Polymer Chemistry
·
2022
·Vol. 13
·期 8
·1098-1106
·
IF 5.364
Junjin Duan,Yi Gong,Dong Chen,Yuhong Ma,Changtong Song,Wantai Yang
In this study, we develop a direct, thermally initiated radical homopolymerization of vinyl ethers mediated by lithium salts CH3OLi and LiI. In the case of vinyl ether monomers having a hydroxyl group, for example, diethyleneglycol monovinyl ether (DEGV), a high molecular weight poly(DEGV) (Mn = 18 700) is produced in a high yield (≥68%) with negligible acetal formation. Most importantly, this method further enables the radical polymerization of alkyl vinyl ether (IBVE) which has no hydroxyl group to form hydrogen bonds to facilitate the radical polymerization. There are no evident structural defects caused by side reactions such as β-scission and hydrogen abstraction as the poly(IBVE) yield is up to about 50% and Mn = 8500. Under similar conditions, the poly(IBVE) yield of the control run is only 16.2%. Density functional theory calculations suggest that the interaction between Li+ and CC–O of IBVE significantly reduces the HOMO–LUMO energy gap from 6.83 eV to 4.61 eV. In addition, the changes in 1H-NMR chemical shifts of CH2CH–O– further support the existence of interaction between Li+ and CC–O. This cation-π complexation between Li+ and vinyl ether can effectively reduce the electron density of the vinyl group and as a result increases the stability of σ-radicals and suppresses unfavorable side reactions.
研究领域:
高分子化学
·
材料科学
·
物理化学
✓ 已验证
产品关联
DOI
高影响因子
Journal of Energy Chemistry
·
2022
·
IF 13.599
Shan Yi,Zhe Su,Wanyu Zhang,Hongli Chen,Yayun Zhang,Bo Niu,Donghui Long
Lithium metal batteries are among the strong contenders to satisfy the ever-increasing needs of energy storage systems, which however suffer from poor composition of the solid electrolyte interphase (SEI) layer and uncontrolled Li dendrites formation. In this regard, we report on the design of an ion-released MgI 2 -doped polyacrylonitrile (PAN) based nanofiber (MPANF) separator, which can lead to conducive SEI layer and dendrite-free Li anode. The combination of the lithophilic MgI 2 nanoparticles with polarized PAN matrix comprehensively functions as a high-compatible interpenetrating network to homogenize ionic transportation and confront dendrite growth. The released I ions introduce the high-ion-conductivity LiI into SEI layer, which could induce the formation of favorable and protective interface layer in the early stage, as embodied in the enrichment of advantageous components such as LiN x O y , Li 2 O, LiF, and Li 3 N. Profited from the high-affinity MPANF separator, the Li||Li symmetric cell achieves an ultra-low voltage hysteresis of 46 mV with an extended lifespan of 580 h. And a prolonged lifetime of 590 cycles with an enhanced specific capacity of 140.1 mAh g −1 and the Coulombic efficiency of 96.2% at 1 C can be obtained in full cells. This work may offer a facile and high-affinity alternative to traditional polymeric separators for high-performance and dendrite-free Li metal batteries.
研究领域:
能源存储系统
·
材料科学
·
电池技术
·
电化学
✓ 已验证
产品关联
DOI
高影响因子
INDUSTRIAL & ENGINEERING CHEMISTRY RESEARCH
·
2022
·
IF 4.326
Zhongkai Wu,Ru Wang,Chuang Yu,Chaochao Wei,Shuai Chen,Cong Liao,Shijie Cheng,Jia Xie
Sulfide electrolytes show great potential as solid electrolytes for all-solid-state batteries due to their high ionic conductivity and low interfacial resistance toward electrode materials. The structure of the P–S framework in the composition of sulfides plays a crucial role in the conductivity. Introducing LiI in the Li3PS4 structure can tailor the P–S frameworks and thus achieve high ionic conductivities. Herein, the dopant of LiI is optimized by high-rotation milling, followed by a sintering route to achieve the highest Li-ion conductivity of 2.3 mS cm–1 for the Li3PS4-50% LiI electrolyte (also denoted as Li7P2S8I) among different compositions. The phase variations and structure evolution of the P–S frameworks in the LiI-doped Li3PS4 electrolytes are carefully investigated in a combination of X-ray diffraction and Raman spectra. All-solid-state Li–S batteries using the prepared Li7P2S8I electrolyte combined with a nano Li2S cathode and a Li–In anode deliver a high initial discharge capacity of 739.7 mA h g–1 and sustain a discharge capacity of 517.7 mA h g–1 after 60 cycles with a capacity retention of 70.0% at 0.13 mA cm–2 at room temperature. When the operating temperature rises to 60 °C, it shows a higher discharge capacity of 862.8 mA h g–1 with fast capacity decay. However, it exhibits stable capacities and superior cycling performance under 0 °C over 70 cycles. Electrochemical impedance spectroscopy and in situ stack-pressure results find that the electrochemical performance differences of the assembled battery at different operating temperatures are associated with the interfacial resistance caused by volume changes. This work provides the strategy to obtain highly conductive sulfide electrolytes for SSBs and unravels the temperature effects on the electrochemical performance of all-solid-state Li–S batteries.
研究领域:
材料科学
·
电化学
·
能源存储
✓ 已验证
DOI
高影响因子
Scientific Reports
·
2025
·Vol. 15
·期 1
·44131
·
IF 3.9
Eissa A. A.,Kamar E. M.,Mousa M. A.,Sameeh M.
This study centers on polyvinyl alcohol and polyaniline films infused with lithium iodide as polymer electrolyte membranes that conduct ions for various electrochemical applications. Electrolyte membranes made from a 90:10 weight percent blend of polyvinyl alcohol (PVA) and polyaniline (PANI) were synthesized with varying amounts of LiI (from 5 to 25% by weight) via solution casting. The samples were analyzed through X-ray diffraction (XRD), Fourier transform infrared (FT-IR), mechanical properties testing, AC impedance spectroscopy, and linear sweep voltammetry (LSV). X-ray diffraction results show that the amorphous nature of PVA enhances with more additives, and LiI incorporation leads to improved mechanical properties in composite samples. FTIR analysis highlighted interactions between PVA and electrolyte components. Notably, the composites’ elongation at break surpassed that of the undoped PVA film, reaching 108 ± 7.1% with increased LiI content. The membrane containing 20 wt% LiI salt showed the highest ionic conductivity of 4.45 × 10 –3 S cm −1 . This top-performing membrane displayed an ionic transference number of 0.991 and demonstrated electrochemical stability at 2.21 V. All composite membranes displayed peaks in the dielectric loss spectra. The dielectric properties of the composites indicate a significant connection between the fluctuations in conductivity and the changes in the mobility and concentration of charge carriers. The composite materials exhibited non-Debye characteristics regarding their dielectric properties.
研究领域:
材料科学
·
高分子化学
·
电化学
·
储能
✓ 已验证
产品关联
DOI
PubMed
高影响因子
JOURNAL OF POLYMER SCIENCE
·
2025
·Vol. 63
·期 8
·1947-1957
·
IF 3.6
Jiaying Tong,Dan Zhao,Jingwen Yao,Dong Chen,Junjin Duan,Yuhong Ma,Wantai Yang
First thought, we tried hexafluoroisopropanol (HFIP) as the hydrogen bonding donor and LiI as a mediator to promote the radical homopolymerization of vinyl ethers. Unexpectedly, an exothermic reaction and significant viscosity increase were observed as the monomer conversion of isobutyl vinyl ether (IBVE) up to 90% at 0°C in the absence of a radical initiator. Therefore, we speculated that it was a cationic rather than a radical polymerization and confirmed with the proton trapping agent 2,6-di-tert-butylpyridine. With anhydrous CH 2 Cl 2 as a solvent, the molecular weights of the PIBVE are in the range of 5900–8900. With a decrease in the reaction temperature to −20°C, the molecular weight distribution is in the range of 1.74–1.19. Moreover, 2-ethylhexyl vinyl ether (EHVE) and cyclohexyl vinyl ether (CHVE) could also undergo a similar polymerization. A plausible cationic polymerization mechanism is proposed that vinyl ethers are initiated by H + which is generated by the reaction of HFIP and LiI. The end groups of PIBVE are composed of -H at the α-end and an aldehyde group -CH 2 CHO (I) or an acetal group -CH 2 CH(OCH 2 CH(CH 3 ) 2 ) 2 (II) at the ω-end. In addition, the end groups for PEHVE and PCHVE are consistent with the above mechanism. Graphical
研究领域:
材料科学
·
高分子化学
✓ 已验证
产品关联
DOI
高影响因子
JOURNAL OF COLLOID AND INTERFACE SCIENCE
·
2023
·
IF 9.9
Xin Dong,Ziqin Liu,Kaiquan He,Pu Hu,Chaoqun Shang
Li metal is a potential anode material for the next generation high-energy–density batteries because of its high theoretical specific capacity. However, the inhomogeneous lithium dendrite growth restrains corresponding electrochemical performance and brings safety concerns. In this contribution, the Li 3 Bi/Li 2 O/LiI fillers are generated by the in-situ reaction between Li and BiOI nanoflakes, which promises corresponding Li anodes (BiOI@Li) showing favorable electrochemical performance. This can be attributed to the bulk/liquid dual modulations: (1) The three-dimensional Bi-based framework in the bulk-phase lowers the local current density and accommodates the volume variation; (2) The LiI dispersed within Li metal is slowly released and dissolved into the electrolyte with the consumption of Li, which will form I − /I 3 − electron pair and further reactivate the inactive Li species. Specifically, the BiOI@Li//BiOI@Li symmetrical cell shows small overpotential and enhanced cycle stability over 600 h at 1 mA cm −2 . Matched with an S-based cathode, the full Li-S battery demonstrates desirable rate performance and cycling stability.
研究领域:
材料科学
·
电化学
·
能源存储
·
纳米材料
·
固态离子学
✓ 已验证
DOI
高影响因子
Journal of Energy Chemistry
·
2022
·
IF 13.599
Haonan Wang,Tianyi Hou,Hang Cheng,Bowen Jiang,Henghui Xu,Yunhui Huang
The development of polymer-based solid-state batteries is severely limited by the low ionic conductivity of solid polymer electrolyte and the instable interface between polymer electrolyte and Li-metal anode. In this work, lithium iodide (LiI) as a bifunctional additive was introduced into the poly(ethylene oxide) (PEO)-based electrolyte to improve the ionic conductivity and to construct a stable interphase at the Li/PEO interface. I − anions offer a strong electrostatic interaction with hydrogen atoms on PEO chains (H PEO ) and forming massive I–H bonds that cross-link PEO chains, decrease crystallinity of PEO, and thus improve Li + interchain transport. In addition, LiI participates in the formation of an inorganic-rich interphase layer, which decreases the energy barrier of Li + transport across the interface and thus inhibits the growth of lithium dendrites. As a result, the composite PEO electrolyte with 2 wt% LiI (PEO-2LiI) presents a very high ionic conductivity of 2.1 × 10 −4 S cm −1 and a critical current density of 2.0 mA cm −2 at 45 °C. Li symmetric cell with this PEO-2LiI electrolyte exhibits a long-term cyclability over 600 h at 0.2 mA cm −2 . Furthermore, solid-state LiFePO 4 and LiNi 0.8 Mn 0.1 Co 0.1 O 2 batteries with the PEO-2LiI electrolyte show an impressive electrochemical performance with outstanding cycling stability and rate capability at 45 °C.
研究领域:
材料科学
·
电化学
·
能源存储
✓ 已验证
产品关联
DOI
高影响因子
ELECTROCHIMICA ACTA
·
2023
·
IF 6.6
Xurui Li,Shuai Liu,Jing Shi,Minghua Huang,Zhicheng Shi,Huanlei Wang,Zhenhua Yan
Solid polymer electrolyte (SPE) as core component of all-solid-state lithium metal battery (ASSLMB) has regained tremendous concerns due to its good flexibility and low cost. However, low ionic conductivity , unstable interphase and unsatisfying cycling stability hinder its practical application in ASSLMB. Herein, we designed a PEO-based SPE (PEO/20PAM/LiI) via adding optimum content of poly (acrylamide) (PAM) and 2 wt% LiI to address above issues. The amide groups (-(C = O)-(N H)) in PAM could effectively facilitate the decomposition of LiTFSI due to the strong coordination of C = O/Li + and N H/TFSI − , significantly releasing more “Free Li + ”. The C = O group also weakens the coordination of Li + /ether oxygen and assists Li + transfer along the PEO chains, providing an efficient transmission pathway for Li + . Furthermore, LiI could facilitate the uniform Li + deposition at the electrode-electrolyte interface and stimulate the formation of stable interfacial layer, restraining the generation of lithium dendrites . The obtained PEO/20PAM/LiI exhibits high ionic conductivity (2.75 × 10 −4 S cm −1 , 35 °C), outstanding mechanical strength (0.55 MPa) and wide electrochemical window (∼ 5 V). The assembled Li symmetric battery could endure high critical current density (CCD, 1.8 mA cm −2 ) and perform Li plating/stripping steadily over 1600 h at 0.1 mA cm −2 at 35 °C. Meanwhile, LiFePO 4 (LFP)/Li ASSLMB with this SPE displays preeminent cycling stability over 250 cycles with high capacity retention (97.3%) and high coulombic efficiency (99.9%) at 0.3 C at 35 °C. This rational design strategy shows great potential in simultaneously realizing high ionic conductivity and good interfacial stability for ASSLMB.
研究领域:
材料科学
·
电化学
✓ 已验证
产品关联
DOI
高影响因子
ELECTROCHIMICA ACTA
·
2022
·
IF 7.336
Guoda Wang,Changgui Lin,Chengwei Gao,Pingping Dong,Bo Liang,Xiang Shen,Qing Jiao
The design of solid electrolyte with resistance to dendrite growth and air stability is essential for the development of all-solid-state Li + cells. The suppression of hydrogen sulfide was well controlled after adding the halide, and a protective layer formed to prevent the PS 4 3− units in the electrolyte from reacting with H 2 O molecules. Moreover, the as-prepared low-temperature phase Li 3 PS 4 -LiI has good resistance to dendrite growth and excellent compatibility with Li metal. The Li/electrolyte/Li symmetric battery exhibits ultra-durable cycle stability for 1350 h at 0.25 mA cm −2 . The details of influence rules of iodide introduction on the network and ions transmission are analyzed and proposed to explore the available electrolytes for all-solid-state battery.
✓ 已验证
DOI
高影响因子
Journal of Physical Chemistry C
·
2023
·
IF 3.7
Wei-Wei Wang,Yu Gu,Chen-Xi Liu,Jiawei Yan,Bing-Wei Mao
The morphology of Li deposition has a profound effect on the cycling performance of a Li-metal battery. However, in situ research studies on the targeted regulation of Li deposition behavior and exploration of the thermodynamic and kinetic factors affecting Li deposition morphology are quite limited. Herein, we employ in situ atomic force microscopy (AFM) to investigate the effects of lithium iodide (LiI) additive on the evolution of Li deposition morphology in propylene carbonate (PC)-based electrolyte. The spherical Li deposits formed via three-dimensional (3D) nucleation and growth partially transform into planar morphology after the addition of 10 mM LiI, leading to a combined 3D nucleation and quasi-two-dimensional (2D) growth behavior. Complemented by X-ray photoelectron spectroscopy (XPS) profiling analysis and AFM nanomechanical characterization, the composition, structure, and properties of solid electrolyte interphases (SEIs) are comprehensively inspected. The SEI formed in the LiI-containing electrolyte bears an inorganic–organic hybrid structure with improved mechanical flexibility, compared with the rigid and thick SEI formed in the basic electrolyte. Meanwhile, the possible interfacial adsorption of Ĩ– contributes to the uniform distribution of Li+ and rapid diffusion of the Li atom. This work reveals the importance of an additive in regulating the Li deposition behavior, which is helpful in improving the Li-metal battery performance.
研究领域:
材料科学
·
电化学
✓ 已验证
产品关联
DOI
高影响因子
ACS Sustainable Chemistry & Engineering
·
2021
·
IF 8.198
Lei Shi,Gan Wang,Jian Li,Meifen Wu,Zhaoyin Wen
The practical applications of Li–O2 batteries are hindered by the large charge polarization. Recently, the development of redox mediators (RMs) brings new hope for constructing low overpotential Li–O2 batteries. However, the “shuttle effect” of RMs causes new problems. Here, based on a low-cost and environmentally friendly biomaterial–bacterial cellulose, a sulfonation strategy was adopted to produce a functional gel polymer electrolyte for LiI-involved Li–O2 batteries. Benefiting from the high-density negatively charged sulfonate groups on the sulfonated bacterial cellulose, the functionalized gel electrolyte can produce strong electrostatic repulsion force to the negatively charged I3– ions to suppress the shuttle effect. As a result, the Li–O2 battery shows a good cycling performance with eliminated self-discharge, and the Li anode is successfully protected by the inhibition of I3– shuttling. This novel approach may provide new insights into the development of functionalized gel polymer electrolytes for Li–O2 batteries with redox mediators.
研究领域:
材料科学
·
电化学
·
能源存储
✓ 已验证
产品关联
DOI
高影响因子
Science China-Materials
·
2022
·Vol. 66
·期 2
·513-521
·
IF 8.64
Zhao Bo-Sheng,Chen Peng,Gao Xue-Ping
Sulfide solid electrolyte is a promising candidate for the development of high-energy lithium-sulfur (Li-S) batteries. However, the concurrent improvement of ionic conductivity, bulk air stability, and compatibility of the electrolyte/electrode interface of sulfide solid electrolyte remains a huge challenge. Herein, we propose a dual-source doping (Sb 2 O 3 and LiI) strategy to prepare a multifunctional sulfide solid electrolyte. Sb 2 O 3 can broaden the transmission path of lithium ions and improve the bulk stability, and LiI can inhibit the generation of lithium dendrites and reduce the electrolyte/electrode resistance. Therefore, the sulfide solid electrolyte can be strengthened in terms of its bulk and interface, thus exhibiting a high ionic conductivity of 1.69 × 10 −3 S cm −1 at 30°C, high air stability, and high electrochemical stability with lithium metal. On this basis, the as-prepared all-solid-state Li-S batteries (ASSLSBs) can exhibit a high specific discharge capacity after being cycled at 0.05 C for 100 cycles at room temperature (833 mA h g −1 ) or 60°C (949 mA h g −1 ). This work provides a rational scheme for the preparation of practical sulfide solid electrolytes and high-performance ASSLSBs.
研究领域:
材料科学
·
能源存储
·
电化学
·
电池技术
✓ 已验证
DOI
高影响因子
危险品化学品经营许可证（带存储）