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Technical Paper

Structure and properties of a nano-carbon composite surface coating for roll-to-roll manufacturing of titanium fuel cell bipolar plates

2023-09-29
2023-32-0138
In the 1st generation Toyota "MIRAI" fuel cell stack, carbon protective surface coating is deposited after individual Ti bipolar plate being press-formed into the desired shape. Such a process has relatively low production speed, not ideal for large scale manufacturing. A new coating concept, consisting of a nanostructured composite layer of titanium oxide and carbon particles, was devised to enable the incorporation of both the surface treatment and the press processes into the roll-to-roll production line. The initial coating showed higher than expected contact resistance, of which the root cause was identified as nitrogen contamination during the annealing step that inhibited the formation of the composite film structure. Upon the implementation of a vacuum furnace chamber as the countermeasure, the issue was resolved, and the improved coating could meet all the requirements of productivity, conductivity, and durability for use in the newer generation of fuel cell stacks.
Technical Paper

New Concept Exhaust Manifold for Next-Generation HEV and PHEV

2023-09-29
2023-32-0062
HEV and PHEV require an improved aftertreatment system to clean the exhaust gas in various driving situations. The efficiency of aftertreatment system is significantly influenced by the residence time of the gas in a catalyst which gas flow has generally strong pulsation. Simulation showed up to 70% reduction of exhaust gas emission if the pulsation could be completely attenuated. A new concept exhaust manifold was designed to minimize pulsation flow by wall impingement, with slight increase of pressure loss. Experimental results with new concept exhaust manifold showed exhaust gas emission were reduced 16% at cold condition and 40% at high-load condition.
Technical Paper

Development of Three-Way Catalysts with Enhanced Cold Performance

2023-04-11
2023-01-0358
Global focus on CO2 reduction and environmental protection is increasing. To comply with stricter exhaust gas regulations and reduce real world emissions, it is becoming increasingly important to improve the performance of three-way catalysts. Therefore, highly efficient conversion of hydrocarbons (HC), carbon monoxide (CO), and nitrogen oxides (NOx) is required. In general, the more active the precious metals used, the better the conversion performance. However, precious metals have supply risks, such as price fluctuation and the uneven distribution of production areas. Therefore, it is necessary to lower emissions while also lowering the amount of precious metals used. This paper focuses on how catalysts are used and describes the development of a new three-way catalyst for the purpose of strengthening cold conversion and decreasing the usage of precious metals.
Technical Paper

Development of 50% Thermal Efficiency S.I. Engine to Contribute Realization of Carbon Neutrality

2023-04-11
2023-01-0241
To prevent global warming, many countries are making efforts to reduce CO2 emissions toward achieving 2050 carbon neutrality. In order to reduce CO2 concentration quickly, in addition to spread of renewable energy and expansion of BEV, it is also important to reduce CO2 emissions by improving thermal efficiency of ICE (internal combustion engine) and utilizing carbon neutral fuels such as synthetic fuels and biofuels. It is well known that lean burn is an effective technology to increase thermal efficiency of engine highly. However, since NOx emission from lean burn engine cannot be reduced with three-way catalyst, there have been issues such as complicated system configuration due to the addition of NOx reduction catalyst or limiting lean operation to narrow engine speed and load in order to meet emission regulation of each country.
Journal Article

Development of a Ceramic EHC

2022-03-29
2022-01-0536
In recent years, electrically heated catalysts (EHCs) have been developed to achieve lower emissions. In several EHC heating methods, the direct heating method, which an electric current is applied directly to the catalyst substrate, can easily activate the catalyst before engine start-up. The research results reported on the use of the direct heating EHC to achieve significant exhaust gas purification during cold start-up [1]. From the perspective of catalyst loading, ceramics is considered to be a better material for the substrate than metal due to the difference in coefficient of thermal expansion between the catalyst and the substrate, but the EHC made of ceramics has difficulties such as controllability of the current distribution, durability and reliability of the connection between the substrate and the electrodes.
Technical Paper

Development of High-Performance FC Stack for the New MIRAI

2021-04-06
2021-01-0740
The first MIRAI was launched in 2014 as the world’s first commercial fuel cell vehicle (FCV) [1]. Compared to the FC stack used in the first MIRAI, the FC stack in the new MIRAI achieved one of the highest volumetric power densities in the world (5.4 kW/L, excluding end plates, 1.5 times higher than the FC stack in the first MIRAI) by adopting a new flow channel for the bipolar plate and an improved electrode [2]. Enhancing the current density is an important means of increasing power performance and reducing size. The bipolar plate functions to distribute gas and drain water inside the cells to stabilize current generation. However, a conventional straight flow channel tends to cause flooding, which makes it difficult to maintain stable current generation. A partially narrow flow channel was developed to enhance oxygen diffusion without the 3D fine-mesh flow field that was adopted in the previous FC stack.
Technical Paper

Development of Three-Way Catalyst with Advanced Coating Layer

2020-04-14
2020-01-0653
Further improvements in catalyst performance are required to help protect the atmospheric environment. However, from the viewpoint of resource availability, it is also necessary to decrease the amount of precious metals used at the active sites of the catalyst. Therefore, a high-performance three-way catalyst with an advanced coating layer has been developed to lower the amount of precious metal usage. Fuel efficiency improvement technologies such as high compression ratios and a large-volume exhaust gas recirculation (EGR) generally tend to increase the ratio of hydrocarbons (HC) to nitrogen oxides (NOx) in exhaust gas. This research focused on the palladium (Pd) loading depth in the coating layer with the aim of improving the hydrocarbon (HC) conversion activity of the catalyst.
Journal Article

On the Role of Nitric Oxide for the Knock-Mitigation Effectiveness of EGR in a DISI Engine Operated with Various Gasoline Fuels

2019-12-19
2019-01-2150
The knock-suppression effectiveness of exhaust-gas recirculation (EGR) can vary between implementations that take EGR gases after the three-way catalyst and those that use pre-catalyst EGR gases. A main difference between pre-and post-catalyst EGR gases is the level of trace species like NO, UHC, CO and H2. To quantify the role of NO, this experiment-based study employs NO-seeding in the intake tract for select combinations of fuel types and compression ratios, using simulated post-catalyst EGR gases as the diluent. The four investigated gasoline fuels share a common RON of 98, but vary in octane sensitivity and composition. To enable probing effects of near-zero NO levels, a skip-firing operating strategy is developed whereby the residual gases, which contain trace species like NO, are purged from the combustion chamber. Overall, the effects of NO-seeding on knock are consistent with the differences in knock limits for preand post-catalyst EGR gases.
Journal Article

Development of Strength Distributed Hot Stamp Parts

2019-04-02
2019-01-0522
1 Structural parts, such as the center pillar, are a multi-layer structure. They are a combination of high-strength panels and high-toughness panels, to control the deformation mode during a crash. If we can make this multi-layered structure as one panel, consisting of different hardness within it, we will be able to make a lightweight part. In this study, we have developed a method to fabricate a ‘lightweight center pillar’ with the following processes. First, the whole panel is hardened by quenching within the hot stamp process. Next, certain areas of the panel are softened by partial tempering. We have found that the temperature zone for softening is between A1 and A3, and it is easy to perform a rapid and accurate tempering by utilizing induction heating around the Curie temperature between A1 and A3 transformation temperature.
Technical Paper

Development of Three-Way Catalysts Enhanced NOx Purifying Activity

2018-04-03
2018-01-0942
Growing concerns about the depletion of raw materials as vehicle ownership continues to increase is prompting automakers to look for ways of decreasing the use of platinum-group metals (PGMs) in the exhaust systems. This research has developed a new catalyst with strong robustness against fluctuations in the exhaust gas and excellent nitrogen oxide (NOx) conversion performance. One of the key technologies is a new OSC material that has low surface area (SA) and high OSC performance. We enhanced the pyrochlore- ceria/zirconia (CZ) which has a very small SA. In order to enhance the heat resistance and promote the OSC reaction, we selected and optimized the additive element. This material showed high OSC performance especially in the temperature range of 400 degrees or less. Another key technology is washcoat structure that has high gas diffusivity by making connected pore in the washcoat (New pore forming technology).
Journal Article

Study of Oxide Supports for PEFC Catalyst

2017-03-28
2017-01-1179
Polymer electrolyte membrane fuel cell (PEFC) systems for fuel cell vehicles (FCVs) require both performance and durability. Carbon is the typical support material used for PEFC catalysts. However, hydrogen starvation at the anode causes high electrode potential states (e.g., 1.3 V with respect to the reversible hydrogen electrode) that result in severe carbon support corrosion. Serious damage to the carbon support due to hydrogen starvation can lead to irreversible performance loss in PEFC systems. To avoid such high electrode potentials, FCV PEFC systems often utilize cell voltage monitor systems (CVMs) that are expensive to use and install. Simplifying PEFC systems by removing these CVMs would help reduce costs, which is a vital part of popularizing FCVs. However, one precondition for removing CVMs is the adoption of a durable support material to replace carbon.
Journal Article

Development of a New Ceramic Substrate with Gas Flow Control Functionality

2017-03-28
2017-01-0919
Emission regulations in many countries and regions around the world are becoming stricter in reaction to the increasing awareness of environment protections, and it has now become necessary to improve the performance of catalytic converters to achieve these goals. A catalytic converter is composed of a catalytically active material coated onto a ceramic honeycomb-structured substrate. Honeycomb substrates play the role of ensuring intimate contact between the exhaust gas and the catalyst within the substrate’s flow channels. In recent years, high-load test cycles have been introduced which require increased robustness to maintain low emissions during the wide range of load changes. Therefore, it is extremely important to increase the probability of contact between the exhaust gas and catalyst. To achieve this contact, several measures were considered such as increasing active sites or geometrical surface areas by utilizing substrates with higher cell densities or larger volumes.
Journal Article

Analysis of Influence of Snow Melting Agents and Soil Components on Corrosion of Decorative Chrome Plating

2016-04-05
2016-01-0539
The dissolution and exfoliation of chromium plating specific to Russia was studied. Investigation and analysis of organic compounds in Russian soil revealed contents of highly concentrated fulvic acid. Additionally, it was found that fulvic acid, together with CaCl2 (a deicing agent), causes chromium plating corrosion. The fulvic acid generates a compound that prevents reformation of a passivation film and deteriorates the sacrificial corrosion effectiveness of nickel.
Technical Paper

Experimental and Numerical Analysis for a Urea-SCR Catalytic Converter

2016-04-05
2016-01-0973
Urea-SCR (Selective Catalytic Reduction) systems are getting a lot of attention as the most promising NOx reduction technology for heavy-duty diesel engine exhaust. In order to promote an effective development for an optimal urea-SCR after-treatment system, it is important to clarify the decomposition behavior of the injected urea and a detailed reaction chemistry of the reactants on the catalyst surface in exhaust gases. In this paper we discuss experimental and numerical studies for the development of a numerical simulation model for the urea-SCR catalyst converter. As a first step, in order to clarify the behavior of reductants in an urea-SCR converter, two types of diagnostic technique were developed; one is for measuring the amount of NH3, and the other is for measuring the amount of total reductants including unreacted urea and iso-cyanic acid. These techniques were applied to examine the behavior of reductants at the inlet and inside the SCR converter.
Technical Paper

Enhancing PtCo Electrode Catalyst Performance for Fuel Cell Vehicle Application

2016-04-05
2016-01-1187
While carbon supported PtCo alloy nanoparticles emerged recently as the new standard catalyst for oxygen reduction reaction in polymer membrane electrolyte fuel cells, further improvement of catalyst performance is still of great importance to its application in fuel cell vehicles. Herein, we report two examples of such efforts, related to the improvements of catalyst preparation and carbon support design, respectively. First, by lowering acid treatment voltage, the effectiveness for the removal of unalloyed Co was enhanced significantly, leading to less Co dissolution during cell operation and about 40% higher catalyst mass activity. It has been also found that the use of nonporous carbon support material promoted mass transfer and resulted in substantial drop of overpotential at high current and low humidity. This result may suggest an effective strategy towards the development of fuel cell systems that operate without additional humidification.
Technical Paper

Improvement of Adhesion Properties between Epoxy Resin and Primer and between Primer and Ni Plating in Hybrid Vehicle Power Semiconductor Module under High Temperature Conditions

2016-04-05
2016-01-0500
In this report, adhesion mechanism between epoxy resin and primer and between primer and Ni platting in Hybrid vehicle (HV) was investigated. Adhesion forces are thought to be a combination of mechanical bond forces (such as anchor effect), chemical bond forces and physical bond forces (such as hydrogen bonding and Van der Waals force). Currently there is insufficient understanding of the adhesion mechanism. In particular, the extent to which the three bond forces contribute to adhesion strength. So the adhesion mechanism of polyimide primers was analyzed using a number of different methods, including transmission electron microscope (TEM) and atomic force microscope (AFM) observation, to determine the contributions of the three bonding forces. Molecular simulation was also used to investigate the relationship between adhesion strength and the molecular structure of the primer.
Journal Article

In-Situ Liquid TEM Study on the Degradation Mechanism of Fuel Cell Catalysts

2016-04-05
2016-01-1192
Electrode catalyst (platinum) degradation represents a major challenge to the performance and durability of polymer electrolyte membrane fuel cells (PEMFCs) in Fuel Cell Vehicles (FCVs). While various mechanisms have been proposed and investigated previously, there is still a need to develop in situ imaging techniques that can characterize and provide direct evidence to confirm the degradation process. In the present study, we report an in situ transmission electron microscopy (TEM) method that enables real time, high-resolution observation of carbon-supported platinum nanoparticles in liquid electrolyte under working conditions. By improving the design of the Micro Electro Mechanical Systems (MEMS) sample holder, the migration and aggregation of neighboring platinum nanoparticles could be visualized consistently and correlated to applied electrode potentials during aging process (i.e., cyclic voltammetry cycles).
Technical Paper

Model-Based OBD Logic Utilizing Adsorption and Desorption Model of NH3 in SCR Catalyst

2016-04-05
2016-01-0960
Urea selective catalytic reduction (SCR) systems are a promising technology for helping to lower NOx emissions from diesel engines. These systems also require on-board diagnostic (OBD) systems to detect malfunctioning catalysts. Conventional OBD methodology for a SCR catalyst involves the measurement of NOx concentration downstream of the catalyst. However, considering future OBD regulations, erroneous diagnostics may occur due to variations in the actual environment. Therefore, to enhance OBD accuracy, a new methodology was examined that utilizes NH3 slip as a new diagnostic parameter in addition to NOx. NH3 slip increases as the NOx reduction performance degrades, because both phenomena are based on deterioration in the capability of the SCR catalyst to adsorb NH3. Furthermore, NH3 can be measured by existing NOx sensors because NH3 is oxidized to NO internally. To make use of NH3 slip, an estimation model was developed.
Technical Paper

Analysis of Sulfur-Related White Smoke Emissions from DPF System

2015-09-01
2015-01-2023
In a Diesel engine with a Diesel particulate filter (DPF) system, high-sulfur fuel causes white smoke containing odorous and harmful pollutants during DPF regeneration. This study investigates the conditions and mechanisms of sulfur-related white smoke generation. Engine and vehicle tests found that sulfur compounds emitted from the engine accumulated on the catalysts in the DPF system and were emitted as white smoke during DPF regeneration. The white smoke was observed when the catalyst temperature was more than 450°C, under conditions such as the early stage of DPF regeneration. Model gas tests were conducted to clarify the mechanism of the white smoke. It was found that SO2 emitted from the engine was oxidized to SO3 on the catalyst, which was then mainly absorbed on the oxidation catalyst support (Al2O3). Then, the absorbed SO3 was desorbed and converted into white smoke.
Journal Article

Application of Reference Governor Using Soft Constraints and Steepest Descent Method to Diesel Engine Aftertreatment Temperature Control

2013-04-08
2013-01-0350
This paper considers an application of reference governor (RG) to automotive diesel aftertreatment temperature control. Recently, regulations on vehicle emissions have become more stringent, and engine hardware and software are expected to be more complicated. It is getting more difficult to guarantee constraints in control systems as well as good control performance. Among model-based control methods that can directly treat constraints, this paper focuses on the RG, which has recently attracted a lot of attention as one method of model prediction-based control. In the RG, references in tracking control are modified based on future prediction so that the predicted outputs in a closed-loop system satisfy the constraints. This paper proposes an online RG algorithm, taking account of the real-time implementation on engine embedded controllers.
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