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Energy Storage Materials · 2022 · IF 20.831

LiF involved interphase layer enabling thousand cycles of LAGP-based solid-state Li metal batteries with 80% capacity retention

Pengfeng Jiang,Jiaqi Cao,Bin Wei,Guoyu Qian,Shaofei Wang,Yuansheng Shi,Guangyuan Du,Xueyi Lu,Chuying Ouyang,Fahe Cao,Xia Lu

The interface compatibility lies in the heart of present investigations on solid-state batteries, now facing significant challenges in practical use. The non-coherent interface structure with the underlying complex electrochemical processes evolves dynamically to pregnant the unfriend seeds to degrade the battery performance. Therefore, interface engineering (or control) in solid-state batteries gives birth to a new theme as ‘the interface is equal to the battery’. In this context, a facile but robust technique is proposed here by smoothing the Li 1.5 Al 0.5 Ge 1.5 P 3 O 12 (LAGP) ceramic pellet with a mirror-like surface, which is found operational in running a solid battery in unprecedentedly a thousand cycles with capacity retention of 80% at 0.5C, 50 °C. Such an unconventional operation is, as a matter of fact, largely decreasing the physically interface contact but proved powerful in guiding the Li-ion homogeneous deposition. Moreover, the self-generated LiF involved interphase layer works efficiently to dynamically balance structural and electrochemical stabilities, where the LiF is introduced by the in-situ polymerization of tiny liquid electrolytes. Hence, the profound results draw the incompatible interface issues forth to the component adjustment of interphases, namely in search for rational descriptions to connect the solid-state electrolyte and electrodes, which probably holds the key to unlocking the high energy density solid-state batteries.

✓ 已验证 DOI 高影响因子
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Energy Storage Materials · 2024 · IF 18.9

Ethyl fluoroacetate with weak Li+ interaction and high oxidation resistant induced low-temperature and high-voltage graphite//LiCoO2 batteries

Laibing Luo,Kean Chen,Ruoyu Cao,Hui Chen,Miaomiao Xia,Along Zhao,Xiaoyang Chen,Weihua Chen,Zhongxue Chen,Yongjin Fang,Yuliang Cao

Lithium-ion batteries (LIBs) operating at low temperature has always been a significant challenge. In this work, Ethyl fluoroacetate (EFA) was utilized as a single solvent to design a low-temperature electrolyte (LTE). The weak Li + -solvent interaction facilitates fast de-solvation process and improved low-temperature performance, while the high oxidation resistance and fluorine-rich electrolyte/electrolyte interface induced by the fluorinated groups enables wide operating voltage and stable cycling of the LIBs . The EFA-based electrolyte endows the high-voltage (4.45 V) Graphite//LiCoO 2 pouch cell with prominent low-temperature adaptability (89.7 % capacity retention retains at −40 °C, and capable of charging at −20 °C) and outstanding cycling performance (87.7 % capacity retention after 400 cycles). This work sheds light on the design of high-voltage and low-temperature electrolytes for lithium-ion batteries.

✓ 已验证 DOI 高影响因子
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Batteries-Basel · 2025 ·Vol. 11 ·期 9 ·334 · IF 4.8

In Situ Engineered Plastic–Crystal Interlayers Enable Li-Rich Cathodes in PVDF-HFP-Based All-Solid-State Polymer Batteries

Fei Zhou,Jinwei Tan,Feixiang Wang,Meiling Sun

All-solid-state lithium batteries (ASSLBs) employing Li-rich layered oxide (LLO) cathodes are regarded as promising next-generation energy storage systems owing to their outstanding energy density and intrinsic safety. Polymer-in-salt solid electrolytes (PISSEs) offer advantages such as high room-temperature ionic conductivity, enhanced Li anode interfacial compatibility, and low processing costs; however, their practical deployment is hindered by poor oxidative stability especially under high-voltage conditions. In this study, we report the rational design of a bilayer electrolyte architecture featuring an in situ solidified LiClO4-doped succinonitrile (LiClO4–SN) plastic–crystal interlayer between a Li1.2Mn0.6Ni0.2O2(LMNO) cathode and a poly (vinylidene fluoride-co-hexafluoropropylene) (PVDF-HFP)-based PISSE. This PISSE/SN–LiClO4configuration exhibits a wide electrochemical stability window up to 4.7 V vs. Li+/Li and delivers a high ionic conductivity of 5.68 × 10−4S cm−1at 25 °C. The solidified LiClO4-SN layer serves as an effective physical barrier, shielding the PVDF-HFP matrix from direct interfacial contact with LMNO and thereby suppressing its oxidative decomposition at elevated potentials. As a result, the bilayer polymer-based cells with the LMNO cathode demonstrate an initial discharge capacity of ∼206 mAh g−1at 0.05 C and exhibit good cycling stability with 85.7% capacity retention after 100 cycles at 0.5 C under a high cut-off voltage of 4.6 V. This work not only provides a promising strategy to enhance the compatibility of PVDF-HFP-based electrolytes with high-voltage cathodes through the facile in situ solidification of plastic interlayers but also promotes the application of LMNO cathode material in high-energy ASSLBs.

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ADVANCED MATERIALS · 2022 ·Vol. 34 ·期 47 ·2206039 · IF 32.086

Ion-Migration Mechanism: An Overall Understanding of Anionic Redox Activity in Metal Oxide Cathodes of Li/Na-Ion Batteries

Yangyang Lai,Huixian Xie,Peng Li,Biao Li,Along Zhao,Laibing Luo,Zewen Jiang,Yongjin Fang,Shengli Chen,Xinping Ai,Dingguo Xia,Yuliang Cao

The anionic redox reaction (ARR) has attracted extensive attention due to its potential to enhance the reversible capacity of cathode materials in Li/Na-ion batteries (LIBs/SIBs). However, the understanding of its activation mechanism is still limited by the insufficient mastering of the underlying thermodynamics and kinetics. Herein, a series of Mg/Li/Zn-substituted Na x MnO 2 and Li x MnO 2 cathode materials are designed to investigate their ARR behaviors. It is found that the ARR can be activated in only Li-substituted Li x MnO 2 and not for Mg- and Zn-substituted ones, while all Mg/Li/Zn-substituted Na x MnO 2 cathode materials exhibit ARR activities. Combining theoretical calculations with experimental results, such a huge difference between Li and Na cathodes is closely related to the migration of substitution ions from the transition metal layer to the alkali metal layer in a kinetic aspect, which generates unique Li(Na)–O–□ TM and/or □ Li/ Na –O–□ TM configurations and reducing reaction activation energy to trigger the ARR. Based on these findings, an ion-migration mechanism is proposed to explain the different ARR behaviors between the Na x MnO 2 and Li x MnO 2 , which can not only reveal the origin of ARR in the kinetic aspect, but also provide a new insight for the development of high-capacity metal oxide cathode materials for LIBs/SIBs.

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Nano Research · 2018 ·Vol. 12 ·期 3 ·517-523 · IF 7.994

Well-defined carbon nanoframes containing bimetal-N-C active sites as efficient bi-functional electrocatalysts for Li-O2 batteries

Liu Tie,Wang Leidanyang,Huang Tao,Yu Aishui

Design and fabrication of framework-structured porous precursors have been regarded as a prospective albeit challenging strategy to obtain bimetal/NC-enriched bifunctional elecrocatalysts. In this work, an effective bottom-up approach involving solution-based self-assembly and a post-annealing process was developed to confine (Co, Zn)-N-C active sites into N-enriched graphitic carbon nanocages. This novel architecture containing N-doped-C stabilized bimetallic nanoparticles derived from ZIF precursors was well-studied by a series of characterization and analysis techniques. Details were given that these well-dispersed (Co, Zn) nanoparticles were encapsulated into the pyridinic-N-dominated graphitic carbon nanocage with a total metal loading of approximately 7.4 at.%. This favorable hierarchical structure not only enhances the electron conductivity, but also owns a sufficient BET surface area facilitating the gas-liquid-solid triphase reaction and producing more space to store discharge products. Importantly, results infer that the interesting nanoframes manifests a satisfying ORR/OER activity and enhanced cell performance whether liquid or solid-state electrolytes are used. As such, our work rationalizes that this type of cage-shaped bimetal-N-C material is promising for high-performance Li-O 2 batteries.

✓ 已验证 DOI 高影响因子
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Small · 2021 ·Vol. 17 ·期 41 ·2102454 · IF 13.281

Interphase Building of Organic–Inorganic Hybrid Polymer Solid Electrolyte with Uniform Intermolecular Li+ Path for Stable Lithium Metal Batteries

Peng Liu,Jianwei Zhang,Lei Zhong,Sheng Huang,Li Gong,Dongmei Han,Shuanjin Wang,Min Xiao,Yuezhong Meng

Lithium (Li) metal has been generally noticed as the most prospective anode for next-generation batteries attributed to its outstanding theoretical capacity and low electrochemical potential. Nevertheless, the unstable solid-electrolyte interphase (SEI) and uncontrollable dendrite growth cause poor reversibility and fetter the practical application of Li metal anodes. Herein, a new organic–inorganic hybrid polymer artificial SEI (POSS-LiBMAB) layer with uniform lithium-ion paths at a molecular level is designed to stabilize Li metal anodes. The SEI layer is constructed by the thiol–ene “click chemistry” reaction between inorganic polyhedral oligomeric silsesquioxane containing eight-mercaptopropyl (POSS-SH) with lithium bis (allylmalonato) borate (LiBMAB) on Li foil. What is more, the POSS-LiBMAB film can be cross-linked and self-reinforced via intermolecular S  C bonds. Benefiting from its flexible polymeric covalent structure and noble inorganic Si 8 O 16 -type cubes, the organic–inorganic hybrid polymer layer is flexible and effectively tolerates the volume change of Li metal anodes during plating/stripping cycles. In addition, this layer shows loose and uniformly distributed electrostatic interaction between Li + and charge delocalized sp 3 boron–oxygen anions, which aids to form a uniform intermolecular Li + path regulating the homogeneous distribution of Li + flux on Li anodes. Finally, the designed POSS–LiBMAB layer has high ionic conductivity and lithium-ion transference number, which can effectively promote Li + diffusion and guide Li deposition beneath the SEI layer. Therefore, with the protection of the POSS-LiBMAB layer, the Li metal anode exhibits stable cycling at 5 mA cm −2 for more than 1000 h, and the LFP//Li full cells also present outstanding cycling stability.

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INDUSTRIAL & ENGINEERING CHEMISTRY RESEARCH · 2022 · IF 4.326

Surface Spinel-Coated and Polyanion-Doped Co-Free Li-Rich Layered Oxide Cathode for High-Performance Lithium-Ion Batteries

Zhanying Chang,Yiming Zhang,Wei He,Jin Wang,Hongfei Zheng,Baihua Qu,Xinghui Wang,Qingshui Xie,Dong-Liang Peng

Li-rich layered oxides (LLOs) are supposed to be the most competitive cathode materials for lithium-ion batteries (LIBs), because of the high theoretical specific capacities (>250 mAh g–1). However, there are some inherent inferiorities, such as the low initial Coulombic efficiency (ICE) and the rapid capacity/voltage decay, that hinder the large-scale commercial applications of LLOs. Herein, we successfully obtained spinel-coated and phosphate-doped Co-free Li-rich layered oxides (Co-free LLOs) by cotreatment methods, using weakly acidic and alkalinity (NH4H2PO4 solution), which could effectively improve the electrochemical performance. The spinel coating could not only accelerate the movement of Li+ but also restrain O2 release, while the doping PO43– could inhibit the transition-metal (TM) migration between the oxygen octahedral site and the oxygen tetrahedral site. The optimized Co-free LLOs cathode treated with 3% NH4H2PO4 solution could deliver a high ICE of 88% and a high discharge capacity up to 159.5 mAh g–1 after 500 cycles at 1C (1C = 250 mA g–1). Moreover, the voltage fading decreases from 0.64 mV to 0.32 mV per cycle during cycling. This work provides new insights for developing high-performance Co-free LLOs cathode materials.

✓ 已验证 DOI 高影响因子
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JOURNAL OF POWER SOURCES · 2019 · IF 7.467

Metal Organic Framework (MOF)-Derived carbon-encapsulated cuprous sulfide cathode based on displacement reaction for Hybrid Mg2+/Li+ batteries

Weiqin Wang,Yuanying Yang,Yanna NuLi,Jingjing Zhou,Jun Yang,Jiulin Wang

We fabricate in-situ carbon-encapsulated cuprous sulfide (Cu 2 S@C) composite through a metal-organic framework (MOF)-derived sulfurization method and compare its electrochemical performance as a displacement reaction cathode of hybrid Mg 2+ /Li + batteries with 0.4 mol L −1 (PhMgCl) 2 -AlCl 3 +1.0 mol L −1 LiCl/THF nucleophilic hybrid electrolyte and 0.2 mol L −1  Mg(HMDS) 2 -(AlCl 3 ) 2 –MgCl 2 +1.0 mol L −1 LiTFSI/DME non-nucleophilic hybrid electrolyte. Benefiting from the intrinsic property of Cu 2 S, well-defined hybrid porous structure and carbon encapsulation derived from MOFs, the Cu 2 S@C composite exhibits 399.2 mA h g −1 discharge capacity and the capacity maintains at approximately 150 mA h g −1 at 0.05 C after 50 cycles in the nucleophilic hybrid electrolyte. The mechanism investigation verifies that the formed Cu 1.96 S in the first discharge process succeeds to transform into MgS and Li 2 S, which results in the reversible displacement reaction dominantly occurring between Cu 1.96 S and Cu during subsequent cycles. When using the non-nucleophilic hybrid electrolyte, an enhanced cycling stability can be achieved due to the mitigation of ionic sulfide dissolution. The present work demonstrates the feasibility of building the structural design of low-cost displacement reaction cathode with more compatible electrolyte, and provides the potential of establishing practical hybrid Mg 2+ /Li + batteries for energy storage.

✓ 已验证 DOI 高影响因子
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JOURNAL OF MATERIALS SCIENCE-MATERIALS IN ELECTRONICS · 2016 ·Vol. 28 ·期 1 ·250-258 · IF 1.798

Electrochemical properties of core–shell nano-Si@carbon composites as superior anode materials for high-performance Li-ion batteries

Chen Hedong,Hou Xianhua,Qu Lina,Qin Haiqing,Ru Qiang,Huang Yuan,Hu Shejun,Lam Kwok-ho

Si@carbon composites have been successfully prepared via spray drying and subsequent calcination using PSA microspheres, nano-silicon and natural graphite as raw materials. Nano-silicon with a 20–100 nm particle size is prepared by radio-frequency electromagnetic induction. Such small nano-silicon particles can effectively accommodate the volume expansion of the Si@carbon anode. Additionally, the unique core–shell structure of Si@carbon composites can effectively alleviate the agglomeration of nano-silicon particles. Electrochemical tests show that the Si/carbon electrode delivers a high initial discharge capacity of approximately 1404.27 mAh g −1 with an initial coulombic efficiency of 82.4 %. The discharge specific capacity remains as high as 73.6 % after 100 charging-discharging cycles, demonstrating the electrode material’s good cycle stability. In addition, the corresponding specific capacity of the Si@carbon composites electrode remains at around 1150 mAh g −1 at a current density of 1 A g −1 . And when the current density is 0.1 A g −1 , its specific capacity can still remain at around 920 mAh g −1 , indicating excellent capacity reversibility. Therefore, Si@carbon composites are superior anode materials for high-performance Li-ion batteries.

✓ 已验证 DOI 高影响因子
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Micro & Nano Letters · 2018 ·Vol. 13 ·期 10 ·1386-1389 · IF 0.841

Hierarchical porous N,O Co-doped carbon/Se composite derived from hydrothermal treated chitosan as Li–Se battery cathode

Chenhao Zhao,Jiangshui Luo,Zhibiao Hu

Seeking for the porous carbon with suitable structure and morphology has been a key to improve the lithium storage performance of carbon/selenium composite. In this work, the hierarchical porous N,O Co-doped carbon has been prepared by an initial hydrothermal carbonisation and subsequent activation route using the chitosan as raw material. The carbon obtained at 600°C possessing primary micropores and surface macropores presents high specific surface area (809. 3 m 2 g −1 ) and low porous size, and the selenium with amorphous structure is uniformly encapsulated into the micropores of this carbon to form carbon/selenium composite. As the cathode materials of lithium ion battery, this composite delivers a discharge capacity of 446.9 mAh g −1 at rate of 0.24 C after 100 cycles. At a high rate of 4.8 C, this composite still shows a stable discharge capacity of 342.8 mAh g −1 . These results suggest that this composite may be promising for practical applications for lithium-selenium battery.

✓ 已验证 DOI 高影响因子
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NEW JOURNAL OF CHEMISTRY · 2018 ·Vol. 42 ·期 5 ·3350-3355 · IF 3.201

Four new quaternary chalcogenides A2Ba7Sn4Q16 (A = Li, Na; Q = S, Se): syntheses, crystal structures determination, nonlinear optical performances investigation

Ailijiang Abudurusuli,Kui Wu,Shilie Pan

Four new quaternary chalcogenides A2Ba7Sn4Q16 (A = Li, Na; Q = S, Se) were successfully synthesized in vacuum-sealed silica tubes for the first time. All of them crystallize in the noncentrosymmetric (NCS) cubic I3d space group with the cell parameters ranging from 14.807 to 15.4163 Å and Z = 4, respectively. Interestingly, their isostructures are different from the structural transformations (from tetragonal to trigonal) appearing in previously reported Na2BaSnQ4 compounds. As observed in their structures, (Na/Ba)Q4 and SnQ4 units alternately connect with each other by sharing corners to build a three-dimensional (3D) framework structure with charge-balanced Ba cations located within tunnels, which is different from the observation that the Na atoms located inside the tunnels formed by the interconnection of the BaS8 and SnS4 units in Na2BaSnS4. Optical properties (diffuse-reflection, IR, and Raman spectra) were also systematically studied and the results indicate that their optical bandgaps are in the range from 1.75 to 2.5 eV. Moreover, the second harmonic generation (SHG) responses of the title compounds were also measured to be about 0.1–0.5 times higher than that of benchmark AgGaS2 under 2.09 μm radiation.

✓ 已验证 DOI 高影响因子
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ELECTROCHIMICA ACTA · 2019 · IF 5.383

Sulfonated polyaniline coated bamboo-derived biochar/sulfur cathode for Li-S batteries with excellent dual conductivity and polysulfides affinity

Yiqi Wei,Yinglin Yan,Yiming Zou,Mangmang Shi,Qijiu Deng,Nana Zhao,Juan Wang,Caiyin You,Rong Yang,Yunhua Xu

The sulfonic acid group exhibits considerable ion affinity. The present work therefore synthesizes, a core-shell composite material having a sulfonated polyaniline shell, and a bamboo-derived porous carbon core loaded with sulfur. The thin, homogeneous shell has a thickness of approximately 20 nm. This composite is employed as a cathode material in Li-S batteries and the electrochemical properties of these devices are systematically investigated. This cathode (containing 64.0 wt% S) exhibits a higher initial discharge capacity (1484 mAh g −1 at 0.1 C), improved cycling stability (853 mAh g −1 after 100 cycles at 0.1 C), and remarkable rate performance (810.2, 682.7 and 353.0 mAh g −1 at 2, 3 and 5 C, respectively). These values are superior to those obtained using a polyaniline shell. Electrochemical impedance spectroscopy and density functional theory calculations are used to elucidate the internal mechanisms of the sulfonated polyaniline shell during cycling. The calculated results demonstrate that the shell possesses extremely high electron and Li ion conductivities, and so enhances the redox reaction kinetics during long-term cycling. It also physically confines and chemically anchors polysulfides , thus limiting the shuttle effect. This cathode design is expected to assist in the future commercialization of Li-S batteries.

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