Journal of Energy Chemistry最新文献_第3页

A binary eutectic electrolyte design for high-temperature interface-compatible Zn-ion batteries 用于高温界面兼容锰离子电池的二元共晶电解质设计

IF 13.1 1区化学 Q1 Energy

Journal of Energy Chemistry

Pub Date : 2024-10-22 DOI: 10.1016/j.jechem.2024.09.068

Guomin Li , Wentao Wen , Kefeng Ouyang , Yanyi Wang , Jianhui Zhu , Ming Yang , Hongwei Mi , Ning Zhao , Peixin Zhang , Dingtao Ma

The deterioration of aqueous zinc-ion batteries (AZIBs) is confronted with challenges such as unregulated Zn²⁺ diffusion, dendrite growth and severe decay in battery performance under harsh environments. Here, a design concept of eutectic electrolyte is presented by mixing long chain polymer molecules, polyethylene glycol dimethyl ether (PEGDME), with H₂O based on zinc trifluoromethyl sulfonate (Zn(OTf)₂), to reconstruct the Zn²⁺ solvated structure and in situ modified the adsorption layer on Zn electrode surface. Molecular dynamics simulations (MD), density functional theory (DFT) calculations were combined with experiment to prove that the long-chain polymer-PEGDME could effectively reduce side reactions, change the solvation structure of the electrolyte and priority absorbed on Zn(002), achieving a stable dendrite-free Zn anode. Due to the comprehensive regulation of solvation structure and zinc deposition by PEGDME, it can stably cycle for over 3200 h at room temperature at 0.5 mA/cm² and 0.5 mAh/cm². Even at high-temperature environments of 60 °C, it can steadily work for more than 800 cycles (1600 h). Improved cyclic stability and rate performance of aqueous Zn||VO₂ batteries in modified electrolyte were also achieved at both room and high temperatures. Beyond that, the demonstration of stable and high-capacity Zn||VO₂ pouch cells also implies its practical application.

水性锌离子电池（AZIBs）的劣化面临着各种挑战，如不规则的 Zn2+ 扩散、枝晶生长以及恶劣环境下电池性能的严重下降。本文提出了一种共晶电解质的设计理念，即在三氟甲基磺酸锌（Zn(OTf)2）的基础上，将长链聚合物分子聚乙二醇二甲醚（PEGDME）与 H2O 混合，重建 Zn2+ 溶解结构，并原位修饰 Zn 电极表面的吸附层。分子动力学模拟（MD）、密度泛函理论（DFT）计算与实验相结合，证明了长链聚合物-PEGDME 能有效减少副反应，改变电解质的溶解结构，优先吸附在 Zn(002) 上，实现了稳定的无树枝状 Zn 阳极。由于 PEGDME 对溶解结构和锌沉积的全面调节，在室温条件下，在 0.5 mA/cm2 和 0.5 mAh/cm2 的条件下，可稳定循环 3200 小时以上。即使在 60 °C 的高温环境下，它也能稳定工作 800 多个循环（1600 小时）。改性电解质中的 Zn||VO2 水电池在室温和高温下的循环稳定性和速率性能也得到了改善。此外，稳定和高容量 Zn||VO2 袋式电池的展示也意味着它的实际应用。

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引用次数: 0

Toward long-life Zn anode using highly polar electrolyte additives 使用高极性电解质添加剂开发长寿命锌阳极

IF 13.1 1区化学 Q1 Energy

Journal of Energy Chemistry

Pub Date : 2024-10-22 DOI: 10.1016/j.jechem.2024.09.065

Nengbin Cai , Hongming Chen , Busheng Zhang , Zijing Liu , Xinbo He , Dan Zhou

Unstable Zn interface caused by rampant dendrite growth and parasitic side reactions always hinders the practical application of aqueous zinc metal batteries (AZMBs). Herein, tyrosine (Tyr) with high molecular polarity was introduced into aqueous electrolyte to modulate the interfacial electrochemistry of Zn anode. In AZMBs, the positively charged side of Tyr can be well adsorbed on the surface of Zn anode to form a water-poor layer, and the exposed carboxylate side can be easily coordinated with Zn²⁺, favoring inducing uniform plating of Zn²⁺ and inhibiting the occurrence of water-induced side reactions. These in turn enable the achievement of highly stable Zn anode. Accordingly, the Zn anodes achieve outstanding cyclic stability (3000 h at 2 mA cm⁻², 2 mA h cm⁻² and 1300 h at 5 mA cm⁻², 5 mA h cm⁻²), high average Coulombic efficiency (99.4% over 3200 cycles), and high depth of discharge (80% for 500 h). Besides, the assembled Zn||NaV₃O₈·1.5H₂O full cells deliver remarkable capacity retention and ultra-long lifetime (61.8% over 6650 cycles at 5 A g⁻¹) and enhanced rate capability (169 mA h g⁻¹ at 5 A g⁻¹). The work may promote the design and deep understanding of electrolyte additives with high molecular polarity for high-performance AZMBs.

树枝状突变和寄生副反应导致的锌界面不稳定一直阻碍着锌金属水电池（AZMB）的实际应用。在此，我们在水电解质中引入了高分子极性的酪氨酸（Tyr）来调节锌阳极的界面电化学。在 AZMBs 中，Tyr 带正电荷的一面可以很好地吸附在 Zn 阳极表面形成贫水层，而暴露在外的羧酸盐一面则很容易与 Zn2+ 配位，有利于诱导 Zn2+ 的均匀电镀，并抑制水引起的副反应的发生。这反过来又使得锌阳极具有高度稳定性。因此，该锌阳极具有出色的循环稳定性（在 2 mA cm-2, 2 mA h cm-2 条件下 3000 小时，在 5 mA cm-2, 5 mA h cm-2 条件下 1300 小时）、高平均库仑效率（3200 个循环中达到 99.4%）和高放电深度（500 小时达到 80%）。此外，组装后的 Zn||NaV3O8-1.5H2O 全电池具有显著的容量保持率和超长寿命（在 5 A g-1 条件下，6650 次循环的寿命为 61.8%），以及更强的速率能力（在 5 A g-1 条件下，169 mA h g-1）。这项工作可促进设计和深入理解用于高性能 AZMB 的高分子极性电解质添加剂。

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引用次数: 0

Long-duration aqueous Zn-ion batteries achieved by dual-salt highly-concentrated electrolyte with low water activity 低水活性双盐高浓缩电解质实现长效水性锌离子电池

IF 13.1 1区化学 Q1 Energy

Journal of Energy Chemistry

Pub Date : 2024-10-19 DOI: 10.1016/j.jechem.2024.09.060

Lvzhang Jiang , Lingbo Yao , Gege Wang , Chang Liu , Xiaowei Chi , Yu Liu

Aqueous Zn-ion batteries have attracted much attention due to their unique high safety and low-cost merits. However, their practical applications are at a slow pace due to their short cycle life, which fundamentally results from the instability of the positive/negative electrode interface in the traditional dilute aqueous electrolytes with high water activity. Developing highly concentrated electrolyte (HCE) has been considered as an effective solution. Unlike previous studies of single salt-based HCE (SS-HCE), herein, a new dual-salt HCE (15 m ZnCl₂ + 10 m NH₄NH₂SO₃ DS-HCE) was proposed for the first time. DS-HCE was proven to simultaneously possess higher conductivity than traditional dilute electrolytes and ultralow water activity of SS-HCE by the regulation of dual high-concentration salts on the solvation structure, which renders the Zn||Zn symmetric cell the record-long cycling life of 2200 h compared with those with SS-HCE (30 m ZnCl₂, 300 h) and other reported HCEs. Additionally, the Zn||NH₄V₄O₁₀ full cell with DS-HCE demonstrated impressed rate capability within a wide-range current densities from 0.1 to 10 A g⁻¹. Moreover, at the high current density of 5 A g⁻¹, the full cell shows almost 100% capacity retention after 4000 cycles, which indicates the promising future of the DS-HCE system for long-duration aqueous Zn-ion batteries.

水性 Zn 离子电池因其独特的高安全性和低成本优势而备受关注。然而，由于传统的高水活性稀释水电解质中正/负电极界面不稳定，导致其循环寿命短，实际应用进展缓慢。开发高浓度电解质（HCE）被认为是一种有效的解决方案。与以往基于单盐的高浓度电解质（SS-HCE）研究不同，本文首次提出了一种新型双盐高浓度电解质（15 m ZnCl2 + 10 m NH4NH2SO3 DS-HCE）。通过双高浓度盐对溶解结构的调节，DS-HCE 被证明同时具有比传统稀释电解质更高的电导率和 SS-HCE 超低的水活性，从而使 Zn||Zn 对称电池的循环寿命达到 2200 h，创下了 SS-HCE（30 m ZnCl2，300 h）和其他已报道 HCE 的循环寿命纪录。此外，采用 DS-HCE 的 Zn||NH4V4O10 全电池在 0.1 至 10 A g-1 的宽电流密度范围内表现出了令人印象深刻的速率能力。此外，在 5 A g-1 的高电流密度下，全电池在 4000 次循环后几乎显示出 100% 的容量保持率，这表明 DS-HCE 系统在长寿命水性 Zn 离子电池中大有可为。

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引用次数: 0

Wide-temperature and high-voltage Li||LiCoO2 cells enabled by a nonflammable partially-fluorinated electrolyte with fine-tuning solvation structure 具有微调溶解结构的不可燃部分氟化电解质可实现宽温高电压钴酸锂电池

IF 13.1 1区化学 Q1 Energy

Journal of Energy Chemistry

Pub Date : 2024-10-19 DOI: 10.1016/j.jechem.2024.10.007

Cheng Chen , Shu Zhang , Caili Xu , Jian Yang , Youzuo Hu , Lingchao Yu , Pengyu Li , Bing Qu , Mengqiang Wu

Efficient, safe, and reliable energy output from high-energy–density lithium metal batteries (LMBs) at all climates is crucial for portable electronic devices operating in complex environments. The performance of corresponding cathodes and lithium (Li) metal anodes, however, faces significant challenges under such demanding conditions. Herein, a nonflammable electrolyte for high-voltage Li||LCO cells has been designed, including partially-fluorinated ethyl 4,4,4-trifluorobutyrate (ETFB) as the key solvent, guided by theoretical calculations. With this ETFB-based electrolyte, Li||LCO cells exhibit enhanced reversible capacities and superior capacity retention at an elevated charge voltage of 4.5 V and a wide operating temperature range spanning from −60 °C to 70 °C. The cells achieve 67.1% discharge capacity at −60 °C, relative to room temperature capacity, and 85.9% 100th-cycle retention at 70 °C. The outstanding properties are attributed to the LiF-rich interphases formed in the ETFB-based electrolyte with a fine-tuned solvation structure, in which the coordination environment in the vicinity of Li⁺ cations and the distance between anion and solvents are subtly adjusted by introducing ETFB. This solvation structure has been mutually elucidated through joint spectra characterizations and atomistic simulations. This work presents a new strategy for the design of electrolytes to achieve all-climate reliable and safe application of LMBs.

高能量密度锂金属电池（LMB）在任何气候条件下都能高效、安全、可靠地输出能量，这对于在复杂环境中工作的便携式电子设备至关重要。然而，在如此苛刻的条件下，相应阴极和锂（Li）金属阳极的性能面临着巨大挑战。在此，我们以理论计算为指导，设计了一种用于高压锂||LCO 电池的不可燃电解质，其中包括作为关键溶剂的部分氟化的 4,4,4-三氟丁酸乙酯（ETFB）。使用这种基于 ETFB 的电解质，锂||LCO 电池在 4.5 V 的较高充电电压和 -60 °C 至 70 °C 的较宽工作温度范围内，均表现出更强的可逆容量和出色的容量保持能力。相对于室温容量，电池在-60 °C时的放电容量达到67.1%，在70 °C时的第100次循环容量保持率达到85.9%。出色的性能归功于在基于 ETFB 的电解质中形成的富含 LiF 的相间，该电解质具有微调的溶解结构，通过引入 ETFB，Li+阳离子附近的配位环境以及阴离子与溶剂之间的距离都得到了微妙的调整。这种溶解结构是通过光谱特性分析和原子模拟共同阐明的。这项工作为电解质的设计提供了一种新策略，从而实现 LMB 在全气候条件下的可靠和安全应用。

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引用次数: 0

Valence electron matching law for MXene-based single-atom catalysts 基于 MXene 的单原子催化剂的价电子匹配定律

IF 13.1 1区化学 Q1 Energy

Journal of Energy Chemistry

Pub Date : 2024-10-19 DOI: 10.1016/j.jechem.2024.10.006

Pei Song , Yuhang Zhou , Zishan Luo , Hang Zhang , Xi Sun , Sen Lu , Zepeng Jia , Hong Cui , Weizhi Tian , Rong Feng , Lingxia Jin , Hongkuan Yuan

Single-atom catalysts (SACs) have attracted considerable interest in the fields of energy and environmental science due to their adjustable catalytic activity. In this study, we investigated the matching of valence electron numbers between single atoms and adsorbed intermediates (O, N, C, and H) in MXene-anchored SACs (M-Ti₂C/M-Ti₂CO₂). The density functional theory results demonstrated that the sum of the valence electron number (V_M) of the interface-doped metal and the valence electron number (V_A) of the adsorbed intermediates in M-Ti₂C followed the 10-valence electron matching law. Furthermore, based on the 10-valence electron matching law, we deduced that the sum of the valence electron number (k) and V_M for the molecular adsorption intermediate interactions in M-Ti₂CO₂ adhered to the 11-valence electron matching law. Electrostatic repulsion between the interface electrons in M-Ti₂CO₂ and H₂O weakened the adsorption of intermediates. Furthermore, we applied the 11-valence electron matching law to guide the design of catalysts for nitrogen reduction reaction, specifically for N₂ → NNH conversion, in the M-Ti₂CO₂ structure. The sure independence screening and sparsifying operator algorithm was used to fit a simple three-dimensional descriptor of the adsorbate (R² up to 0.970) for catalyst design. Our study introduced a valence electron matching principle between doped metals (single atoms) and adsorbed intermediates (atomic and molecular) for MXene-based catalysts, providing new insights into the design of high-performance SACs.

单原子催化剂（SAC）因其可调节的催化活性而在能源和环境科学领域引起了广泛关注。在本研究中，我们研究了 MXene-anchored SACs（M-Ti2C/M-Ti2CO2）中单原子与吸附中间产物（O、N、C 和 H）之间价电子数的匹配。密度泛函理论结果表明，M-Ti2C 中界面掺杂金属的价电子数（VM）与吸附中间产物的价电子数（VA）之和遵循 10 价电子匹配定律。此外，根据 10 价电子匹配定律，我们推断出 M-Ti2CO2 中分子吸附中间体相互作用的价电子数（k）和 VM 之和遵循 11 价电子匹配定律。M-Ti2CO2 和 H2O 中界面电子之间的静电排斥削弱了中间产物的吸附。此外，我们还应用 11 价电子匹配定律来指导氮还原反应催化剂的设计，特别是 M-Ti2CO2 结构中 N2 → NNH 转化催化剂的设计。我们使用确定的独立性筛选和稀疏化算子算法拟合了一个简单的吸附剂三维描述符（R2 高达 0.970），用于催化剂设计。我们的研究为基于 MXene 的催化剂引入了掺杂金属（单原子）和吸附中间体（原子和分子）之间的价电子匹配原理，为高性能 SAC 的设计提供了新的见解。

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引用次数: 0

Design principles of novel Zn fluorocarboxylate protection layer toward durable dendrite-free Zn metal anodes 新型氟羧酸锌保护层的设计原理--实现耐用的无枝晶锌金属阳极

IF 13.1 1区化学 Q1 Energy

Journal of Energy Chemistry

Pub Date : 2024-10-18 DOI: 10.1016/j.jechem.2024.10.004

Biao Ma , Xiaolong Cheng , Licheng Miao , Xinping Tao , Pengcheng Shi , Yu Shao , Shikuo Li , Hui Zhang , Fangzhi Huang , Yu Jiang

Aqueous Zn ion batteries (ZIBs) have received extensive attention due to their intrinsic safety, high abundance, and low cost. However, uncontrolled dendrite growth and water-induced side reactions at electrode/electrolyte interfaces hinder the advancement of ZIBs. Herein, density functional theory (DFT) calculation indicates that Zn heptafluorobutyrate can facilitate uniform Zn²⁺ deposition by leveraging the abundant zincophilic groups (e.g., –COO⁻ and –CF) and inhibit water-induced side reactions due to the presence of hydrophobic carbon chains. A Zn heptafluorobutyrate protective layer (denoted as ZFA) is constructed on the metallic Zn surface in situ by acid etching process to control Zn²⁺ desolvation and nucleation behaviors, ensuring enhanced reversibility and stability of Zn anodes. Consequently, the Zn@ZFA anode demonstrates stable operation for more than 2200 h at 1 mA cm⁻² and over 7300 cycles at 40 mA cm⁻², with high Coulombic efficiency of 99.8% over 1900 cycles at 5 mA cm⁻². Impressively, Zn@ZFA||VO₂ full cell achieves exceptional cycle life (204 mA h g⁻¹ after 750 cycles at 3 A g⁻¹) and remarkable rate performance (236 mA g⁻¹ at 10 A g⁻¹). This work provides an insightful guidance for constructing a protection layer of dendrite-free Zn anodes for high-performance ZIBs.

锌离子水电池（ZIBs）因其固有的安全性、高丰度和低成本而受到广泛关注。然而，在电极/电解质界面上不受控制的枝晶生长和水引发的副反应阻碍了 ZIB 的发展。在此，密度泛函理论（DFT）计算表明，七氟丁酸锌可利用丰富的亲锌基团（如 -COO- 和 -CF）促进 Zn2+ 的均匀沉积，并因疏水碳链的存在而抑制水引起的副反应。通过酸蚀刻工艺在金属锌表面原位构建了七氟丁酸锌保护层（简称 ZFA），以控制 Zn2+ 的脱溶和成核行为，从而确保提高锌阳极的可逆性和稳定性。因此，Zn@ZFA 阳极在 1 mA cm-2 下可稳定运行 2200 小时以上，在 40 mA cm-2 下可稳定运行 7300 个周期以上，在 5 mA cm-2 下可稳定运行 1900 个周期以上，库仑效率高达 99.8%。令人印象深刻的是，Zn@ZFA||VO2 全电池实现了超长的循环寿命（在 3 A g-1 条件下循环 750 次后达到 204 mA h g-1）和卓越的速率性能（在 10 A g-1 条件下达到 236 mA g-1）。这项工作为构建高性能 ZIB 的无枝晶 Zn 阳极保护层提供了深刻的指导。

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引用次数: 0

Upcycling of monomers derived from waste polyester plastics via electrocatalysis 通过电催化技术实现废聚酯塑料单体的升级再循环

IF 13.1 1区化学 Q1 Energy

Journal of Energy Chemistry

Pub Date : 2024-10-18 DOI: 10.1016/j.jechem.2024.10.005

Haoye Wang , Richard Lee Smith Jr , Xinhua Qi

Electrocatalysis offers efficient and targeted conversion of monomers derived from waste polyester plastics to chemical products under ambient temperature and pressure conditions. This review provides analysis of research on electrochemical upgrading of monomers derived from waste polyester plastics published from 2021 to present. Factors for assessing upgrading of waste polyester plastics include alkaline hydrolysis pretreatment, indices of electrochemical reaction process (activity, stability, and techno-economic analysis), separation, and product recovery. Types of depolymerization monomers and their value-added products are summarized along with electrocatalytic mechanisms and reaction pathways. Notably, cathode coupled reactions offer significant value for anodic waste plastic oxidation during electrolysis processes. Development of bifunctional electrocatalysts can reduce the cost of coupled systems and complexity of the electrolyzer. Upgrading and recycling of waste plastic monomers using electrocatalytic technology should undergo downstream processing to form high-value products containing C–N and C–S derived functional groups obtained from depolymerized monomers. Electrochemical conversion and upgrading of monomers derived from waste polyester plastics can contribute to industrialization and global economies and help to realize environmental sustainability.

在常温常压条件下，电催化技术可将从废聚酯塑料中提取的单体高效、有针对性地转化为化学产品。本综述分析了 2021 年至今发表的有关废聚酯塑料单体电化学升级的研究。评估废聚酯塑料升级的因素包括碱性水解预处理、电化学反应过程指标（活性、稳定性和技术经济分析）、分离和产品回收。此外，还总结了解聚单体的类型及其增值产品，以及电催化机理和反应途径。值得注意的是，阴极耦合反应为电解过程中的阳极废塑料氧化提供了重要价值。开发双功能电催化剂可以降低耦合系统的成本和电解槽的复杂性。利用电催化技术升级和回收废塑料单体时，应进行下游处理，以形成从解聚单体中获得的含有 C-N 和 C-S 衍生官能团的高价值产品。利用电化学技术转化和升级从废弃聚酯塑料中提取的单体，可为工业化和全球经济做出贡献，并有助于实现环境的可持续发展。

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引用次数: 0

Integrating Cu+/Cu0 sites on porous nitrogen-doped carbon nanofibers for stable and efficient CO2 electroreduction to multicarbon products 在多孔掺氮碳纳米纤维上整合 Cu+/Cu0 位点，稳定高效地将二氧化碳电还原为多碳产品

IF 13.1 1区化学 Q1 Energy

Journal of Energy Chemistry

Pub Date : 2024-10-17 DOI: 10.1016/j.jechem.2024.09.059

Yicheng Chao , Jiahao Zhang , Qinyue Wu , Xinfei Fan , Xie Quan , Yanming Liu

The Cu⁺/Cu⁰ sites of copper-based catalysts are crucial for enhancing the production of multicarbon (C₂₊) products from electrochemical CO₂ reduction reaction (eCO₂RR). However, the unstable Cu⁺ and insufficient Cu⁺/Cu⁰ active sites lead to their limited selectivity and stability for C₂₊ production. Herein, we embedded copper oxide (CuO_x) particles into porous nitrogen-doped carbon nanofibers (CuO_x@PCNF) by pyrolysis of the electrospun fiber film containing ZIF-8 and Cu₂O particles. The porous nitrogen-doped carbon nanofibers protected and dispersed Cu⁺ species, and its microporous structure enhanced the interaction between CuO_x and reactants during eCO₂RR. The obtained CuO_x@PCNF created more effective and stable Cu⁺/Cu⁰ active sites. It showed a high Faradaic efficiency of 62.5% for C₂₊ products in H-cell, which was 2 times higher than that of bare CuO_x (∼31.1%). Furthermore, it achieved a maximum Faradaic efficiency of 80.7% for C₂₊ products in flow cell. In situ characterization and density functional theory (DFT) calculation confirmed that the N-doped carbon layer protected Cu⁺ from electrochemical reduction and lowered the energy barrier for the dimerization of *CO. Stable and exposed Cu⁺/Cu⁰ active sites enhanced the enrichment of *CO and promoted the C–C coupling reaction on the catalyst surface, which facilitated the formation of C₂₊ products.

铜基催化剂的 Cu+/Cu0 位点对于提高电化学二氧化碳还原反应（eCO2RR）中多碳（C2+）产物的产量至关重要。然而，不稳定的 Cu+ 和不足的 Cu+/Cu0 活性位点导致它们在生产 C2+ 时的选择性和稳定性有限。在此，我们通过热解含有 ZIF-8 和 Cu2O 颗粒的电纺纤维膜，将氧化铜（CuOx）颗粒嵌入多孔掺氮碳纳米纤维（CuOx@PCNF）中。多孔掺氮碳纳米纤维保护并分散了 Cu+ 物种，其微孔结构增强了 eCO2RR 过程中 CuOx 与反应物之间的相互作用。获得的 CuOx@PCNF 创造了更有效、更稳定的 Cu+/Cu0 活性位点。在 H-cell 中，C2+ 产物的法拉第效率高达 62.5%，是裸 CuOx（31.1%）的 2 倍。此外，在流动池中，C2+ 产物的法拉第效率最高可达 80.7%。原位表征和密度泛函理论（DFT）计算证实，掺杂 N 的碳层保护了 Cu+ 免受电化学还原，并降低了 *CO 的二聚化能垒。稳定和暴露的 Cu+/Cu0 活性位点增强了 *CO 的富集，促进了催化剂表面的 C-C 偶联反应，从而促进了 C2+ 产物的形成。

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引用次数: 0

Platinum modification of metallic cobalt defect sites for efficient electrocatalytic oxidation of 5-hydroxymethylfurfural 铂修饰金属钴缺陷位点以实现 5-羟甲基糠醛的高效电催化氧化

IF 13.1 1区化学 Q1 Energy

Journal of Energy Chemistry

Pub Date : 2024-10-17 DOI: 10.1016/j.jechem.2024.09.054

Haoyu Zhan , Baixue Cheng , Yankun Lu , Danning Xing , Xingshuai Lv , Huining Huang , Thomas Frauenheim , Tao Wang , Peng Zhou

Co₃O₄ possesses both direct and indirect oxidation effects and is considered as a promising catalyst for the oxidation of 5-hydroxymethylfurfural (HMF). However, the enrichment and activation effects of Co₃O₄ on OH⁻ and HMF are weak, which limits its further application. Metal defect engineering can regulate the electronic structure, optimize the adsorption of intermediates, and improve the catalytic activity by breaking the symmetry of the material, which is rarely involved in the upgrading of biomass. In this work, we prepare Co₃O₄ with metal defects and load the precious metal platinum at the defect sites (Pt-Vco). The results of in-situ characterizations, electrochemical measurements, and theoretical calculations indicate that the reduction of Co–Co coordination number and the formation of Pt–Co bond induce the decrease of electron filling in the antibonding orbitals of Co element. The resulting upward shift of the d-band center of Co combined with the characteristic adsorption of Pt species synergically enhances the enrichment and activation of organic molecules and OH⁻ species, thus exhibiting excellent HMF oxidation activity (including a lower onset potential (1.14 V) and 19 times higher current density than pure Co₃O₄ at 1.35 V). In summary, this work explores the adsorption enhancement mechanism of metal defect sites modified by precious metal in detail, provides a new option for improving the HMF oxidation activity of cobalt-based materials, broadens the application field of metal defect based materials, and gives an innovative guidance for the functional utilization of metal defect sites in biomass conversion.

Co3O4 具有直接和间接氧化作用，被认为是一种很有前景的 5-hydroxymethylfurfural (HMF) 氧化催化剂。然而，Co3O4 对 OH- 和 HMF 的富集和活化效应较弱，限制了其进一步应用。金属缺陷工程可以调节电子结构，优化中间产物的吸附，并通过打破材料的对称性来提高催化活性，而这在生物质升级中很少涉及。在这项工作中，我们制备了具有金属缺陷的 Co3O4，并在缺陷位点上负载贵金属铂（Pt-Vco）。原位表征、电化学测量和理论计算的结果表明，Co-Co 配位数的减少和 Pt-Co 键的形成导致 Co 元素反键轨道中电子填充的减少。由此产生的 Co 的 d 带中心上移与 Pt 物种的吸附特性协同增强了有机分子和 OH- 物种的富集和活化，从而表现出优异的 HMF 氧化活性（包括较低的起始电位（1.14 V）和比纯 Co3O4 高 19 倍的电流密度（1.35 V））。综上所述，该研究详细探讨了贵金属修饰金属缺陷位点的吸附增强机理，为提高钴基材料的 HMF 氧化活性提供了新的选择，拓宽了金属缺陷基材料的应用领域，为金属缺陷位点在生物质转化中的功能化利用提供了创新性指导。

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引用次数: 0

Decoupling the roles of grain boundary strength and grain size hidden in grain-level electro-chemo-mechanical failure of solid-state electrolyte 解耦固态电解质晶界强度和晶粒尺寸隐蔽性在晶粒级电化学机械破坏中的作用

IF 13.1 1区化学 Q1 Energy

Journal of Energy Chemistry

Pub Date : 2024-10-17 DOI: 10.1016/j.jechem.2024.09.058

Ming Xu , Xuyang Wang , Zhengqian Jin , Xingxing Jiao , Ya Gao , Zhongxiao Song , Xieyu Xu , Kai Xi , Yangyang Liu

Garnet lithium lanthanum zirconium oxide (Li₇La₃Zr₂O₁₂, LLZO) is a benchmark solid-state electrolyte (SSE) material receiving considerable attention owing to its high conductivity and chemical stability against Li metal. Although its electro-chemo-mechanical failure mechanisms have been much investigated, the equivocal roles of grain boundary strength and grain size of LLZO remain under-explored, hindering further performance improvements. Here we decoupled the effects of grain size and grain boundary strength of polycrystalline LLZO via the combination of electrochemical kinetics and the cohesive zone model. We discovered that the disintegration of LLZO is initiated by the accumulation of local displacements, which strongly relates to the changes in both grain size and grain boundary strength. However, variations in grain boundary strength affect the diffusion and propagation pathways of damage, while the failure of LLZO is determined by the grain size. Large LLZO grains facilitate transgranular damage under low grain boundary strength, which can alter local chemo-mechanics within the bulk of LLZO, leading to more extensive damage propagation. The results showcase the structure optimization pathways by preferentially controlling the growth of lithium dendrites at grain boundaries and their penetration in garnet-type SSE.

石榴石锂镧锆氧化物（Li7La3Zr2O12，LLZO）是一种基准固态电解质（SSE）材料，因其对金属锂具有高导电性和化学稳定性而受到广泛关注。尽管对其电化学机械失效机制进行了大量研究，但对 LLZO 晶界强度和晶粒大小的作用仍未充分探讨，这阻碍了其性能的进一步提高。在此，我们结合电化学动力学和内聚区模型，解耦了多晶 LLZO 的晶粒尺寸和晶界强度的影响。我们发现，LLZO 的解体是由局部位移的累积开始的，这与晶粒尺寸和晶界强度的变化密切相关。然而，晶界强度的变化会影响损伤的扩散和传播途径，而 LLZO 的破坏则由晶粒大小决定。大的 LLZO 晶粒有利于在低晶界强度下发生跨晶粒损伤，这会改变 LLZO 块体内部的局部化学力学，导致更广泛的损伤传播。研究结果展示了通过优先控制锂枝晶在晶界的生长及其在石榴石型 SSE 中的穿透来优化结构的途径。

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