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A Spanish research group has developed a new method for obtaining carbon materials with excellent properties such as electrocatalysts in fuel cells or metal-air batteries. They are characterized by their outstanding catalytic activity and low manufacturing cost, making them candidates to replace the current platinum-based catalysts. Catalyst manufacturing companies interested in the commercial exploitation of this technology via patent licensing or technical cooperation agreements are sought.
It is essential to find new forms of energy generation that reduce the harmful effects of fossil fuels and increase the energy efficiency of the devices used. In this sense, hydrogen-based energy systems are the great candidates for solving these problems, and, in fact, they are the main system of the future for the automobile industry, and for the storage and use of renewable energies.
Currently, the performance and efficiency of fuel cells are not optimized. The main limiting factor is the use of platinum as a catalyst to accelerate electrode reactions. Platinum is a scarce metal, it has a high cost, platinum nanoparticles agglomerate during use (reducing its catalytic activity), and the presence of small traces of carbon monoxide or methanol can completely poison the catalyst, rendering it unusable.
A Spanish university has developed a low-cost and single-stage new method for the synthesis of carbon materials for their application as electrocatalysts of the oxygen reduction reaction in alkaline medium in fuel cells, or in metal-air batteries.
This is a synthesis method that allows metal-free catalysts to be obtained from a nitrogen-rich polymer (e.g. polyaniline or copolymers containing aniline in their monomer units), without the need of supports (template or sacrificial materials), or other materials that increase the cost of the product.
The synthesis procedure is based on a pre-treatment to avoid any contamination of the atmosphere, followed by a heat treatment in an inert atmosphere at temperatures above 1100ºC.
It is important to point out that the two key factors to be taken into account in order to obtain carbon materials that can act as electrocatalysts in the oxygen reduction reaction with high performance are:
a) Temperature treatment: the increase in temperature generates important changes in catalytic activity, reaching values in the samples obtained using the present method as high as those obtained by commercial catalysts based on platinum nanoparticles.
b) Precursor used: although catalytic activity improves with temperature increase, only polyaniline and its derivatives produce catalytic activity with values similar to commercial platinum catalysts.
Carbon materials resulting from this method have a high dispersion capacity in an aqueous medium, which facilitates the formation of suspensions for later preparation of the catalysts. These suspensions remain stable over a long period of time.
This technology makes it possible to obtain metal-free carbon materials for application as excellent electrocatalysts in the oxygen reduction reaction under alkaline conditions in hydrogen or methanol low temperature fuel cells, or in metal-air batteries. Therefore, this technology finds its application in the following industrial sectors: Fuel cells, metal-air batteries, automobile, energy production and storage.
The university is mainly looking for manufacturers of catalysts and electrocatalysts for fuel cells/metal-air batteries interested in acquiring this technology for its commercial exploitation through license agreement. The company should be responsible for the development of the industrial prototype, the validation of the technology, its installation and its introduction into the market. The university will be ready to provide technical assistance in each step, if required.
However, the university would be also interested in establishing technical cooperation agreements to further develop the laboratory-scale prototype, to find new applications or to adapt it to the company’s needs. The goal of this type of collaboration would be increasing the technology readiness level for a future commercial exploitation of the patent. The university would offer its support based on their know-how; while, the partner sought would provide its expertise to help improve this invention. The university would offer this partner a preferential option to acquire this technology in exclusivity.
Although thermal treatment of polymers containing aniline in their monomer units is known within the state of the art, the present method differs from the other procedures in the following aspects:
1) Heat treatment temperature is higher than 1100ºC. In this way, carbon materials get a structural order, electrical conductivity and catalytic activity similar to commercial platinum-based catalysts, being, therefore, excellent substitutes for these, because production cost is radically lower.
2) No templates or sacrificial structures are used (which increase the number of stages of synthesis and the cost of manufacturing the catalyst).
3) The method described in this invention is very simple and is carried out in a single-stage.
4) The adequate selection of precursors, being polyaniline and its derivatives the most appropriate for obtaining carbon materials with excellent catalytic activity in an alkaline medium (similar to commercial platinum-based catalysts).
The main advantages of this novel method and the synthesized carbon materials are listed below:
• It does not require special equipment.
• The synthesis method has a high performance.
• Low cost of the synthesis method: manufacturing cost to obtain this type of materials is radically lower than current commercial catalysts. It uses low cost precursors. So, this method reduce the total cost of the fuel cell.
• Synthesized carbon materials are easy to handle: they are dispersed easily in an aqueous medium at room temperature.
• They have an excellent electrocatalytic activity for oxygen reduction reaction in alkaline medium.
• They have a great stability, which gives them a longer useful working time (durability) than current platinum-based electrodes of fuel cells or metal-air batteries.
• They are resistant to methanol or carbon monoxide poisoning.
• They are environmentally friendly materials, since they are metal-free catalysts.
These novel electrocatalysts have been successfully synthesized at laboratory scale. Kinetic parameters obtained for these new electrocatalysts, whose values are similar to those obtained by commercial platinum-based catalysts, are listed below:
• Starting potential of the reaction = 0.94 V.
• Half-wave potential = 0.85 V.
• Limiting current density = 5.8 mA·cm-2.
• Number of transferred electrons = 3.9 (determined by rotating ring-disk electrode (RRDE)).
Other measured parameters:
• Pyrolysis yield - see Figure 1.
• When a temperature above 1000ºC is used, a significant change occurs in the final carbon materials. Specifically, at 1100ºC these materials acquire a catalytic activity almost identical to commercial platinum-based catalyst (see Figure 2b), both in starting potential of the reaction and in current density limit, making them clear candidates for replacing platinum-based catalysts in fuel cells. However, an increase in the heat treatment temperature above 1100ºC does not lead to an improvement in the catalytic activity of the synthesized material. Regarding the number of electrons transferred, a factor related to hydrogen peroxide performance (see Figure 2a), hydrogen peroxide values below 5% have been measured in the useful working range of fuel cells (i.e. between 0.6 and 1.0 vs reversible hydrogen electrode (RHE)), indicating that it prevents formation of by-products detrimental to the life-time of fuel cells.
• Stability - see Figure 3.
• Effect of other copolymers containing aniline - see Figure 4.
• Effect of different inert atmospheres (argon, nitrogen, etc.) during the synthesis procedure - see Figure 5.
• Effect of mass/flow ratio in the final pyrolysis yield - see Figure 6.
Spanish patent granted. PCT applied for.
- Type of partner sought: Industry.
- Specific area of activity of the partner: Manufacturers of catalysts and electrocatalysts for fuel cells; Manufacturers of catalysts and electrocatalysts for metal-air batteries.
- Task to be performed:
* In the license agreement: to buy a license for the technology, to further develop it to the industrial scale and to introduce it into the market.
* In the technical cooperation agreement: to provide their expertise in order to collaborate with the scientists on further development and improvements of the technology. The company should identify technical requirements and/or market and client’s needs in order to carry out further technical development so that the market readiness will be increased and the technology could be commercially exploited.