Guo JF, Chen YF, Sun CB
… +3 more, Gu YC, Ma C, Mei TS
J Am Chem Soc
· 2026 Jun · PMID 42378098
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The construction of C(sp)-C(sp) bonds remains a fundamental challenge in synthetic chemistry. Herein, we interrogate a photoelectrochemical strategy for the cross-coupling of aliphatic carboxylic acids with alkyl halides...The construction of C(sp)-C(sp) bonds remains a fundamental challenge in synthetic chemistry. Herein, we interrogate a photoelectrochemical strategy for the cross-coupling of aliphatic carboxylic acids with alkyl halides. This dual catalytic system synergistically integrates anodic photoinduced ligand-to-metal charge transfer (LMCT) with cathodic nickel-mediated electroreduction. Exploiting the photolysis of a carboxylate-metal complex, our approach enables the mild generation of alkyl radicals at the anode, bypassing the necessity for high-energy irradiation or harsh oxidative conditions. Concurrently, the cathode facilitates the selective reduction of Ni(II) to Ni(I), which engages the alkyl halide and mediates the subsequent radical cross-coupling. This protocol provides an alternative method for assembling complex molecular architectures under exceptionally mild conditions, representing a distinct advance in synthetic photoelectrochemistry.
Nutting CLA, Combe A, Yilmaz G
… +3 more, Napier R, Feringa BL, Becer CR
J Am Chem Soc
· 2026 Jun · PMID 42378073
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Molecular motors, known for their ability to undergo controlled unidirectional rotation under external stimuli, have gained growing interest for their potential applications in biological systems and smart materials. Mea...Molecular motors, known for their ability to undergo controlled unidirectional rotation under external stimuli, have gained growing interest for their potential applications in biological systems and smart materials. Meanwhile, glycosylated macromolecules are utilized in lectin-binding, making them potential candidates to combat pathogenesis, cancer, and biofilms. However, glycopolymers are limited by their current inability to adapt in response to external stimuli, restricting their potential for future precision therapies. By integrating multivalent glycopolymeric structures with first-generation molecular rotary motors, it becomes possible to control carbohydrate-lectin interactions using intrinsic motor functions. Herein, we present photoadaptive glycopolymer-based first-generation molecular motors functionalized with immunologically important monosaccharides, β-d-glucopyranoside and β-d-mannopyranoside. The lectin-binding properties were subsequently investigated using surface plasmon resonance with DC-SIGN and Langerin, key players within the human innate immune system. Additionally, a competition assay with the envelope glycoprotein of HIV, namely gp120, was conducted to ascertain the inhibitory potential of these photoresponsive glycopolymer-based molecular motors. It was established that the light-controlled conformation of the molecular motor impacted both the overall binding affinity and half-maximal inhibitory concentration values. These findings create opportunities to control the binding affinity of glycopolymers and emphasize the potential of light-driven glycopolymers to modulate key interactions in cell-specific targeted delivery of therapeutics.
J Am Chem Soc
· 2026 Jun · PMID 42378043
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Lactams are cyclic amide building blocks of fundamental importance within synthetic chemistry and drug discovery. Despite their ubiquity, general and convenient methods to interconvert between ring sizes are scarce. Here...Lactams are cyclic amide building blocks of fundamental importance within synthetic chemistry and drug discovery. Despite their ubiquity, general and convenient methods to interconvert between ring sizes are scarce. Herein, we disclose a new and general strategy enabling the direct dehomologation of lactams, via formal deletion of α-methylene units, streamlining access to a series of valuable medium-to-small-sized lactams from their homologues. This transformation is made possible in a one-pot, two-step sequence, comprising initial amide α-oxidation using an oxoammonium salt, followed by oxidative decarboxylation using readily available -CPBA. The utility of this approach is demonstrated in the ring size scanning of several biologically relevant, drug-like examples, and is extended to the preparation of a diverse range of β-amino acid derivatives, through a net dehomologation-transamidation process from a simple lactam starting material.
Lends A, Lamon G, Vallet A
… +5 more, Grélard A, Morvan E, Aimanianda V, Schanda P, Loquet A
J Am Chem Soc
· 2026 Jun · PMID 42377973
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The one-bond proton-carbon coupling constant (J) is an insightful probe of carbohydrate configuration. Equatorial and axial protons at the C position typically exhibit distinct J values, enabling NMR measurements to dist...The one-bond proton-carbon coupling constant (J) is an insightful probe of carbohydrate configuration. Equatorial and axial protons at the C position typically exhibit distinct J values, enabling NMR measurements to distinguish α- and β-configurations in carbohydrates. In principle, such measurements could provide insights into carbohydrates in the cell walls of intact microbes. However, traditionally, these measurements are performed by solution NMR with carbohydrates that were extracted, solubilized and fractionated, leaving the biological relevance of the measurements uncertain. Here, we demonstrate that H-detected solid-state NMR with fast magic-angle spinning allows quantitative measurements of J couplings for mobile capsular polysaccharides, directly on submilligram amounts of pathogenic cells. Our approach is demonstrated on intact cells of the pathogenic yeast . High-resolution proton-detected spectra enabled the determination of coupling constants for five mobile polysaccharide units of the cryptococcal capsule, revealing their native configurations and confirming previous solution NMR-based anomeric configuration assignments.
Yin J, Liu X, Meng Z
… +5 more, Shi Y, Zhang G, Ding B, Ye F, Wang P
J Am Chem Soc
· 2026 Jun · PMID 42376778
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Classic chemical protein synthesis is constrained by slow kinetics and millimolar concentration requirements, limiting access to large or hydrophobic proteins because of solubility issues. Existing auxiliary strategies g...Classic chemical protein synthesis is constrained by slow kinetics and millimolar concentration requirements, limiting access to large or hydrophobic proteins because of solubility issues. Existing auxiliary strategies generally demand harsh installation/removal conditions and are incompatible with expressed protein ligation (EPL), limiting their utility for complex targets. To overcome this, a photocleavable picolyl (Pic) linker was developed that enables postsynthetic installation of bio-orthogonal inverse-electron-demand Diels-Alder (IEDDA) reagents onto synthetic peptides and expressed proteins under mild conditions. This strategy uses rapid IEDDA kinetics to enhance effective peptide concentration, enabling efficient ligation at low concentrations. The ligation of expressed G-CSF and SARS-CoV-2 RBD fragments at micromolar concentrations demonstrates the practicality of this method, whereas conventional methods fail to achieve efficient ligation. IEDDA ligation, EPL, desulfurization/Pic linker cleavage can be performed in one pot, overcoming low-concentration synthesis bottlenecks and serving as a powerful tool for accessing challenging hydrophobic or large proteins.
J Am Chem Soc
· 2026 Jun · PMID 42374990
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Crystal structure determination from low-resolution diffraction data is challenging due to the lack of a general-purpose method for solving the crystallographic phase problem. We have developed a graph neural network, Gr...Crystal structure determination from low-resolution diffraction data is challenging due to the lack of a general-purpose method for solving the crystallographic phase problem. We have developed a graph neural network, GraPhAI, and propose a new and efficient diffraction data representation in a graph form for deep learning. The trained GraPhAI models are intended for ab initio phasing of down to 2 Å resolution data of typical unit-cell volume centrosymmetric crystal structures. The success rate is above 80% for structures containing an atom with ≥ 19 (e.g., metal-organic frameworks, coordination compounds, or inorganic structures). For purely organic crystal structures, the success so far is limited.
Dou Y, Zhu W, Wang Q
… +7 more, Wei Y, Yao HB, Yang Y, Kong X, Jin S, Liu H, Ji H
J Am Chem Soc
· 2026 Jun · PMID 42374988
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Understanding the intrinsic stage-transition kinetics of lithium-graphite intercalation compounds is central to elucidating the electrochemical performance of graphite anodes in Li-ion batteries, yet quantitatively resol...Understanding the intrinsic stage-transition kinetics of lithium-graphite intercalation compounds is central to elucidating the electrochemical performance of graphite anodes in Li-ion batteries, yet quantitatively resolving how individual staging phases transform into one another in real time remains experimentally challenging because neighboring staging phases possess closely related structures and compositions, and their transient coexistence is difficult to deconvolute with sufficient temporal resolution. Here, we establish a stage-resolved kinetic metrology based on time-resolved, in situ C magic-angle-spinning solid-state NMR of C-enriched graphite, enabling direct, quantitative tracking of the evolution of LiC phases during chemically driven delithiation. The large stage-dependent C chemical-shift dispersion, combined with the >150-fold signal-to-noise enhancement afforded by isotope enrichment, allows minute-scale acquisition and robust spectral deconvolution of coexisting stage-1 (LiC), stage-2 (LiC), and dilute-stage (LiC) components. Under quasi-equilibrium oxidative delithiation, staging proceeds predominantly through sequential two-phase transitions, LiC → Li.C and LiC → LiC, each well described by Johnson-Mehl-Avrami-Kolmogorov kinetics, consistent with diffusion-limited phase-boundary propagation. This kinetic analysis identifies the dense-stage LiC → LiC transformation as the intrinsic kinetic bottleneck. When the balance between surface Li removal and intraparticle Li redistribution is perturbed, the staging pathway becomes overlapping and heterogeneous, leading to early emergence of higher-stage phases and extended multiphase coexistence. In these regimes, an effective-order cascade model quantitatively captures the coupled evolution of successive stage transitions. These results reveal how intrinsic stage-transition kinetics and transport constraints jointly govern homogeneous versus heterogeneous delithiation in graphite, and provide a general NMR-based framework for time-resolved quantification of staging transformations in intercalation materials.
J Am Chem Soc
· 2026 Jun · PMID 42374692
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Fluorescent nucleobase analogues (FBAs) are powerful reporters of nucleic acid structure and dynamics, yet strategies for programming their functional behavior directly at the hydrogen-bonding interface of DNA remain lim...Fluorescent nucleobase analogues (FBAs) are powerful reporters of nucleic acid structure and dynamics, yet strategies for programming their functional behavior directly at the hydrogen-bonding interface of DNA remain limited. Here, we introduce a nucleobase design strategy that enables conformational programming within DNA through site-specific incorporation of a 6-amino adenine analogue (A) using a nosyl-protected phosphoramidite compatible with standard solid-phase synthesis. Postsynthetic condensation with aldehydes generates a structurally diverse library of hydrazone nucleobases with tunable electronic and conformational properties at the position. Screening identified exceptionally bright FBAs (up to 4.5 × 10 M cm), with visible excitation and emission maxima, and quantum yields ranging from 0.004-0.863, depending on conformation, sequence context, local environment, and metal binding. Hydrazone formation can be highly fluorogenic with >120-fold increases in brightness for a coumarin-derived system, enabling real-time monitoring of reaction progress. Kinetic and thermodynamic analyses revealed that product formation and stability are strongly gated by nucleic acid structure: single-stranded DNA (ssDNA) supports rapid formation ( ≈ 10 M s) and highly stable products ( ≈ 10 M), whereas duplex DNA exhibits slower association rates and greater sequence selectivity than ssDNA. Notably, an ortho-phenolic hydrazone (A) forms an intramolecular hydrogen bond to that stabilizes an -conformation of the hydrazone, thereby preserving selective pairing with thymidine while gating access to alternative functional states. Correct base pairing suppresses Zn coordination and tautomer-dependent spectral transitions of A, whereas base pair mismatches restore conformational freedom, enabling metal ion complexation with distinct absorbance/emission signatures. Collectively, this work establishes a general hydrazone-based platform for programming functional states at hydrogen-bonding interfaces, transforming a native hydrogen-bonding face into a modular chemical handle for tuning structure, reactivity, and optical responses within duplex and single-stranded DNA.
Maddala NG, Pai MH, Ingebrand T
… +1 more, Manthiram A
J Am Chem Soc
· 2026 Jun · PMID 42374644
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Ethers as electrolyte cosolvents in sodium-ion batteries (SIBs) provide favorable Na solvation and interfacial properties, but their low oxidative stability limits their use in high-voltage SIBs. Herein, we address this...Ethers as electrolyte cosolvents in sodium-ion batteries (SIBs) provide favorable Na solvation and interfacial properties, but their low oxidative stability limits their use in high-voltage SIBs. Herein, we address this limitation via molecular tuning of ether cosolvents for high-voltage (4.2 V) hard carbon || NaNiFeMnO full cells. Tetrahydropyran (THP) is functionalized with a nitrile group to form tetrahydropyran-4-carbonitrile (THPCN). To delineate the effect of nitrile functionalization and benchmark ether against a conventional carbonate, THP, THPCN, and diethyl carbonate (DEC) are evaluated as cosolvents with ethylene carbonate. Nitrile functionalization lowers the HOMO energy of the ether, extends the electrolyte stability window, and alters Na solvation. Spectroscopic techniques and molecular dynamics simulations reveal that THPCN exhibits predominantly aggregate-dominated solvation (95.1%) with weakened Na-solvent interactions, producing the most anion-rich environment relative to DEC and THP cosolvents. THPCN-modified solvation promotes the formation of highly conductive, fluorine-enriched interphases that suppress parasitic reactions. Pouch full cells with THPCN sustained ∼600 cycles at 4.2 V, outperforming THP and DEC. Operando gas analysis reveals that THPCN reduces CO generation by 45% and H generation by 30% relative to THP. The findings demonstrate nitrile functionalization as a molecular design strategy to stabilize ethers and enable high-voltage SIBs.
Bartos P, Obijalska E, Pietrzak A
… +1 more, Kaszyński P
J Am Chem Soc
· 2026 Jun · PMID 42374639
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Selective oxidation of the sulfur atom in two S--annulated Blatter radicals with Oxone gives racemic sulfoxides, one of which was resolved into enantiomers and characterized by electronic circular dichroism (ECD). They a...Selective oxidation of the sulfur atom in two S--annulated Blatter radicals with Oxone gives racemic sulfoxides, one of which was resolved into enantiomers and characterized by electronic circular dichroism (ECD). They are the first examples of a potentially broad class of centrally chiral radicals, in which the endocyclic chirality center in the π polycyclic radical skeleton represents a new paradigm in the structural chemistry of radicals. A higher ratio of Oxone gives analogous endocyclic sulfones. The resulting stable radicals were characterized by spectroscopic (UV-vis, ECD, EPR), electrochemical, XRD, and DFT methods.
Xie J, Zeng L, Yuan W
… +11 more, Li X, Zou C, Tan T, Huang Z, Wei Y, Sun F, Liu Y, Qin R, Kang J, Zhang Q, Wang Y
J Am Chem Soc
· 2026 Jun · PMID 42374172
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Decomposing ammonia to produce hydrogen is a promising approach to address challenges in hydrogen storage and transport. While Ru-based catalysts have demonstrated high activity, their long-term stability under industria...Decomposing ammonia to produce hydrogen is a promising approach to address challenges in hydrogen storage and transport. While Ru-based catalysts have demonstrated high activity, their long-term stability under industrial conditions remains a critical hurdle. Here, we develop a reductive synthesis strategy to fabricate rod-shaped ceria (CeO-Rod) featuring high-density oxygen vacancy clusters, where Ru clusters are effectively anchored via robust Ru-O-Ce linkages formed at 450 °C under N atmosphere. The resulting Ru/CeO-Rod-450N catalyst achieves an impressive 99.0% NH conversion at 450 °C, approaching the thermodynamic equilibrium (99.6%), and shows exceptional stability over 1000 h of operation. Integrated experimental characterization and density functional theory calculations reveal that the abundant Ce species and oxygen vacancy clusters create an electron-rich surface with high electron conductivity, which facilitates hydrogen spillover from Ru clusters onto CeO to form dynamic Ce-OH groups. The reversible formation and dehydrogenation of these hydroxyl groups accelerate H release while suppressing hydrogen poisoning of Ru active sites. By continuously removing adsorbed H atoms via spillover, this mechanism promotes N-N coupling and lowers the energy barrier for the rate-limiting N desorption step. This work offers a general strategy for designing highly efficient and stable ammonia decomposition catalysts through rational construction of interfacial active sites.
Jiang W, Wu X, Jing H
… +7 more, Tao Y, Han C, Liu T, Zhang G, Li R, Su C, Liu B
J Am Chem Soc
· 2026 Jun · PMID 42373559
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Selective photocatalytic epoxidation of olefins provides a green approach to chemical transformation, but it remains challenging because of competing water oxidation and olefin overoxidation. Herein, inspired by natural...Selective photocatalytic epoxidation of olefins provides a green approach to chemical transformation, but it remains challenging because of competing water oxidation and olefin overoxidation. Herein, inspired by natural photosynthesis, we demonstrate a Br/BrO-mediated solar-fuel generator, which allows for simultaneous H evolution and olefin epoxidation at two separate reactor chambers. In this design, the ErBiOCl (EBOC) semiconductor drives H evolution in the presence of Br ions under visible light irradiation, while the generated BrO species diffuse to a dark reactor chamber to selectively oxidize olefins. The rapid Br oxidation kinetics on the (010)/(100) facets of EBOC effectively suppresses the water oxidation reaction. More importantly, the decoupled system design prevents direct contact of olefins with the EBOC semiconductor, mitigating the olefin overoxidation. As a result, continuous H production is achieved, accompanied by an olefin-to-epoxide selectivity as high as 97%, significantly higher than that obtained in a conventional single-compartment reactor system. This work demonstrates an effective mediator-assisted strategy to suppress both competing side reactions and undesired reaction pathways in photocatalysis, providing a promising route for the rational design of efficient artificial photosynthetic platforms.
Han L, Yu H, Ning M
… +7 more, Xi Z, Wang S, Li H, Dong K, Peng J, Jin H, Cheng HM
J Am Chem Soc
· 2026 Jun · PMID 42372217
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Low-iridium cobalt spinel oxides are promising anode catalysts for proton-exchange membrane water electrolyzers (PEMWEs), but their practical application remains limited by the structural instability of Ir-O-Co motifs at...Low-iridium cobalt spinel oxides are promising anode catalysts for proton-exchange membrane water electrolyzers (PEMWEs), but their practical application remains limited by the structural instability of Ir-O-Co motifs at high current densities. Here, we show that the simultaneous incorporation of Mn and Ir into the octahedral (O) sites of CoO to form IrCoMnO markedly enhances both acidic oxygen evolution activity and durability. In contrast to the single-doped analogues, in which Mn is predominantly stabilized as Jahn-Teller-active Mn in CoMnO and Ir exists as less oxidized Ir in IrCoO, IrCoMnO exhibits an optimized local coordination environment with Jahn-Teller-suppressed Mn and high-valence Ir species at the O sites. This distinctive local coordination chemistry enhances structural robustness while promoting catalytic activity under operating conditions. In a practical PEMWE, IrCoMnO sustains stable operation for 2800 h at 0.5-1.0 A cm, outperforming most reported low-Ir-loading catalysts. This work highlights the importance of coordination asymmetry in the design of durable electrocatalysts for clean energy conversion.
Wang W, Zhang SJ, Hao J
… +2 more, Chen Q, Qiao SZ
J Am Chem Soc
· 2026 Jun · PMID 42372071
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Zinc-bromine (Zn-Br) flow batteries are promising for grid-scale energy storage due to their high safety, low cost, and scalable architecture. However, their application remains constrained by cathode-side polybromide sh...Zinc-bromine (Zn-Br) flow batteries are promising for grid-scale energy storage due to their high safety, low cost, and scalable architecture. However, their application remains constrained by cathode-side polybromide shuttle and anode-side Zn dendrite formation and hydrogen evolution reactions (HER). Here, we propose a bidomain engineering strategy that employs acetylcholine (ACh) as a dual-functional electrolyte additive to simultaneously address the challenges of both sides. On the cathode side, the quaternary ammonium group of ACh complexes with polybromides upon charging to increase their molecular size, thereby effectively inhibiting the polybromide shuttle. On the anode side, the acetyl group of ACh rapidly absorbs onto the Zn surface to form a water-depleted interface, inducing uniform Zn plating/stripping with suppressed HER. Consequently, the cycling life of Zn-Br flow batteries with a single ACh additive is extended by nearly 80-fold, from 80 cycles to over 6400 cycles, demonstrating highly durable cycling stability, together with an outstanding cumulative plating capacity of 128 Ah cm. This finding demonstrates that dual-function electrolyte design provides a viable pathway for grid-scale application of high-rate and long-life Zn-Br flow batteries.
Yu L, Zhang J, Zhang X
… +6 more, Wu X, Liu R, Au CH, Ogawa H, Tong R, Nakamura H
J Am Chem Soc
· 2026 Jun · PMID 42371970
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Among ribosomally synthesized and post-translationally modified peptides (RiPPs), there exist cyclic peptides featuring rigid and highly linear biaryl linkages. These biaryl cyclic peptides often exhibit unique structura...Among ribosomally synthesized and post-translationally modified peptides (RiPPs), there exist cyclic peptides featuring rigid and highly linear biaryl linkages. These biaryl cyclic peptides often exhibit unique structural characteristics absent in conventional cyclic peptides, and many display valuable biological activities. Nevertheless, the supply of such biaryl-bridged cyclic peptides and their analogs has been constrained by their intrinsic rigidity. In this study, we report a systematic and comprehensive synthetic strategy for incorporating ten distinct natural and artificial biaryl/triaryl linkages into arbitrary peptide linkers, inspired by RiPP architectures. This unified synthetic platform, which combines electrochemical decarboxylative C-C bond formation with Larock macrocyclization, enables (i) systematic access to RiPP derivatives from readily available building blocks and (ii) facile preparation of fluorine-containing RiPPs, which are of particular importance in medicinal chemistry, as well as biaryl-bridged cyclic peptides spanning diverse ring sizes. In addition, several of the cihunamide analogs synthesized in this study exhibited antibacterial activity.
Li H, Yang T, Zhao Y
… +9 more, Pan R, Peng J, Lai Y, Zhang J, Liu X, Zhu G, Zhang L, Chi YR, Xie Y
J Am Chem Soc
· 2026 Jun · PMID 42371795
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Most conventional alkene synthesis reactions (e.g., elimination et al.) inherently favor the formation of thermodynamically more stable -isomers, posing a long-standing challenge for direct access to -alkenes. Here, we r...Most conventional alkene synthesis reactions (e.g., elimination et al.) inherently favor the formation of thermodynamically more stable -isomers, posing a long-standing challenge for direct access to -alkenes. Here, we report the reprogramming of a thiamine diphosphate (ThDP)-dependent enzyme to catalyze a formal dehalogenative elimination that overrides this intrinsic thermodynamic bias, enabling the direct and selective synthesis of -α,β-unsaturated carboxylic acids. In contrast to classical approaches that rely on substrate control, directing groups, or complex ligand architectures, our strategy harnesses the enzyme's confined active site to achieve kinetic control exclusively via noncovalent interactions─representing a fundamentally distinct and more sustainable approach to stereochemical programming. This transformation diverts the enzyme from its native function in C-C bond formation by channeling the Breslow intermediate toward a homoenolate-mediated pathway, wherein specific noncovalent interactions stabilize the syn-periplanar geometry required for -selective dehalogenative elimination. Through rational active-site engineering, the stereochemical trajectory can be inverted to furnish the complementary -isomer, enabling stereodivergent synthesis from a common scaffold. This work establishes a biocatalytic platform that addresses a critical gap in -alkene synthesis, expands the catalytic repertoire of ThDP-dependent enzymes, and provides a sustainable alternative to conventional methodologies.
Jin Y, Fang H, Pan H
… +5 more, Zhang Z, Liu C, Yang L, Zhou Z, Han H
J Am Chem Soc
· 2026 Jun · PMID 42371747
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Colloidal nanocrystals are generally regarded as rigid solid entities, rarely exhibiting the structural adaptability observed in molecular cages, such as fullerenes, which can undergo carbon framework reduction and encap...Colloidal nanocrystals are generally regarded as rigid solid entities, rarely exhibiting the structural adaptability observed in molecular cages, such as fullerenes, which can undergo carbon framework reduction and encapsulate guest cations without structural reorganization. Here, by creating two enantiomeric pairs of high-nuclearity copper sulfide nanoclusters with a mixed-valence Cu(II)/Cu(I) configuration, we endow these nanoscale assemblies with an intrinsic capacity for electron uptake under mild reducing conditions. The resulting charge imbalance provides an effective thermodynamic driving force that realizes a positively charged metal ion migrating inward through multiple atomic layers and occupying the cluster core. This system thus represents a rare example of a nanocluster platform that simultaneously combines reduction tolerance and structural robustness, preserving its atomic framework despite the incorporation of a single atom effectively modifying the electronic structure, particularly the local chirality. In situ absorption and circular dichroism spectroscopies establish that the transformation proceeds through a continuous, single-particle process rather than a fragmentation-reconstruction pathway, while ex situ pair distribution function analysis resolves key local steps in the structural evolution, offering mechanistic insights into this unique migration behavior.
Tan HY, Luo JD, Liu L
… +17 more, Luo CP, Cheng XB, Ma ZT, Shi Z, Wang Y, Wang ZW, Hao XD, Wan C, Sun L, Gong K, Wang L, Fan L, Jiao S, Zheng X, Liang Z, Yin YC, Yao HB
J Am Chem Soc
· 2026 Jun · PMID 42371676
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All-solid-state lithium batteries (ASSLBs) offer improved energy density and safety over traditional liquid-electrolyte systems. However, their practical use is limited by the rigidity of inorganic lithium superionic con...All-solid-state lithium batteries (ASSLBs) offer improved energy density and safety over traditional liquid-electrolyte systems. However, their practical use is limited by the rigidity of inorganic lithium superionic conductors, which require impractically high stack pressures (>50 MPa) to maintain close solid-solid contacts during cycling. We introduce the idea of incorporating nonmetal-chlorine chemical bonds into the conductive network to make rigid conductors more flexible. Because nonmetal-chlorine chemical bonds (e.g., P-Cl, Si-Cl) exhibit low bond dissociation energies, they can undergo facile rotation and torsion, thereby facilitating Li migration and framework deformability. A liquid SiCl activation method is developed to introduce these chemical bonds, yielding a soft superionic conductor, LiPSiZrClO. This material shows a high room-temperature Li conductivity of 4.55 mS cm and a low Young's modulus of 2.09 GPa. This combination enables over 3000 cycles of ultrahigh-nickel cathode LiNiCoMnO at a high current density of 3 mA cm, and even allows for stable operation of ASSLBs with no capacity decay after 300 cycles under a low stack pressure of 5 MPa, much lower than the usual 50 MPa needed for most inorganic superionic conductors. Additionally, this chemical-bond-tuning method works with various nonmetal centers (P, Si, C, S), providing a flexible strategy for designing deformable superionic conductors suitable for low-pressure ASSLBs.