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Red phosphorus anode, attributed to its high specific capacity of 2596 mAh g-1, is expected to improve the energy density of Na-ion batteries. However, the P anode currently is unsatisfactory for practical usage due to the large volume expansion beyond 300%, which brings out uncontrolled brittle failure. To address this challenge, we here design a nacre-like phosphorus anode by resilient graphene oxide staggered together. The staggered structure simultaneously offers mechanical strength and interwoven toughness. Finite element modeling reveals that the sodiation stress from P nanoparticles will be transferred into interlayer pillars as the elastic medium to release sodiation stress. The prepared anode achieves an ultrahigh areal capacity of 13 mAh cm-2 at a mass loading of 5.8 mg cm-2. Notably, the volume change of the anode is limited to approximately 8.2% at full sodiation, significantly lower than that of the traditional phosphorus electrodes.
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The construction of a continuous ionic/electronic pathway is critical for Si-based sulfide all-solid-state batteries (ASSBs) with the advantages of high-energy density and high-cycle stability. However, a significant impediment arises from the parasitic reaction occurring between the ionic sulfide solid-state electrolyte and electronic carbon additive, posing a formidable challenge. Additionally, the fabrication of electrodes necessitates stringent operational conditions, further limiting practical applicability. Herein, an ionic-electronic dual conductive binder for the fabrication of robust silicon anode under ambient air conditions in the absence of high-cost and air-sensitive sulfide solid-state electrolyte for ASSBs is reported. This binder incorporates in situ reduced silver nanoparticles into a high-strength polymer rich in ether bonds, establishing a conductive pathway for lithium ions and electrons. With the binder-composited Si anode, the half-cell exhibits a remarkable capacity of 1906.9 mAh g-1 and stable cycling for 500 cycles at a current density of 2 C (4.4 mA cm-2) under a low stack pressure of 5 MPa. The full cell using Ni0.9Co0.075Mn0.025O2 (NCM90) exhibits a remark cycling stability within 2000 cycles at 5 C (8 mA cm-2). This work presents an inspired design of functional binders for large-scale manufacture and mild operation in a low-cost way for Si anodes in ASSBs.
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Extensive investigations have proven the effectiveness of elastic binders in settling the challenge of structural damage posed by volume expansion of high-capacity anode used in nanoscale silicon. However, the sluggish ionic conductivity of polymer binder severely restricts the electrode reactions, making it unsuitable for practical applications. Inspired by the biological tissues with rapid neurotransmission and robust muscles, we propose a biomimetic binder that contains ionic conductive polymer (by polymerization reaction of poly(ethylene glycol) diglycidyl ether and polyethylenimine) and rigid polymer backbone (polyacrylic acid), which can effectively mitigate both Li-ion transport resistance and lithiation stress to stabilize the silicon nanoparticles during cycles. Consequently, the silicon anode with biomimetic binder achieves a rate capability of 1897 mAh g-1 at 8.0 A g-1 and capacity retention of 87% after 150 cycles under areal capacity upon 3.0 mAh cm-2. These results demonstrate the possibility of decoupling ionic conductivity from mechanical properties toward practical high-capacity anodes for energy-dense batteries.
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The advancement of Li-metal batteries is significantly impeded by the presence of unstable solid electrolyte interphase and Li dendrites upon cycling. Herein, we present an innovative approach to address these issues through the synergetic regulation of solid electrolyte interphase mechanics and Li crystallography using yttrium fluoride/polymethyl methacrylate composite layer. Specifically, we demonstrate the in-situ generation of Y-doped lithium metal through the reaction of composite layer with Li metal, which reduces the surface energy of the (200) plane, and tunes the preferential crystallographic orientation to (200) plane from conventional (110) plane during Li plating. These changes effectively passivate Li metal, thereby significantly reducing undesired side reactions between Li and electrolytes by 4 times. Meanwhile, the composite layer with suitable modulus (~1.02 GPa) can enhance mechanical stability and maintain structural stability of SEI. Consequently, a 4.2 Ah pouch cell with high energy density of 468 Wh kg-1 and remarkable capacity stability of 0.08% decay/cycle is demonstrated under harsh condition, such as high-areal-capacity cathode (6 mAh cm-2), lean electrolyte (1.98 g Ah-1), and high current density (3 mA cm-2). Our findings highlight the potential of reactive composite layer as a promising strategy for the development of stable Li-metal batteries.
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Quasiperiodic patterns and crystals-having long range order without translational symmetry-have fascinated researchers since their discovery. In this study, we report on new p-terphenyl-based T-shaped facial polyphiles with two alkyl end chains and a glycerol-based hydrogen-bonded side group that self-assemble into an aperiodic columnar liquid quasicrystal with 12-fold symmetry and its periodic liquid-crystalline approximants with complex superstructures. All represent honeycombs formed by the self-assembly of the p-terphenyls, dividing space into prismatic cells with polygonal cross-sections. In the perspective of tiling patterns, the presence of unique trapezoidal tiles, consisting of three rigid sides formed by the p-terphenyls and one shorter, incommensurate, and adjustable side by the alkyl end chains, plays a crucial role for these phases. A delicate temperature-dependent balance between conformational, entropic and space-filling effects determines the role of the alkyl chains, either as network nodes or trapezoid walls, thus resulting in the order-disorder transitions associated with emergence of quasiperiodicity. In-depth analysis suggests a change from a quasiperiodic tiling involving trapezoids to a modified one with a contribution of trapezoid pair fusion. This work paves the way for understanding quasiperiodicity emergence and develops fundamental concepts for its generation by chemical design of non-spherical molecules, aggregates, and frameworks based on dynamic reticular chemistry.
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Lithium metal batteries (LMBs) are the most promising high energy density energy storage technologies for electric vehicles, military, and aerospace applications. LMBs require further improvement to operate efficiently when chronically or routinely exposed to high temperatures. Electrolyte engineering with high temperature tolerance and electrode compatibility has been essential to the development of LMBs. In this review, the primary obstacles to achieving high-temperature LMBs are first explored. Subsequently, electrolyte tailoring options, such as lithium salt optimization, solvation structure modification, and the addition of additives are reviewed in detail. In addition, the feasibility of utilizing LMBs at high temperatures has been investigated. In conclusion, this study provides insights and perspectives for future research on electrolyte design at high temperatures.
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Lithium (Li) metal, a promising anode for high-energy-density rechargeable batteries, typically grows along the low-surface energy (110) plane in the plating process, resulting in uncontrollable dendrite growth and unstable interface. Herein, an unexpected Li growth behavior by lanthanum (La) doping is reported: the preferred orientation turns to (200) from (110) plane, enabling 2D nuclei rather than the usual 1D nuclei upon Li deposition and thus forming a dense and dendrite-free morphology even at an ultrahigh areal capacity of 10 mAh cm-2 . Noticeably, La doping further decreases the reactivity of Li metal toward electrolytes, thereby establishing a stable interface. The dendrite-free, stable Li anode enables a high average Coulombic efficiency of 99.30% at 8 mAh cm-2 for asymmetric Li||LaF3 -Cu cells. A 3.1 Ah LaF3 -Li||LiNi0.8 Co0.1 Mn0.1 O2 pouch cell at a high energy density (425.73 Wh kg-1 ) with impressive cycling stability (0.0989% decay per cycle) under lean electrolyte (1.76 g Ah-1 ) and high cathode loading (5.77 mAh cm-2 ) using this doped Li anode is further demonstrated.
RESUMO
Lithium- and manganese-rich layered oxides (LMLOs, ≥ 250 mAh g-1 ) with polycrystalline morphology always suffer from severe voltage decay upon cycling because of the anisotropic lattice strain and oxygen release induced chemo-mechanical breakdown. Herein, a Co-free single-crystalline LMLO, that is, Li[Li0.2 Ni0.2 Mn0.6 ]O2 (LLNMO-SC), is prepared via a Li+ /Na+ ion-exchange reaction. In situ synchrotron-based X-ray diffraction (sXRD) results demonstrate that relatively small changes in lattice parameters and reduced average micro-strain are observed in LLNMO-SC compared to its polycrystalline counterpart (LLNMO-PC) during the charge-discharge process. Specifically, the as-synthesized LLNMO-SC exhibits a unit cell volume change as low as 1.1% during electrochemical cycling. Such low strain characteristics ensure a stable framework for Li-ion insertion/extraction, which considerably enhances the structural stability of LLNMO during long-term cycling. Due to these peculiar benefits, the average discharge voltage of LLNMO-SC decreases by only ≈0.2 V after 100 cycles at 28 mA g-1 between 2.0 and 4.8 V, which is much lower than that of LLNMO-PC (≈0.5 V). Such a single-crystalline strategy offers a promising solution to constructing stable high-energy lithium-ion batteries (LIBs).
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Stable and soluble redox-active nitroxyl radicals are highly desired for high-capacity and long-life aqueous zinc hybrid flow batteries (AZHFBs). Here we report a "π-π" conjugated imidazolium and "p-π" conjugated acetylamino co-functionalized 2,2,6,6-tetramethylpiperidine-N-oxyl (MIAcNH-TEMPO) as stable catholyte for AZHFBs. The incorporation of double-conjugate substituents could delocalize the electron density of the N-O head and thus remarkably stabilize the radical and oxoammonium forms of TEMPO, avoiding the side reaction of ring-opening. Consequently, the applied MIAcNH-TEMPO/Zn AZHFB demonstrates the hardly time-dependent stability with a constant capacity retention of 99.95 % per day over 16.7â days at a high concentration catholyte of 1.5â M and high current density of 50â mA cm-2 . This proposed molecular engineering strategy based on electron density regulation of redox-active structures displays an attractive efficacy and thus represents a remarkable advance in high-performance AZHFBs.
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Alleviating large stress is critical for high-energy batteries with large volume change upon cycling, yet this still presents a challenge. Here, a gradient hydrogen-bonding binder is reported for high-capacity silicon-based anodes that are highly desirable for the next-generation lithium-ion batteries. The well-defined gradient hydrogen bonds, with a successive bond energy of -2.88- -10.04 kcal mol-1 , can effectively release the large stress of silicon via the sequential bonding cleavage. This can avoid recurrently abrupt structure fracture of traditional binder due to lack of gradient energy dissipation. Certainly, this regulated binder endows stable high-areal-capacity silicon-based electrodes >4 mAh cm-2 . Beyond proof of concept, this work demonstrates a 2 Ah silicon-based pouch cell with an impressive capacity retention of 80.2% after 700 cycles (0.028% decay/cycle) based on this gradient hydrogen-bonding binder, making it more promising for practical application.
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A stable rod-like sulfonated viologen (R-Vi) derivative is developed through a spatial-structure-adjustment strategy for neutral aqueous organic redox flow batteries (AORFBs). The obtained R-Vi features four individual methyl groups on the 2,2',6,6'-positions of the 4,4'-bipyridine core ring. The tethered methyls confine the movement of the alkyl chain as well as the sulfonic anion, thus driving the spatial structure from sigmoid to rod shape. The R-Vi with weak charge attraction and large molecular dimension displays an ultralow membrane permeability that is only 14.7 % of that of typical sigmoid viologen. Moreover, the electron-donating effect of methyls endows R-Vi with the lowest redox potential of -0.55â V vs. SHE among one-electron-storage viologen-based AORFBs. The AORFB with the R-Vi anolyte and a K4 Fe(CN)6 catholyte exhibits an energy efficiency up to 87 % and extremely low capacity-fade rate of 0.007 % per cycle in 3200 continuous cycles.
RESUMO
Due to an ultrahigh theoretical specific capacity of 3860 mAh g-1, lithium (Li) is regarded as the ultimate anode for high-energy-density batteries. However, the practical application of Li metal anode is hindered by safety concerns and low Coulombic efficiency both of which are resulted fromunavoidable dendrite growth during electrodeposition. This study focuses on a critical parameter for electrodeposition, the exchange current density, which has attracted only little attention in research on Li metal batteries. A phase-field model is presented to show the effect of exchange current density on electrodeposition behavior of Li. The results show that a uniform distribution of cathodic current density, hence uniform electrodeposition, on electrode is obtained with lower exchange current density. Furthermore, it is demonstrated that lower exchange current density contributes to form a larger critical radius of nucleation in the initial electrocrystallization that results in a dense deposition of Li, which is a foundation for improved Coulombic efficiency and dendrite-free morphology. The findings not only pave the way to practical rechargeable Li metal batteries but can also be translated to the design of stable metal anodes, e.g., for sodium (Na), magnesium (Mg), and zinc (Zn) batteries.
RESUMO
An organic dye, Basic blue 3 (BB3), was reported for the first time as a two-electron catholyte for aqueous redox flow batteries. The exceptional stability of BB3 enabled the full battery to achieve a high capacity retention of >99.991% per cycle during 1500 cycles.
RESUMO
Redox-active 2,2,6,6-tetramethylpiperidine-1-oxyl (TEMPO) derivatives have recently been investigated to expand the choice of catholyte for aqueous flow batteries (AFBs). However, the effects of substituent R in 4-position on redox potential and corresponding capacity fading mechanism are still unclear. Here, we conduct comparative studies of four R-TEMPO with R = -OH, -NH2, -COOH, and -NHCOCH3 in zinc hybrid AFBs. Experimental and theoretical analyses reveal that low-radical head charge population sum and radical energy, depending on R in 4-position, play a critical role in enhancing redox potential and cycling life of R-TEMPO. The electronic effect brought along by N-acetyl could redistribute the charge and lower systematic energy, making the ring-opening joint sturdy and therefore suppress the side reactions. Accordingly, the 4-NHCOCH3-TEMPO/Zn battery achieves a high capacity retention of >99.65%/day and an open-circuit voltage of 1.71 V. Our findings on the effects of substituent are greatly anticipated to boost the high-energy density, long-life, and eco-friendly TEMPO-based AFBs.
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Metallic phase (1T) MoS2 has been regarded as an appealing material for hydrogen evolution reaction. In this work, a novel interface-induced strategy is reported to achieve stable and high-percentage 1T MoS2 through highly active 1T-MoS2 /CoS2 hetero-nanostructure. Herein, a large number of heterointerfaces can be obtained by interlinked 1T-MoS2 and CoS2 nanosheets in situ grown from the molybdate cobalt oxide nanorod under moderate conditions. Owing to the strong interaction between MoS2 and CoS2 , high-percentage of metallic-phase (1T) MoS2 of 76.6% can be achieved, leading to high electroconductivity and abundant active sites compared to 2H MoS2 . Furthermore, the interlinked MoS2 and CoS2 nanosheets can effectively disperse the nanosheets so as to enlarge the exposed active surface area. The near zero free energy of hydrogen adsorption at the heterointerface can also be achieved, indicating the fast kinetics and excellent catalytic activity induced by heterojunction. Therefore, when applied in hydrogen evolution reaction (HER), 1T-MoS2 /CoS2 heterostructure delivers low overpotential of 71 and 26 mV at the current density of 10 mA cm-2 with low Tafel slops of 60 and 43 mV dec-1 , respectively in alkaline and acidic conditions.
RESUMO
Potassium-ion batteries have attracted increasing attention for next-generation energy storage systems due to their high energy density and abundance of potassium. However, the lack of suitable anode highly hampers its practical application due to the large ionic radius of K+ . Herein, a Se3 P4 @mesoporous carbon (Se3 P4 @C) composite is reported as a high-performance anode for potassium-ion batteries. The Se3 P4 @C composite is synthesized through an in situ combination reaction between red phosphorus and Se within a porous carbon matrix. In this way, the nano-sized Se3 P4 is well confined in the porous carbon and thus exhibits a close contact with the carbon matrix. This can significantly improve the conductivity and alleviate the volume change during the cycling process. As a result, the Se3 P4 @C exhibits a high reversible initial capacity of 1036.8 mAh g-1 at a current density of 50 mA g-1 as well as an excellent cycle performance with a capacity decay of 0.07% per cycle over 300 cycles under 1000 mA g-1 . In terms of high specific capacity and stable cycling performance, the Se3 P4 @C anode is a promising candidate for advanced potassium-ion batteries.
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A series of mesoporous germanium materials were synthesized via the self-templating method. Germanium tetrachloride and sodium potassium alloy were utilized as germanium precursor and reducing agent, respectively. The by-products, NaCl and KCl, could be considered as the in-situ templates. The characterization results showed that the mesopores could be obtained, when the salts were removed by water washing. Moreover, the crystalline germanium could also be achieved, when the calcination temperature is as high as 500⯰C. However, when the calcination temperatures are 300⯰C, the as-received mesoporous germanium materials are amorphous. When evaluated as anode for lithium-ion batteries (LIBs), the obtained mesoporous germanium exhibits outstanding cycling stability, showing a high reversible specific capacity of 803â¯mAâ¯hâ¯g-1 after 100 cycles, as well as enhanced rate performance (655â¯mAâ¯hâ¯g-1 at 1â¯C rate).
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Silicon-based materials are promising anodes for next-generation lithium-ion batteries, owing to their high specific capacities. However, the huge volume expansion and shrinkage during cycling result in severe displacement of silicon particles and structural collapse of electrodes. Here we report the use of a supremely elastic gel polymer electrolyte to address this problem and realize long-term stable cycling of silicon monoxide anodes. The high elasticity of the gel polymer electrolyte is attributed to the use of a unique copolymer consisting of a soft ether domain and a hard cyclic ring domain. Consequently, the displacement of silicon monoxide particles and volume expansion of the electrode were effectively reduced, and the damage caused by electrode cracking is alleviated. A SiO|LiNi0.5Co0.2Mn0.3O2 cell shows 70.0% capacity retention in 350 cycles with a commercial-level reversible capacity of 3.0 mAh cm-2 and an average Coulombic efficiency of 99.9%.
RESUMO
Red phosphorus (P) has recently gained wide attention because of the high theoretical capacity of 2596 mA h/g, which has been regarded as promising anode material for lithium-ion batteries (LIBs). However, the actual application of red P in LIBs is hampered by the huge expansion of volume and low electronic conductivity. Herein, we design a kind of red phosphorus/crumpled nitrogen-doped graphene (P/CNG) nanocomposites with high capacity density and great rate performance as anode material for LIBs. This anode material was rationally fabricated through the scalable ball-milling method. The nanocomposite structure of P/CNG improves the electron conductivity and alleviates volume change of raw red P because of the three-dimension (3D) framework, massive defects and active sites of CNG sheets. As expected, the P/CNG composite shows excellent electrochemical performances, including high capacity (2522.6 mA h/g at 130 mA/g), remarkable rate capability (1340.5 mA h/g at 3900 mA/g), and great cyclability (1470.1 mA h/g at 1300 mA/g for 300 cycles). This work may provide a broad prospect for a great rate performance of P-based anode material for LIBs.
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Despite high energy density and low cost, rechargeable Na-CO2 batteries are highly hindered by the poor reversibility of the discharge product Na2CO3. Herein, we demonstrate a porous ketjen black carbon-supported ruthenium nanoparticle (Ru@KB) cathode, which can remarkably promote the reversibility and thus leads to an excellent cycling performance.