Dissertations / Theses on the topic 'Gas diffusion electrodes (GDE)'

Thesis: Ph. D., Massachusetts Institute of Technology, Department of Chemical Engineering, February, 2021
Cataloged from the official PDF of thesis.
Includes bibliographical references (pages 219-233).
Electrochemical carbon dioxide reduction (CO2R) is increasingly recognized as a viable technology for the generation of chemicals using carbon dioxide (CO₂) recovered from industrial exhaust streams or directly captured from air. If powered with low-carbon electricity, CO2R processes have the potential to reduce emissions from chemicals production. Historically, three-electrode analytical cells have been used to study catalyst activity, selectivity, and stability with a goal of incorporating proven materials into larger devices. However, it has been recognized that the limited CO₂ flux through bulk volumes of liquid electrolyte limit the effective reaction rate of CO₂ when using promising catalyst systems.
Gas-fed electrolyzers adapted from commercial water electrolyzer and fuel cell technologies have motivated researchers to explore combinations of porous electrodes, catalyst layers, and electrolytes to achieve higher areal productivity and favorable product selectivities. Present art demonstrates that high current density production (>200 mA cm₋²) of valuable chemicals at moderate cell voltages (ca. 3-4 V) is achievable at ambient conditions using electrolysis devices with catalyst-coated gas diffusion electrodes (GDEs). However, beyond short durations (1-10 h) stable performance outcomes for flowing electrolyte systems remain elusive as electrolyte often floods electrode pores, blocking diffusion pathways for CO₂, diminishing CO2R selectivity, and constraining productivity. Systematic study of the driving forces that induce electrode flooding is needed to infer reasonable operational envelopes for gas-fed electrolyzers as full-scale industrial devices are developed.
In this thesis, I investigate GDE wettability as a prominent determinant of gas-fed flowing electrolyte CO₂ electrolyzer durability. To do this, I combine experimental and computational approaches. First, I use a flow cell platform to study transient evolution of activity, selectivity, and saturation to identify failure modes, including liquid pressurization, salt precipitation, electrowetting, and liquid product enrichment. Next, I use material wettability properties and reactor mass balances to estimate how enriched liquid product streams might defy non-wetting characteristics of current GDE material sets. Finally, I construct computational electrode models and vary surface chemistry descriptors to predict transport properties in partially saturated electrodes. Specifically, I consider how saturation evolves in response to relevant scenarios (i.e., electrowetting and liquid products) that challenge CO₂ electrolyzer durability.
by McLain E. Leonard.
Ph. D.
Ph.D. Massachusetts Institute of Technology, Department of Chemical Engineering

Philosophiae Doctor - PhD
The need for simplified polymer electrolyte membrane fuel cell (PEMFCs) systems, which do not require extensive fuel processing, has led to increased study in the field of high temperature polymer electrolyte membrane fuel cells (HT-PEMFCs) applications. Although these HT-PEMFCs can operate with less complex systems, they are not without their own challenges; challenges which are introduced due to their higher operation temperature. This study aims to address two of the main challenges associated with HT-PEMFCs; the need for alternative catalyst layer (CL) ionomers and the prevention of excess phosphoric acid (PA) leaching into the CL. The first part of the study involves the evaluation of suitable proton conducting materials for use in the CL of high temperature membrane electrode assemblies (HT-MEAs), with the final part of the study focusing on development of a novel MEA architecture comprising an acid controlling region. The feasibility of the materials in HT-MEAs was evaluated by comparison to standard MEA configurations.

Polymer electrolyte fuel cells (PEFC) convert the chemically bound energy in a fuel, e.g. hydrogen, directly into electricity by an electrochemical process. Examples of future applications are energy conversion such as combined heat and power generation (CHP), zero emission vehicles (ZEV) and consumer electronics. One of the key components in the PEFC is the membrane / electrode assembly (MEA). Both the membrane and the electrodes consist of proton conducting polymers (ionomers). In the membrane, properties such as gas permeability, high proton conductivity and sufficient mechanical and chemical stability are of crucial importance. In the electrodes, the morphology and electrochemical characteristics are strongly affected by the ionomer content. The primary purpose of the present thesis was to develop experimental techniques and to use them to characterise proton conducting polymers and membranes for PEFC applications electrochemically at, or close to, fuel cell operating conditions. The work presented ranges from polymer synthesis to electrochemical characterisation of the MEA performance. The use of a sulfonated dendritic polymer as the acidic component in proton conducting membranes was demonstrated. Proton conducting membranes were prepared by chemical cross-linking or in conjunction with a basic functionalised polymer, PSU-pyridine, to produce acid-base blend membranes. In order to study gas permeability a new in-situ method based on cylindrical microelectrodes was developed. An advantage of this method is that the measurements can be carried out at close to real fuel cell operating conditions, at elevated temperature and a wide range of relative humidities. The durability testing of membranes for use in a polymer electrolyte fuel cell (PEFC) has been studied in situ by a combination of galvanostatic steady-state and electrochemical impedance measurements (EIS). Long-term experiments have been compared to fast ex situ testing in 3 % H2O2 solution. For the direct assessment of membrane degradation, micro-Raman spectroscopy and determination of ion exchange capacity (IEC) have been used. PVDF-based membranes, radiation grafted with styrene and sulfonated, were used as model membranes. The influence of ionomer content on the structure and electrochemical characteristics of Nafion-based PEFC cathodes was also demonstrated. The electrodes were thoroughly investigated using various materials and electrochemical characterisation techniques. Electrodes having medium Nafion contents (35<x<45 wt %) showed the best performance. The mass-transport limitation was essentially due to O2 diffusion in the agglomerates. The performance of cathodes with low Nafion content (<30 wt %) is limited by poor kinetics owing to incomplete wetting of platinum (Pt) by Nafion, by proton migration throughout the cathode as well as by O2 diffusion in the agglomerates. At large Nafion content (>45 wt %), the cathode becomes limited by diffusion of O2 both in the agglomerates and throughout the cathode. Furthermore, models for the membrane coupled with kinetics for the hydrogen electrode, including water concentration dependence, were developed. The models were experimentally validated using a new reference electrode approach. The membrane, as well as the hydrogen anode and cathode characteristics, was studied experimentally using steady-state measurements, current interrupt and EIS. Data obtained with the experiments were in good agreement with the modelled results.
QC 20101014

Polymer electrolyte fuel cells (PEFC) convert the chemically bound energy in a fuel, e.g. hydrogen, directly into electricity by an electrochemical process. Examples of future applications are energy conversion such as combined heat and power generation (CHP), zero emission vehicles (ZEV) and consumer electronics. One of the key components in the PEFC is the membrane / electrode assembly (MEA). Both the membrane and the electrodes consist of proton conducting polymers (ionomers). In the membrane, properties such as gas permeability, high proton conductivity and sufficient mechanical and chemical stability are of crucial importance. In the electrodes, the morphology and electrochemical characteristics are strongly affected by the ionomer content. The primary purpose of the present thesis was to develop experimental techniques and to use them to characterise proton conducting polymers and membranes for PEFC applications electrochemically at, or close to, fuel cell operating conditions. The work presented ranges from polymer synthesis to electrochemical characterisation of the MEA performance.

The use of a sulfonated dendritic polymer as the acidic component in proton conducting membranes was demonstrated. Proton conducting membranes were prepared by chemical cross-linking or in conjunction with a basic functionalised polymer, PSU-pyridine, to produce acid-base blend membranes. In order to study gas permeability a new in-situ method based on cylindrical microelectrodes was developed. An advantage of this method is that the measurements can be carried out at close to real fuel cell operating conditions, at elevated temperature and a wide range of relative humidities. The durability testing of membranes for use in a polymer electrolyte fuel cell (PEFC) has been studied in situ by a combination of galvanostatic steady-state and electrochemical impedance measurements (EIS). Long-term experiments have been compared to fast ex situ testing in 3 % H2O2 solution. For the direct assessment of membrane degradation, micro-Raman spectroscopy and determination of ion exchange capacity (IEC) have been used. PVDF-based membranes, radiation grafted with styrene and sulfonated, were used as model membranes. The influence of ionomer content on the structure and electrochemical characteristics of Nafion-based PEFC cathodes was also demonstrated. The electrodes were thoroughly investigated using various materials and electrochemical characterisation techniques. Electrodes having medium Nafion contents (3545 wt %), the cathode becomes limited by diffusion of O2 both in the agglomerates and throughout the cathode. Furthermore, models for the membrane coupled with kinetics for the hydrogen electrode, including water concentration dependence, were developed. The models were experimentally validated using a new reference electrode approach. The membrane, as well as the hydrogen anode and cathode characteristics, was studied experimentally using steady-state measurements, current interrupt and EIS. Data obtained with the experiments were in good agreement with the modelled results. Keywords: polymer electrolyte fuel cell, proton conducting membrane, porous electrode, gas permeability, degradation, water transport

Kyoto University (京都大学)
0048
新制・課程博士
博士(農学)
甲第20425号
農博第2210号
新制||農||1047(附属図書館)
学位論文||H29||N5046(農学部図書室)
京都大学大学院農学研究科応用生命科学専攻
(主査)教授 加納 健司, 教授 宮川 恒, 教授 三芳 秀人
学位規則第4条第1項該当

Fármacos tem sido foco de diversas estudos e pesquisas devido à constatação de sua ocorrência em diversos compartimentos ambientais. Esses compostos, com destaque para os antibióticos, apresentam biodegradação limitada e contínua introdução nos sistemas hídricos devido ao descarte incorreto, eliminação por excreção de parte da dose ingerida e, principalmente, pelo processo de fabricação nas indústrias farmacêuticas. Como as formas convencionais de tratamento têm se mostrado pouco efetivas, a tecnologia eletroquímica associada aos processos oxidativos avançados (POA) têm se mostrado uma maneira eficiente na degradação desses compostos. Em diversos estudos, os eletrodos de difusão gasosa (EDG) são apresentados como uma opção promissora no que diz respeito à eletrogeração de peróxido de hidrogênio, uma das principais fontes de radical hidroxila utilizado nos POA. Nesse aspecto, surgem estudos sobre modificadores que podem atuar como catalisadores nesse processo. Neste trabalho estudou-se o comportamento eletroquímico de dois modificares orgânicos suportados em matriz condutora de carbono Printex 6L. Os compostos orgânicos escolhidos, pertencentes a classe das quinonas, foram a 2-terc-butil-9,10-antraquinona (TBA) e a 9,10 fenantraquinona (FQA). Os estudos foram realizados em um eletrodo de disco/anel rotatório (RRDE), depositando-se uma microcamada porosa, contendo ou não o modificador, sobre o carbono vítreo deste eletrodo. Através dos resultados de voltametria cíclica e linear pode-se avaliar a geração de peróxido de hidrogênio, que foi superior para as microcamadas com adição dos modificadores. O material com 0,5% (m/m) de FQA mostrou-se o mais eficiente entre todos, com 30% de rendimento a mais quando comparado à matriz Printex e 6% maior quando comparada a mesma quantidade de TBA na produção do peróxido. Estudou-se também a eficiência da FQA para a produção de peróxido de hidrogênio (H2O2) a partir da reação de redução do oxigênio gasoso (O2), em eletrodos de difusão gasosa (EDG). Considerando os cinco eletrodos estudados (Printex não modificado e modificado com 0,1, 0,5, 1,0 e 2,0% de FQA) foi realizada uma avaliação sobre qual eletrodo seria o mais apto a ser utilizado nos trabalhos de degradação dos fármacos. Para isso fez-se a análise da concentração de peróxido de hidrogênio eletrogerada, o consumo energético e a cinética envolvida no processo. Os resultados mostraram um aumento significativo na produção de peróxido para os eletrodos modificados com 0,5 e 1,0% de FQA. Sendo que o eletrodo sem modificação atingiu um máximo de 215 ppm de H2O2 em um potencial de -1,4 V com um consumo energético de 29 kWh kg-1 de H2O2. O eletrodo modificado com 0,5% de FQA alcançou 566 pmm de H2O2 em um potencial de -1,4 V com um consumo energético de 14 kWh kg-1 de H2O2. Estudou-se também a degradação dos antibióticos amoxicilina e ampicilina (AMX e AMP) com anodos condutores comerciais de diamante dopados com boro. A influência da densidade de corrente aplicada (15, 30 e 60 mA cm-2) para o mesmo eletrólito de suporte (3 g / L de Na2SO4) e a mesma concentração inicial de antibióticos (100 mg dm-3 cada) foi avaliada. A mineralização total dos antibióticos foi atingida. Além disso, o processo foi encontrado para ser mais eficiente na densidade de corrente de 30 mA cm-2. Os resultados demonstram a importância dos processos eletroquímicos mediados na degradação de AMX e AMP. Esta influência foi confirmada por alguns testes em que a eletrólise foi acoplada à radiação UV ou à radiação ultrassônica. O uso de radiação UV resulta em uma degradação menos eficiente, enquanto que o ultrassom melhora um pouco a taxa de mineralização quando comparado ao processo eletrolítico simples.
Drugs have been the focus of several studies and researches due to the finding of their occurrence in several environmental compartments. These compounds, especially antibiotics, present limited biodegradation and continuous introduction into water systems because of incorrect disposal, elimination by excretion of part of the ingested dose and, mainly, by the manufacturing process in the pharmaceutical industries. As conventional mode of treatment have been shown to be ineffective, electrochemical technology associated with advanced oxidative processes (POA) has been shown to be an efficient way of degradation of these compounds. In several studies, gas diffusion electrodes (EDG) are presented as a promising option with respect to hydrogen peroxide electrogeneration, one of the main sources of hydroxyl radical used in POAs. In this aspect, studies on modifiers appear that can act as catalysts in this process. In this work the electrochemical behavior of two organic modifiers supported in Printex 6L carbon matrix was studied. The organic compounds chosen, belonging to the class of quinones, were 2-tert-butyl-9,10-anthraquinone (TBA) and 9,10-phenanthraquinone (FQA). The studies were performed on a rotating disk / ring electrode (RRDE), depositing a porous micro-layer, containing or not the modifier, on the glassy carbon of this electrode. Through the results of cyclic and linear voltammetry the generation of hydrogen peroxide can be evaluated, which was superior to the micro-layers with addition of the modifiers. The material with 0.5% (w / w) of FQA was the most efficient of all, with 30% more yield when compared to the Printex matrix and 6% higher when compared to the same amount of TBA in peroxide production . It was also studied the efficiency of the FQA for the production of hydrogen peroxide (H2O2) from the reduction reaction of gaseous oxygen (O2) in gaseous diffusion electrodes (EDG). Considering the five electrodes studied (Printex not modified and modified with 0.1, 0.5, 1.0 and 2.0% of FQA) an evaluation was made on which electrode would be the most suitable to be used in the degradation works of the drugs. For that, the analysis of the hydrogen peroxide concentration, the energy consumption and the kinetics involved in the process were analyzed. The results showed a significant increase in peroxide production for electrodes modified with 0.5 and 1.0% of FQA. Since the unmodified electrode reached a maximum of 215 ppm of H2O2 at a potential of -1.4 V with an energy consumption of 29 kWh kg-1 of H2O2. The electrode modified with 0.5% of FQA reached 566 pmm of H2O2 at a potential of -1.4 V with an energetic consumption of 14 kWh kg-1 of H2O2. The degradation of antibiotics amoxicillin and ampicillin (AMX and AMP) with commercial boron-doped diamond conducting anodes was also studied. The influence of the applied current density (15, 30 and 60 mA cm-2) for the same support electrolyte (3 g / L Na2SO4) and the same initial concentration of antibiotics (100 mg dm-3 each) was evaluated. Total mineralization of antibiotics was achieved. In addition, the process was found to be more efficient at current density of 30 mA cm-2. The results demonstrate the importance of the electrochemical processes mediated in the degradation of AMX and AMP. This influence was confirmed by some tests in which the electrolysis was coupled to UV radiation or to ultrasonic radiation. The use of UV radiation results in less efficient degradation, while ultrasound improves the rate of mineralization somewhat compared to the simple electrolyte process.

Neste trabalho foi estudado o comportamento eletroquímico de materiais à base de carbono Printex 6L, sem e com a adição de compostos orgânicos da classe das quinonas (2-terc-butil-9,10-antraquinona (TBA) e 2-etil-9,10-antraquinona (EA)) para a produção de peróxido de hidrogênio (H2O2) a partir da reação de redução do oxigênio gasoso (O2). Na primeira etapa, foi utilizada a técnica de microcamada porosa depositada sobre um eletrodo de disco/anel rotatório, sendo que a partir dos resultados obtidos foram confeccionados eletrodos de difusão gasosa (EDG) para a eletrogeração de H2O2. Os melhores resultados utilizando a microcamada porosa foram para os materiais com a adição dos modificadores, sendo que o material com 1,0% (m/m) de TBA na demonstrou ser o mais eficiente na geração de peróxido de hidrogênio, apresentando eficiência 20% maior comparado ao Printex 6L sem modificador. Com o eletrodo de difusão gasosa confeccionado com o composto orgânico escolhido, na melhor porcentagem de adição mássica de modificador, obteve-se a concentração de 301 mg L-1, sendo que com o eletrodo confeccionado com Printex 6L sem modificador obteve-se a concentração de 175 mg L-1, sob as mesmas condições experimentais. A eficiência cinética também apresentou os mesmos resultados quanto à eficiência dos materiais escolhidos, sendo de 5,94 mg L-1 min-1 para o material com 1,0% de TBA, no potencial de -1,0 V (vs. ECS), e de 3,05 mg L-1 min-1 para o eletrodo de difusão gasosa sem modificador, no potencial de -0,8 V (vs. ECS).
In this work, the electrochemistry behavior of the materials prepared with Printex 6L, with and without addition of organic compounds of the class of quinones, being the compounds: 2-tert-butyl-9,10-anthraquinone (TBA) and 2-ethyl-9,10-anthraquinone (EA). These materials were used to promote the electrogeneration of hydrogen peroxide through the oxygen reduction reaction. In the first phase, it was used the technique of porous microlayer deposited on the rotating ring/disk electrode, and after has been confectioned gas diffusion electrodes (GDE). The best results using the porous microlayer were for the materials with addition of modifiers, and the material with 1.0% (m/m) of 2-terc-butyl-9,10-anthraquinone was demonstrated to be the most efficient in generating hydrogen peroxide, presenting an efficiency 20% higher when compared to Printex 6L without the modifier. The gas diffusion electrode made with the chosen organic compound, in the best massic percentage of modifier, obtained the concentration of 301 mg L-1, and the electrode made with Printex 6L without the modifier obtained the maximum concentration of 175 mg L-1, under the same experimental conditions. The kinect efficiency also demonstrated the same results regarding the efficiency of the chosen materials, which means 5.94 mg L-1 min-1 for the material with 1.0% of 2-terc-butyl-9,10-anthraquinone, in the potential of -1.0 V(vs. SCE), and 3.05 mg L-1 min-1 for the gas diffusion electrode without the modifier, in the potential of -0.8 V (vs. SCE).

Among the obstacles for the commercialization of the MoltenCarbonate Fuel Cell (MCFC), the dissolution of thestate-of-the-art lithiated NiO cathode is considered as aprimary lifetime limiting constraint. Development ofalternative cathode materials is considered as a main strategyfor solving the cathode dissolution problem. LiFeO₂and LiCoO₂had earlier been reported as the most promisingalternative materials; however, they could not satisfactorilysubstitute the lithiated NiO. On the other hand, ternarycompositions of LiFeO₂, LiCoO₂and NiO are expected to combine some desirableproperties of each component. The aim of this work was todevelop alternative cathode materials for MCFC in the LiFeO₂-LiCoO₂-NiO ternary system. It was carried out byinvestigating electronic conductivity of the materials, firstin the form of bulk pellets and then in ex-situ sinteredporous-gas-diffusion cathodes, and evaluating theirelectrochemical performance by short-time laboratory-scale celloperations.

Materials in the LiFeO₂-NiO binary system and five ternary sub-systems,each with a constant molar ratio of LiFeO₂:NiO while varying LiCoO₂content, were studied. Powders withcharacteristics appropriate for MCFC cathode fabrication couldbe obtained by the Pechini method. The particle size of LiFeO₂-LiCoO₂-NiO powders considerably depends on thecalcination temperature and the material composition. Theelectrical conductivity study reveals the ability of preparingLiFeO₂-LiCoO₂-NiO materials with adequate electricalconductivity for MCFC cathode application.

A bimodal pore structure, appropriate for the MCFC cathode,could be achieved in sintered cathodes prepared usingporeformers and sub-micron size powder. Further, this studyindicates the nature of the compromise to be made between theelectrical conductivity, phase purity, pore structure andporosity in optimization of cathodes for MCFC application. Cellperformance comparable to that expected for the cathode in acommercial MCFC could be achieved with cathodes prepared from20 mole% LiFeO₂- 20 mole% LiCoO₂- 60 mole% NiO ternary composition. It shows aniR-corrected polarization of 62 mV and a iR-drop of 46 mV at acurrent density of 160 mAcm^-2at 650 °C. Altogether, this study revealsthe possibility of preparing LiFeO₂-LiCoO₂-NiO cathode materials suitable for MCFCapplication.

Keywords: molten carbonate fuel cell (MCFC), MCFC cathode,LiFeO₂-LiCoO₂-NiO ternary compositions, electrical conductivity,porous gas diffusion electrodes, polarization, electrochemicalperformance, post-cell characterization.

In recent years an emphasis has been placed on the development of alternative and clean energy sources to reduce the global use of fossil fuels. One of these alternatives entails the use of H2 as an energy carrier, which can be obtained amongst others using thermochemical processes, for example the hybrid sulphur process (HyS). The HyS process is based on the thermal decomposition of sulphuric acid into water, sulphur dioxide and oxygen. The subsequent chemical conversion of the sulphur dioxide saturated water back to sulphuric acid and hydrogen is achieved in an electrolyser using a platinum coated proton exchange membrane. This depolarised electrolysis requires a theoretical voltage of only 0.158 V compared to water electrolysis requiring approximately 1.23 V. One of the steps in the development of this technology at the North-West University, entailed the establishment of the platinum coating technology which entailed two steps; firstly using newly obtained equipment to manufacture the membrane electro catalyst assemblies (MEA’s) and gas diffusion electrodes (GDE’s) and secondly to test these MEA’s and GDE’s using sulphur dioxide depolarized electrolysis by comparing the manufactured MEA’s and GDE’s to commercially available MEA’s and GDE’s. Different MEA’s and GDE’s were manufactured using both a screen printing (for the microporous layer deposition) and a spraying technique. The catalyst loadings were varied as well as the type and thickness of the proton exchange membranes used. The proton exchange membranes that were included in this study were Nafion 117®, sPSU-PBIOO and SfS-PBIOO membranes whereas the gas diffusion layer consisted of carbon paper with varying thicknesses (EC-TP01-030 – 0.11 mm and EC-TP01-060 – 0.19mm). MEA and GDE were prepared by first preparing an ink that was used both for MEA and GDE spraying. The MEA’s were prepared by spraying various catalyst coatings onto the proton exchange membranes containing 0.3, 0.6 and 0.9 mg/cm2 platinum respectively. The GDE’s were first coated by a micro porous carbon layer using the screen printing technique in order to attain a suitable surface for catalyst deposition. Using the spraying technique GDE’s containing 0.3, 0.6, 0.9 mg/cm2 platinum were prepared. After SEM analysis, the MEA’s and GDE’s performance was measured using SO2 depolarized electrolysis. From the electrolysis experiments, the voltage vs. current density generated during operation, the hydrogen production, the sulphuric acid generation and the hydrogen production efficiency was obtained. From the results it became clear that while the catalyst loading had little effect on performance there were a number of factors that did have a significant influence. These included the type of proton exchange membrane, the membrane thickness and whether the catalyst coating was applied to the proton exchange membrane (MEA) or to the gas diffusion layer (GDE). During SO2 depolarized electrolysis VI curves were generated which gave an indication of the performance of the GDE’s and MEA’s. The best preforming GDE was GDE-3 (0.46V @ 320 mA/cm2), which included a GDE EC-TP01-060, while the best preforming MEA’s were NAF-4 (0.69V @ 320mA/cm2) consisting of a Nafion117 based MEA and PBI-1 (0.43V @ 320mA/cm2) made from a sPSU-PBIOO blended membrane. During hydrogen production it became clear that the GDE’s produced the most hydrogen (best was GDE-02 a in house manufactured GDE yielding 67.3 mL/min @ 0.8V), followed by the Nafion® MEA’s (best was NAF-4 a commercial MEA yielding 57.61 mL/min @ 0.74V) and the PBI based MEA’s. , (best was PBI-2 with 67.11 mL/min @ 0.88V). Due to the small amounts of acid produced and the SO2 crossover, a significant error margin was observed when measuring the amount of sulphuric acid produced. Nonetheless, a direct correlation could still be seen between the acid and the hydrogen production as had been expected from literature. The highest sulphuric acid concentrations produced using the tested GDE’s and MEA’s from this study were the in-house manufactured GDE-01 (3.572mol/L @ 0.8V), the commercial NAF-4 (4.456mol/L @ 0.64V) and the in-house manufactured PBI-2 (3.344mol/L @ 0.8V). The overall efficiency of the GDE’s were similar, ranging from less than 10% at low voltages (± 0.6V) increasing to approximately 60% at ± 0.8V. For the MEA’s larger variation was observed with NAF-4 reaching efficiencies of nearly 80% at 0.7V. In terms of consistency of performance it was shown that the Nafion MEA’s preformed most consistently followed by the GDE’s and lastly the PBI based MEA’s which for the PBI based membranes can probably be ascribed to the significant difference in thickness of the thin PBI vs. the Nafion based membranes. In summary the study has shown the results between the commercially obtained and the in-house manufactured GDE’s and MEA’s were comparable confirming the suitability of the coating techniques evaluated in this study.
MSc (Chemistry), North-West University, Potchefstroom Campus, 2014

碩士
元智大學
化學工程與材料科學學系
98
A series of Pt-based catalysts consisting of Pt, Pt-Co and Pt-Zn was combined against CNT (carbon nanotube)/CP (carbon paper) support that made from CCVD, and used as anode catalysts for proton exchange membrane fuel cell. The catalysts were deposited on the CNTs by using microwave-assisted reduction using ethylene glycol as reducing agent. The Pt deposits with an average size of 2-5 nm were uniformly coated over the surface of oxidized CNTs. The resulting catalysts were characteried by electrochemical test, TGA, XRD, HR-TEM, SEM, ESCA and membrane electrode assembly (MEA) test. The catalysts displayed not only fairly good electrochemical activity but also durability. The analysis of AC impedance spectra associated with equivalent circuit revealed that the appearance of CNTs significantly redued both connect and charge transfer resistances, leading to a low equivalent series resistance ~0.22 Ω. With the aid of CNTs, well dispersion of catalysts enabled the reversibly rapid redox kinetic since the electron transport efficiently passed through a one-dimensional pathway. As the results of MEA test, the performance of the home-made catalyst is better than that of commercial catalyst. The improvement of performance can attributed： (i)the addition of CNTs, (ii)dispersion of particles and (iii) particle size in the catalysts. The results shed some lights on how use of CNT/CP composite and microwave-assisted method hold promise for application of high-performance gas diffusion electrode.

碩士
元智大學
化學工程與材料科學學系
96
In this research, a carbon membrane with well-aligned pore structure is synthesized by template method. This carbon membrane is used together with Pt sols for improving performance of PEMFCs. Epoxy solution is deposited into pore of a commercially available AAO (anodic aluminum oxide) membrane. After carbonization under N2 environment at elevated temperature, the carbon-AAO composite is subjected to a 2-step AAO removal procedure. By controlling the extent of AAO removal in the first step, and the use of a second carbon-filling-and-carbonization procedure, we achieve a continuous carbon membrane with pore structure replicating that of AAO template. In this study, we use different solvents and additivies (involved Nafion and Carbon) over Pt sols to compare the ink stability. We use Contact angle, precipitation, Particle size distribution and Zata potential to analyze the stability of ink. The result shows that the addition of IPA and MeOH over Pt sols forces quick precipitation. We prepared thinner electrode made of Pt sols, but its performance decreases quickly from 35 to 70oC.However, the trend is reverse compared to Pt/C. The preparation of the electrode in combination with Pt sols and One-dimensional carbon material improves mass transport limitation.

博士
國立交通大學
材料科學與工程學系
100
We employed an amorphous citrate precursor (ACP) method to synthesize stoichiometric La0.6Ca0.4Co0.8Ru0.2O3 powders. Besides, a variety of La0.6Ca0.4CoxRu1-xO3 perovskite oxide (x=0, 0.2, 0.4, 0.6, 0.8, and 1) were fabricated by solid-state reaction (SSR) method to form oxide powder with various ruthenium (Ru) ratios. X-ray diffraction profiles (XRD) of the as-synthesized powders exhibited the major phase identical is La0.6Ca0.4CoO3, indicating successful incorporation of Ru4+ at the Co cation sites. ACP-derived La0.6Ca0.4Co0.8Ru0.2O3 exhibited a higher H2O2 decomposition rate in KOH solution as opposed to that of ACP-derived La0.6Ca0.4CoO3, which suggested an improved catalytic ability for the oxygen reduction reaction (ORR). In ORR and hydrogen evolution reaction (HER) I-V polarization curves, the SSR-derived La0.6Ca0.4CoxRu1-xO3/BP2000 revealed an enhanced bi-functional catalytic ability in comparison with those of La0.6Ca0.4CoO3/BP2000. La0.6Ca0.4CoIr0.25O3.5-δ was prepared by a mechanical alloying process from mixtures of La0.6Ca0.4CoO3 and IrO2. The ACP method was employed to prepare perovskite La0.6Ca0.4Co0.8Ir0.2O3 as a bi-functional electrocatalyst for ORR and HER in an alkaline electrolyte. The XRD pattern of the as-synthesized powders exhibited the major phase is La0.6Ca0.4CoO3, indicating successful incorporation of Ir4+ at the Co cation sites. Supported on carbon Nanocapsules (CNCs), the La0.6Ca0.4CoIr0.25O3.5-δ and La0.6Ca0.4Co0.8Ir0.2O3 particles demonstrated superior performances than those of La0.6Ca0.4CoO3 in both charging and discharging I-V polarizations. For Ru and Ir doped into La0.6Ca0.4CoO3, the electrochemical capabilities displayed similar performance for the ORR. In life time determinations, La0.6Ca0.4Co0.8Ir0.2O3/CNCs delivered a stable and sustainable behavior with moderate degradation. In addition to synthesis of suitable electrocatalyst, the other critical issue is to identify appropriate material as electrocatalyst support. Therefore, a resorcinol–formaldehyde (R-F) condensation reaction catalyzed by acetic acid (C) is employed to prepare the carbon ambient gels for electrochemical double layer capacitors. The samples was fabricated with a R:F ratio of 1:2 and R:C ratios of 5:1 and 10:1, followed by solvent exchange, pyrolysis, and CO2 activation. The solvent exchange allowed negligible structure contraction upon drying, and after CO2 treatment, we were able to produce porous carbons with a surface area of 3419 m2g-1. Electrochemical analysis including cyclic voltammetry (CV), current reversal chronopotentiometry (CRC), and impedance spectroscopy are conducted using a titanium cavity electrode so relevant capacitive characteristics and kinetic parameters could be determined. Both CV and CRC results indicate specific capacitances and life time behaviors are comparable or even better than those of BP 2000.

博士
中興大學
材料科學與工程學系所
98
In this thesis, the ultra-hydrophobic and micro-porous electrodes (MPEs) fabricated by a reactive ion etcher with the fluorocarbon plasmas ratio of 1.5, 4, and 6, respectively, are successfully demonstrated and applied on gas diffusion layer for proton exchange membrane fuel cell. The chemical composition of the film on carbon cloth surface is characterized by X-ray photoelectron spectroscopy (XPS) and hydrophobic groups such as –CF2 and –CF3 groups were then detected, which were very similar to polytrafluoroethlene (PTFE), in addition, the surface morphology, hydrophilic/hydrophobic property and electron conductivity of the as-prepared GDL was fully characterized. The water contact angle and SEM microstructure image of the CF4, CHF3 plasma-treated GDL are both indicated as ∼130◦. Furthermore, the F/C ratio of fluorine-based precursor is the main parameter to adjust the conductivity, porosity, and ultrahydrophobicity of the electrodes. When the electrodes are fabricated with a F/C ratio of fluorine-based precursor of 1.5, it has a much more stable output density, with an optimal power output of 350 mW/cm2 corresponding to a current density of 800 mA/cm2, than that fabricated with a F/C ratio of fluorine-based precursor of 4 during the long-duration test. Besides, the PEMFC measurements show that GDL with a CHF3 prepared Teflon-like film thickness of 1.2 um modules has the best performance with a maximum power density of 520 mW/cm2. However, cell performance tends to decline when the film thickness is increased to 2.7 um, a result which is ascribed to the great sheet resistance and Teflon-like film cracks of the GDL.

abstract: This work aimed to characterize and optimize the variables that influence the Gas Diffusion Layer (GDL) preparation using design of experiment (DOE) approach. In the process of GDL preparation, the quantity of carbon support and Teflon were found to have significant influence on the Proton Exchange Membrane Fuel Cell (PEMFC). Characterization methods like surface roughness, wetting characteristics, microstructure surface morphology, pore size distribution, thermal conductivity of GDLs were examined using laser interferometer, Goniometer, SEM, porosimetry and thermal conductivity analyzer respectively. The GDLs were evaluated in single cell PEMFC under various operating conditions of temperature and relative humidity (RH) using air as oxidant. Electrodes were prepared with different PUREBLACK® and poly-tetrafluoroethylene (PTFE) content in the diffusion layer and maintaining catalytic layer with a Pt-loading (0.4 mg cm-2). In the study, a 73.16 wt.% level of PB and 34 wt.% level of PTFE was the optimal compositions for GDL at 70 °C for 70% RH under air atmosphere. For most electrochemical processes the oxygen reduction is very vita reaction. Pt loading in the electrocatalyst contributes towards the total cost of electrochemical devices. Reducing the Pt loading in electrocatalysts with high efficiency is important for the development of fuel cell technologies. To this end, this thesis work reports the approach to lower down the Pt loading in electrocatalyst based on N-doped carbon nanotubes derived from Zeolitic Imidazolate Frameworks (ZIF-67) for oxygen reduction. This electrocatalyst perform with higher electrocatalytic activity and stability for oxygen reduction in fuel cell testing. The electrochemical properties are mainly due to the synergistic effect from N-doped carbon nanotubes derived from ZIF and Pt loading. The strategy with low Pt loading forecasts in emerging highly active and less expensive electrocatalysts in electrochemical energy devices. This thesis focuses on: (i) methods to obtain greater power density by optimizing content of wet-proofing agent (PTFE) and fine-grained, hydrophobic, microporous layer (MPL); (ii) modeling full factorial analysis of PEMFC for evaluation with experimental results and predicting further improvements in performance; (iii) methods to obtain high levels of performance with low Pt loading electrodes based on N-doped carbon nanotubes derived from ZIF-67 and Pt.
Dissertation/Thesis
Masters Thesis Mechanical Engineering 2016