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1.
All-solid-state polymer lithium-ion batteries are ideal choice for the next generation of rechargeable lithium-ion batteries due to their high energy, safety and flexibility. Among all polymer electrolytes, PEO-based polymer electrolytes have attracted extensive attention because they can dissolve various lithium salts. However, the ionic conductivity of pure PEO-based polymer electrolytes is limited due to high crystallinity and poor segment motion. An inorganic filler SiO2 nanospheres and a plasticizer Succinonitrile (SN) are introduced into the PEO matrix to improve the crystallization of PEO, promote the formation of amorphous region, and thus improve the movement of PEO chain segment. Herein, a PEO18−LiTFSI−5 %SiO2−5 %SN composite solid polymer electrolyte (CSPE) was prepared by solution-casting. The high ionic conductivity of the electrolyte was demonstrated at 60 °C up to 3.3×10−4 S cm−1. Meanwhile, the electrochemical performance of LiFePO4/CSPE/Li all-solid-state battery was tested, with discharge capacity of 157.5 mAh g−1 at 0.5 C, and capacity retention rate of 99 % after 100 cycles at 60 °C. This system provides a feasible strategy for the development of efficient all-solid-state lithium-ion batteries.  相似文献   

2.
We prepared the polyethylene oxide (PEO)-based composite membrane electrolytes which contained the specialized ionic liquids and the inorganic filler of Li7La3Zr2O12 (LLZO). Mixtures of ionic liquids and tetragonal inorganic fillers were used as additives to prepare composite electrolytes for an application of all solid-state lithium ion batteries (ASLBs). In order to improve the ionic conductivity of composite membranes, we studied the structural change and the electrochemical behaviors as a function of the amounts of solvated ionic liquids (ILs). The addition effect of solvated ILs showed the higher ionic conductivity such as 10?4 S/cm at 55 °C by reducing the crystalline character of polymer based composite, resulting in the enhanced ion conducting property. The hybrid composite membranes were successfully made in flexible form, and have an excellent thermal and electrochemical stability. Finally, the electrochemical performance of the half-cell was evaluated, and it was confirmed that the ion-conducting characteristics were influenced and controlled by the effect of ILs.  相似文献   

3.
All-solid electrolyte instead of frequently-used inflammable electrolyte can enhance the security and energy density of batteries effectively. However, the low ionic conductivity lead to increased lithium dendrites and increased resistance of the cell at 30 °C. In this work, non-toxic and low-cost hydroxypropyl methylcellulose (HPMC) was introduced simultaneously with non-polluting hectorite (Ht) into polyoxyethylene (PEO) to obtain novel composite solid-state electrolytes (CSEs). The optimized CSEs has a high ionic conductivity (1.1×10−3 S/cm) at 30 °C. This work demonstrates that the novel PEO-HPMC@Ht CSEs are extremely promising.  相似文献   

4.
In this study, the composite polymer electrolytes (CPEs) were prepared by solution casting technique. The CPEs consisted of PEO/PMMA blend as a host matrix doped with LiClO4. Propylene carbonate (PC) was used as plasticizer and a small amount of imidazolium salt-supported amorphous silica (IS-AS) as a filler was prepared by the sol–gel method. At room temperature, the highest conductivity was obtained for the composition having PEO–PMMA–LiClO4–PC–4wt. % IS-AS with a value of 1.15 × 10?4 S/cm. In particular, the CPE using the IS-AS filler showed a higher conductivity than any other sample (fumed silica, amorphous silica). Studies of differential scanning calorimetry and scanning electron microscopy indicated that the ionic conductivity increase was due to an expansion in the amorphous phase which enhances the flexibility of polymeric chains and the homogeneous structure of CPEs. It was found that the ionic conductivity and interfacial resistance stability of CPEs was significantly improved by the addition of IS-AS. In other words, the resistance stability and maximum ambient ionic conductivity of CPEs containing IS-AS filler were better than CPEs containing any other filler.  相似文献   

5.
Solid composite polymer electrolytes consisting of polyethylene oxide (PEO), LiClO4, and porous inorganic–organic hybrid poly (cyclotriphosphazene-co-4, 4′-sulfonyldiphenol) (PZS) nanotubes were prepared using the solvent casting method. Differential scanning calorimetry and scanning electron microscopy were used to determine the characteristics of the composite polymer electrolytes. The ionic conductivity, lithium ion transference number, and electrochemical stability window can be enhanced after the addition of PZS nanotubes. The electrochemical impedance showed that the conductivity was improved significantly. Maximum ionic conductivity values of 1.5 × 10−5 S cm−1 at ambient temperature and 7.8 × 10−4 S cm−1 at 80 °C were obtained with 10 wt.% content of PZS nanotubes, and the lithium ion transference number was 0.35. The good electrochemical properties of the solid-state composite polymer electrolytes suggested that the porous inorganic–organic hybrid polyphosphazene nanotubes had a promising use as fillers in SPEs and the PEO10–LiClO4–PZS nanotube solid composite polymer electrolyte might be used as a candidate material for lithium polymer batteries.  相似文献   

6.
A series of copolymers of predominantly poly(ethylene oxide) (PEO) with biphenyl (BP) units in the backbone were synthesized. The solid polymer electrolytes (SPEs) were prepared from these copolymers (BP-PEG) employing lithium perchlolate (LiClO4) as a lithium salt and their ionic conductivities were investigated to exploit the structure–ionic conductivity relationships as a function of chain length ratio between the flexible PEO chains and rigid BP units. The ionic conductivity increases with increasing PEO length in BP-PEG. The salt concentrations in BP-PEG/LiClO4 complexes were also changed and the results show that maximum conductivity is obtained at [EO]/[Li+]≈8. The reasons for these findings are discussed in terms of the number of charge carriers and the mobility of the polymer chain.  相似文献   

7.
《印度化学会志》2023,100(4):100959
The polymer-ceramic composite electrolytes have great application potential for next-generation solid state lithium batteries, as they have the merits to eliminate the problem of liquid organic electrolytes and enhancing chemical/electrochemical stability. However, polymer-ceramic composite electrolytes show poor ionic conductivity, which greatly hinders their practical applications. In this work, the addition of plasticizer ethylene carbonate (EC) into polymer-ceramic composite electrolyte for lithium batteries effectively promotes the ionic conductivity. A high ionic conductivity can be attained by adding 40 wt% EC to the polyethylene oxide (PEO)/polyvinylidene fluoride (PVDF)-Li7La3Zr2O12 (LLZO) based polymer-ceramic composite electrolytes, which is 2.64 × 10−4 S cm−1 (tested at room temperature). Furthermore, the cell assembled with lithium metal anode, this composite electrolyte, and LiFePO4 cathode can work more than 80 cycles at room temperature (tested at 0.2 C). The battery delivers a high reversible specific capacity after 89 cycles, which is 119 mAh g−1.  相似文献   

8.
A novel single lithium‐ion (Li‐ion) conducting polymer electrolyte is presented that is composed of the lithium salt of a polyanion, poly[(4‐styrenesulfonyl)(trifluoromethyl(S‐trifluoromethylsulfonylimino)sulfonyl)imide] (PSsTFSI?), and high‐molecular‐weight poly(ethylene oxide) (PEO). The neat LiPSsTFSI ionomer displays a low glass‐transition temperature (44.3 °C; that is, strongly plasticizing effect). The complex of LiPSsTFSI/PEO exhibits a high Li‐ion transference number (tLi+=0.91) and is thermally stable up to 300 °C. Meanwhile, it exhibits a Li‐ion conductivity as high as 1.35×10?4 S cm?1 at 90 °C, which is comparable to that for the classic ambipolar LiTFSI/PEO SPEs at the same temperature. These outstanding properties of the LiPSsTFSI/PEO blended polymer electrolyte would make it promising as solid polymer electrolytes for Li batteries.  相似文献   

9.
A series of copolymers of predominantly poly(ethylene oxide) (PEO) with mono-phenyl (HQ), biphenyl (BP) units, or both of them (HQ/BP) in the backbone were synthesized. The solid polymer electrolytes (SPEs) were prepared from three different types of copolymers (HQ-PEG, BP-PEG, and HQ/BP-PEG) employing lithium perchlorate (LiClO4) as a lithium salt at a fixed salt concentration of [EO]/[Li+]=8. Their ionic conductivities were investigated to exploit the structure–ionic conductivity relationships as a function of structural change in rigid phenyl units and chain length ratio between flexible PEO chain and rigid phenyl units. As more rigid phenyl units were incorporated in the backbone chain, the formation inter- and intra-molecular complex with LiClO4 became weaker and lower ionic conductivities were observed. And it was also found that higher ionic conductivity is obtained with increasing PEO chain length because inter- and intra-molecular dissociation power of PEO increases.  相似文献   

10.
New solid polymer electrolytes are developed for a lithium power source used at the temperatures up to 100°C. Polyester diacrylate (PEDA) based on oligohydroxyethylacrylate and its block copolymers with polyethylene glycol were offered for polymer matrix formation. The salt used was LiClO4. The ionic conductivity of electrolytes was measured in the range of 20 to 100°C using the electrochemical impedance method. It is shown that the maximum conductivity in the whole temperature range is characteristic of the electrolyte based on the PEDA copolymer and polyethylene glycol condensation product (2.8 × 10?6 S cm?1 at 20°C, 1.8 × 10?4 S cm?1 at 95°C).  相似文献   

11.
Composition solid electrolytes (1 ? x)LiClO4-xMgO are synthesized and their physicochemical properties are studied. According to the data of differential scanning calorimetry, for sufficiently high oxide concentrations, all lithium perchlorate is present in the composite in the amorphous state. Impedance spectroscopic studies demonstrate that the conductivity of composites passes through a maximum at x = 0.8?0.9, reaching ~10?2 S/cm at 200°C. Based on voltammetric characteristics, it is shown that the voltage of electrochemical decomposition of composites in vacuum does not exceed 3.5–4.0 V, decreasing to 1.8–2.0 V in humid atmosphere. The conductivity of studied composites in vacuum may apparently be attributed to lithium ions, and these solid electrolytes can be used in solid-state electrochemical lithium cells.  相似文献   

12.
Polymer–ceramic composite electrolytes are emerging as a promising solution to deliver high ionic conductivity, optimal mechanical properties, and good safety for developing high‐performance all‐solid‐state rechargeable batteries. Composite electrolytes have been prepared with cubic‐phase Li7La3Zr2O12 (LLZO) garnet and polyethylene oxide (PEO) and employed in symmetric lithium battery cells. By combining selective isotope labeling and high‐resolution solid‐state Li NMR, we are able to track Li ion pathways within LLZO‐PEO composite electrolytes by monitoring the replacement of 7Li in the composite electrolyte by 6Li from the 6Li metal electrodes during battery cycling. We have provided the first experimental evidence to show that Li ions favor the pathway through the LLZO ceramic phase instead of the PEO‐LLZO interface or PEO. This approach can be widely applied to study ion pathways in ionic conductors and to provide useful insights for developing composite materials for energy storage and harvesting.  相似文献   

13.
Zn-I2 batteries have attracted attention due to their low cost, safety, and environmental friendliness. However, their performance is still limited by the irreversible growth of Zn dendrites, hydrogen evolution reactions, corrosion, and shuttle effect of polyiodide. In this work, we have prepared a new porous polymer (CD-Si) by nucleophilic reaction of β-cyclodextrin with SiCl4, and CD-Si is applied to the solid polymer electrolyte (denoted PEO/PVDF/CD-Si) to solve above-mentioned problems. Through the anchoring of the CD-Si, a conductive network with dual transmission channels was successfully constructed. Due to the non-covalent anchoring effect, the ionic conductivity of the solid polymer electrolytes (SPE) can reach 1.64×10−3 S cm−1 at 25 °C. The assembled symmetrical batteries can achieve highly reversible dendrite-free galvanizing/stripping (stable cycling for 7500 h at 5 mA cm−2 and 1200 h at 20 mA cm−2). The solid-state Zn-I2 battery shows an ultra-long life of over 35,000 cycles at 2 A g−1. Molecular dynamics simulations are performed to elucidate the working mechanism of CD-Si in the polymer matrix. This work provides a novel strategy towards solid electrolytes for Zn-I2 batteries.  相似文献   

14.
Solid polymer electrolytes (SPEs) with high ionic conductivity and acceptable mechanical properties are of particular interest for increasing the performance of batteries. In the present work, SPEs based on poly(ethylene oxide)/poly (vinyl pyrrolidone) (PEO/PVP) with various lithium salts were prepared by solvent casting technique. The amorphous nature of the polymer-salt complex was studied by X-ray diffraction analysis. The complexation of the prepared electrolytes was confirmed by Fourier transform infrared analysis. Ionic conductivity as a function of frequency was studied at various temperatures in the range of 303–353 K. The maximum ionic conductivity value was found to be 1.08 × 10?5 S/cm for the film containing lithium bis trifluoromethane sulfonoimide (LiN[CF3SO2]2) at room temperature and the temperature dependent ionic conductivity values seem to obey Vogel-Tamman-Fulcher relation. Thermogravimetry was used to ascertain the thermal stability of the electrolytes. Photoluminescence measurements demonstrated that the sample having maximum ionic conductivity shows the minimum luminescence intensity. Ultra violet-visible analysis reveals that the values of the band gap energies were changed with the addition of various lithium salts. Porosity of the sample containing lithium bis trifluoromethane sulfonoimide (LiN[CF3SO2]2) was studied by Atomic force microscope.  相似文献   

15.
Various iodide ion conducting polymer electrolytes have been studied as candidate materials for fabricating photoelectrochemical (PEC) solar cells and energy storage devices. In this study, enhanced ionic conductivity values were obtained for the ionic liquid tetrahexylammonium iodide containing polyethylene oxide (PEO)-based plasticized electrolytes. The analysis of thermal properties revealed the existence of two phases in the electrolyte, and the conductivity measurements showed a marked conductivity enhancement during the melting of the plasticizer-rich phase of the electrolyte. Annealed electrolyte samples showed better conductivity than nonannealed samples, revealing the existence of hysteresis. The optimum conductivity was shown for the electrolytes with PEO:salt = 100:15 mass ratio, and this sample exhibited the minimum glass transition temperature of 72.2 °C. For this optimum PEO to salt ratio, the conductivity of nonannealed electrolyte was 4.4 × 10−4 S cm−1 and that of the annealed sample was 4.6 × 10−4 S cm−1 at 30 °C. An all solid PEC solar cell was fabricated using this annealed electrolyte. The short circuit current density (I SC), the open circuit voltage (V OC), and the power conversion efficiency of the cell are 0.63 mA cm−2, 0.76 V, and 0.47% under the irradiation of 600 W m−2 light.  相似文献   

16.
Electrolytes with high lithium-ion conductivity, better mechanical strength and large electrochemical window are essential for the realization of high-energy density lithium batteries. Polymer electrolytes are gaining interest due to their inherent flexibility and nonflammability over conventional liquid electrolytes. In this work, lithium garnet composite polymer electrolyte membrane (GCPEM) consisting of large molecular weight (Wavg ~?5?×?106) polyethylene oxide (PEO) complexed with lithium perchlorate (LiClO4) and lithium garnet oxide Li6.28Al0.24La3Zr2O12 (Al-LLZO) is prepared by solution-casting method. Significant improvement in Li+ conductivity for Al-LLZO containing GCPEM is observed compared with the Al-LLZO free polymer membrane. Maximized room temperature (30 °C) Li+ conductivity of 4.40?×?10?4 S cm?1 and wide electrochemical window (4.5 V) is observed for PEO8/LiClO4?+?20 wt% Al-LLZO (GCPEM-20) membrane. The fabricated cell with LiCoO2 as cathode, metallic lithium as anode and GCPEM-20 as electrolyte membrane delivers an initial charge/discharge capacity of 146 mAh g?1/142 mAh g?1 at 25 °C with 0.06 C-rate.  相似文献   

17.
To obtain solid polymer electrolytes (SPEs) having high ionic conductivity together with mechanical integrity, we have synthesized polystyrene (PSt)‐polyether (PE) diblock copolymers via one‐pot anionic polymerization. The PSt block is expected to aggregate to act as hard fillers in the SPE to enhance the mechanical property. The PE block consists of random copolymer (P(EO‐r‐MEEGE)) of ethylene oxide (EO) and 2‐(2‐methoxyethoxy) ethyl glycidyl ether (MEEGE) in different molar ratios ([EO]/[MEEGE] = 100/0, 86/14, 75/25, 68/32, and 41/59). The introduction of the MEEGE moiety in PEO reduced the crystallinity of PEO, and the fast motion of the MEEGE side chain caused plasticization of the PE block, thereby contributing to the fast ion transport. SPEs were fabricated by mixing the obtained diblock copolymer (PSEx) and lithium bis(trifluoromethanesulfonyl) amide (LiTFSA) with [Li]/[O] = 0.05. Ionic conductivity of the obtained SPEs was dependent on the molar ratio of EO in the PE block (x) as well as the weight fraction of PE block (fPE) in the block copolymer. PSE0.86 (fPE = 0.65) exhibited high ionic conductivity (3.3 × 10?5 S cm?1 at 30°C; 1.1 × 10?4 S cm?1 at 60°C) comparable with that of P(EO‐r‐MEEGE) (PE0.85; fPE = 1.00) (9.8 × 10?5 S cm?1 at 30°C; 4.0 × 10?4 S cm?1 at 60°C).  相似文献   

18.
Solid lithium electrolytes in the Li4-3x Fe x GeO4 system were synthesized. Their phase composition, thermal behavior, and electrical conductivity were studied in the temperature interval 300–750°C. Introduction of Fe3+ ions into lithium orthogermanate leads to the formation of a γ-Li3PO4-type structure and to a sharp increase in the conductivity, with a maximum reached at x = 0.075–0.15: about 10?1 S cm?1 at 300°C and more than 1 S cm?1 at 700°C. The main current carriers are interstitial Li+ cations weakly bound with the rigid framework. Owing to high conductivity, the electrolytes studied are of interest for use in high-temperature electrochemical devices.  相似文献   

19.
A new kind of polymer electrolyte is prepared from N-methyl-N-propylpiperidinium bis (trifluoromethanesulfonyl) imide (PP1.3TFSI), polyethylene oxide (PEO), and lithium bis (trifluoromethanesulfonyl) imide (LiTFSI). IR and X-ray diffraction results demonstrate that the addition of ionic liquid decreases the crystallization of PEO. Thermal and electrochemical properties have been tested for the solid polymer electrolytes, the addition of the room temperature molten salt PP1.3TFSI to the conventional P(EO)20LiTFSI polymer electrolyte leads to the improvement of the thermal stability and the ionic conductivity (x = 1.27, 2.06 × 10−4 S cm−1 at room temperature), and the reasonable lithium transference number is also obtained. The Li/LiFePO4 cell using this polymer electrolyte shows promising reversible capacity, 120 mAh g−1 at room temperature and 164 mAh g−1 at 55 °C.  相似文献   

20.
The lithium-conducting solid electrolytes in the Li4 ? 2x Cd x GeO4 (0 ≤ x ≤ 0.6) system are synthesized. Their crystal structure and temperature and concentration dependences of conductivity are studied. The specimens with the highest conductivity have a γ-Li3PO4-derivative structure. The solid solutions with x = 0.15–0.25 are stable at the room temperature, whereas the specimens with x ≥ 0.3 decompose yielding Li2CdGeO4 below 310 ± 10°C. Li3.6Cd0.2GeO4 solid solution exhibits the highest conductivity (5.25 × 10?2 S cm?1 at 300°C). The factors, which affect the conductivity of synthesized solid electrolytes, are considered.  相似文献   

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