Developing all-solid-state polymer electrolytes(SPEs) with high electrochemical performances and stability is of great importance for exploiting of high energy density and safe batteries. Herein, ether linkage and imi...Developing all-solid-state polymer electrolytes(SPEs) with high electrochemical performances and stability is of great importance for exploiting of high energy density and safe batteries. Herein, ether linkage and imidazolium ionic liquid(ILs) are incorporated into the multi-armed polymer backbone though the series and parallel way. The parallel polymeric ionic liquid(P-P(PEGMA-IM)) maximizes the synergistic effect of ILs and ether linkage, which endowed the material with low crystallinity and high flame retardancy. The P-P(PEGMA-IM) based P-SPE presents a high ionic conductivity of 0.489 m S/cm at 60°C, an excellent lithium-ion transference number of 0.46 and a wide electrochemical window of 4.87 V.The assembled lithium metal battery using P-SPE can deliver a capacity of 151 m Ah/g at 0.2 C, and the capacity retention ratio reaches 82% with a columbic efficiency beyond 99%. The overpotential of P-SPE based symmetric battery is 0.08 V, and there is no apparent magnifying even after 130 h cycling. This new design provides a new avenue for exploitation of advanced SPEs for the next-generation batteries.展开更多
In this study,a series of epoxy-based azo molecular glasses with four-arm architecture was synthesized based on an intermediate(MDGA-AN),which was obtained from ring-opening reaction between 4,4'-methylene-bis(N,N...In this study,a series of epoxy-based azo molecular glasses with four-arm architecture was synthesized based on an intermediate(MDGA-AN),which was obtained from ring-opening reaction between 4,4'-methylene-bis(N,N’-diglycidylaniline)and N-methylaniline.The azo compounds were then synthesized through azo-coupling reaction between MDGA-AN and diazonium salts of 4-nitroaniline,4-aminobenzonitrile,4-aminobenzoic acid,4-fluoroaniline and 4-methoxyaniline,respectively.The azo compounds were thoroughly characterized and the photoresponsive properties of their solid films were investigated at three different wavelengths(λex=488,532 and 589 nm).The results show that the electron-withdrawing groups on the azo chromophores can significantly affect the absorption band positions in visible light range,which shift to the longer wavelength with the enhanced push-pull effect.Both photoinduced birefringence and surface-relief-grating formation are closely related to the electronwithdrawing groups and excitation wavelengths of the actinic light,which show significant influences on the growth rates and saturated values of the photoinduced variations.In this series,the azo molecular glasses containing cyano and carboxyl groups as the electron-withdrawing groups show the significantly higher efficiency for both the photoinduced birefringence growth and the SRG formation compared with others under the same light irradiation conditions.The capability of the materials as a photo-storage medium is demonstrated by holographic recording.展开更多
In view of few attention on star-shaped molecules containing triphenylamine(TPA)unit asπ-linker,a series of small four-armed molecules,consisting of octyloxy-substituted 2,1,3-benzothiadiazole(DOBT)or 4-octyl-2-thien...In view of few attention on star-shaped molecules containing triphenylamine(TPA)unit asπ-linker,a series of small four-armed molecules,consisting of octyloxy-substituted 2,1,3-benzothiadiazole(DOBT)or 4-octyl-2-thienyl functionalized DOBT as the core,TPA asπ-bridge and 4-methylphenyl or 4-methoxyphenyl groups as terminal units,was designed and synthesized.The effects ofπbridges and substitute groups on molecular photoe-lectric performance and photovoltaic performance were fully explored.With the help of the additional thiophene-linkers incorporation,3-octylthienyl substituted molecule with end-capping 4-methylphenyl(T-BTTPAM)and 3-octylthienyl substituted molecule with end-capping 4-methoxyphenyl(T-BTTPAOM)showed stronger and broader absorption,as well as higher charge mobilities compared to the molecules without thiophene-linkers(BTTPAM and BTTPAOM).Additionally,changing substitute groups from methyl to methoxy helped BTTPAOM and T-BTTPAOM achieve better absorption properties than BTTPAM and T-BTTPAM,respectively.When paired with PC61BM as the electron acceptor to fabricate solution-processed photovoltaic devices,the four materials gave high open-circuit voltage(Voc)values over 0.90 V.These results demonstrate that our materials are promising candidates as donor materials for organic solar cells(OSCs),and further device optimization is in progress in our laboratory.展开更多
基金National Natural Science Foundation of China (No. 51303083)the Natural Science Foundation of Jiangsu Province (No. BK20191293)the Fundamental Research Funds for the Central Universities (No. 30920021123) for financial support。
文摘Developing all-solid-state polymer electrolytes(SPEs) with high electrochemical performances and stability is of great importance for exploiting of high energy density and safe batteries. Herein, ether linkage and imidazolium ionic liquid(ILs) are incorporated into the multi-armed polymer backbone though the series and parallel way. The parallel polymeric ionic liquid(P-P(PEGMA-IM)) maximizes the synergistic effect of ILs and ether linkage, which endowed the material with low crystallinity and high flame retardancy. The P-P(PEGMA-IM) based P-SPE presents a high ionic conductivity of 0.489 m S/cm at 60°C, an excellent lithium-ion transference number of 0.46 and a wide electrochemical window of 4.87 V.The assembled lithium metal battery using P-SPE can deliver a capacity of 151 m Ah/g at 0.2 C, and the capacity retention ratio reaches 82% with a columbic efficiency beyond 99%. The overpotential of P-SPE based symmetric battery is 0.08 V, and there is no apparent magnifying even after 130 h cycling. This new design provides a new avenue for exploitation of advanced SPEs for the next-generation batteries.
基金financial support from the National Natural Science Foundation of China(Nos.51773108 and 51233002)
文摘In this study,a series of epoxy-based azo molecular glasses with four-arm architecture was synthesized based on an intermediate(MDGA-AN),which was obtained from ring-opening reaction between 4,4'-methylene-bis(N,N’-diglycidylaniline)and N-methylaniline.The azo compounds were then synthesized through azo-coupling reaction between MDGA-AN and diazonium salts of 4-nitroaniline,4-aminobenzonitrile,4-aminobenzoic acid,4-fluoroaniline and 4-methoxyaniline,respectively.The azo compounds were thoroughly characterized and the photoresponsive properties of their solid films were investigated at three different wavelengths(λex=488,532 and 589 nm).The results show that the electron-withdrawing groups on the azo chromophores can significantly affect the absorption band positions in visible light range,which shift to the longer wavelength with the enhanced push-pull effect.Both photoinduced birefringence and surface-relief-grating formation are closely related to the electronwithdrawing groups and excitation wavelengths of the actinic light,which show significant influences on the growth rates and saturated values of the photoinduced variations.In this series,the azo molecular glasses containing cyano and carboxyl groups as the electron-withdrawing groups show the significantly higher efficiency for both the photoinduced birefringence growth and the SRG formation compared with others under the same light irradiation conditions.The capability of the materials as a photo-storage medium is demonstrated by holographic recording.
文摘In view of few attention on star-shaped molecules containing triphenylamine(TPA)unit asπ-linker,a series of small four-armed molecules,consisting of octyloxy-substituted 2,1,3-benzothiadiazole(DOBT)or 4-octyl-2-thienyl functionalized DOBT as the core,TPA asπ-bridge and 4-methylphenyl or 4-methoxyphenyl groups as terminal units,was designed and synthesized.The effects ofπbridges and substitute groups on molecular photoe-lectric performance and photovoltaic performance were fully explored.With the help of the additional thiophene-linkers incorporation,3-octylthienyl substituted molecule with end-capping 4-methylphenyl(T-BTTPAM)and 3-octylthienyl substituted molecule with end-capping 4-methoxyphenyl(T-BTTPAOM)showed stronger and broader absorption,as well as higher charge mobilities compared to the molecules without thiophene-linkers(BTTPAM and BTTPAOM).Additionally,changing substitute groups from methyl to methoxy helped BTTPAOM and T-BTTPAOM achieve better absorption properties than BTTPAM and T-BTTPAM,respectively.When paired with PC61BM as the electron acceptor to fabricate solution-processed photovoltaic devices,the four materials gave high open-circuit voltage(Voc)values over 0.90 V.These results demonstrate that our materials are promising candidates as donor materials for organic solar cells(OSCs),and further device optimization is in progress in our laboratory.
