Ultra‐High Initial Coulombic Efficiency Induced by Interface Engineering Enables Rapid, Stable Sodium Storage

Wan, Yanhua; Song, Keming; Chen, Weihua; Qin, Changdong; Zhang, Xixue; Zhang, Jiyu; Dai, Hongliu; Hu, Zhe; Yan, Pengfei; Liu, Chuntai; Sun, Shuhui; Chou, Shu Lei; Shen, Changyu

doi:10.1002/anie.202102368

Cited by 163 publications

(107 citation statements)

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“…Furthermore, the impressive high ICE of the 2D-Bi confirms the high electron utilization and very little electrolyte consumption. [37] To prove the repeatability of the results, many cells were tested. As shown in Figure 3a, the average ICE of the 2D-Bi is 87.5% and the open-circuit voltage (OCV) is 1.64 V. The high reversible capacity in the initial cycle of the electrode is mainly due to a very small amount of electrolyte decomposition in etherbased electrolyte.…”

Section: Resultsmentioning

confidence: 99%

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From 0D to 3D: Dimensional Control of Bismuth for Potassium Storage with Superb Kinetics and Cycling Stability

Cheng

Sun

et al. 2021

Advanced Energy Materials

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energy storage systems. [7][8][9] Thus, it is highly desired to develop new energy storage systems based on more abundant elements (such as sodium and potassium). [10,11] Compared with LIBs and sodium-ion batteries (NIBs), potassiumion batteries (KIBs) are one of the most ideal alternatives due to abundant potassium resources, lower redox potential of K + /K than that of Na + /Na (−2.93 V vs −2.71 V), similar "rocking-chair" reaction mechanism, and smaller Stokes radius in common electrolyte (K + (3.6 Å) < Na + (4.6 Å) < Li + (4.8 Å)). [12,13] Therefore, KIBs have lower production cost which has been considered as potential candidates for large-scale energy storage systems. [14] The biggest challenge for the development of KIBs is to find suitable electrode materials, because the repeated insertion/extraction of large K-ion radius would result in sluggish diffusion kinetics and electrode destruction. [15,16] Until now, many efforts have been devoted to pursue suitable electrode materials for highperformance K-ion storage. Among all kinds of anode materials, alloy-type anodes have been distinguished as promising candidates owing to its suitable voltage platform, high theoretical capacity, and high energy density. [17,18] Bismuth (Bi), an environment-friendly alloy anode material, has demonstrated a bright prospect in KIBs. [19][20][21] Based on the complete alloying reaction (Bi → K 3 Bi), it can deliver a high theoretical capacity of 385 mA h g −1 and a low reaction voltage of 0.34 V. However, huge volumetric change (506% for forming K 3 Bi) during charging/discharging and the derived electrode pulverization lead to poor cyclability and short cycle-life. [22] To address these issues, enormous efforts have been made to optimize the electrochemical properties of Bi-based anodes via appropriate structure design, such as hybridizing with carbonaceous matrix, [23] alloying with other metal, [24] and designing ultra-small nanoparticles. [25] Generally, the dimensionality of the reported Bi-based materials can be categorized into 0D, 1D, 2D, and 3D morphologies. [26] Different-dimensional structures show their unique performances based on surface and structural characteristics. Compared to 3D microsized materials, 0D-structured nanoparticles possess short diffusion length in all directions and large electrolyte-electrode contact area. Lu's group reported 0D Bi nanoparticles embedded in carbon matrix, delivering high capacity and steady long cycle (121 mA h g −1 after 700 cycles at 1 A g −1 ). [27] The 1D nanostructure exhibits Bismuth-based anode for potassium ion batteries (KIBs) has gained great attention due to its high volumetric specific capacity (3800 mA h mL −1 ). However, the Bi-based materials face a huge volumetric change upon the cycling process. Herein, the dimensionality manipulation in the Bi-anode is focused to realize superior electrochemical performance. The morphological evolution rules of 0D, 1D, 2D, and 3D Bi anodes upon the potassiation/depotassiation process are clarified. Thereinto, the 2D-Bi tran...

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Section: Resultsmentioning

confidence: 99%

“…The mechanism for the SEI formation of the 2D-Bi in the ether-based electrolyte was revealed by density functional theory (DFT) calculations. [37] In the structure where PF 6…”

Section: Resultsmentioning

confidence: 99%

From 0D to 3D: Dimensional Control of Bismuth for Potassium Storage with Superb Kinetics and Cycling Stability

Cheng

Sun

et al. 2021

Advanced Energy Materials

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“…This finding also elucidates the significantly enhanced Na + transport kinetics in the ether electrolytes of the reported carbon-based anodes. [34][35][36][37] The outstanding Na-ion storage kinetics and rate performance of MHCS-Zn in compatible ether electrolyte stimulate us to investigate its low-temperature performance. It can be seen from Figure 5a-c the battery nearly remains the constant capacity of 175 mAh g -1 at 0 °C between current densities of 0.1-3 A g -1 .…”

Section: Resultsmentioning

confidence: 99%

“…In addition to the structure design, compatible electrolytes play an important role in the practicability of nanocarbon anodes. [35][36][37] Porous or nanoscale carbons with high surface area are suffered from low initial Coulomb efficiency (ICE) in traditional ester-based electrolyte due to the serious side reactions. Fortunately, ether-based electrolyte can significantly improve the ICE from the formation of stable and thin SEI film.…”

Section: Introductionmentioning

confidence: 99%

A General Synthesis of Mesoporous Hollow Carbon Spheres with Extraordinary Sodium Storage Kinetics by Engineering Solvation Structure

Yang

Zhao

et al. 2021

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Porous and hollow carbon materials have great superiority and prospects in electrochemical energy applications, especially for surface charge storage due to the high active surface. Herein, a general strategy is developed to synthesize mesoporous hollow carbon spheres (MHCS) with controllable texture and compositions by the synergistic effect of dopamine polymerization and metal catalysis (Cu, Bi, Zn). Mesoporous MHCS–Cu and MHCS–Bi are regular spheres, while mesoporous MHCS–Zn possesses an inward concave texture, and simultaneously has a very high surface area of 1675.5 m2 g‐1 and lower oxygen content through the catalytic deoxygenation effect. MHCS–Zn displays an exceptional sodium storage kinetics and excellent long cycling life with 171.9 mAh g‐1 after 2500 cycles at 5 A g‐1 in compatible ether‐based electrolytes. Such electrolyte enables enhanced solvated Na+ transport kinetics with appropriate electrostatic interactions at the surface of carbon anode as revealed by molecular dynamics simulations and molecular surface electrostatic potential calculations. Such an anode also displays basically constant capacity working at 0 °C, and still delivers 140 mAh g‐1 at 3 A g‐1 under ‐20 °C. Moreover, MHCS–Zn anode is coupled with Na3V2(PO4)3 cathode to construct a hybrid capacitor, which exhibits a high energy density of 145 Wh Kg‐1 at a very high power of 8009 W kg‐1.

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“…[ 1,2 ] As for tremendous urban traffic and large‐scale energy storage markets, Na ion batteries seem to be attractive alternatives owing to their reasonable operating voltage, low costs, and abundant reserves. [ 3,4 ] However, these applications have meanwhile put forward much higher security demands, which urgently requires the upgradation of flowable and flammable liquid organic electrolytes with much safer solid‐state electrolytes (SSEs). [ 5–7 ] Especially, the application of inorganic ceramic SSE with high ionic conductivity, a wide electrochemical stability window, and superior chemical stability is believed to match with Na‐metal anodes and high‐voltage cathodes, thus improving the energy density and security of integrated energy storage facilities.…”

Section: Introductionmentioning

confidence: 99%

Liquid Metal‐Organic Frameworks In‐Situ Derived Interlayer for High‐Performance Solid‐State Na‐Metal Batteries

Miao

Wang

Sun

et al. 2021

Advanced Energy Materials

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Despite recent progress in solid‐state Na‐metal batteries (SSNBs) based on inorganic solid‐state electrolytes (SSEs), Na dendrite propagation due to interfacial Na+ transport inhomogeneity and heterogeneous Na stripping/plating processes, greatly hinders the improvement of the cycling stability of SSNBs. Herein, the characteristics and propagation mechanism of Na dendrite growth in SSNBs are comprehensively analyzed. Confronted with Na dendrites, a novel strategy is developed to in‐situ modify a SSE surface with a liquid metal–organic frameworks (MOFs) precursor. The interlayer is directly obtained from high‐temperature monophasic liquid MOFs, not interfering with intermediate recrystallization, thus endowing superior uniformity. It can improve interfacial compatibility with the Na‐anode and homogenize e−/Na+ transport kinetics, leading to spatially even Na nucleation and thus a transition of Na deposition behavior from dendrites to a lateral flat‐shape growth tendency. Furthermore, the obtained sodiophilicity interlayer shows isotropous and stable characteristics to alleviate stress/strain and maintain excellent interfacial stability during cycling. Therefore, the assembled Na symmetric batteries demonstrate a top‐level time‐terminated critical current density of 1.0 mA cm−2, and the integrated full cells show a stable cycling performance for 500 cycles at 1 C. The presented liquid MOFs in‐situ derived strategy to suppress dendrites propagation is expected to be promising for other solid‐state batteries.

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Ultra‐High Initial Coulombic Efficiency Induced by Interface Engineering Enables Rapid, Stable Sodium Storage

Cited by 163 publications

References 50 publications

From 0D to 3D: Dimensional Control of Bismuth for Potassium Storage with Superb Kinetics and Cycling Stability

From 0D to 3D: Dimensional Control of Bismuth for Potassium Storage with Superb Kinetics and Cycling Stability

A General Synthesis of Mesoporous Hollow Carbon Spheres with Extraordinary Sodium Storage Kinetics by Engineering Solvation Structure

Liquid Metal‐Organic Frameworks In‐Situ Derived Interlayer for High‐Performance Solid‐State Na‐Metal Batteries

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