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ADVANCED FUNCTIONAL MATERIALS · 2024 ·Vol. 34 ·期 40 ·2404044 · IF 18.5

Regulation of both Bulk and Surface Structure by W/S Co-Doping for Li-Rich Layered Cathodes with Remarkable Voltage and Capacity Stability

Zhenkun Liu,Xiangli Che,Wei Wang,Gesong Huang,Wenjie Huang,Chenyu Liu,Qi Liu,Ye Zhu,Zhan Lin,Dong Luo

Lithium-rich layered oxides (LLOs) have gained significant attention due to their high capacity of over 250 mAh g −1 , which originates from the charge compensation of oxygen anions activated under high voltage. However, the charge compensation of oxygen anions is prone to over-oxidation, leading to serious irreversible oxygen release, surface-interface reactions, and structural evolution. These detriments make LLOs undergo fast voltage decay and capacity fading, which have hindered their practical applications for many years. Herein, this work develops a multifunctional co-doping strategy and constructs W─O bonds with strong bonding interaction and covalence, low bond energy Li─S bonds with non-binding electrons near the Fermi level, and continuous and homogeneous surface spinel-like layer induced by W/S co-doping. Their synergistic effect significantly mitigates the irreversible oxygen release and surface-interface reactions and improves structural stability of Li-rich layered cathodes. Thus, the designed and prepared Co-free Li-rich layered cathode (Li 1.232 Mn 0.574 Ni 0.191 W 0.003 O 1.995 S 0.005 ) delivers superior voltage and capacity stability. Its capacity retention after 400 cycles is as large as 86%, and its voltage decay rate from the 10th to the 400th cycle is only 0.626 mV cycle −1 .

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Energy Storage Materials · 2024 · IF 18.9

Regulating Li+ transport behavior by cross-scale synergistic rectification strategy for dendrite-free and high area capacity polymeric all-solid-state lithium batteries

Xinyang Li,Jie Feng,Yanan Li,Na Li,Xin Jia,Yinshui Wang,Shujiang Ding

The inability to effectively inhibit the lithium (Li) dendrite growth is identified as the real culprit hindering the practical application of polyethylene oxide (PEO)-based electrolytes. Herein, a novel PEO composite electrolyte with ion rectifier is developed based on the cross-scale synergistic rectification strategy. At the micro-scale, the array structure of the ion rectifier suppresses the growth of PEO crystals and their distribution in the non-ionic conduction direction through space confinement, alleviating ion-migration crosstalk and enabling polymer chain rectification. Furthermore, the matrix contains abundant copper ions and oxygen-containing groups that inhibit anion conduction and accelerate Li + migration at the nanoscale, respectively, to achieve ion flow rectification. Implementing this strategy results in a uniform, fast, and stable Li + migration/diffusion behavior from the electrolyte to anode interface. The critical current density of the PEO electrolyte is increased to 2.5 mA cm −2 , indicating a significant improvement in dendrite growth inhibition. Impressively, the composite electrolytes exhibit long-term stability (>4000 h at 0.2 mA cm −2 ) and ultra-high current-density tolerance (>200 h at 1 mA cm −2 ). Moreover, the composite electrolytes enable stable cycling of high-area-capacity (3.11 mAh cm −2 , 20 mg cm −2 ) LiFePO 4 /Li pouch cells, highlighting the importance of this strategy for the practical application of PEO electrolytes.

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ACS Applied Materials & Interfaces · 2023 · IF 9.5

LiNO3-Assisted Succinonitrile-Based Solid-State Electrolyte for Long Cycle Life toward a Li-Metal Anode via an In Situ Thermal Polymerization Method

Maoxia Yang,Shaomin Li,Gen Zhang,Mengjie Huang,Jidong Duan,Yanhua Cui,Bo Yue,Hao Liu

Succinonitrile (SN)-based electrolytes have a great potential for the practical application of all-solid-state lithium-metal batteries (ASSLMBs) due to their high room-temperature ionic conductivity, broad electrochemical window, and favorable thermal stability. Nevertheless, the poor mechanical strength and low stability toward Li metal hinder the further application of SN-based electrolytes to ASSLMBs. In this work, the LiNO3-assisted SN-based electrolytes are synthesized via an in situ thermal polymerization method. With this method, the mechanical problem is negligible, and the stability of the electrolyte enhances tremendously toward Li metal due to the addition of LiNO3. The LiNO3-assisted electrolytes exhibit a high ionic conductivity of 1.4 mS cm–1 at 25 °C, a wide electrochemical window (0–4.5 V vs Li+/Li), and excellent interfacial compatibility with Li (stable for over 2000 h at a current density of 0.1 mA cm–1). The LiFePO4/Li cells with the LiNO3-assisted electrolytes present significantly enhanced rate capability and cycling performance compared to the control group. NCM622/Li batteries also exhibit good cycling and rate performances with a voltage range of 3.0 to 4.4 V. Furthermore, ex situ SEM and XPS are employed. A compact interface is observed on Li anode after cycling, and the polymerization of SN is found to be suppressed. This paper will promote the development of practical application of SN-based ASSLMBs.

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JOURNAL OF MATERIALS SCIENCE & TECHNOLOGY · 2022 · IF 10.319

Synergistic engineering of cobalt selenide and biomass-derived S, N, P co-doped hierarchical porous carbon for modulation of stable Li-S batteries

Yang Lin,Song He,Zhiyong Ouyang,Jianchao Li,Jie Zhao,Yanhe Xiao,Shuijin Lei,Baochang Cheng

Hierarchical porous carbon co-doped with heterogeneous atoms has attracted much attention thanks to sizable internal void space accommodating electrolyte, high-density microporous structure physically confining polysulfides (LPS), and heterogeneous atoms serving as active sites to capture LPS. However, solely relying on carbon material defects to capture LPS proves ineffective. Hence, metal compounds must be introduced to chemisorb LPS. Herein, cobalt ions are in-situ grown on the polydopamine layer coated on the surface of biomass-derived S, N, P co-doped hierarchical porous carbon (SNP-PC). Then a layer of nitrogen-doped porous carbon (MPC) dotted with CoSe nanoparticles is acquired by selenizing. Thus, a strong-polar/weak-polar composite material of SNP-PC studded with CoSe nanoparticles is obtained (SNP-PC@MPC@CoSe). Button cells assembled with SNP-PC@MPC@CoSe-modified separator enable superb long-cycle stability and satisfactory rate performance. An excellent rate capacity of 796 mAh g −1 at a high current rate of 4 C with an ultra-low capacity fading of 0.06% over 700 cycles can be acquired. More impressively, even in a harsh test condition of 5.65 mg cm −2 sulfur loading and 4 μL mg −1 ratio of electrolyte to active materials, the battery can still display a specific capacity of 980 mAh g −1 (area capacity of ∼5.54 mAh cm −2 ) at 0.1 C. This work provides a promising route toward high-performance Li-S batteries.

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INORGANIC CHEMISTRY · 2022 · IF 5.436

Manipulating the Spin State of Fe Sites via Fe–O–Si Bridge Bonds for Enhanced Polysulfide Redox Kinetics in the Li–S Battery

Qiang Zhang,Ranxiao Ao,Ruijie Gao,Huaming Yang

Transition metals with 3d unoccupied orbitals have superior catalytic activity, but inherent high spin suppresses their adsorption capability, leading to sluggish polysulfide conversion kinetics for Li–S batteries. Herein, we provide Fe–O–Si bridge bonds to manipulate eg filling and induce a high-to-medium spin transition of Fe3+ sites, which enhances polysulfide adsorption and facilitates sulfur redox reaction kinetics. The resultant cathodes exhibit outstanding performances under high sulfur loading, which can deliver a high battery specific energy of 1061 mA h·g–1 even after 100 cycles in Li–S pouch batteries. This work provides new insights into the kinetic and multi-step conversion mechanism of the sulfur redox reaction process, helping in the understanding and design of spin-dependent catalysts.

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JOURNAL OF MATERIALS SCIENCE-MATERIALS IN ELECTRONICS · 2016 ·Vol. 28 ·期 1 ·487-492 · IF 1.798

Effects of Mn doping on dielectric and ferroelectric characteristics of lead-free (K, Na, Li)NbO3 thin films grown by chemical solution deposition

Zhang Xinxiu,Liu Jinsong,Zhu Kongjun,Wang Jing,Li Ziquan,Qiu Jinhao

High-quality lead-free piezoelectric x Mn-doped (K 0.48 Na 0.52 ) 0.985 Li 0.015 NbO 3 films (KNLN; x  = 0, 0.01, 0.02, 0.03) were successfully deposited onto Pt(111)/Ti/SiO 2 /Si(100) substrates by sol–gel method. Effects of Mn substitution on the microstructure, dielectric properties, ferroelectric properties, and leakage current of the KNLN films were investigated in detail. Mn-doping can significantly improve the ferroelectric properties and decrease the leakage current of KNLN films. Optimal dielectric properties were obtained in films doped with 2 mol% Mn, whose dielectric constant and dielectric loss at 1 kHz were 875 and 0.030, respectively. In addition, well-saturated ferroelectric P - E hysteresis loop with large remanent polarization (2 P r ) and coercive field ( E c ) of 22.5 μC/cm 2 and 65 kV/cm were obtained in 2 mol% Mn-doped KNLN film at an applied electric field of 200 kV/cm.

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Materials Today Bio · 2024 · IF 8.7

Immune regulation enhances osteogenesis and angiogenesis using an injectable thiolated hyaluronic acid hydrogel with lithium-doped nano-hydroxyapatite (Li-nHA) delivery for osteonecrosis

Yue Luo,Zhouyuan Yang,Xin Zhao,Donghai Li,Qianhao Li,Yang Wei,Luyao Wan,Meng Tian,Pengde Kang

Osteonecrosis is a devastating orthopedic disease in clinic that generally occurs in the femoral head associating with corticosteroid use up to 49 % in patients. In particular, glucocorticoids induced osteonecrosis of the femoral head is closely related to the local immune response that characterized by abnormal macrophage activation and inflammatory cell infiltration at the necrotic site, forming a pro-inflammatory microenvironment dominated by M1 macrophages, and thus leads to failure of bone repair and regeneration. Here, we report a bone regeneration strategy that constructs an immune regulatory biomaterial platform using an injectable thiolated hyaluronic acid hydrogel with lithium-doped nano-hydroxyapatite (Li-nHA@Gel) delivery for osteonecrosis treatment. Li-nHA@Gel achieved a sustain and longterm release of Li ions, which might enhance M2 macrophage polarization through the activation of the JAK1/STAT6/STAT3 signaling pathway, and the following induced pro-repair immune microenvironment mediated the enhancement of the osteogenic and angiogenic differentiation. Moreover, both in vitro and in vivo studies indicated that Li-nHA@Gel enhanced M2 macrophage polarization, osteogenesis, and angiogenesis, and thus promoted the bone and blood vessel formation. Taken together, this novel bone immunomodulatory biomaterial platform that promotes bone regeneration by enhancing M2 macrophage polarization, osteogenesis, and angiogenesis could be a promising strategy for osteonecrosis treatment.

✓ 已验证 DOI PubMed 高影响因子
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JOURNAL OF RARE EARTHS · 2023 · IF 4.9

Simultaneous enhancement of red luminescence and thermal stability of a novel red phosphor: A Li+-Eu3+ co-occupied site strategy in BaAl2Ge2O8 lattices

Wei Zhang,Changjian Wang,Xusheng Qiao,Xianping Fan

The rapid development of phosphor-converted white light emitting diodes (pc-WLEDs) requires new red phosphors with efficient and thermally stable luminescence for high-quality warm-white lighting. However, it is still a challenge to discover red phosphors with facile synthesis, high internal quantum efficiency (IQE), excellent thermal stability and high color purity. Herein, a novel red-emitting Eu 3+ activated barium dialuminum digermanate (BaAl 2 Ge 2 O 8 , BAGO) phosphor showing strong red emission at 610 nm was prepared. The IQE is improved from 32.91% to 78.84% by employing a charge compensation strategy. The lithium-ion co-doped BAGO:Eu 3+ phosphor exhibits a nearly twofold increase in integral photoluminescence (PL) intensity and the high color purity reaches 94.17%. Impressively, the PL intensity of the BAGO:Eu 3+ ,Li + phosphor drops by only 2.6% at 150 °C of that at room temperature. Finally, the pc-WLED using the red BAGO:Eu 3+ ,Li + phosphor exhibits white light with the chromaticity coordinate of (0.3515, 0.3495), a high color-rendering index of 92 and a low correlated color temperature of 4746 K. All these results manifest that BAGO:Eu 3+ ,Li + phosphor is a suitable red phosphor for near-ultraviolet (NUV) chip-based pc-WLEDs.

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CHEMICAL ENGINEERING JOURNAL · 2023 · IF 15.1

Polycaprolactone-poly(vinylidene fluoride) blended composite polymer electrolyte with enhanced high power performance and interfacial stability for all-solid-state Li metal batteries

Dexuan Pei,Yuhang Li,Shuo Huang,Min Liu,Jianhe Hong,Shuen Hou,Hongyun Jin,Guozhong Cao

Polycaprolactone (PCL) based composite polymer electrolytes (CPEs) is a promising candidate applied in all-solid-state Li metal batteries (LMBs). However, vexing issues such as poor power performances and unstable interface layers are frequently observed. To address these issues, poly(vinylidene fluoride) (PVDF) with high dissociation of Li salts and good compatibility against Li metal are introduced into PCL to prepare blended CPEs. The PCL-PVDF blended CPEs obtain a high ionic conductivity of 1.38 × 10 -4 S·cm −1 and a high lithium ion transference number of 0.89 at 60 °C, owing to the high dissociation coming from the PVDF. Particularly, the Li//P5-CPEs-40 %//Li symmetrical battery can work steadily over 800 h at a high current density of 0.25 mA·cm −2 . Furthermore, the LiFePO 4 //P5-CPEs-40 %//Li batteries exhibit high capacity retention of 84.9 % for 500cycles at 3.0 C. The excellent cycling stability for the LMBs is considered to be originated from the LiF containg SEI layer that formed during cycling. This study provides new perspectives to develop new CPEs with high power performances and stable interface for LMBs.

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CHEMICAL ENGINEERING JOURNAL · 2022 · IF 16.744

In-situ constructing slow-release Li-Al-O interface layer for lithium metal batteries to enhance interface stability and suppress lithium dendrite growth

Dexuan Pei,Ziying Liu,Rui Ma,Shuo Huang,Shuen Hou,Min Liu,Guozhong Cao,Hongyun Jin

Composite polymer electrolytes (CPEs) have shown extraordinary promise for use in all-solid-state lithium metal batteries (LMBs) because of their tunable merits in ionic conductivity and mechanical flexibility. Their practical application is however hindered by the poor interface stability and the uncontrollable Li dendrite formation. Addressing these two issues, we report an in-situ formed Li-Al-O interface layer between CPEs and Li metal anode by introducing Al 2 O 3 nanoparticles in CPEs. X-ray photoelectron spectroscopy results indicated that the CPE-Al 2 O 3 could slowly release Al atoms which react with Li metal to form the current Li-Al-O interface layer. We highlight that the Li-Al-O interface layer can stabilize lithium deposition/stripping over 1400 h in lithium symmetric batteries, and afford an impressive cycle life of 300 cycles in LiFePO 4 -Li batteries with almost no capacity loss. The present findings demonstrate that in-situ constructing a slow-release Li-Al-O interface layer is an easy and effective approach to stabilize the solid electrolyte interface and suppress the Li dendrites growth. Furthermore, the obtained batteries show excellent cycling stability, indicating the strategy with in-situ formed CPEs shed light on improving the processability of fabrication of high-performance electrolytes.

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JOURNAL OF POWER SOURCES · 2019 · IF 7.467

Li super ionic conducting glasses and glass ceramics in the Li1+xGaxGe2-xP3O12 system: Solid state nuclear magnetic resonance and electrical conductivity study

Zonghui Zhang,Lili Hu,Haizheng Tao,Jinjun Ren

Glassy precursors in the Li 1+ x Ga x Ge 2- x P 3 O 12 system are prepared by melting and casting. The glasses are annealed at the crystallization peak temperatures to obtain glass ceramics with Na-superionic conducting structure. The ionic conductivity can be significantly increased by substituting Ge with Ga and Li. The highest ionic conductivity of the glass ceramics is 9.74 × 10 −5  S cm −1 at 20 °C. Multiple magic angle spinning nuclear magnetic resonance (MAS NMR) techniques are used to characterize the structural transitions from glasses to their glass ceramic counterparts. 71 Ga and 31 P MAS NMR spectra have shown that the local structures of the glasses are distinctly modified after crystallization. The second coordinated shells of Ga 3+ ions are consisted of phosphorus in both glasses and glass ceramics although their coordination numbers change. The glassy precursors show homonuclear segregations such as P-O-P and Ge-O-Ge linkages. However, the glass ceramics are homogeneous, in which per phosphorus tetrahedron connects with total four Ga and Ge, forming four different phosphorus species (Q 0 (4-n)Ge, nGa (n = 0, 1, 2, and 3)). A random distribution model can be used to quantitatively predict the population of every Q 0 (4-n)Ge, nGa species, if the compositions are known. A correlation between local structure and ionic conductivity is proposed.

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Materials Today Chemistry · 2023 · IF 7.3

In situ formation of TiB2 and TiH2 catalyzed Li/Mg based dual-cation borohydride with a low onset dehydrogenation temperature below 100 °C

C. Jiang,X. Wang,X. Xiao,M. Piao,Y. Jia,J. He,L. Hu,Y. Zou,L. Sun,L. Chen

Chemical complex borohydride is a promising hydrogen storage material due to its large gravimetric and volumetric hydrogen capacities. However, the high dehydrogenation temperature and sluggish kinetics still place strong restrictions on its practical application in the hydrogen storage field. In this work, a synergetic approach of partial cation substitution and catalysis is developed to enhance the hydrogen storage properties of LiBH 4 . The Li/Mg based dual-cation borohydride (LiMg 2 (BH 4 ) 5 , LMBH) was successfully synthesized by wet chemical ball milling of LiBH 4 and MgCl 2 . The optimal (LMBH (4.5:1) sample, LiBH 4 and MgCl 2 in molar ratios of 4.5:1, possesses a maximum hydrogen desorption capacity (11.27 wt%) and the outstanding initial decomposition temperature (∼250 °C). Importantly, the LMBH (4.5:1) doped with TiF 3 shows a remarkable onset dehydrogenation temperature as low as 97.2 °C, which is about 190 °C lower than that of pristine LiBH 4 . The LMBH (4.5:1) doped with TiF 3 system releases 7.98 wt% H 2 within 170 min below 350 °C. And the dehydrogenation product of doped composite can reversibly absorb ∼4.72 wt% H 2 at a relatively moderate temperature of 280 °C, which is substantially lower than the reversible hydrogen absorption temperature of previous modified borohydride systems. Based on the structural characteristic analyses, the TiF 3 reacts with LMBH (4.5:1) to in-situ form actual catalytic components of TiB 2 and TiH 2 as the actual catalysts for LMBH (4.5:1), resulting in the improved hydrogen re/dehydrogenation properties. The synergetic modification of Li/Mg dual-cation substitution and TiB 2 /TiH 2 catalysis may lead to the development of light-metal borohydrides with outstanding hydrogen storage properties.

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