbonyl (−C=O) group of ester solvent, Li⁺ can diffuse orderly and quickly on −NR₃ of polymer, significantly increasing the ionic conductivity of QSE to 3.69 mS cm⁻¹. Moreover, −NR₃ of polymer can induce in situ and uniform generation of Li₃N and LiN_xO_y in SEI. As a result, the Li||NCM811 batteries (50 μm Li foil) with this QSE show an excellent stability of 220 cycles at ≈1.5 mA cm⁻², 5 times to those with conventional QSE. LMBs with LiFePO₄ can stably run for ≈8300 h. This work demonstrates an attractive concept for improving ionic conductivity of QSE, and also provides an important step for developing advanced LMB with high cycle stability and safety.     

The Universal Super Cation-Conductivity in Multiple-cation Mixed Chloride Solid-State Electrolytes

As exciting candidates for next-generation energy storage, all-solid-state lithium batteries (ASSLBs) are highly dependent on advanced solid-state electrolytes (SSEs). Here, using cost-effective LaCl₃ and CeCl₃ lattice (UCl₃-type structure) as the host and further combined with a multiple-cation mixed strategy, we report a series of UCl₃-type SSEs with high room-temperature ionic conductivities over 10⁻³ S cm⁻¹ and good compatibility with high-voltage oxide cathodes. The intrinsic large-size hexagonal one-dimensional channels and highly disordered amorphous phase induced by multi-metal cation species are believed to trigger fast multiple ionic conductions of Li⁺, Na⁺, K⁺, Cu⁺, and Ag⁺. The UCl₃-type SSEs enable a stable prototype ASSLB capable of over 3000 cycles and high reversibility at −30 °C. Further exploration of the brand-new multiple-cation mixed chlorides is likely to lead to the development of advanced halide SSEs suitable for ASSLBs with high energy density.     

Stabilizing Solid-state Lithium Metal Batteries through In Situ Generated Janus-heterarchical LiF-rich SEI in Ionic Liquid Confined 3D MOF/Polymer Membranes

Pursuing high power density lithium metal battery with high safety is essential for developing next-generation energy-storage devices, but uncontrollable electrolyte degradation and the consequence formed unstable solid-electrolyte interface (SEI) make the task really challenging. Herein, an ionic liquid (IL) confined MOF/Polymer 3D-porous membrane was constructed for boosting in situ electrochemical transformations of Janus-heterarchical LiF/Li₃N-rich SEI films on the nanofibers. Such a 3D-Janus SEI-incorporated into the separator offers fast Li⁺ transport routes, showing superior room-temperature ionic conductivity of 8.17×10⁻⁴ S cm⁻¹ and Li⁺ transfer number of 0.82. The cryo-TEM was employed to visually monitor the in situ formed LiF and Li₃N nanocrystals in SEI and the deposition of Li dendrites, which is greatly benefit to the theoretical simulation and kinetic analysis of the structural evolution during the battery charge and discharge process. In particular, this membrane with high thermal stability and mechanical strength used in solid-state Li||LiFePO₄ and Li||NCM-811 full cells and even in pouch cells showed enhanced rate-performance and ultra-long life spans.     

Ionic Liquid Electrolyte with Weak Solvating Molecule Regulation for Stable Li Deposition in High-Performance Li−O2 Batteries

Li−O₂ batteries with bis(trifluoromethanesulfonyl)imide-based ionic liquid (TFSI-IL) electrolyte are promising because TFSI-IL can stabilize O₂⁻ to lower charge overpotential. However, slow Li⁺ transport in TFSI-IL electrolyte causes inferior Li deposition. Here we optimize weak solvating molecule (anisole) to generate anisole-doped ionic aggregate in TFSI-IL electrolyte. Such unique solvation environment can realize not only high Li⁺ transport parameters but also anion-derived solid electrolyte interface (SEI). Thus, fast Li⁺ transport is achieved in electrolyte bulk and SEI simultaneously, leading to robust Li deposition with high rate capability (3 mA cm⁻²) and long cycle life (2000 h at 0.2 mA cm⁻²). Moreover, Li−O₂ batteries show good cycling stability (a small overpotential increase of 0.16 V after 120 cycles) and high rate capability (1 A g⁻¹). This work provides an effective electrolyte design principle to realize stable Li deposition and high-performance Li−O₂ batteries.     

Postsynthetic-Modified PANI/MOF Composites with Tunable Thermoelectric and Photoelectric Properties

A 3D Co-based metal–organic framework ( Co-MOF ) with two kinds of large pores filled by free Co²⁺ ions and ligands was synthesized and characterized. To expand the MOF structure and conductivity, the free Co²⁺ ions and ligands were exchanged by conductive ionic liquid EtpyBr and photosensitive AgNO₃ through single crystal-to-single crystal transformation, which produced structure-changed 3D MOFs Co-MOF-Br and Co-Ag-MOF , which were characterized by single-crystal X-ray diffraction. Incorporating small quantities of doped polyaniline (PANI) with redox activity into the pores could further tune the stability and conductivity of the three MOFs. The PANI/MOFs all show outstanding electrical conductivity (≈10⁻² S cm⁻¹), and PANI/ Co-MOF-Br has the largest p-type Seebeck coefficient of 66.6 μV K⁻¹. PANI/ Co-MOF-Br and PANI/ Co-Ag-MOF have 4 and 15 times higher photocurrent density compared with PANI/ Co-MOF , respectively. This work sheds light on the design of advanced electrically conductive 3D MOFs.     

Adsorption of hydrogen and methane on intrinsic and alkali metal cations-doped Zn<Subscript>2</Subscript>(NDC)<Subscript>2</Subscript>(diPyTz) metal–organic framework using GCMC simulations

In this study, the adsorption of hydrogen and methane on the Zn₂(NDC)₂(diPyTz) [(NDC = 2,6-naphthalenedicarboxylate, diPyTz = di-3,6-(4-pyridyl)-1,2,4,5-tetrazine)] metal–organic framework (MOF) and the effect of its doping with alkali metal cations (Li⁺, Na⁺, K⁺) were investigated using Grand Canonical Monte Carlo simulations. The results indicated that the triply catenating Zn₂(NDC)₂(diPyTz), possessing small pores preferentially adsorbed hydrogen. Doping of Zn₂(NDC)₂(diPyTz) with alkali metal cations enhanced the hydrogen adsorption on the MOF. However, this enhancement became weaker as the atomic number of metal cation increased. The simulation results showed that the hydrogen adsorption on the Li⁺-doped Zn₂(NDC)₂(diPyTz) was almost 2.35 times greater than that of the corresponding undoped MOF at low pressure and room temperature. This suggests that the doping of MOFs with alkali metal cations especially lithium is a desired strategy for hydrogen storage. Furthermore, the results revealed that the adsorption of hydrogen on the Zn₂(NDC)₂(diPyTz) was higher than that of methane at room temperature.     

Olefin-Linked Covalent Organic Frameworks with Electronegative Channels as Cationic Highways for Sustainable Lithium Metal Battery Anodes

Despite the enormous interest in Li metal as an ideal anode material, the uncontrollable Li dendrite growth and unstable solid electrolyte interphase have plagued its practical application. These limitations can be attributed to the sluggish and uneven Li⁺ migration towards Li metal surface. Here, we report olefin-linked covalent organic frameworks (COFs) with electronegative channels for facilitating selective Li⁺ transport. The triazine rings and fluorinated groups of the COFs are introduced as electron-rich sites capable of enhancing salt dissociation and guiding uniform Li⁺ flux within the channels, resulting in a high Li⁺ transference number (0.85) and high ionic conductivity (1.78 mS cm⁻¹). The COFs are mixed with a polymeric binder to form mixed matrix membranes. These membranes enable reliable Li plating/stripping cyclability over 700 h in Li/Li symmetric cells and stable capacity retention in Li/LiFePO₄ cells, demonstrating its potential as a viable cationic highway for accelerating Li⁺ conduction.     

Covalent Organic Framework with Multi-Cationic Molecular Chains for Gate Mechanism Controlled Superionic Conduction in All-Solid-State Batteries

Although solid-state batteries (SSBs) are high potential in achieving better safety and higher energy density, current solid-state electrolytes (SSEs) cannot fully satisfy the complicated requirements of SSBs. Herein, a covalent organic framework (COF) with multi-cationic molecular chains (COF-MCMC) was developed as an efficient SSE. The MCMCs chemically anchored on COF channels were generated by nano-confined copolymerization of cationic ionic liquid monomers, which can function as Li⁺ selective gates. The coulombic interaction between MCMCs and anions leads to easier dissociation of Li⁺ from coordinated states, and thus Li⁺ transport is accelerated. While the movement of anions is restrained due to the charge interaction, resulting in a high Li⁺ conductivity of 4.9×10⁻⁴ S cm⁻¹ and Li⁺ transference number of 0.71 at 30 °C. The SSBs with COF-MCMC demonstrate an excellent specific energy density of 403.4 Wh kg⁻¹ with high cathode loading and limited Li metal source.     

Overcoming Diffusion Limitation of Faradaic Processes: Property-Performance Relationships of 2D Conductive Metal-Organic Framework Cu3(HHTP)2 for Reversible Lithium-Ion Storage

Faradaic reactions including charge transfer are often accompanied with diffusion limitation inside the bulk. Conductive two-dimensional frameworks (2D MOFs) with a fast ion transport can combine both—charge transfer and fast diffusion inside their porous structure. To study remaining diffusion limitations caused by particle morphology, different synthesis routes of Cu-2,3,6,7,10,11-hexahydroxytriphenylene (Cu₃(HHTP)₂), a copper-based 2D MOF, are used to obtain flake- and rod-like MOF particles. Both morphologies are systematically characterized and evaluated for redox-active Li⁺ ion storage. The redox mechanism is investigated by means of X-ray absorption spectroscopy, FTIR spectroscopy and in situ XRD. Both types are compared regarding kinetic properties for Li⁺ ion storage via cyclic voltammetry and impedance spectroscopy. A significant influence of particle morphology for 2D MOFs on kinetic aspects of electrochemical Li⁺ ion storage can be observed. This study opens the path for optimization of redox active porous structures to overcome diffusion limitations of Faradaic processes.     

Lithium aluminate-doped lithium orthosilicate: Sol-gel ceramics and lithium dynamics

Dense ceramics (Li_4+xSi_1−xAl_xO₄ with 0 ≤ x ≤ 0.3) are obtained by sintering at 700–900°C, without prior calcination, of sol-gel powders prepared by an alkoxide-hydroxide route. In comparison with the pure lithium orthosilicate (3 × 10⁻⁴ S · cm⁻¹ at 350°C), only a slight enhancement of the ionic conductivity is noted for monophase ceramics with Li₄SiO₄-type structure (5 × 10⁻⁴ S · cm⁻¹ at 350°C for x = 0.3). Higher conductivity (2 × 10⁻² S · cm⁻¹ at 350°C) is observed for an heterogeneous material formed of a lithium silicoaluminate phase (x = 0.2) with the Li₄SiO₄-type structure coexisting with lithium hydroxide. In this two-phase material, ac conductivity and ⁷Li spin-lattice relaxation data are consistent with the formation of a new kinetic path, via a thin layer along the interface, which enhances the lithium mobility.     

De-Linker-Enabled Exceptional Volumetric Acetylene Storage Capacity and Benchmark C2H2/C2H4 and C2H2/CO2 Separations in Metal–Organic Frameworks

An ideal adsorbent for separation requires optimizing both storage capacity and selectivity, but maximizing both or achieving a desired balance remain challenging. Herein, a de-linker strategy is proposed to address this issue for metal–organic frameworks (MOFs). Broadly speaking, the de-linker idea targets a class of materials that may be viewed as being intermediate between zeolites and MOFs. Its feasibility is shown here by a series of ultra-microporous MOFs (SNNU-98-M, M=Mn, Co, Ni, Zn). SNNU-98 exhibit high volumetric C₂H₂ uptake capacity under low and ambient pressures (175.3 cm³ cm⁻³ @ 0.1 bar, 222.9 cm³ cm⁻³ @ 1 bar, 298 K), as well as extraordinary selectivity (2405.7 for C₂H₂/C₂H₄, 22.7 for C₂H₂/CO₂). Remarkably, SNNU-98-Mn can efficiently separate C₂H₂ from C₂H₂/CO₂ and C₂H₂/C₂H₄ mixtures with a benchmark C₂H₂/C₂H₄ (1/99) breakthrough time of 2325 min g⁻¹, and produce 99.9999 % C₂H₄ with a productivity up to 64.6 mmol g⁻¹, surpassing values of reported MOF adsorbents.     

A Black Phosphorus–Graphite Composite Anode for Li-/Na-/K-Ion Batteries

Black phosphorus (BP) is a desirable anode material for alkali metal ion storage owing to its high electronic/ionic conductivity and theoretical capacity. In-depth understanding of the redox reactions between BP and the alkali metal ions is key to reveal the potential and limitations of BP, and thus to guide the design of BP-based composites for high-performance alkali metal ion batteries. Comparative studies of the electrochemical reactions of Li⁺, Na⁺, and K⁺ with BP were performed. Ex situ X-ray absorption near-edge spectroscopy combined with theoretical calculation reveal the lowest utilization of BP for K⁺ storage than for Na⁺ and Li⁺, which is ascribed to the highest formation energy and the lowest ion diffusion coefficient of the final potassiation product K₃P, compared with Li₃P and Na₃P. As a result, restricting the formation of K₃P by limiting the discharge voltage achieves a gravimetric capacity of 1300 mAh g⁻¹ which retains at 600 mAh g⁻¹ after 50 cycles at 0.25 A g⁻¹.     

Directed Dehydration of Na4Sn2S6 ⋅ 5H2O Generates the New Compound Na4Sn2S6: Crystal Structure and Selected Properties

The new thiostannate Na₄Sn₂S₆ was prepared by directed crystal water removal from the hydrate Na₄Sn₂S₆ ⋅ 5H₂O at moderate temperatures. While the structure of the hydrate comprises isolated [Sn₂S₆]⁴⁻ anions, that of the anhydrate contains linear chains composed of corner-sharing SnS₄ tetrahedra, a structural motif not known in thiostannate chemistry. This structural rearrangement requires bond-breakage in the [Sn₂S₆]⁴⁻ anion, movements of the fragments of the opened [Sn₂S₆]⁴⁻ anion and Sn−S−Sn bond formation. Simultaneously, the coordination environment of the Na⁺ cations is significantly altered and the in situ formed NaS₅ polyhedra are joined by corner- and edge-sharing to form a six-membered ring. Time-dependent in situ X-ray powder diffraction evidences very fast rehydration into Na₄Sn₂S₆ ⋅ 5H₂O during storage in air atmosphere, but recovery of the initial crystallinity requires several days. Impedance spectroscopy demonstrates a mediocre room-temperature Na⁺ ion conductivity of 0.31 μS cm⁻¹ and an activation energy for ionic transport of E_a=0.75 eV.     

A Shuttle-Free Solid-State Cu−Li Battery Based on a Sandwich-Structured Electrolyte

Cu−Li batteries leveraging the two-electron redox property of Cu can offer high energy density and low cost. However, Cu−Li batteries are plagued by limited solubility and a shuttle effect of Cu ions in traditional electrolytes, which leads to low energy density and poor cycling stability. In this work, we rationally design a solid-state sandwich electrolyte for solid-state Cu−Li batteries, in which a deep-eutectic-solvent gel with high Cu-ion solubility is devised as a Cu-ion reservoir while a ceramic Li_1.4Al_0.4Ti_1.6(PO₄)₃ interlayer is used to block Cu-ion crossover. Because of the high ionic conductivity (0.55 mS cm⁻¹ at 25 °C), wide electrochemical window (>4.5 V vs. Li⁺/Li), and high Cu ion solubility of solid-state sandwich electrolyte, a solid-state Cu−Li battery demonstrates a high energy density of 1 485 Wh kg_Cu⁻¹and long-term cyclability with 97 % capacity retention over 120 cycles. The present study lays the groundwork for future research into low-cost solid-state Cu−Li batteries.     

Locally Concentrated Ionic Liquid Electrolytes Enabling Low-Temperature Lithium Metal Batteries

Lithium metal is a promising anode material for next-generation high-energy-density batteries but suffers from low stripping/plating Coulombic efficiency and dendritic growth particularly at sub-zero temperatures. Herein, a poorly-flammable, locally concentrated ionic liquid electrolyte with a wide liquidus range extending well below 0 °C is proposed for low-temperature lithium metal batteries. Its all-anion Li⁺ solvation and phase-nano-segregation solution structure are sustained at low temperatures, which, together with a solid electrolyte interphase rich in inorganic compounds, enable dendrite-free operation of lithium metal anodes at −20 °C and 0.5 mA cm⁻², with a Coulombic efficiency of 98.9 %. As a result, lithium metal batteries coupling thin lithium metal anodes (4 mAh cm⁻²) and high-loading LiNi_0.8Co_0.15Al_0.05O₂ cathodes (10 mg cm⁻²) retain 70 % of the initial capacity after 100 cycles at −20 °C. These results, as a proof of concept, demonstrate the applicability of locally concentrated ionic liquid electrolytes for low-temperature lithium metal batteries.     

Polystyrene Sulfonate Threaded through a Metal–Organic Framework Membrane for Fast and Selective Lithium‐Ion Separation

Extraction of lithium ions from salt‐lake brines is very important to produce lithium compounds. Herein, we report a new approach to construct polystyrene sulfonate (PSS) threaded HKUST‐1 metal–organic framework (MOF) membranes through an in situ confinement conversion process. The resulting membrane PSS@HKUST‐1‐6.7, with unique anchored three‐dimensional sulfonate networks, shows a very high Li⁺ conductivity of 5.53×10^?4 S cm^?1 at 25 °C, 1.89×10^?3 S cm^?1 at 70 °C, and Li⁺ flux of 6.75 mol m^?2 h^?1, which are five orders higher than that of the pristine HKUST‐1 membrane. Attributed to the different size sieving effects and the affinity differences of the Li⁺, Na⁺, K⁺, and Mg²⁺ ions to the sulfonate groups, the PSS@HKUST‐1‐6.7 membrane exhibits ideal selectivities of 78, 99, and 10296 for Li⁺/Na⁺, Li⁺/K⁺, Li⁺/Mg²⁺ and real binary ion selectivities of 35, 67, and 1815, respectively, the highest ever reported among ionic conductors and Li⁺ extraction membranes.     

Dependence of solar cell performance on the nature of alkaline counterion in gel polymer electrolytes containing binary iodides

Performance of dye-sensitized nano-crystalline TiO₂ thin film-based photo-electrochemical solar cells (PECSCs) containing gel polymer electrolytes is largely governed by the nature of the cation in the electrolyte. Dependence of the photovoltaic performance in these quasi-solid state PECSCs on the alkaline cation size has already been investigated for single cation iodide salt-based electrolytes. The present study reports the ionic conductivity dependence on the nature of alkaline cations (counterion) in a gel polymer electrolyte based on binary iodides. Polyacrylonitrile-based gel polymer electrolyte series containing binary iodide salts is prepared using one of the alkaline iodides (LiI, NaI, KI, RbI, and CsI) and tetrapropylammonium iodide (Pr₄NI). All the electrolytes based on binary salts have shown conductivity enhancement compared to their single cation counterparts. When combined with Pr₄NI, each of the Li⁺, Na⁺, K⁺, Rb⁺, and Cs⁺ cation containing iodide salts incorporated in the gel electrolytes has shown a room temperature conductivity enhancement of 85.59, 12.03, 12.71, 20.77, and 15.36%, respectively. The conductivities of gel electrolytes containing binary iodide systems with Pr₄NI and KI/RbI/CsI are higher and have shown values of 3.28, 3.43, and 3.23 mS cm⁻¹, respectively at room temperature. The influence of the nature of counterions on the performance of quasi-solid state dye-sensitized solar cells is investigated by assembling two series of cells. All the binary cationic solar cells have shown more or less enhancements of open circuit voltage, short circuit current density, fill factor, and efficiency compared to their single cation counterparts. This work highlights the importance of employing binary cations (a large and a small) in electrolytes intended for quasi-solid state solar cells. The percentage of energy conversion efficiency enhancement shown for the PECSCs made with electrolytes containing Pr₄NI along with Li⁺, Na⁺, K⁺, Rb⁺, and Cs⁺ iodides is 260.27, 133.65, 65.27, 25.32, and 8.36%, respectively. The highest efficiency of 4.93% is shown by the solar cell containing KI and Pr₄NI. However, the highest enhancements of ionic conductivity as well as the energy conversion efficiency were exhibited by the PECSC made with Li⁺-containing binary cationic electrolyte.

     

Enhanced Separation of Potassium Ions by Spontaneous K+‐Induced Self‐Assembly of a Novel Metal–Organic Framework and Excess Specific Cation–π Interactions

A novel metal–organic framework (MOF) was fabricated by spontaneous K⁺‐induced supramolecular self‐assembly with the embedded tripodal ligand units. When the 3D ligand was loaded onto Fe₃O₄@mSiO₂ core‐shell nanoparticles, it could effectively separate K⁺ ions from a mixture of Na⁺, K⁺, Mg²⁺, and Ca²⁺ ions through nanoparticle‐assisted MOF crystallization into a Fe₃O₄@mSiO₂@MOF hybrid material. Excess potassium ions could be extracted because of the specific cation–π interaction between K⁺ and the aromatic cavity of the MOF, leading to enhanced separation efficiency and suggesting a new application for MOFs.     

Improving the Electrocatalytic Activity of a Nickel-Organic Framework toward the Oxygen Evolution Reaction through Vanadium Doping

Metal-organic frameworks (MOFs) have been considered as potential oxygen evolution reaction (OER) electrocatalysts owning to their ultra-thin structure, adjustable composition, high surface area, and high porosity. Here, we designed and fabricated a vanadium-doped nickel organic framework (V_1−x−Ni_xMOF) system by using a facile two-step solvothermal method on nickel foam (NF). The doping of vanadium remarkably elevates the OER activity of V_1−x−Ni_xMOF, thus demonstrating better performance than the corresponding single metallic Ni-MOF, NiV-MOF and RuO₂ catalysts at high current density (>400 mA cm⁻²). V_0.09−Ni_0.91MOF/NF provides a low overpotential of 235 mV and a small Tafel slope of 30.3 mV dec⁻¹ at a current density of 10 mA cm⁻². More importantly, a water-splitting device assembled with Pt/C/NF and V_0.09−Ni_0.91MOF/NF as cathode and anode yielded a cell voltage of 1.96 V@1000 mA cm⁻², thereby outperforming the-state-of-the-art RuO₂⁽⁺⁾||Pt/C⁽⁻⁾. Our work sheds new insight on preparing stable, efficient OER electrocatalysts and a promising method for designing various MOF-based materials.