Synthesis of Highly Stretchable, Mechanically Tough, Zwitterionic Sulfobetaine Nanocomposite Gels
药学 专业文献 翻译
药学专业文献翻译Enzymatic Synthesis and Antioxidant Properties of Poly (rutin) 聚(芦丁)的酶促合成与抗氧化性质†‡†‡††Motoichi Kurisawa, Joo Eun Chung, Hiroshi Uyama,* and Shiro Kobayashi*Abstract 摘要Rutin, quercetin-3-rutinoside, is one of the most famous glycosides of flavonoid and widely present in many plants. In this study, we performed an oxidative polymerization of rutin using Myceliophthora laccase as catalyst in a mixture of methanol and buffer to produce a flavonoid polymer and evaluated antioxidant properties of the resultant polymer. Under selected conditions , the polymer with molecular weight of several thousands was obtained in good yields. The resulting polymer was readily soluble in water, DMF, and DMSO, although rutin monomer showed very low water solubility. UV measurement showed that the polymer had broad transition peaks around 255 and 350 nm in water, which were red-shifted in an alkaline solution. Electron spin resonance (ESR) measurement showed the presence of a radical in the polymer. The polymer showed greatly improved superoxide scavenging activity and inhibition effects on human low-density lipoprotein (LDL) oxidation initiated by 2,2‘-azobis(2-amidino-propane) dihydrochloride (AAPH), compared with the rutin monomer. The polymer also protected endothelial cells from oxidative injuryinduced by AAPH as a radical generator with a much greater effect than the rutin monomer.芦丁，槲皮素芸香糖苷，是最著名的黄酮类糖苷之一，广泛存在于很多植物中。
nature
本科生科研训练题目高能量密度柔性赝电容器中的二维磷酸氧钒超薄结构（翻译）院系物理科学与技术学院专业物理学基地班年级2012级学生姓名李赫学号**********二0一三年十二月二十日natureCOMMUNICATIONS2013年2月5号收到稿件2013年8月12日接受稿件2013年9月12日发表稿件DOI: 10.1038/ncomms3431高能量密度柔性赝电容器中的二维磷酸氧钒超薄结构二维材料一直以来在柔性薄膜型超级电容器，以及表现有关灵活性，超薄度甚至透明度的强劲优势上都是一个理想的构建平台。
要探索新的具有高电化学活性的二维赝电容材料，我们需要获得具有高能量密度的柔性薄膜超级电容器。
这里我们介绍一个无机石墨烯类似物，a1钒，一种少于6个电子层的磷酸盐超薄纳米片来作为一个有发展前景的材料去构建柔性全固态超薄赝电容器。
这种材料展示了一个在水溶液中氧化还原电位(~1.0V)接近纯水电化学窗口电压（1.23V）的赝电容柔性平面超级电容器。
通过层层组装构建出的柔性薄膜型超级电容器的氧化还原电位高达1.0V，比容量高达8360.5 μF∙cm-2，能量密度达1.7 mWh ∙cm-2，功率密度达5.2 mW∙cm-2。
现在，便携式消费电子产品的需求在快速增长，如柔性显示器，手机和笔记本电脑，极大推动了在全固态下的柔性能源设备的开发。
作为未来一代的储能装置，柔性薄膜型超级电容器在全固态下提供柔韧性，超薄型和透明度的协同效益。
在不同的类型的超级电容器中，与电双层电容器相比，赝电容器因为自身的高活性表面的电极材料可以快速发生的氧化还原反应而具有明显优势。
与锂离子电池相比，它表现出更高的能量密度，以及更高的功率密度。
因此，承载着为实现高性能的柔性薄膜型超级电容器的全固态伟大的承诺（FUSA）与电容行为。
具有赝电容特性的二维（2D）类石墨烯材料代表着一个有前途的方向可以去实现全固态下的高能量密度柔性超级电容器，和潜在的优良的机械柔性。
Highly Efficient Solar Cell Polymers Developed
Highly Efficient Solar Cell Polymers Developed viaFine-Tuning of Structural and Electronic Properties Yongye Liang,†Danqin Feng,†Yue Wu,‡Szu-Ting Tsai,‡Gang Li,*,‡Claire Ray,†and Luping Yu*,†Department of Chemistry and the James Franck Institute,The Uni V ersity of Chicago, 929E.57th Street,Chicago,Illinois60637,and Solarmer Energy Inc.,3445Fletcher A V enue,El Monte,California91731Received February27,2009;E-mail:lupingyu@;gangl@Abstract:This paper describes synthesis and photovoltaic studies of a series of new semiconducting polymers with alternating thieno[3,4-b]thiophene and benzodithiophene units.The physical properties of these polymers werefinely tuned to optimize their photovoltaic effect.The substitution of alkoxy side chains to the less electron-donating alkyl chains or introduction of electron-withdrawingfluorine into the polymer backbone reduced the HOMO energy levels of polymers.The structural modifications optimized polymers’spectral coverage of absorption and their hole mobility,as well as miscibility with fulleride,and enhanced polymer solar cell performances.The open circuit voltage,V oc,for polymer solar cells was increased by adjusting polymer energy levels.It was found thatfilms withfinely distributed polymer/fulleride interpenetrat-ing network exhibited improved solar cell conversion efficiency.Efficiency over6%has been achieved in simple solar cells based onfluorinated PTB4/PC61BMfilms prepared from mixed solvents.The results proved that polymer solar cells have a bright future.IntroductionSemiconducting polymers have shown physical properties similar to those of typical inorganic semiconductors,although the underlying mechanisms are usually different from each other.1Photovoltaic effect is one of these properties that stimulate people’s enthusiasm because solar energy conversion into electricity is the cleanest way to harvest this vast renewable energy source.So far,the most efficient architecture to build polymeric photovoltaic solar cells is the bulk heterojunction (BHJ)structure prepared by mixing electron-rich polymers and electron-deficient fullerides.2This approach can be easily implemented and allows a quick survey of the best composition of polymeric activefilms.Detailed studies by many groups in the past years have identified poly(3-hexylthiophene)(P3HT) as the most attractive donor material.Power conversion ef-ficiency(PCE)of about5%has been achieved in solar cells based on P3HT/[6,6]-phenyl-C61-butyric acid methyl ester (PC61BM)derivatives.3Although it is significant progress in a relatively short period of research time,it is still far away from commercial viability.4After an exhaustive research effort,it becomes increasingly apparent that the PCE of solar cells based on P3HT/PC61BM is approaching its limit.New materials exhibiting better performance are needed in order to achieve the desired performance in these types of solar cells for practical application.5The performance of polymer solar cells is characterized by three parameters:open-circuit voltage(V oc),short-circuit current density(J sc),andfill-factor(FF),all of which are related to the PCE by the following equation:PCE)(V oc×J sc×FF)/ (I p×M),where I p is the power density of the incident lightirradiation and M is spectral mismatch factor.It has been realized that the ideal polymer in BHJ structure should exhibit a broad absorption with high coefficient in the solar spectrum,high hole mobility,suitable energy level matching to fulleride,and appropriate compatibility with fulleride to form bicontinuous interpenetrating network on a nanoscale.6It is difficult to design a polymer to fulfill all these requirements.Current polymer solar cells often suffer from small values in some or all of these parameters due to a variety of issues related to the nature of materials and device engineering.So far,besides the P3HT system,there are very few polymer solar cell systems reported which exceed5%in power conversion efficiency.7†The University of Chicago.‡Solarmer Energy Inc.(1)Skotheim,T.A.;Reynolds J.Handbook of conducting polymers;CRC:London,2007.(2)(a)Yu,G.;Gao,J.;Hummelen,J.C.;Wudl,F.;Heeger,A.J.Science1995,270,1789.(b)Gnes,S.;Neugebauer,H.;Sariciftci,N.S.Chem.Re V.2007,107,1324.(3)(a)Li,G.;Shrotriya,V.;Huang,J.S.;Yao,Y.;Moriarty,T.;Emery,K.;Yang,Y.Nat.Mater.2005,4,864.(b)Ma,W.L.;Yang,C.Y.;Gong,X.;Lee,K.H.;Heeger,A.J.Ad V.Funct.Mater.2005,15, 1617.(c)Li,G.;Shrotriya,V.;Yao,Y.;Yang,Y.J.Appl.Phys.2005, 98,043704.(4)Scharber,M.;Muhlbacher,D.;Koppe,M.;Denk,P.;Waldauf,C.;Heeger,A.J.;Brabec,C.Ad V.Mater.2006,18,789.(5)Thompson,B.C.;Frechet,J.M.J.Angew.Chem.,Int.Ed.2008,47,58.(6)Roncali,J.Macromol.Rapid Commun.2007,28,1761.(7)(a)Muhlbacher,D.;Scharber,M.;Morana,M.;Zhu,Z.G.;Waller,D.;Gaudiana,R.;Brabec,C.Ad V.Mater.2006,18,2884.(b)Peet,J.;Kim,J.Y.;Coates,N.E.;Ma,W.L.;Moses,D.;Heeger,A.J.;Bazan,G.C.Nat.Mater.2007,6,497.(c)Wang,E.G;Wang,L;Lan,L.F.;Luo,C.;Zhuang,W.L.;Peng,J.B.;Cao,Y.Appl.Phys.Lett.2008,92,33307.(d)Hou,J.H.;Chen,H.Y.;Zhang,S.Q.;Li,G.;Yang,Y.J.Am.Chem.Soc.2008,130,16144.Published on Web05/19/200910.1021/ja901545q CCC:$40.75 2009American Chemical Society 77929J.AM.CHEM.SOC.2009,131,7792–7799Recently,we have developed a new polymer,namely PTB1,based on alternating thieno[3,4-b ]thiophene and benzodithiophene units (Figure 1).Simple single-layer polymer solar cells exhibited solar conversion efficiency of 4.8%based on PTB1/PC 61BM BHJ structure and 5.6%on PTB1/PC 71BM structure.8The J sc and FF obtained from such polymer solar cells are among the highest values reported for solar cell system based on low-band-gap polymers.However,the V oc of the polymer solar cells is relatively small,just about 0.56-0.58V.In this paper,we describe our results in the development of new polymers which exhibit higher solar cell conversion efficiencies.These polymers were developed via synthetic fine-tuning of their structural and electronic properties.Experimental SectionMaterials.Otherwise stated,all of the chemicals are purchased from Aldrich and used as received.The 4,6-dihydrothieno[3,4-b ]thiophene-2-carboxylic acid (1),94,6-dibromothieno[3,4-b ]thiophene-2-carboxylic esters,81,5-bis(trimethyltin)-4,8-dioctylbenzo[1,2-b :4,5-b ’]dithiophene,7and benzo[1,2-b:4,5-b ′b ′]dithiophene-4,8-dione 10were synthesized according to the procedures reported in the literature.Other monomers were synthesized according to Scheme 1.3-Fluoro-4,6-dihydrothieno[3,4-b ]thiophene-2-carboxylic acid (2).The 4,6-dihydrothieno[3,4-b ]thiophene-2-carboxylic acid (1.46g,7.85mmol)was dissolved in 60mL of THF and cooled in an acetone/dry ice bath under nitrogen protection.Butyllithium solution ((6.9mL,17.3mmol)was added dropwise with stirring.The(8)Liang,Y.Y.;Wu,Y.;Feng,D.Q.;Tsai,S.T.;Son,H.J.;Li,G.;Yu,L.P.J.Am.Chem.Soc.2009,131,56.(9)Yao,Y.;Liang,Y.Y.;Shrotriya,V.;Xiao,S.Q.;Yu,L.P.;Yang,Y.Ad V .Mater.2007,19,3979.(10)Beimling,P;Ko mehl,G.Chem.Ber.1986,119,3198.Figure 1.Synthetic routes for polymers PTB1-PTB6and structure of PC 61BM.Scheme 1.Synthesis Routes forMonomersJ.AM.CHEM.SOC.9VOL.131,NO.22,20097793Highly Efficient Solar Cell Polymers A R T I C L E Sresulting mixture was kept in a dry ice bath for1h.Then N-fluorobenzenesulfonimide(3.22g,10.2mmol)in20mL of THF was added dropwise,and the solution was stirred at RT overnight. The reaction was quenched with50mL of water,and the organic solvent was removed by evaporation at reduced pressure.The solid residue was collected byfiltration and purified by chromatography on silica with ethyl acetate.A mixture of 1.30g containing fluorinated product and unfluorinated reactant with a4:1ratio was obtained.The calculated mass offluorinated product is1.04g,65%. 1HNMR(D6-DMSO):δ4.01-4.05(2H,t,J)3Hz),4.20-4.24 (2H,t,J)3Hz).MS(EI):Calcd,204.0;found(M-1)-,202.9. Octyl3-Fluoro-4,6-dihydrothieno[3,4-b]thiophene-2-carboxyl-ate(3).The raw materials of2(1.30g,6.3mmol),DCC(1.58g), and DMAP(260mg)were added to a50mL round-bottomflask with CH2Cl2(15mL).1-Octanol(8.22g,63mmol)was added to theflask and then stirred for20h under N2protection.The reaction mixture was poured to100mL of water and extracted with CH2Cl2. The organic phase was dried by sodium sulfate,and the solvent was removed.Column chromatography on silica gel using hexane/ CH2Cl2)1/1yielded the title compound as an oil(1.42g,71%). 1HNMR(CDCl3):δ0.85-0.91(3H,t,J)6Hz),1.22-1.45(10H, m),1.68-1.76(2H,m),3.99-4.02(2H,t,J)3Hz),4.15-4.18 (2H,t,J)3Hz),4.24-4.29(2H,t,J)6Hz).MS(EI):Calcd, 316.1;found(M+1)+,317.0.Octyl3-Fluorothieno[3,4-b]thiophene-2-carboxylate(5).A solution of compound3(1.42g,4.5mmol))in100mL of ethyl acetate was stirred and cooled in a dry ice bath.MCPBA(0.78g, 4.5mmol)in30mL of ethyl acetate was added dropwise to the reaction solution.The resulting mixture was stirred overnight.The solvent was removed by evaporation,and the residue contained a crude product of4and3-chlorobenzoic acid.The residue was refluxed in acetic anhydride for2.5h.The mixture was cooled, and the solvent was removed by evaporation.The residue was purified byflash chromatography on silica gel with hexanes/ dichloromethane(2:1)to give compound5(0.95g,67%).1HNMR (CDCl3):0.85-0.92(3H,t,J)7Hz),1.23-1.48(10H,m), 1.70-1.80(2H,m),4.30-4.35(2H,t,J)7Hz),7.27-7.29(1H, d,J)3Hz),7.65-7.67(1H,d,J)3Hz).Octyl4,6-Dibromo-3-fluorothieno[3,4-b]thiophene-2-carboxyl-ate(6).To a solution of compound5(0.95g,3.0mmol)in10mL of DMF was added dropwise a solution of NBS(1.34g,7.56mmol) in10mL of DMF under nitrogen protection in the dark.The reaction mixture was stirred at RT for24h.Then it was poured into saturated sodium sulfite solution in an ice-water bath and extracted with dichloromethane.The organic phase was collected and dried by sodium sulfate.Removal of the solvent and column purification on silica get using dichloromethane/hexane(1/4)yielded the target product(0.98g,69%)as a light yellow solid.1HNMR (CDCl3):0.85-0.92(3H,t,J)7Hz),1.23-1.48(10H,m), 1.70-1.80(2H,m),4.30-4.35(2H,t,J)7Hz).MS(EI):Calcd, 469.9;found(M+1)+,471.9.4,8-Bis(2-ethylhexyloxy)benzo[1,2-b:4,5-b′]dithiophene(8).The benzo[1,2-b:4,5-b′]dithiophene-4,8-dione(1.0g,4.5mmol)was mixed with zinc dust(0.65g,10mmol)in aflask.Ethanol(4mL) and NaOH solution(15mL,20%)were added,and the mixture was refluxed for1h.2-Ethylhexyl p-toluenesulfonate(4.3mL)was added in portions with stirring until the color changed to red.The resulting precipitate wasfiltered;thefiltrate was diluted with100 mL of water and extracted with chloroform(100mL).The organic extraction was dried with anhydrous sodium sulfate and evaporated in vacuo.Column chromatography on silica gel using dichlo-romethane and hexanes mixed eluents yielded the compound8as a light yellow oil(0.80g,40%).1HNMR(CDCl3):δ0.72-0.90 (12H,m),1.10-1.38(16H,m),1.50-1.62(2H,m),3.84-3.97(4H, m),7.32-7.36(2H,d,J)5Hz),7.46-7.50(2H,d,J)5Hz). MS(EI):Calcd,446.2;found(M+1)+,447.2.2,6-Bis(trimethyltin)-4,8-bis(2-ethylhexyloxy)benzo[1,2-b:4,5-b′]dithiophene(9).Compound8(0.62g,1.4mmol)was dissolved in20 mL of anhydrous THF and cooled in an acetone/dry ice bath under nitrogen protection.Butyllithium solution(1.4mL,3.5mmol)was added dropwise with stirring,after the addition the mixture was kept in a dry ice bath for30min and at RT for30min.The mixture was cooled in the dry ice bath and trimethyltin chloride solution(4.2mL, 4.2mmol,1M in hexane)was added,and the mixture was stirred at RT overnight.The mixture was quenched with50mL of water and extracted with hexanes.The organic extraction was dried with anhydrous sodium sulfate and evaporated in vacuo.Recrystallization of the residue from isopropanol yield the compound9as colorless needles(0.8670g,80%).1HNMR(CDCl3):δ0.43(18H,s),0.90-1.10 (12H,m),1.33-1.85(18H,m),1.54-1.58(4H,m),4.15-4.23(4H, d,J)5Hz),7.51(2H,s).4,8-Dioctynbenzo[1,2-b:4,5-b′]dithiophene(10).Isopropylmag-nesium chloride(2M solution,12mL,24mmol)was added dropwise to a solution of1-octyne(2.97g,27mmol)at RT.The reaction mixture was heated up to60°C and stirred for100min. It was cooled to RT,and benzo[1,2-b:4,5-b′]dithiophene-4,8-dione (1g,4.53mmol)was added.The reaction mixture was heated up to60°C and kept for60min.It was then cooled to RT,and7g of SnCl2in HCl solution(16mL10%)was added dropwise to the reaction mixture.The reaction mixture was heated at65°C for60 min,then cooled down to room temperature,and poured into100 mL of water.It was extracted with50mL of hexanes twice.The organic phase was combined and dried with anhydrous Na2SO4, and the organic solvent was removed by vacuum evaporation.The residue was purified by column chromatography on silica with hexanes/dichloromethane(3/1,volume ratio),yielding compound 10(1.66g,90%).1HNMR(CDCl3):δ0.88-0.96(6H,t,J)5 Hz),1.32-1.42(8H,m),1.53-1.63(4H,m),1.68-1.77(4H,m), 2.61-2.66(4H,t,J)7Hz),7.48-7.51(2H,d,J)6Hz), 7.56-7.58(2H,d,J)6Hz).MS(EI):Calcd,406.2;found(M+ 1)+,407.1.4,8-Dioctylbenzo[1,2-b:4,5-b′]dithiophene(11).To the solution of compound2(1.66g,4.07mmol)in75mL of THF was added Pd/C(0.45g,10%),and the reaction mixture was kept in a hydrogen atmosphere for18h at RT.The mixture wasfiltered with Celite, and the solvent was removed by vacuum evaporation.The residue was purified by column chromatography on silica with hexane as the eluent,yielding compound11(0.95g,56%)as white solids. 1HNMR(CDCl3):δ0.85-0.92(6H,t,J)7Hz),1.20-1.40(16H, m),1.40-1.50(4H,m),1.76-1.84(4H,m),3.13-3.21(4H,t,J)8Hz),7.43-7.45(2H,d,J)6Hz),7.46-7.48(2H,d,J)6 Hz).MS(EI):Calcd,414.2;found(M+1)+,415.2.2,6-Bis(trimethyltin)-4,8-dioctylbenzo[1,2-b:4,5-b′]dithiophene (12).Compound3(0.95g,2.3mmol)was dissolved in20mL of anhydrous THF and cooled in an acetone/dry ice bath under nitrogen protection.Butyllithium solution(2.3mL,5.7mmol)was added dropwise with stirring.The mixture was kept in a dry ice bath for 30min and then at RT for30min.The mixture was cooled in the dry ice bath,and6.5mL(6.5mmol)of trimethyltin chloride solution (1M in hexane)was added and stirred at RT for overnight.The mixture was quenched with50mL of water and extracted with hexanes.The organic extraction was dried with anhydrous sodium sulfate and evaporated in vacuo.Recrystallization of the residue from isopropanol yields the titled compound12(0.50g,88%). 1HNMR(CDCl3):δ0.45(18H,s),0.87-0.91(6H,t,J)7Hz), 1.25-1.42(16H,m),1.42-1.51(4H,m),1.76-1.85(4H,m), 3.17-3.23(4H,t,J)8Hz),7.49(2H,s).Synthesis of Polymers.PTB4.Octyl-6-dibromo-3-fluo-rothieno[3,4-b]thiophene-2-carboxylate(6)(236mg,0.50mmol) was weighted into a25mL round-bottomflask.2,6-Bis(trim-ethyltin)-4,8-bis(2-ethylhexyloxy)benzo[1,2-b:4,5-b′]dithiophe-ne(9)(386mg,0.50mmol)and Pd(PPh3)4(25mg)were added. Theflask was subjected to three successive cycles of vacuum followed by refilling with argon.Then,anhydrous DMF(2mL) and anhydrous toluene(8mL)were added via a syringe.The polymerization was carried out at120°C for12h under nitrogen protection.The raw product was precipitated into methanol and collected byfiltration.The precipitate was dissolved in chloro-7794J.AM.CHEM.SOC.9VOL.131,NO.22,2009A R T I C L E S Liang et al.form and filtered with Celite to remove the metal catalyst.The final polymers were obtained by precipitating in hexanes and drying in vacuum for 12h,yielding PTB4(309mg,82%).1HNMR (CDCl 2CDCl 2):δ0.80-2.40(45H,br),3.90-4.70(6H,br),7.00-7.90(2H,br).GPC:M w (19.3×103g/mol),PDI (1.32).PTB2,PTB3,PTB5,and PTB6are synthesized according to the same procedure as PTB4with respective monomers.The 1HNMR and gel permeation chromatography (GPC)data of the polymers are listed below.PTB2.1HNMR (CDCl 2CDCl 2):δ0.70-2.42(45H,br),3.90-4.80(6H,br),6.70-8.00(3H,br).GPC:M w (23.2×103g/mol),PDI (1.38).PTB3.1HNMR (CDCl 2CDCl 2):δ0.70-2.35(45H,br),2.90-3.40(4H,br),4.20-4.70(2H,br),6.70-8.20(3H,br).GPC:M w (23.7×103g/mol),PDI (1.49).PTB5.1HNMR (CDCl 2CDCl 2):δ0.90-2.40(45H,br),3.90-4.70(6H,br),7.00-7.60(2H,br),7.60-8.10(1H,br).GPC:M w (22.7×103g/mol),PDI (1.41).PTB6.1HNMR (CDCl 2CDCl 2):δ0.70-2.42(53H,br),3.90-4.80(6H,br),6.70-8.00(3H,br).GPC:M w (25.0×103g/mol),PDI (1.50).Characterization.1H NMR spectra were recorded at 400or 500MHz on Bruker DRX-400or DRX-500spectrometers,respectively.Molecular weights and distributions of polymers were determined by using GPC with a Waters Associates liquid chromatograph equipped with a Waters 510HPLC pump,a Waters 410differential refractometer,and a Waters 486tunable absorbance detector.THF was used as the eluent and polystyrene as the standard.The optical absorption spectra were taken by a Hewlett-Packard 8453UV -vis spectrometer.Cyclic voltammetry (CV)was used to study the electrochemical properties of the polymers.For calibration,the redox potential of ferrocene/ferrocenium (Fc/Fc +)was measured under the same conditions,and it is located at 0.09V to the Ag/Ag +electrode.It is assumed that the redox potential of Fc/Fc +has an absolute energy level of -4.80eV to vacuum.11The energy levels of the highest (HOMO)and lowest unoccupied molecular orbital (LUMO)were then calculated according to the following equationswhere φox is the onset oxidation potential vs Ag/Ag +and φred is the onset reduction potential vs Ag/Ag +.Hole mobility was measured according to a similar method described in the literature,12using a diode configuration of ITO/poly(ethylenedioxythiophene)doped with poly(styrenesulfonate)(PEDOT:PSS)/polymer/Al by taking current -voltage current in the range of 0-6V and fitting the results to a space charge limited form,where the SCLC is described bywhere ε0is the permittivity of free space,εr is the dielectric constant of the polymer,µis the hole mobility,V is the voltage drop across the device,L is the polymer thickness,and V )V appl -V r -V bi ,where V appl is the applied voltage to the device,V r is the voltage drop due to contact resistance and series resistance across the electrodes,and V bi is the built-in voltage due to the difference in work function of the two electrodes.The resistance of the device was measured using a blank configuration ITO/PEDOT:PSS/Al andwas found to be about 10-20Ω.The V bi was deduced from the best fit of the J 0.5versus V appl plot at voltages above 2.5V and is found to be about 1.5V.The dielectric constant,εr ,is assumed to be 3in our analysis,which is a typical value for conjugated polymers.The thickness of the polymer films is measured by using AFM.Device Fabrication.The polymers PTB1-PTB6were codis-solved with PC 61BM in 1,2-dichlorobenzene (DCB)in the weight ratio of 1:1,respectively.PTB1,PTB2,and PTB6concentrations are 10mg/mL,while PTB3,PTB4,and PTB5concentrations are 13mg/mL.For the last three polymer solutions,we also studied mixed solvent effect with about 3%(volume)1,8-diiodooctance,also used to further improve the final device performances.ITO-coated glass substrates (15Ω/0)were cleaned stepwise in detergent,water,acetone,and isopropyl alcohol under ultrasoni-cation for 15min each and subsequently dried in an oven for 5h.A thin layer (∼30nm)of PEDOT:PSS (Baytron P VP A14083)was spin-coated onto ITO surface which was pretreated by ultraviolet ozone for 15min.Low-conductivity PEDOT:PSS was chosen to minimize measurement error from device area due to lateral conductivity of PEDOT:PSS.After being baked at 120°C for ∼20min,the substrates were transferred into a nitrogen-filled glovebox (<0.1ppm O 2and H 2O).A polymer/PCBM composites layer (ca.100nm thick)was then spin-cast from the blend solutions at 1000rpm on the ITO/PEDOT:PSS substrate without further special treatments.Then the film was transferred into a thermal evaporator which is located in the same glovebox.A Ca layer (25nm)and an Al layer (80nm)were deposited in sequence under the vacuum of 2×10-6torr.The effective area of film was measured to be 0.095cm 2.Current -Voltage Measurement.The fabricated device was encapsulated in a nitrogen-filled glovebox by UV epoxy (bought fromEpoxyTechnology)andcoverglass.Thecurrentdensity -voltage (J -V)curves were measured using a Keithley 2400source-measure unit.The photocurrent was measured under AM 1.5G illumination at 100mW/cm 2under the Newport Thermal Oriel 911921000W solar simulator (4in.×4in.beam size).The light intensity was determined by a monosilicon detector (with KG-5visible color filter)calibrated by National Renewable Energy Laboratory (NREL)to minimize spectral mismatch.External quantum efficiencies (EQEs)were measured at UCLA by using a lock-in amplifier (SR830,Stanford Research Systems)with current preamplifier (SR570,Stanford Research Systems)under short-circuit conditions.The devices were illuminated by mono-chromatic light from a xenon lamp passing through a monochro-mator (SpectraPro-2150i,Acton Research Corporation)with a typical intensity of 10µW.Prior to incident on the device,the monochromic incident beam is chopped with a mechanical chopper connected to the lock-in amplifier and then focused on the testing pixel of the device.The photocurrent signal is then amplified by SR570and detected with SR830.A calibrated mono silicon diode with known spectral response is used as a reference.Conductive Atomic Force Microscopy (CAFM)Measure-ment.All CAFM measurements were done under ambient condi-tions using a commercial scanning probe microscope (Asylum Research,MFP-3D).Platinum-coated,contact-mode AFM canti-levers with spring constant of 0.2N/m and tip radius of ca.25nm (Budget Sensors)were used to map out the hole-current of films in the dark using contact mode.The deflection set point is 0.3V and bias voltage is -2V for all the sample measurements,and the conditions used to prepare the films are the same to make the solar cell device.Results and DiscussionSynthesis.The encouraging results of polymer PTB1leadus to select the polymer backbone as the structural platform to investigate structure/property relationship and to search for new polymers with improved solar cell performance.8The PTB1(11)Pommerehne,J.;Vestweber,H.;Guss,W.;Mahrt,R.F.;Bassler,H.;Porsch,M.;Daub,J.Ad V .Mater.1995,7,551.(12)(a)Malliaras,G.G.;Salem,J.R.;Brock,P.J.;Scott,C.Phys.Re V .B 1998,58,13411.(b)Goh,C.;Kline,R.J.;McGehee,M.D.;Kadnikova,E.N.;Frechet,J.M.J.Appl.Phys.Lett.2005,86,122110.E HOMO )-(φox +4.71)(eV)E LUMO )-(φred +4.71)(eV)J )9ε0εr µV 2/8L 3J.AM.CHEM.SOC.9VOL.131,NO.22,20097795Highly Efficient Solar Cell Polymers A R T I C L E Swas designed based on the concept that the thienothiophene moiety can support the quinoidal structure and lead to narrow polymer band gap,which is crucial to efficiently harvesting solar energy.Since the thienothiophene moiety is very electron-rich,an electron-withdrawing ester group is introduced to stabilize the resulting polymers.Indeed,the results confirmed our design idea.9However,we also noticed that the long n -dodecyl side chain is grafted on the thieno[3,4-b ]thiophene ester in PTB1,which may decrease the miscibility of the conjugated polymer with PC 61BM and affect the formation of effective interpenetrat-ing network.13The small V oc value indicates the need to adjust the HOMO -LUMO energy level relative to fullerides.4With these considerations in mind,we have synthesized six related polymers as shown in Figure 1.The polymerization was carried out via the Stille polycon-densation reaction.14The corresponding monomers were syn-thesized according to Scheme 1.To shorten the dodecyl ester chain in PTB1,an n -octyl side chain substituted polymer was synthesized.However,this polymer exhibits poor solubility,which limits its processing ability,and was not studied further.Soluble PTB2was synthesized with shortened and branched side chains.For comparison,a bulkier branched side chain,2-butyloctyl,was used in PTB6.The branched side chain can also be grafted to the benzodithiophene,which leads to PTB5with two 2-ethylhexyloxy side chains attached to the ben-zodithiophene ring.The alkoxy groups grafted on ben-zodithiophene ring are strong electron-donating groups that can raise the HOMO energy level of the polymer.15This will lead to the reduction in V oc ,detrimental to the performance of polymer solar cells.4In order to further adjust the polymer’s electronic properties,PTB3with less electron-donating alkyl chains in benzodithiophene was synthesized.To further lower the HOMO level,a second electron-withdrawing group can be introduced to the 3position of the thieno[3,4-b ]thiophene ring.Fluorine is a good candidate to functionalize the 3position because fluorine has a high electronegativity.The size of the fluorine atom is small,which will introduce only small steric hindrance for the configurationand packing of the polymer.16The fluorinated thieno[3,4-b ]thiophene was synthesized via a modified route previously reported for ester-substituted thieno[3,4-b]thiophene (Scheme 1).9The fluorine was introduced to the fused ring unit from 4,6-dihydrothieno[3,4-b ]thiophene-2-carboxylic acid after depro-tonation by using BuLi and reacting with PhSO 2NF.The fluorinated acid was first converted to ester and then dibromo-substituted thieno[3,4-b ]thiophene.Initially,we attempted to introduce fluorine atom to PTB1(R 1)n -dodecyl,R 2)n -octyloxy).The obtained polymer exhibited poor solubility and only dissolves in dichlorobenzene over 100°C,which makes it difficult to prepare uniform films.To increase the solubility,benzodithiophene substituted with branch side chains was used,and the fluorinated polymer,PTB4,was obtained.The structures of polymers were characterized with 1HNMR spectroscopy,all consistent with the proposed ones.Gel permeation chromatography (GPC)studies showed that these polymers have similar weight-averaged molecular weights between 19.3and 25.0kg/mol with a relatively narrow polydispersity index (PDI)between 1.25and 1.50.The results indicate that the changes in monomer structures did not lead to significant changes in polymerization reaction.These polymers have good solubility in chlorinated solvents,such as chloroform and chlorobenzene.Thermogravimetric analyses (TGA)indicate that the polymers are stable up to about 200°C.Electrochemical and Optical Properties.The HOMO and LUMO energy levels of the polymers were determined by cyclic voltammetry (CV),and the results are summarized in Figure 2a.The HOMO energy levels of the polymers are very close except for PTB3and PTB4.From the comparison of PTB2and PTB3,it was noticed that the substitution of octyloxy side chain to octyl side chain lowered the HOMO energy level of the polymer from -4.94to paring PTB4and PTB5,polymers with same side chain patterns,it is clear that the introduction of the electron-withdrawing fluorine in the polymer backbone significantly lowered the HOMO level.The film absorption spectra of the polymers are showed in Figure 2b,and characteristics of the polymer absorption are summarized in Table 1.All these polymers show very similar absorption spectra;the changes of the absorption peak and onset point among the polymers are within 25nm.(13)Thompson,B.C.;Kim,B.J.;Kavulak,D.F.;Sivula,K.;Mauldin,C.;Frechet,J.M.J.Macromolecules 2007,40,7425.(14)Bao,Z.N.;Chan,W.K.;Yu,L.P.J.Am.Chem.Soc.1995,117,12426.(15)Daoust,G.;Leclerc,M.Macromolecules 1991,24,455.(16)Babudri,F.;Farinola,G.M.;Naso,F.;Ragni,mun.2007,1003.Figure 2.(a)HOMO and LUMO energy levels of the polymers.Energy levels of PC 61BM are listed for comparison.(b)UV -vis absorption spectra of thepolymer films.7796J.AM.CHEM.SOC.9VOL.131,NO.22,2009A R T I C L E S Liang et al.Hole Mobility.The hole mobility of the polymers is measured according to method based on the space charge limited current (SCLC)model,12and the results are plotted in Figure3.The hole mobilities of4.7×10-4,4.0×10-4,7.1×10-4,7.7×10-4,4.0×10-4,and2.6×10-4cm2/V·s are found for PTB1, PTB2,PTB3,PTB4,PTB5,and PTB6,respectively.A small decrease of the polymer hole mobility is observed after the introduction of bulky branched side chains to the polymer backbones.It is expected that the bulky side chains may increase the steric hindrance for intermolecular packing,so the hole mobility decreases.This explains that the largest decrease of the hole mobility happens to PTB6,which has the bulkiest 2-butyloctyl side chain on the ester group.It is interesting to note that the alkyl-grafted PTB3has higher mobility than the alkoxy-grafted PTB2,though they both have similar side chain patterns.PTB4has the largest hole mobility of7.7×10-4cm2/ V·s among these polymers.It has been reported that there is a strongπ-stacking interaction between the electron-deficientfluorinated aromatic rings and the electron-rich nonfluorinated ones in thefluorine-substituted aromatic moieties.17The increase of mobility influorinated PTB4is probably due to the increase in intermolecular packing between thefluorinated backbone. Detailed studies by using grazing angle X-ray diffraction are in progress to elucidate polymer structures and will be presented in a future publication.Photovoltaic Properties.Photovoltaic properties of the poly-mers were investigated in solar cell structures of ITO/PEDOT: PSS/polymer:PC61BM(1:1,wt ratio)/Ca/Al.The polymer active layers were spin-coated from a dichlorobenzene solution.Figure 4shows the photo J-V curves of the polymer solar cells under AM1.5condition at100mW/cm2.Representative characteristics of the solar cells are summarized in Table2.Generally,the bulky side chain grafted polymers show larger V oc than PTB1, as they have lower HOMO energy levels.The alkyl-substituted PTB3has an enhanced V oc compared to PTB2,which is expected from the HOMO energy level difference.Thefluori-nated polymer PTB4devices showed a larger V oc than PTB5. However,except for PTB2and PTB3,the other polymer solar cells suffer obvious decrease in short-circuit current(J sc)and fill factor(FF)compared to the PTB1solar cell.Further studies by using transmission electron microscopy(TEM)indicated that the poor solar cell performances in PBT3-PTB6are related to the nonoptimized morphology,which has a large effect on the BHJ polymer solar cell performance(Figure5).18The TEM images of PTB2/PC61BM blendfilm showfiner features comparable to the PTB1one,which may be due to the increase in the miscibility of the polymer with PC61BM after shortening the dodecyl side chain into the2-ethylhexyl side chain.As a result,J sc and FF in the PTB2solar cell are slightly larger than the PTB1one.However,large domains are observed in their PC61BM blendfilms of PTB5or PTB6.The bulky side chains reduce the miscibility of polymer with PC61BM,leading to better phase separation between polymer chains and PC61BM mol-ecules.As a result,the interfacial areas of charge separation in PTB5or PTB6are reduced,and the polymer solar cell performances are diminished.It is not coincident that the PTB6 has the largest feature sizes(150-200nm)in the TEM image and its solar cell performance is the worst.With the same side chain patterns as PTB5,thefluorinated PTB4also suffers the nonoptimized morphology,as shown by the large features(over 100nm)in the TEM image of PTB4/PC61BM blendfilm. Although PTB4shows the lowest HOMO energy level and the largest hole mobility,its photovoltaic performance in simple polymer/PC61BM solar cells is modest(3.10%).Comparing (17)Feast,W.;Lovenich,P.W.;puschmann,H.;Taliani, C.Chem.Commun.2001,505.(18)(a)Yang,X.N.;Loos,J.Macromolecules2007,40,1353.(b)Li,G;Yao,Y.;Yang,H.C.;Shrotriya,V.;Yang,G.W.;Yang,Y.Ad V.Funct.Mater.2007,17,1636.Table1.Molecular Weight and Absorption Properties of the Polymerspolymers M w(kg/mol)PDIµpeak(nm)µonset(nm)E g opt(eV) PTB122.9 1.25687,638786 1.58 PTB223.2 1.38683,630780 1.59 PTB323.7 1.49682,628777 1.60 PTB419.3 1.32682,627762 1.63 PTB522.7 1.41677,623764 1.62PTB625.0 1.50675,6307681.61Figure3.J0.5vs V plots for the polymerfilms.The solid lines arefits of the data points.The thickness of thefilms is indicated in theplots.Figure4.Current-voltage characteristics of polymer/PC61BM solar cells under AM1.5condition(100mW/cm2).Table2.Characteristic Properties of Polymer Solar Cells polymers V oc(V)J sc(mA/cm2)FF(%)PCE(%)PTB10.5812.565.4 4.76PTB20.6012.866.3 5.10PTB30.7413.156.8 5.53PTB40.769.2044.5 3.10PTB50.6810.343.1 3.02PTB60.627.7447.0 2.26PTB3a0.7213.958.5 5.85PTB4a0.7413.061.4 5.90(6.10b) PTB5a0.6610.758.0 4.10a Devices prepared from mixed solvents dichlorobenzene/diiodooctance (97/3,v/v).b Value after spectral correction.J.AM.CHEM.SOC.9VOL.131,NO.22,20097797Highly Efficient Solar Cell Polymers A R T I C L E S。
正十八烷基化聚（苯乙烯-co-马来酰亚胺）梳状聚合物制备及表征
梳状聚合物因受到聚合物主链和侧链的影响[1-3]，其热性能、结晶行为不同于传统线性分子[4-5]。
通过控制聚合物主链的刚性、侧链接枝度和长度以及极性态，可实现疏水或亲水转变、刺激响应性、多级组装等功能特征[1，6]。
梳状聚合物的主链类型、侧链长度和主侧链键接方式对其链堆积方式和侧链结晶有很大的影响。
研究者们已经制备了刚性、半刚性和柔性主链的梳状聚合正十八烷基化聚（苯乙烯-co-马来酰亚胺）梳状聚合物制备及表征石海峰，王延鹏（天津工业大学材料科学与工程学院，天津300387）摘要：为探究由聚（苯乙烯-co-马来酸酐）（SMA ）和正十八烷基胺（C 18NH 2）所构成的梳状聚合物主侧链间不同键接方式对其结构和性能的影响，以SMA 为主链，以C 18NH 2为侧链，通过酰胺反应（开环反应）和酰亚胺反应（闭环反应），制备了十八烷基化聚（苯乙烯-co-马来酸酐）（SMAC18N ）和聚（苯乙烯-co-马来酰亚胺）（SMIC18N ）梳状聚合物；通过傅里叶红外光谱（FTIR ）、X 射线衍射（XRD ）、差示扫描量热分析（DSC ）、热重分析（TGA ）等方法对比研究了SMAC18N 和SMIC18N 梳状聚合物的热行为和结晶行为。
结果表明：SMAC18N 出现明显侧链结晶行为，而SMIC18N 未出现热行为和结晶现象；SMIC18N 的热失重温度为370益，而SMAC18N 为202益；SMIC18N 表现出明显疏水能力，疏水角为101.9毅。
这说明主侧链键接方式对侧链烷基有序堆积结构和热性能有显著影响。
关键词：聚（苯乙烯-co-马来酸酐）（SMA ）；正十八烷基胺；梳状聚合物；热性能；结晶行为中图分类号：TB325.2文献标志码：A 文章编号：员远苑员原园圆源载（圆园22）园1原园园34原05Preparation and characterization of octadecylated poly （styrene-co-maleimide ）comb-like polymerSHI Hai-feng ，WANG Yan-peng（School of Material Science and Engineering ，Tiangong University ，Tianjin 300387，China ）Abstract ：In order to explore the influence of different bonding methods between the main side chains of comb -likepolymers composed of poly渊styrene -co -maleic anhydride冤渊SMA冤and n -octadecylamine渊C 18NH 2冤on its structure and performance袁octadecylated poly渊styrene -co -maleic anhydride冤渊SMAC18N冤and poly渊styrene -co -maleimi -de冤渊SMIC18N冤comb -like polymers were prepared via amide reaction渊ring opening reaction冤and imide reaction 渊ring -closing reaction冤with SMA as the main chain and C 18NH 2as the side chain.The thermal and crystallization behavior of SMAC18N and SMIC18N comb -like polymers were compared and studied by Fourier temperature infrared spectroscopy渊FTIR冤袁X -ray diffraction渊XRD冤袁differential scanning calorimetry渊DSC冤袁thermogravi -metric analysis 渊TGA冤and other methods.The results showed that SMAC18N had obvious side chain crystalliza -tion behavior袁while SMIC18N had no thermal behavior and crystallization.The thermal weight loss temperature of SMIC18N was 370益袁while SMAC18N was 202益.SMIC18N showed obvious hydrophobic ability袁with a hydrophobic angle of 101.9毅.This showed that the main side chain bonding mode had a significant impact on theordered stacking structure and thermal properties of side chain alkyl groups.Key words ：SMA曰octadecylamine曰comb -like polymer曰thermal properties曰crystallization behaviorDOI ：10.3969/j.issn.1671-024x.2022.01.006第41卷第1期圆园22年2月Vol.41No.1February 2022天津工业大学学报允韵哉砸晕粤蕴韵云栽陨粤晕GONG 哉晕陨灾耘砸杂陨栽再收稿日期：2021-02-28基金项目：国家自然科学基金资助项目（21875163）通信作者：石海峰（1975—），男，博士，教授，博士生导师，主要研究方向为高分子结构化材料。
含席夫碱结构碳点缓蚀剂的简易可扩展制备及性能研究
第52卷第10期表面技术2023年10月SURFACE TECHNOLOGY·229·含席夫碱结构碳点缓蚀剂的简易可扩展制备及性能研究李雪琪a,b,c，何闯a,b,c，于坷坷a,b,c，罗启灵a,b,c，龙武剑a,b,c*（深圳大学a.滨海城市韧性基础设施教育部重点实验室b.广东省滨海土木工程耐久性重点实验室 c.土木与交通工程学院，广东 深圳 518060）摘要：目的克服目前制备碳点（Carbon dots, CDs）缓蚀剂存在的耗时、耗能等缺点，在室温下一步制备含席夫碱结构的CDs缓蚀剂，并研究其对Q235碳钢的缓蚀性能。
方法设计了一种简易、可扩展的制备方法，以邻苯二胺和对苯醌为前驱体，无需高温加热便可在室温下反应2 h，从而获得含席夫碱结构的CDs。
利用TEM等方法对其结构进行表征，并采用UV和PL光谱评估其在HCl溶液中的长期分散稳定性。
通过失重法、电化学测试方法研究了不同浓度CDs对Q235碳钢在1 mol/L HCl溶中的缓蚀性能。
通过SEM和三维轮廓测量仪分析腐蚀后碳钢表面形貌及化学组成，提出CDs的缓蚀机理。
结果CDs含C=N键，具有多种含氧、含氮基团，有利于其在钢表面的吸附。
CDs在HCl溶液中具有长期分散稳定性。
当添加浓度为200 mg/L 时，其对碳钢在1 mol/L HCl溶液中的缓蚀效率可达到95.05%。
CDs为混合型缓蚀剂，能够同时抑制阴极和阳极反应。
CDs在碳钢表面的吸附方式遵循Langmuir等温吸附模型，其缓蚀机理为通过物理和化学吸附方式在碳钢表面形成一层保护膜，从而抑制碳钢的腐蚀。
结论成功为CDs缓蚀剂的合成提供了一种简易、可扩展、高效、省时的方法，而且证明了具有席夫碱结构的CDs对碳钢在1 mol/L HCl溶液中的腐蚀具有显著的抑制能力。
关键词：碳点；缓蚀剂；席夫碱；吸附；可扩展制备中图分类号：TG147; TB34 文献标识码：A 文章编号：1001-3660(2023)10-0229-12DOI：10.16490/ki.issn.1001-3660.2023.10.018Facile Preparation and Characterization of Carbon Dots with Schiff Base Structures Toward an Efficient Corrosion InhibitorLI Xue-qi a,b,c, HE Chuang a,b,c, YU Ke-ke a,b,c, LUO Qi-ling a,b.c, LONG Wu-jian a,b,c*(a. Key Lab of Coastal Urban Resilient Infrastructure, b. Guangdong Provincial Key Laboratory of Durability for Marine CivilEngineering, c. College of Civil and Transportation Engineering, Shenzhen University, Guangdong Shenzhen 518060, China) ABSTRACT: This work aims to design a facile and scalable approach to prepare carbon dots (CDs) with Schiff base structures收稿日期：2022-09-09；修订日期：2023-02-06Received：2022-09-09；Revised：2023-02-06基金项目：国家自然科学基金-山东联合基金（U2006223）；新型功能化碳点提升滨海环境混凝土氯离子固化能力及其机理研究（52208273）；深圳市科技计划项目（JCYJ20190808151011502）；广东省重点领域研发计划项目（2019B111107003）。
高性能锂离子电池用N掺杂C-Sn交联纳米纤维自支撑电极的理性设计（英文）
物 理 化 学 学 报Acta Phys. -Chim. Sin. 2024, 40 (3), 2305007 (1 of 11)Received: May 8, 2023; Revised: June 5, 2023; Accepted: June 20, 2023; Published online: June 28, 2023. *Correspondingauthors.Emails:***************(T.Y.);***************.cn(L.-F.C.)The project was supported by the National Natural Science Foundation of China (52374301, U1960107, 22075269, U2230101, GG2090007003), the Anhui Provincial Major Science and Technology Project (202203a05020048), the Fundamental Research Funds for the Central Universities (N2123001, WK2480000007), the Anhui Provincial Hundred Talents Program, the Hefei Innovative Program for Overseas Excellent Scholar (BJ2090007002), USTC Startup Program (KY2090000062, KY2090000098, KY2090000099), the Performance Subsidy Fund for Key Laboratory of Dielectric and Electrolyte Functional Material Hebei Province (22567627H).国家自然科学基金(52374301, U1960107, 22075269, U2230101, GG2090007003), 安徽省科技重大专项(202203a05020048), 中央高校基本业务费(N2123001, WK2480000007), 安徽省百人计划(青年)项目, 合肥市留学人员创新项目(BJ2090007002), 中国科学技术大学启动基金(KY2090000062, KY2090000098, KY2090000099), 河北省电介质与电解质功能材料重点实验室绩效补助经费(22567627H)资助© Editorial office of Acta Physico-Chimica Sinica[Article] doi: 10.3866/PKU.WHXB202305007 Rational Design of Cross-Linked N-Doped C-Sn Nanofibers as Free-Standing Electrodes towards High-Performance Li-Ion Battery AnodesYing Li 1, Yushen Zhao 1,2, Kai Chen 3, Xu Liu 1,2, Tingfeng Yi 1,2,*, Li-Feng Chen 3,*1 School of Materials Science and Engineering, Northeastern University, Shenyang 110819, China.2 Key Laboratory of Dielectric and Electrolyte Functional Material Hebei Province, School of Resources and Materials, NortheasternUniversity at Qinhuangdao, Qinhuangdao 066004, Hebei Province, China.3 CAS Key Laboratory of Mechanical Behavior and Design of Materials (LMBD), Department of Thermal Science and EnergyEngineering, School of Engineering Science, University of Science and Technology of China, Hefei 230026, China.Abstract: Li-ion batteries (LIBs) have been considered as one of the most promising power sources for electric vehicles, portable electronics and electrical equipment because of their long cycle life and high energy density. The free-standing electrodes without binder, current collector and conductive agent can effectively obtain lager energy density as compared to the traditional electrodes where the addition of inactive components is required. In addition, the free-standing electrode plays an important role in developing flexible electronic devices. Currently, conventional graphite isstill the main commercial anode material, but its theoretical specific capacity is limited, and the rate performance is poor. In recent years, the high temperature pyrolytic hard carbon has attracted wide attention due to its higher theoretical specific capacity and more defects than graphite carbon. Moreover, polymer polyacrylonitrile (PAN) can be used as the raw material for preparation of free-standing anodes without any conductive additives or binders by electrospinning technique. Meanwhile, it is beneficial to reduce the production cost and simplify the manufacturing procedures of electrode. However, PAN-based hard carbon anode materials also have certain problems, such as low conductivity, poor rate performance, unsatisfactory cycling stability, and inferior initial Coulombic efficiency (CE). In addition, soft carbon has advantages of high carbon yield, good conductivity, superior cycling stability, high initial CE and relatively low price, but its specific capacity is generally lower than that of hard carbon materials. Based on above analysis, carbon anode materials with good electrochemical performance can be obtained by combining hard carbon and soft carbon, but the specific capacity of carbon materials is still low. Tin (Sn), as an anode material for LIBs, has a high theoretical specific capacity (994 mAh·g −1) and a low lithium alloying voltage. Nonetheless, the practical use of Sn anode has been limited by its huge volume change (theoretically ∼260%) during the repeated alloying-dealloying process, resulting in large pulverization and cracking, which triggers the rapid capacity fading. Hence, in order to increase the specific capacity of carbon anode materials of LIBs, the C-Sn composite film with uniform Sn nanoparticles embedded in N-doped carbon nanofibers was prepared byelectrospinning method following by a low-temperature carbonization process. The film was directly used as a free-standingelectrode for LIBs and exhibited good electrochemical performance, and the introduction of Sn significantly improved the electrochemical properties of the carbon nanofiber film. The formed fibrous structure after Sn was uniformly coated with carbon can promote the conduction of ions and electrons, and effectively buffers the volume change of Sn nanoparticles during cycling, thus effectively preventing pulverization and agglomeration. The C-Sn-2 electrode with a Sn content of about 25.6% has the highest specific capacity and best rate performance among all samples. The electrochemical test results show that, the charge (discharge) capacity reaches 412.7 (413.5) mAh·g−1 at a current density of 2 A·g−1 even after 1000 cycles. Density functional theory (DFT) calculations show that N-doped amorphous carbon has good affinity with lithium, which is conducive to anchoring the Sn x Li y alloy formed after alloying reaction on the carbon surface, thereby relieving the volume change of Sn during charge-discharge. This article provides a feasible strategy for the design of high-performance lithium storage materials.Key Words: Free-standing electrode; Carbon nanofiber; Metallic Sn; Li-ion battery; Cycling stability高性能锂离子电池用N掺杂C-Sn交联纳米纤维自支撑电极的理性设计李莹1，赵钰燊1,2，陈凯3，刘旭1,2，伊廷锋1,2,*，陈立锋3,*1东北大学材料科学与工程学院，沈阳 1108192东北大学秦皇岛分校资源与材料学院，河北省电介质与电解质功能材料重点实验室，河北秦皇岛 0660043中国科学院材料力学行为与设计重点实验室，中国科学技术大学工程科学学院热科学和能源工程系，合肥 230026摘要：为了提高碳材料作为锂离子电池负极材料的比容量，将氮掺杂的碳纤维与高容量的Sn进行复合。