[Background and purposes]Proton exchange membrane fuel cells(PEMFCs),which convert hydrogen energy directly into electrical energy and water,have received overwhelming attention,owing to their potential to significant...[Background and purposes]Proton exchange membrane fuel cells(PEMFCs),which convert hydrogen energy directly into electrical energy and water,have received overwhelming attention,owing to their potential to significantly reduce energy consumption,pollution emissions and reliance on fossil fuels.Bipolar plates are the major part and key component of PEMFCs stack,which provide mechanical strength,collect and conduct current segregate oxidants and reduce agents.They contribute 70-80%weight and 20-30%cost of a whole stack,while significantly affecting the power density.There are three types plates,including metal bipolar plate,graphite bipolar plate and composite bipolar plate.Stainless steel bipolar plates,as one of metal bipolar plate,exhibit promising manufacturability,competitive cost and durability among various metal materials.However,stainless steel would be corroded in the harsh acid(pH 2-5)and humid PEMFCs environment,whereas the leached ions will contaminate the membrane.In addition,the passivated film formed on the surface will increase the interfacial contact resistance(ICR).In order to improve the corrosion resistance and electrical conductivity of steel bipolar plates,surface coatings are essential.Metal nitride coatings,metal carbide coatings,polymer coatings and carbon-based coatings have been introduced in recent years.Carbon-based coatings,mainly including a-C(amorphous Carbon),Ta-C(Tetrahedral amorphous carbon)and DLC(diamond-like carbon),have attracted considerable attention from both academia and industry,owing to their superior performance,such as chemical inertness,mechanical hardness and electrical conductivity.However,Ta-C films as protective coating of PEMFCs have been rarely reported,due to the difficulty in production for industrial application.In this paper,multi-layer Ta-C composite films were produced by using customized industrial-scale vacuum equipment to address those issues.[Methods]Multiple layered Ta-C coatings were prepared by using PIS624 equipment,which assembled filtered cathodic arc evaporation,ion beam and magnetron sputtering into one equipment,while SS304 and silicon specimens were used as substrate for testing and analysis.Adhesion layer and intermediate layer were deposited by using magnetron sputtering at deposition temperature of 150℃and pressure of 3×10^(−1) Pa,while the sputtering current was set to be 5 A and bias power to be 300 V.The Ta-C layer was coated at arc current of 80-100 A,bias voltage of 1500 V and gas flow of 75 sccm.A scanning electron microscope(CIQTEK SEM3200)was used to characterize surface morphology,coating structure and cross-section profile of the coatings.Raman spectrometer(LabRam HR Evolution,HORIBA JOBIN YVON)was used to identify the bonding valence states.Electrochemical tests were performed by using an electrochemical work station(CHI760,Shanghai Chenhua Instrument Co.,Ltd.),with the traditional three electrode system,where saturated Ag/AgCl and platinum mesh were used as the reference electrode and counter electrode,respectively.All samples were mounted in plastic tube and sealed with epoxy resin,with an exposure area of 2.25 cm^(2),serving as the working electrode.Electrochemical measurements were carried out in simulated PEMFCs cathode environment in 0.5 mol·L^(−1) H_(2)SO_(4)+5 ppm F−solution,at operating temperature of 70℃.As the cathode environment was harsher than the anode environment,all the samples are stabilized at the open-circuit potential(OCP)for approximately 30 min before the EIS measurements.ICR between bipolar plates and GDL was a key parameter affecting performance of the PEMFCs stack.The test sample sandwiched between 2 pieces of carbon paper(simulate gas diffusion layer,GDL)was placed between 2 gold-plated copper electrodes at a compaction pressure of 1.4 MPa,which was considered to be the conventional compaction pressure in the PEMFCs.Under the same conditions,the resistance of a single carbon paper was measured as well.The ICR was calculated according to the formula ICR=1/2(R2−R1)×S,where S was the contact area between GDL and coated stainless steel BPPs.All data of ICR were measured three times for averaging.[Results]The coatings deposited by filtered cathodic arc technology were compact and smooth,which reduced coating porosity and favorable to corrosion resistance.The coating thickness of adhesion and intermediate layers were 180 nm,while the protective Ta-C coating thickness was about 300 nm,forming multiple coating to provide stronger protection for metal bipolar plates.Cr,Ti,Nb and Ta coatings were selected as adhesion layers for comparison.According to electrochemical test,Ta and Nb coatings have higher corrosion resistance.However,Ta and Nb materials would be costly when they are used for mass production.Relatively,Cr and Ti materials were cost effective.Hence,a comprehensive assessment was indispensable to decide the materials to be selected as adhesion layer.Ta-TiN and Ti-TiN combined adhesion and intermediate layer exhibited stronger corrosion resistance,with the corrosion current to be less than 10^(−6) A·cm^(−2).Ta-C protective coating deposited by using filtered cathodic arc technology indicated displayed higher corrosion resistance,with the average corrosion density to be about 1.26×10^(−7) A·cm^(−2).Ta-C coating also shown larger contact angle,with the highest hydrophobicity,which was one of the important advantages for Ta-C,in terms of corrosion resistance.According to Raman spectroscopy,the I(D)/I(G)=549.8/1126.7=0.487,with the estimated fraction of sp^(3) bonding to be in the range of 5154%.The intermediate layer TiN has higher conductivity than the CrN layer.Considering cost,corrosion performance and ICR result,the Ti-TiN layer combination is recommended for industrial scale application.[Conclusions]Multiple layer coating structure of Ta-C film had stronger corrosion resistance;with more than 50%sp^(3) content,while it also had larger water contact angle and higher corrosion resistance than DLC film.The filtered arcing deposition technology was able to make the film to be more consistent and stable than normal arcing technology in terms of the preparation of Ta-C.The coating displayed corrosion density of 1.26×10^(−7) A·cm^(−2) and ICR of less than 5 mΩ·cm^(2),far beyond technical target of 2025 DOE(US Department of Energy).This indicated that the mass-production scale coating technology for PEMFC bipolar plates is highly possible.展开更多
A new method of manufacturing micro-flow channels on graphite composite bipolar plate(GCBPP) microplaning using specially designed multi-tooth tool is proposed. In this method, several or even dozens of parallel micro...A new method of manufacturing micro-flow channels on graphite composite bipolar plate(GCBPP) microplaning using specially designed multi-tooth tool is proposed. In this method, several or even dozens of parallel micro-flow channels ranging from 100 μm to 500 μm in width can be produced simultaneously. But, edge chippings easily occur on the rib surface of GCBPP during microplaning due to brittleness of graphite composites. Experimental results show that edge chippings result in the increase of contact resistance between bipolar plate and carbon paper at low compaction force. While the edge chippings scarcely exert influence on the contact resistance at high compaction force. Contrary to conventional view, the edge chippings can significantly improve performance of microfuel cell and big edge chippings outperform small edge chippings. In addition, the influence of technical parameters on edge chippings was investigated in order to obtain big, but not oversized edge chippings.展开更多
Two tetrasubstituted carbazole derivatives TBICz and TOXDCz have been designed and synthesized,which possess the twist skeletons and exhibit excellent thermal and morphological stabilities.Utilizing these novel compou...Two tetrasubstituted carbazole derivatives TBICz and TOXDCz have been designed and synthesized,which possess the twist skeletons and exhibit excellent thermal and morphological stabilities.Utilizing these novel compounds as host material,high efficiency solution-processed green phosphorescent organic light-emitting diodes(PhOLEDs)have been achieved.The high triplet energies of TBICz and TOXDCz ensure efficient energy transfer from the host to the phosphor and triplet exciton confinement on the phosphor.Solution-processable green phospho⁃rescent devices employing Ir(ppy)3 as guest and the two tetrasubstituted carbazole derivatives as hosts exhibit high ef⁃ficiencies.The best EL performance is achieved for the TBICz-based device,with a maximum current efficiency of 27.3 cd/A,a maximum power efficiency of 15.9 lm/W,and a maximum external quantum efficiency of 7.8%,which provides more host material options for solution-processed OLEDs.展开更多
目的探讨抑郁障碍和双相障碍患者脑白质网络节点强度的差异,分析患者不同脑区的结构连接受损情况及其在鉴别中的作用。方法纳入91例基线诊断为抑郁发作的患者,经过≥9年的自然观察随访后,最终确定23例维持抑郁障碍诊断(单相组)和18例维...目的探讨抑郁障碍和双相障碍患者脑白质网络节点强度的差异,分析患者不同脑区的结构连接受损情况及其在鉴别中的作用。方法纳入91例基线诊断为抑郁发作的患者,经过≥9年的自然观察随访后,最终确定23例维持抑郁障碍诊断(单相组)和18例维持双相障碍诊断(双相组)的患者纳入分析。同时纳入30名健康对照者(对照组)。受试者在入组时均接受弥散张量成像扫描,采用确定性纤维追踪技术构建脑白质结构加权网络。比较三组间脑白质网络的节点连接强度差异,进一步采用受试者操作特征(receiver operator characteristic,ROC)曲线评估差异脑区对抑郁障碍和双相障碍鉴别诊断的价值。结果双相组在左前扣带回的节点强度较单相组降低(3.89±0.76 vs.4.74±0.60),在右尾状核(4.94±1.26 vs.3.46±0.99)、右苍白球(1.98±0.67 vs.1.25±0.29)的节点强度较单相组升高(P<0.01,FWE校正)。左前扣带回、右尾状核、右苍白球3个脑区的连接强度联合鉴别抑郁障碍和双相障碍绘制ROC曲线,曲线下面积(area under the curve,AUC)为0.95(95%CI:0.91~0.99;P<0.01),敏感度0.89,特异度0.87。结论脑结构网络的节点强度差异可以作为一个潜在的影像学生物标志物识别抑郁障碍和双相障碍,联合差异脑区的节点强度可以得到更好的识别率。展开更多
含分布式电源(distributed generation,DG)的双极直流配电系统是未来配电网发展的重要形态之一,但由于DG接入方式、数量、容量、位置以及系统正负极负荷不平衡对系统静暂态电压稳定性影响不同,目前相关研究尚缺乏对此问题的分析。该文...含分布式电源(distributed generation,DG)的双极直流配电系统是未来配电网发展的重要形态之一,但由于DG接入方式、数量、容量、位置以及系统正负极负荷不平衡对系统静暂态电压稳定性影响不同,目前相关研究尚缺乏对此问题的分析。该文首先将DG等效为受控电流源,推导分析了DG接入方式、容量及负荷不平衡度对系统静态下电压不平衡度的影响;其次,基于单极故障下光伏型DG与交流电网暂态放电情况,推导分析了DG接入方式、位置、容量与系统暂态电压稳定性的关系;再者,基于多目标蜣螂优化算法提出以系统静暂态电压稳定性与DG接入成本为目标的DG接入方案规划方法,采用熵权逼近理想解排序法(technique for order preference by similarity to ideal solution,TOPSIS)法筛选出DG接入的最佳折中方案。最后在Matlab/Simulink仿真平台搭建改进IEEE14、IEEE33双极直流配电系统验证该文所提优化方法的普适性和有效性。展开更多
基金Major Science and technology projects of Anhui Province (202103a05020003)。
文摘[Background and purposes]Proton exchange membrane fuel cells(PEMFCs),which convert hydrogen energy directly into electrical energy and water,have received overwhelming attention,owing to their potential to significantly reduce energy consumption,pollution emissions and reliance on fossil fuels.Bipolar plates are the major part and key component of PEMFCs stack,which provide mechanical strength,collect and conduct current segregate oxidants and reduce agents.They contribute 70-80%weight and 20-30%cost of a whole stack,while significantly affecting the power density.There are three types plates,including metal bipolar plate,graphite bipolar plate and composite bipolar plate.Stainless steel bipolar plates,as one of metal bipolar plate,exhibit promising manufacturability,competitive cost and durability among various metal materials.However,stainless steel would be corroded in the harsh acid(pH 2-5)and humid PEMFCs environment,whereas the leached ions will contaminate the membrane.In addition,the passivated film formed on the surface will increase the interfacial contact resistance(ICR).In order to improve the corrosion resistance and electrical conductivity of steel bipolar plates,surface coatings are essential.Metal nitride coatings,metal carbide coatings,polymer coatings and carbon-based coatings have been introduced in recent years.Carbon-based coatings,mainly including a-C(amorphous Carbon),Ta-C(Tetrahedral amorphous carbon)and DLC(diamond-like carbon),have attracted considerable attention from both academia and industry,owing to their superior performance,such as chemical inertness,mechanical hardness and electrical conductivity.However,Ta-C films as protective coating of PEMFCs have been rarely reported,due to the difficulty in production for industrial application.In this paper,multi-layer Ta-C composite films were produced by using customized industrial-scale vacuum equipment to address those issues.[Methods]Multiple layered Ta-C coatings were prepared by using PIS624 equipment,which assembled filtered cathodic arc evaporation,ion beam and magnetron sputtering into one equipment,while SS304 and silicon specimens were used as substrate for testing and analysis.Adhesion layer and intermediate layer were deposited by using magnetron sputtering at deposition temperature of 150℃and pressure of 3×10^(−1) Pa,while the sputtering current was set to be 5 A and bias power to be 300 V.The Ta-C layer was coated at arc current of 80-100 A,bias voltage of 1500 V and gas flow of 75 sccm.A scanning electron microscope(CIQTEK SEM3200)was used to characterize surface morphology,coating structure and cross-section profile of the coatings.Raman spectrometer(LabRam HR Evolution,HORIBA JOBIN YVON)was used to identify the bonding valence states.Electrochemical tests were performed by using an electrochemical work station(CHI760,Shanghai Chenhua Instrument Co.,Ltd.),with the traditional three electrode system,where saturated Ag/AgCl and platinum mesh were used as the reference electrode and counter electrode,respectively.All samples were mounted in plastic tube and sealed with epoxy resin,with an exposure area of 2.25 cm^(2),serving as the working electrode.Electrochemical measurements were carried out in simulated PEMFCs cathode environment in 0.5 mol·L^(−1) H_(2)SO_(4)+5 ppm F−solution,at operating temperature of 70℃.As the cathode environment was harsher than the anode environment,all the samples are stabilized at the open-circuit potential(OCP)for approximately 30 min before the EIS measurements.ICR between bipolar plates and GDL was a key parameter affecting performance of the PEMFCs stack.The test sample sandwiched between 2 pieces of carbon paper(simulate gas diffusion layer,GDL)was placed between 2 gold-plated copper electrodes at a compaction pressure of 1.4 MPa,which was considered to be the conventional compaction pressure in the PEMFCs.Under the same conditions,the resistance of a single carbon paper was measured as well.The ICR was calculated according to the formula ICR=1/2(R2−R1)×S,where S was the contact area between GDL and coated stainless steel BPPs.All data of ICR were measured three times for averaging.[Results]The coatings deposited by filtered cathodic arc technology were compact and smooth,which reduced coating porosity and favorable to corrosion resistance.The coating thickness of adhesion and intermediate layers were 180 nm,while the protective Ta-C coating thickness was about 300 nm,forming multiple coating to provide stronger protection for metal bipolar plates.Cr,Ti,Nb and Ta coatings were selected as adhesion layers for comparison.According to electrochemical test,Ta and Nb coatings have higher corrosion resistance.However,Ta and Nb materials would be costly when they are used for mass production.Relatively,Cr and Ti materials were cost effective.Hence,a comprehensive assessment was indispensable to decide the materials to be selected as adhesion layer.Ta-TiN and Ti-TiN combined adhesion and intermediate layer exhibited stronger corrosion resistance,with the corrosion current to be less than 10^(−6) A·cm^(−2).Ta-C protective coating deposited by using filtered cathodic arc technology indicated displayed higher corrosion resistance,with the average corrosion density to be about 1.26×10^(−7) A·cm^(−2).Ta-C coating also shown larger contact angle,with the highest hydrophobicity,which was one of the important advantages for Ta-C,in terms of corrosion resistance.According to Raman spectroscopy,the I(D)/I(G)=549.8/1126.7=0.487,with the estimated fraction of sp^(3) bonding to be in the range of 5154%.The intermediate layer TiN has higher conductivity than the CrN layer.Considering cost,corrosion performance and ICR result,the Ti-TiN layer combination is recommended for industrial scale application.[Conclusions]Multiple layer coating structure of Ta-C film had stronger corrosion resistance;with more than 50%sp^(3) content,while it also had larger water contact angle and higher corrosion resistance than DLC film.The filtered arcing deposition technology was able to make the film to be more consistent and stable than normal arcing technology in terms of the preparation of Ta-C.The coating displayed corrosion density of 1.26×10^(−7) A·cm^(−2) and ICR of less than 5 mΩ·cm^(2),far beyond technical target of 2025 DOE(US Department of Energy).This indicated that the mass-production scale coating technology for PEMFC bipolar plates is highly possible.
基金Project(51075155)supported by the National Natural Science Foundation of ChinaProject(2013ZZ017)supported by the Fundamental Research Funds for the Central Universities,China
文摘A new method of manufacturing micro-flow channels on graphite composite bipolar plate(GCBPP) microplaning using specially designed multi-tooth tool is proposed. In this method, several or even dozens of parallel micro-flow channels ranging from 100 μm to 500 μm in width can be produced simultaneously. But, edge chippings easily occur on the rib surface of GCBPP during microplaning due to brittleness of graphite composites. Experimental results show that edge chippings result in the increase of contact resistance between bipolar plate and carbon paper at low compaction force. While the edge chippings scarcely exert influence on the contact resistance at high compaction force. Contrary to conventional view, the edge chippings can significantly improve performance of microfuel cell and big edge chippings outperform small edge chippings. In addition, the influence of technical parameters on edge chippings was investigated in order to obtain big, but not oversized edge chippings.
文摘Two tetrasubstituted carbazole derivatives TBICz and TOXDCz have been designed and synthesized,which possess the twist skeletons and exhibit excellent thermal and morphological stabilities.Utilizing these novel compounds as host material,high efficiency solution-processed green phosphorescent organic light-emitting diodes(PhOLEDs)have been achieved.The high triplet energies of TBICz and TOXDCz ensure efficient energy transfer from the host to the phosphor and triplet exciton confinement on the phosphor.Solution-processable green phospho⁃rescent devices employing Ir(ppy)3 as guest and the two tetrasubstituted carbazole derivatives as hosts exhibit high ef⁃ficiencies.The best EL performance is achieved for the TBICz-based device,with a maximum current efficiency of 27.3 cd/A,a maximum power efficiency of 15.9 lm/W,and a maximum external quantum efficiency of 7.8%,which provides more host material options for solution-processed OLEDs.
文摘目的探讨抑郁障碍和双相障碍患者脑白质网络节点强度的差异,分析患者不同脑区的结构连接受损情况及其在鉴别中的作用。方法纳入91例基线诊断为抑郁发作的患者,经过≥9年的自然观察随访后,最终确定23例维持抑郁障碍诊断(单相组)和18例维持双相障碍诊断(双相组)的患者纳入分析。同时纳入30名健康对照者(对照组)。受试者在入组时均接受弥散张量成像扫描,采用确定性纤维追踪技术构建脑白质结构加权网络。比较三组间脑白质网络的节点连接强度差异,进一步采用受试者操作特征(receiver operator characteristic,ROC)曲线评估差异脑区对抑郁障碍和双相障碍鉴别诊断的价值。结果双相组在左前扣带回的节点强度较单相组降低(3.89±0.76 vs.4.74±0.60),在右尾状核(4.94±1.26 vs.3.46±0.99)、右苍白球(1.98±0.67 vs.1.25±0.29)的节点强度较单相组升高(P<0.01,FWE校正)。左前扣带回、右尾状核、右苍白球3个脑区的连接强度联合鉴别抑郁障碍和双相障碍绘制ROC曲线,曲线下面积(area under the curve,AUC)为0.95(95%CI:0.91~0.99;P<0.01),敏感度0.89,特异度0.87。结论脑结构网络的节点强度差异可以作为一个潜在的影像学生物标志物识别抑郁障碍和双相障碍,联合差异脑区的节点强度可以得到更好的识别率。
文摘含分布式电源(distributed generation,DG)的双极直流配电系统是未来配电网发展的重要形态之一,但由于DG接入方式、数量、容量、位置以及系统正负极负荷不平衡对系统静暂态电压稳定性影响不同,目前相关研究尚缺乏对此问题的分析。该文首先将DG等效为受控电流源,推导分析了DG接入方式、容量及负荷不平衡度对系统静态下电压不平衡度的影响;其次,基于单极故障下光伏型DG与交流电网暂态放电情况,推导分析了DG接入方式、位置、容量与系统暂态电压稳定性的关系;再者,基于多目标蜣螂优化算法提出以系统静暂态电压稳定性与DG接入成本为目标的DG接入方案规划方法,采用熵权逼近理想解排序法(technique for order preference by similarity to ideal solution,TOPSIS)法筛选出DG接入的最佳折中方案。最后在Matlab/Simulink仿真平台搭建改进IEEE14、IEEE33双极直流配电系统验证该文所提优化方法的普适性和有效性。
