能源化学最新文献

The sluggish kinetics of the oxygen reduction reaction (ORR) is the bottleneck for various electrochemical energy conversion devices. Regulating the electronic structure of electrocatalysts by ligands has received particular attention in deriving valid ORR electrocatalysts. Here, the surface electronic structure of Pt-based noble metal aerogels (NMAs) was modulated by various organic ligands, among which the electron-withdrawing ligand of 4-methylphenylene effectively boosted the ORR electrocatalysis. Theoretical calculations suggested the smaller energy barrier for the transformation of O* to OH* and downshift the d-band center of Pt due to the interaction between 4-methylphenylene and the surface metals, thus enhancing the ORR intrinsic activity. Both Pt₃Ni and PtPd aerogels with 4-methylphenylene decoration performed significant enhancement in ORR activity and durability in different media. Remarkably, the 4-methylphenylene modified PtPd aerogel exhibited the higher half-wave potential of 0.952 V and the mass activity of 10.2 times of commercial Pt/C. This work explained the effect of electronic structure on ORR electrocatalytic properties and would promote functionalized NMAs as efficient ORR electrocatalysts.

The unabated carbon dioxide (CO₂) emission into the atmosphere has exacerbated global climate change, resulting in extreme weather events, biodiversity loss, and an intensified greenhouse effect. To address these challenges and work toward carbon (C) neutrality and reduced CO₂ emissions, the capture and utilization of CO₂ have become imperative in both scientific research and industry. One cutting-edge approach to achieving efficient catalytic performance involves integrating green bioconversion and chemical conversion. This innovative strategy offers several advantages, including environmental friendliness, high efficiency, and multi-selectivity. This study provides a comprehensive review of existing technical routes for carbon sequestration (CS) and introduces two novel CS pathways: the electrochemical-biological hybrid and artificial photosynthesis systems. It also thoroughly examines the synthesis of valuable C_n products from the two CS systems employing different catalysts and biocatalysts. As both systems heavily rely on electron transfer, direct and mediated electron transfer has been discussed and summarized in detail. Additionally, this study explores the conditions suitable for different catalysts and assesses the strengths and weaknesses of biocatalysts. We also explored the biocompatibility of the electrode materials and developed novel materials. These materials were specifically engineered to combine with enzymes or microbial cells to solve the biocompatibility problem, while improving the electron transfer efficiency of both. Furthermore, this review summarizes the relevant systems developed in recent years for manufacturing different products, along with their respective production efficiencies, providing a solid database for development in this direction. The novel chemical-biological combination proposed herein holds great promise for the future conversion of CO₂ into advanced organic compounds. Additionally, it offers exciting prospects for utilizing CO₂ in synthesizing a wide range of industrial products. Ultimately, the present study provides a unique perspective for achieving the vital goals of “peak shaving” and C-neutrality, contributing significantly to our collective efforts to combat climate change and its associated challenges.

Exploring effective iridium (Ir)-based electrocatalysts with stable iridium centers is highly desirable for oxygen evolution reaction (OER). Herein, we regulated the incorporation manner of Ir in Co₃O₄ support to stabilize the Ir sites for effective OER. When anchored on the surface of Co₃O₄ in the form of Ir(OH)₆ species, the created Ir-OH-Co interface leads to a limited stability and poor acidic OER due to Ir leaching. When doped into Co₃O₄ lattice, the analyses of X-ray absorption spectroscopy, in-situ Raman, and OER measurements show that the partially replacement of Co in Co₃O₄ by Ir atoms inclines to cause strong electronic effect and activate lattice oxygen in the presence of Ir-O-Co interface, and simultaneously master the reconstruction effect to mitigate Ir dissolution, realizing the improved OER activity and stability in alkaline and acidic environments. As a result, Ir_lat@Co₃O₄ with Ir loading of 3.67 wt% requires 294 ± 4 mV / 285 ± 3 mV and 326 ± 2 mV to deliver 10 mA cm⁻² in alkaline (0.1 M KOH / 1.0 M KOH) and acidic (0.5 M H₂SO₄) solution, respectively, with good stability.

CsPbI₂Br perovskite solar cells (PSCs) have drawn tremendous attention due to their suitable bandgap, excellent photothermal stability, and great potential as an ideal candidate for top cells in tandem solar cells. However, the abundant defects at the buried interface and perovskite layer induce severe charge recombination, resulting in the open-circuit voltage (V_oc) output and stability much lower than anticipated. Herein, a novel buried interface management strategy is developed to regulate interfacial carrier dynamics and CsPbI₂Br defects by introducing ammonium tetrafluoroborate (NH₄BF₄), thereby resulting in both high CsPbI₂Br crystallization and minimized interfacial energy losses. Specifically, NH₄⁺ ions could preferentially heal hydroxyl groups on the SnO₂ surface and balance energy level alignment between SnO₂ and CsPbI₂Br, enhancing charge transport efficiency, while BF₄⁻ anions as a quasi-halogen regulate crystal growth of CsPbI₂Br, thus reducing perovskite defects. Additionally, it is proved that eliminating hydroxyl groups at the buried interface enhances the iodide migration activation energy of CsPbI₂Br for strengthening the phase stability. As a result, the optimized CsPbI₂Br PSCs realize a remarkable efficiency of 17.09% and an ultrahigh V_oc output of 1.43 V, which is one of the highest values for CsPbI₂Br PSCs.

Lithium-sulfur battery (LSB) has brought much attention and concern because of high theoretical specific capacity and energy density as one of main competitors for next-generation energy storage systems. The widely commercial application and development of LSB is mainly hindered by serious “shuttle effect” of lithium polysulfides (LiPSs), slow reaction kinetics, notorious lithium dendrites, etc. In various structures of LSB materials, array structured materials, possessing the composition of ordered micro units with the same or similar characteristics of each unit, present excellent application potential for various secondary cells due to some merits such as immobilization of active substances, high specific surface area, appropriate pore sizes, easy modification of functional material surface, accommodated huge volume change, enough facilitated transportation for electrons/lithium ions, and special functional groups strongly adsorbing LiPSs. Thus many novel array structured materials are applied to battery for tackling thorny problems mentioned above. In this review, recent progresses and developments on array structured materials applied in LSBs including preparation ways, collaborative structural designs based on array structures, and action mechanism analyses in improving electrochemical performance and safety are summarized. Meanwhile, we also have detailed discussion for array structured materials in LSBs and constructed the structure-function relationships between array structured materials and battery performances. Lastly, some directions and prospects about preparation ways, functional modifications, and practical applications of array structured materials in LSBs are generalized. We hope the review can attract more researchers' attention and bring more studying on array structured materials for other secondary batteries including LSB.

For large-scale in-service electric vehicles (EVs) that undergo potential maintenance, second-hand transactions, and retirement, it is crucial to rapidly evaluate the health status of their battery packs. However, existing methods often rely on lengthy battery charging/discharging data or extensive training samples, which hinders their implementation in practical scenarios. To address this issue, a rapid health estimation method based on short-time charging data and limited labels for in-service battery packs is proposed in this paper. First, a digital twin of battery pack is established to emulate its dynamic behavior across various aging levels and inconsistency degrees. Then, increment capacity sequences (△Q) within a short voltage span are extracted from charging process to indicate battery health. Furthermore, data-driven models based on deep convolutional neural network (DCNN) are constructed to estimate battery state of health (SOH), where the synthetic data is employed to pre-train the models, and transfer learning strategies by using fine-tuning and domain adaptation are utilized to enhance the model adaptability. Finally, field data of 10 EVs exhibiting different SOHs are used to verify the proposed methods. By using the △Q with 100 mV voltage change, the SOH of battery packs can be accurately estimated with an error around 3.2%.

Despite the presence of LiF components in the solid electrolyte interphase (SEI) formed on the graphite anode surface by conventional electrolyte, these LiF components primarily exist in an amorphous state, rendering them incapable of effectively inhibiting the exchange reaction between lithium ions and transition metal ions in the electrolyte. Consequently, nearly all lithium ions within the SEI film are replaced by transition metal ions, resulting in an increase in interphacial impedance and a decrease in stability. Herein, we demonstrate that the SEI film, constructed by fluoroethylene carbonate (FEC) additive rich in crystalline LiF, effectively inhibits the undesired Li⁺/Co²⁺ ion exchange reaction, thereby suppressing the deposition of cobalt compounds and metallic cobalt. Furthermore, the deposited cobalt compounds exhibit enhanced structural stability and reduced catalytic activity with minimal impact on the interphacial stability of the graphite anode. Our findings reveal the crucial influence of SEI film composition and structure on the deposition and hazards associated with transition metal ions, providing valuable guidance for designing next-generation electrolytes.

The balance between cationic redox and oxygen redox in layer-structured cathode materials is an important issue for sodium batteries to obtain high energy density and considerable cycle stability. Oxygen redox can contribute extra capacity to increase energy density, but results in lattice instability and capacity fading caused by lattice oxygen gliding and oxygen release. In this work, reversible Mn²⁺/Mn⁴⁺ redox is realized in a P3-Na_0.65Li_0.2Co_0.05Mn_0.75O₂ cathode material with high specific capacity and structure stability via Co substitution. The contribution of oxygen redox is suppressed significantly by reversible Mn²⁺/Mn⁴⁺ redox without sacrificing capacity, thus reducing lattice oxygen release and improving the structure stability. Synchrotron X-ray techniques reveal that P3 phase is well maintained in a wide voltage window of 1.5–4.5 V vs. Na⁺/Na even at 10 C and after long-term cycling. It is disclosed that charge compensation from Co/Mn-ions contributes to the voltage region below 4.2 V and O-ions contribute to the whole voltage range. The synergistic contributions of Mn²⁺/Mn⁴⁺, Co²⁺/Co³⁺, and O²⁻/(O_n)²⁻ redox in P3-Na_0.65Li_0.2Co_0.05Mn_0.75O₂ lead to a high reversible capacity of 215.0 mA h g⁻¹ at 0.1 C with considerable cycle stability. The strategy opens up new opportunities for the design of high capacity cathode materials for rechargeable batteries.

Transition metal phosphides (TMPs) have been regarded as alternative hydrogen evolution reaction (HER) and oxygen evolution reaction (OER) catalysts owing to their comparable activity to those of noble metal-based catalysts. TMPs have been produced in various morphologies, including hollow and porous nanostructures, which are features deemed desirable for electrocatalytic materials. Templated synthesis routes are often responsible for such morphologies. This paper reviews the latest advances and existing challenges in the synthesis of TMP-based OER and HER catalysts through templated methods. A comprehensive review of the structure–property–performance of TMP-based HER and OER catalysts prepared using different templates is presented. The discussion proceeds according to application, first by HER and further divided among the types of templates used—from hard templates, sacrificial templates, and soft templates to the emerging dynamic hydrogen bubble template. OER catalysts are then reviewed and grouped according to their morphology. Finally, prospective research directions for the synthesis of hollow and porous TMP-based catalysts, such as improvements on both activity and stability of TMPs, design of environmentally benign templates and processes, and analysis of the reaction mechanism through advanced material characterization techniques and theoretical calculations, are suggested.

BiVO₄ (BVO) is a promising material as the photoanode for use in photoelectrochemical applications. However, the high charge recombination and slow charge transfer of the BVO have been obstacles to achieving satisfactory photoelectrochemical performance. To address this, various modifications have been attempted, including the use of ferroelectric materials. Ferroelectric materials can form a permanent polarization within the layer, enhancing the separation and transport of photo-excited electron-hole pairs. In this study, we propose a novel approach by depositing an epitaxial BiFeO₃ (BFO) thin film underneath the BVO thin film (BVO/BFO) to harness the ferroelectric property of BFO. The self-polarization of the inserted BFO thin film simultaneously functions as a buffer layer to enhance charge transport and a hole-blocking layer to reduce charge recombination. As a result, the BVO/BFO photoanodes showed more than 3.5 times higher photocurrent density (0.65 mA cm⁻²) at 1.23 V_RHE under the illumination compared to the bare BVO photoanodes (0.18 mA cm⁻²), which is consistent with the increase of the applied bias photon-to-current conversion efficiencies (ABPE) and the result of electrochemical impedance spectroscopy (EIS) analysis. These results can be attributed to the self-polarization exhibited by the inserted BFO thin film, which promoted the charge separation and transfer efficiency of the BVO photoanodes.