Relevance
The hydrogen generation, storage and further use as a fuel are the key issues in the widespread development of hydrogen energy in general. The main reason for the hydrogen generation is its environmentally friendly generation without a carbon footprint. In the case of the mobile storage and transportation of the obtained raw materials, there is an increasing interest in new multicomponent alloys that allow accumulating hydrogen in itself in a chemically bound state. Such materials can be used as a temporary storage tank for hydrogen, or as ready-made fuel rods.
In connection with the above, the main idea of the presented Program is the development of innovative devices, materials and technologies for the hydrogen generation, storage and transportation with further electricity generation.
The main research will be carried out by RSE “National Nuclear Center of the Republic of Kazakhstan” (NNC RK), which has a modern experimental scientific and technological base, highly qualified personnel and many years of experience in the orientation of the declared Program. The leading domestic laboratories and research centers will be involved in solving the Program individual tasks at the NJSC S. Amanzholov East Kazakhstan University, NJSC Al-Farabi Kazakh National University and NJSC K. Satpayev Kazakh National Research Technical University.
The Program goal is to develop the innovative technologies, materials and devices for the hydrogen generation and storage, as well as for the electrochemical generation of electricity based on it, taking into account the energy resources and needs of the Republic of Kazakhstan.
Program objectives:
Scientific novelty:
The Project scientific novelty lies in the fact that:
– the methodological recommendations for the research in the generation of hydrogen and carbon, as well as materials science data on solid products of the methane pyrolysis reaction in a microwave discharge will be issued in Kazakhstan for the first time;
– new 2D materials of the MXene family will be used to decrease the overpotential for hydrogen evolution and reduce the energy consumption for the hydrogen generation by electrolysis;
– Kazakhstan's first demonstration system for storing and transporting hydrogen based on hydrogen-intensive, multi-acting intermetallic compounds will be developed;
– polymer-carbon composite materials based on micro- and nanocrystals of cellulose for generation a three-dimensional mesoporous hydrogen capacitor as well as the materials for FR MEU based on nanostructured zirconium oxide will be developed for the first time;
– new polymer-carbon and nanocomposite materials based on agricultural waste and annual plants for hydrogen storage and transportation will be produced;
– a reserve for commercialization in the Kazakh market for the production of Ni-MeH batteries with the synthesis of anode material will be created.
The Program expected outcomes.
Direct outcomes:
Orientation 1. Hydrogen generation
1.1. Development of a method for hydrogen generation as a result of methane pyrolysis in a microwave discharge:
– the methodological recommendations for the research in the generation of hydrogen and carbon as a result of the methane pyrolysis reaction in a microwave discharge;
– increasing the efficiency of the degree of methane decomposition when generating hydrogen by plasma pyrolysis using a microwave discharge;
– the materials science data of solid products of the methane pyrolysis reaction in the microwave discharge.
1.2. Optimization of the structure and composition of two-dimensional catalysts for the electrochemical hydrogen generation by the electrolysis of solutions:
– the development of catalysts with decreased overpotential for hydrogen evolution;
– establishing the relationship between the nature and number of surface functional groups of 2D materials on its catalytic properties in the hydrogen evolution processes;
– assessing the economic efficiency of using 2D materials as catalysts for the electrochemical hydrogen generation.
Orientation 2. Innovative materials and technologies for hydrogen storage and transportation
2.1. Development of a universal LaNi5-based alloy system for metal hydride applications:
– developing optimized compositions and structures of LaNi5-based metal hydride hydrogen storage systems to achieve high hydrogen capacity;
– performing a comprehensive study of the structural and phase state and physical properties of LaNi5-based hydrogen storage systems with varying the chemical composition, high-energy processing, and consolidation method over a wide range of hydrogen operating temperatures;
– creating the samples of finely dispersed effective hydrogen-absorbing materials based on LaNi5 for the reversible hydrogen storage.
2.2 Experimental and theoretical analysis of hydrogen absorption in LaNi5-based metal hydride systems:
– experimental determining the resource of reversible hydrogen absorption capacity of finely dispersed LaNi5-based hydrogen storage systems under the conditions of multiple hydrogenation/dehydrogenation loads.
2.3 Development of hydrogen-intensive composite materials:
– developing a method for generation hydrogen-intensive polymer-carbon composite materials;
– a development technology and pilot model of 3D microporous hydrogen capacitors based on micro- and nanocrystalline cellulose and modified carbon materials.
Orientation 3. Conversion of hydrogen into electric power
3.1. Materials for low-temperature fuel rods:
– the results of the study on the test of the electrode materials and the MEU block, a comparative analysis of the proposed materials, as well as the results of tests of the operability of sorbent materials and an assessment of the possibility of their application in the electrochemical and metal hydride method of the hydrogen accumulation;
– the test samples of the composite silicon electrode structures and the FR membrane electrode unit.
3.2. Catalytic system for the low-temperature FRs:
– the technology for the synthesis of catalytic systems for low-temperature FRs;
– the materials with catalytic systems for hydrogen conversion.
3.3. Development and optimization of anode and cathode materials for hydrogen-based electrochemical energy converters:
– a method for producing membranes of 2D porous hydrogen capacitors based on micro- and nanocrystalline cellulose and modified carbon materials;
– the technology for the development of 3D microporous hydrogen capacitors based on micro- and nanocrystalline cellulose and graphene-like materials;
– a pilot model of the low-temperature FR with the improved or new catalytic systems for converting hydrogen energy into the electric one.
Final outcome:
Orientation 1. Hydrogen generation
1.1. A method for hydrogen generation as a result of methane pyrolysis in a microwave discharge.
1.2. An effective catalyst for electrochemical hydrogen generation.
1.3. An optimized hydrogen generation process by electrolysis.
Orientation 2. Innovative materials and technologies for the hydrogen generation and transportation.
2.1. A method of production and laboratory samples of finely dispersed effective hydrogen-absorbing materials based on LaNi5 for the reversible hydrogen storage.
2.2. A set of data on technical and operational characteristics of finely dispersed composite systems for hydrogen storage based on LaNi5.
2.3. Hydrogen-intensive polymer-carbon composite material for the storage and transportation of hydrogen based on micro- and nanocrystalline cellulose and modified carbon materials.
Orientation 3. Conversion of hydrogen into electricity
3.1. The materials for low-temperature fuel rods.
3.2. The development of carriers and catalytic systems for low-temperature FRs for the hydrogen energy based on modified activated carbon and mono- and bimetallic nanoparticles of palladium, copper, nickel and iron.
3.3. An anode material based on a hydrogen-absorbing material for electrochemical conversion and storage of hydrogen.
3.4 The cathode material for metal–hydride energy storage.
3.5 An upgraded electrochemical energy converter (battery) based on developed cathode and anode materials.
A MEU test sample of the low-temperature fuel rod.
Hydrogen-intensive polymer-carbon composite material for the storage and transportation of hydrogen based on micro- and nanocrystalline cellulose and modified carbon materials, as well as a catalytic system for the low-temperature FRs for hydrogen energy.
Kazakhstan's first compact hydrogen storage and transportation system in the form of containers (5-10 L battery cylinders) filled with granular intermetallic alloys with high hydrogen capacity.
Expected scientific results as part of the Program.
As part of the program, the following will be published:
– 9 articles in peer-reviewed scientific publications in the scientific field of the Program, included in the 1st (first), 2nd (second) and/or 3rd (third) quartile of impact factor in the Web of Science database and/or having a CiteScore percentile in the Scopus database of at least 50 (fifty);
– 14 articles in the journals recommended by CHEQAC;
– 3 monographs of Kazakhstani publishing houses;
– 5 intellectual property objects (patents) registered at the National Institute of Intellectual Property of the Republic of Kazakhstan;
– the Program results will be tested in the framework of the relevant national and international scientific conferences, symposiums and seminars;
– the level of technological readiness at the Program completion stage according to the TRL Methodology (dated July 18, 2023 No. 112-nzh) is 3/4 level.
OUTCOMES FOR 2023:
Section 1.
The maximum degree of methane decomposition using a microwave discharge was determined, and experimental data with minimal energy consumption were also determined (Technical Reference No. 12-230-02/169 dated 21.11.2023).
New catalytic systems were selected to reduce the hydrogen evolution overpotential (Research Report No. 1 dated 08.12.2023).
Section 2.
Approaches to the formation and management of the structural and phase state of LaNi5-based metal hydride storage systems were developed (Technical Reference No. 12-230-02/181 dated 01.12.2023).
A method for producing hydrogen-intensive polymer-carbon composite materials was developed. Micro- and nanocrystals of cellulose were obtained to produce a three-dimensional mesoporous hydrogen capacitor (Research Report No. 1 dated 08.12.2023).
Section 3.
The work was carried out on the development of macroporous silicon electrode structures with the through channels, on the walls of which the catalytic layers and mesoporous silicon membranes were coated (Research Report No. 1 dated 08.12.2023).
The work was carried out on the development of the materials and design of electrodes based on porous silicon with the nanocatalysts coated on their surface, the modification of the properties of the electrode structures by controlling the porosity level and modification of the graphene structures (Research Report No. 1 dated 08.12.2023).
The optimal carrier based on activated carbon was selected and a method for their modification was developed: acid and heat treatment of rice husks and sunflower husks (Research Report No. 1 dated 08.12.2023).
The work was done on the development of new materials and compositions for a metal hydride electrode with high specific capacity and stability (Research Report No. 2 dated 08.12.2023).
The new materials and compositions were developed for a metal hydride electrode with high specific capacity and stability (Research Report No. 2 dated 08.12.2023).
01.01.01. Determination of the maximum degree of methane decomposition using the microwave discharge, as well as the determination of the experimental data with minimal energy consumption
The stage supervisor is Tulenbergenov T.R., a researcher at IAE Branch
An analysis of scientific papers on the plasma pyrolysis of methane using a microwave discharge was carried out, during which it was revealed that the gaseous nitrogen or argon should be used as the initiator of the discharge in order to reduce the energy consumption for the methane decomposition; the temperature in the reaction chamber should be from 1000 °C, since the methane pyrolysis occurs at a high temperature; for the stability of the microwave discharge, it is necessary to inject the gas in a swirling stream at atmospheric pressure with a flow rate from 0.05 nl/min to 10 nl/min and at a temperature in the range from 200 °C to 1000 °C, with a variation in the microwave discharge power in the range from 600 W to 6000 W. Also, it is necessary to use catalysts to increase the efficiency of the plasma chemical reaction in the hydrogen generation. It was found that carbon catalysts and the carbon catalysts alloyed with metals had better stability and a lower deactivation rate compared to metal catalysts, but had a worse methane conversion compared to the metal catalysts. As a rule, the nickel-based metal catalysts and nickel-doped carbon catalysts had higher activity than the others.
01.02.01. Selection of new catalytic systems to reduce the hydrogen evolution overpotential
The stage supervisor is Tulenbergenov T.R., a researcher at IAE Branch
The importance of the electrolysis process of the aqueous solutions for the hydrogen generation was considered and the prospects of combining the installations for the hydrogen generation with the renewable energy sources were shown. The problem of the increased energy consumption for the hydrogen generation and the ways to solve it were shown. The main electrolytes (acidic and alkaline) for the hydrogen generation by the solution electrolysis were considered. The advantages and disadvantages of the acidic and alkaline electrolytes were shown, on the basis of which the choice was made in favor of alkaline electrolytes due to their lower energy consumption and higher productivity (hundreds of H2 m3/h for alkaline versus tens of H2 m3/h for the acidic solutions). The effect of the electrode materials on the energy consumption of the process as a whole was studied and a list of existing electrode materials for generating hydrogen by the electrochemical method was listed. The criteria for assessing the selection of electrode materials for HER were considered in detail, which will be used in the future in the study and optimization of electrode materials in the practical part.
01.03.01. Development of the approaches to the formation and management of the structural and phase state of LaNi5-based metal hydride storage systems
The stage supervisor is Mukhamedova N.M. PhD, Senior Researcher at IAE Branch
As a result of the theoretical analysis of foreign scientific and technical literature, it was established that LaNi5-based materials are very promising as materials for hydrogen storage. The addition of alloying elements such as V, Mg, Al, and Co makes it possible to affect the kinetics of hydrogen sorption and desorption. It was found that the improved kinetics of multicomponent composites is explained by the fact that hydride nucleation occurs more easily in the presence of a larger number of the phase boundaries. It is known that the duration of the mechanical synthesis affects the structure of powder mixtures. Long processing periods can lead to increased energy and the mechanical stress intensification, which facilitates a more uniform distribution of alloying components and the formation of a more stable material structure. However, it should be taken into consideration that long treatment periods can also lead to an increase in temperature, which can affect the processes of diffusion and segregation of components, therefore, the optimal treatment duration should be carefully adjusted. The use of various time intervals of mechanical synthesis will allow identifying the optimal time that provides the best synthesis results, including maximizing particle size reduction and obtaining a homogeneous microstructure.
01.05.01. Development of a method for producing hydrogen-intensive polymer-carbon composite materials. Production of micro- and nanocrystals of cellulose for the generation of a three-dimensional mesoporous hydrogen capacitor
The stage supervisor is Mukhamedova N.M. PhD, Senior Researcher at IAE Branch
Based on the conducted analytical review, it was revealed that the possibility of obtaining biomaterials through the effective disposal of agricultural waste is high. In this regard, the study found that carbon materials were extracted from sunflower seed husks and soy husks, and the yield was 28.6% for soy husks, which is 2% more than that of the sunflower seed husks. It turns out that the yield of cellulose from the obtained natural material is 50.69% of the sunflower seed husk and 12% more than that of soybean husk. In addition, the content of α-cellulose is 67.53%. It was about 10% more than that of the soybean husk. The chemical structure of all obtained materials was studied by the IR method for the coincidence of carbon and cellulose. According to the surface morphology, it was found that the carbon obtained from two raw materials had a reticulated, portioned shape, and cellulose had a fibrous structure. This means that we see that the obtained materials have the physicochemical properties inherent in hydrogen storage and transfer materials.
01.06.01. Development of macroporous silicon electrode structures with through channels, the walls of which are coated with catalytic layers and mesoporous silicon membranes
The stage supervisor is Miniyazov A.Zh., a Laboratory Head at IAE Branch
As part of the implementation of the Project objectives, a macroporous ma-Si was produced it meets the requirements for the FR electrodes. The requirements for the impurity composition of silicon depend on its use in the specific devices. Since the content of impurities in the silicon samples was very low, therefore, the atomic emission method of analysis with inductively coupled plasma was used and a method for determining the content of a small number of chemical elements was developed. A mesoporous silicon membrane material was developed, the pore size was 98-140 nm, the porosity was 29-35%, the surface area was 260-280 m2/g, the resistivity was 2~6*104 ohms⋅cm. As part of the research, the material was developed for a composite mesoporous silicon membrane in which porous silicon was the matrix and a gel proton-conducting electrolyte was the filler. Pore etching to a great depth is usually limited by the process of electrolyte depletion along the channel depth and manifests itself as a violation of the passivation of the walls, leading to pore etching in the direction to the side. The main advantages of using the porous silicon are the reduction of electrolyte leaching from the polymer structure during the membrane sealing. The experiments were conducted to develop the composite samples based on mesoporous silicon, which could serve as a promising material for fabricating the silicon electrodes. The promising nanocatalysts for a porous silicon matrix were identified. The choice was due to the fact that the catalysts with a size of less than 1.5 nm have a decrease in activity due to a decrease in the coordination number, and the specific surface area of the catalyst decreases, and, consequently, the activity decreases with an increase in the size.
01.06.02. Development of materials and design of electrodes based on porous silicon with nanocatalysts coated their surface, modification of the properties of electrode structures by controlling the porosity level and modification of graphene structures
The stage supervisor is Miniyazov A.Zh., a Laboratory Head at IAE Branch
The properties of the composites obtained by impregnation of the developed silicon samples in the synthesized solutions were studied. The samples of the initial silicon substrates were exposed in the modifying solutions, then washed from the SAA and solvent and dried at room temperature. It was found that when washing the samples with distilled water for 15-20 minutes, no more than 10% of the nanoparticles were removed from the composite surface. Annealing at 4500 C for 3 hours was used to remove the SAA completely; after such treatment, the surfactant is completely removed from the surface. By changing the integral intensity of the optical absorption spectra, it was found that up to 17.9% of palladium and up to 19.0% of platinum in the initial solutions were adsorbed onto porous silicon during the primary impregnation. The active phase of the catalyst was obtained from back-micellar solutions with palladium and platinum nanoparticles by the method of radiation-chemical reduction of metal ions under the anaerobic conditions. The reverse micelles were micro drops of an aqueous solution – the pools stabilized by a surface-active agent (SAA) in an organic solvent. It is possible to control the size of the formed particles by varying the synthesis conditions (reagent concentrations).
01.07.01 Selection of the optimal carrier based on activated carbon, and the development of a method for their modification: acid and heat treatment of RH and SH. Study of the physico-chemical properties
The stage supervisor is Miniyazov A.Zh., a Laboratory Head at IAE Branch
The condition of the coal produced from agricultural waste (sunflower, soy and rice husks) after acid treatment with its initial state was studied. It was found that the coal could also be produced from three different agricultural wastes, although the yield of rice husks was 10-15% higher than that of soybeans with sunflower. It could be seen that the yield of coal decreased after the acid treatment, it was found that the acid affected the excipients contained in the coal and reduced the yield, passing into the solution in the form of a suspension. It was found among the produced coals that the initial state of sunflower husk coal, the acid-washed state, was higher compared to others, but on the contrary, the rice husk was 10-25% lower, and the humidity was 5-5. 5 times lower even after acid washing compared to sunflower husk, the concentration showed that washing with 50% acid content lead to an increase in humidity. It was found that the coal from agricultural waste retained its original porous structure after acid washing, while maintaining its adsorption capacity, polarity, and thermal stability. It was found that among the coals produced from those three types of waste, the ash content of rice husks was 10-15 times higher than that of the coal produced from other soybean and sunflower husks. It was established that the coals produced from the waste were sorption stable in their initial state; the acid destroyed the pores in their structure after the acid washing. It was found that the initial state of the produced coal and even after the acid washing did not show a large difference in the proportion of oxygen-containing groups. In general, the results of the thermo-gravimetric analysis of the coal from the sunflower, soy and rice husks showed that it did not undergo significant changes in the temperature decomposition and mass losses, based on the results of the study, given that the coal from agricultural waste, that is, from sunflower, soy and rice husks, had high physical and chemical properties and had every reason to be used instead of commercial activated carbon.
01.08.01. Development of new materials and compositions for a metal hydride electrode with high specific capacity and stability
The stage supervisor is Miniyazov A.Zh., a Laboratory Head at IAE Branch
The existing methods of hydrogen production were considered and their profitability was analyzed. The current schemes of hydrogen generation were shown, indicating that in all cases it was necessary to use the hydrogen storage stations for its subsequent use. A scheme of energy storage by the operation of a hydrogen proton in an electrochemical current source was presented, in which there was no stage of storage of molecular hydrogen.
01.08.02. Assessment of the operability of hydrogen absorbent materials of Kazakh origin as electrode materials for electrochemical energy conversion sources
The stage supervisor is Miniyazov A.Zh., a Laboratory Head at IAE Branch
The design of the Ni-MeH battery was demonstrated with the test and determination of the real Ni-MeH parameters. During the Project implementation, a group of researchers oriented at synthesizing the anode material of that battery, optimize its properties and create a foundation for the commercialization of that battery in the market of Kazakhstan.
OUTCOMES FOR 2024:
Section 1.
The guidelines were developed for the selection of catalysts for the use in the microwave discharge when obtaining hydrogen and carbon (Guidelines No. 14-250-02/45 dated 30.10.2024).
An analysis of the relationship between the nature and number of surface functional groups of 2D materials and their catalytic properties in hydrogen evolution processes was performed (Act No. 14-250-02/4a dated 15.07.2024).
Section 2.
The samples of finely dispersed effective hydrogen-absorbing materials based on LaNi5+Mex for the reversible storage of hydrogen by alloying with Al, V and other metals were obtained and their properties depending on the obtaining modes were studied (Act 12-230-02/67 dated 27.03.2024, Protocol No. 12-230-02/145 dated 28.06.2024, Protocol No. 14-250-02/18a dated 26.08.2024).
The data on the resource of the reversible hydrogen-absorbing capacity of the fine-dispersed hydrogen storage systems based on LaNi5+Mex under the conditions of multiple hydrogenation/dehydrogenation loads were obtained. The main factors determining the cyclic stability of hydrides were the temperature range of large irreversible deformations, pressures, and structural and phase states (Act No. 12-230-02/144 dated 28.06.2024, Act No. 14-250-02/42 dated 28.10.24).
The results of a studying an effective copolymerizing material by an individual reaction of cellulose microfibers with AAm and PAAm using MBAAm as a crosslinking agent. The optimal amount of the cellulose nanofibers for giving the mechanical strength to the condensers. The data on the physical and chemical and mechanical properties of the obtained materials. The samples of a 3D mesoporous hydrogen condenser with improved sorption characteristics will be obtained by modifying graphene-like materials, the optimal type, quantity, and ratio of the modifier will be determined, and physical chemical properties will be studied (Act No. 14-250-02/5a dated 31.07.2024).
Section 3.
The results of studying the test of electrode materials and the MEU block, a comparative analysis of the proposed materials, as well as the results of testing the operability of sorbent materials and an assessment of the possibility of hydrogen accumulation in the electrochemical and metal hydride method (Act No. 14-250-02/48 dated 31.10.2024).
The properties of the macroporous silicon specific resistance were established, a solid electrolyte material was developed, and the data on its properties were obtained. The experimental work was carried out on the chemical etching of pores on the initial silicon wafers by a step-by-step process (Protocol No. 14-250-02/49 dated 31.10.2024).
Optimal modifying agents were obtained and the mode of modifying the activated carbon to be used as a carrier was determined. Rice husks, soybean husks and sunflower husks collected in Kyzylorda and the East Kazakhstan region were used as the materials for fabricating the activated carbon. The activation process included the chemical treatment with various reagents, such as KOH, NaOH, HSO₄ (5% and 15%), HCl (5%), NaCl (5%) and HPO₄ (15%), which increased the carbon adsorption properties (Act No. 14-250-02/42a dated 28.10.2024).
The ready-made samples of the activated carbon for deposition of transition metal nanoparticles were obtained and their physical and chemical characteristics were established. Monometallic (10Pd/ACm, 10Cu/ACm, 10Fe/ACm) and bimetallic (3Pd-7Cu/ACm, 3Pd-7Fe/ACm) catalysts were synthesized by wet impregnation of the carbon carriers followed by the reduction of metal ions using NaBH4 (Act No. 14-250-02/50 dated 31.10.2024).
The technology of developing 3D microporous hydrogen condensers based on micro- and nanocrystalline cellulose and graphene-like materials were developed. The 3D mesoporous condenser development technology included the synthesis, modification and testing of materials to achieve the optimal characteristics such as high sorption capacity, mechanical strength and thermal stability (Act No. 14-250-02/37a dated 02.10.2024).
The data on the degree of preservation of the characteristics of the composite electrode at low temperatures were obtained. The study showed that KOH-based electrolyte was the most effective for LaNi5-based batteries to operate at low temperatures. It turned out that the anions such as CO32-, PO43- and F- improved the electrochemical behavior, while others, such as NO3- and I- showed poor efficiency (Act No. 14-250-02/51 dated 31.10.2024).
01.01.02. Determination of the maximum degree of methane decomposition using the microwave discharge, as well as the determination of experimental data with minimal energy consumption
The stage supervisor is Tulenbergenov T.R., a senior researcher at IAE Branch
An analysis was performed on the selection of catalysts to be used in the microwave discharge during the hydrogen and carbon production. A literature review on the production of hydrogen and carbon as a result of methane pyrolysis in the microwave discharge using catalysts was given. The experimental studies on the production of hydrogen by the methane pyrolysis in the microwave discharge at a PM-6 applied research facility were carried out. The results of the experiments without a catalyst were presented, showing the effect of the installation parameters (the microwave discharge power and gas consumption) on the methane conversion degree. It was established that increasing the power of a microwave magnetron did not lead to an increase in the degree of the methane conversion and hydrogen selectivity. Also, an increase in the methane volume consumption did not contribute to an increase in the concentration of hydrogen, the target product. The experiments were carried out to determine the maximum degree of the methane decomposition using a metal catalyst with the different nickel content. It was established that the Ni content increasing in the metal catalyst was effective in increasing the degree of methane conversion and hydrogen selectivity. The catalyst with a content of 8 at.% of nickel deposited electrochemically showed the maximum value of hydrogen selectivity. The technology for the hydrogen production using a catalyst in a microwave discharge with a maximum degree of methane conversion was up to (32 ± 2)% and the hydrogen selectivity of up to (85 ± 1)% with a microwave discharge power of 0.6 kW, the methane consumption of 0.25 ± 0.05 l/min and argon (8 ± 0.2) l/min.
01.02.02. Studying the effect of the surface groups of 2D materials on the catalytic properties of the hydrogen evolution process
The stage supervisor is Tulenbergenov T.R., a senior researcher at IAE Branch
The results of the conducted experiments to study the effect of the surface groups of 2D materials on the catalytic properties of the hydrogen evolution process showed that MXene, oxidized for three days (overvoltage minus 301 mV at 10 mA/cm2), and MXene, modified with sulfur during the gradual heating, had the highest catalytic activity in HER (hydrogen evolution reaction) among the studied catalysts (minus 180 mV). Despite the fact that the overvoltage values were higher than for a platinum catalyst (minus 130 mV for pure platinum), they were still lower than for precious metals such as gold, silver and palladium – minus 720 mV, minus 700 mV and minus 400 mV, respectively. Moreover, a comparison of the MXene/S–1 obtained in this work with the base metal catalysts from other studies showed that its efficiency corresponded to the average level of the HER catalysts developed in the world. Thus, the literature contains data on less efficient materials (minus 300 mV on NiFeLDH-NS@DG10, -320 mV on Co9S8@NOSC-900) and more efficient ones (minus 15 mV on MoNi4 alloy, minus 29 mV on F-Ni3S4), as well as those on the same level as the one we obtained. The catalyst was minus 185 mV on NiCo2O4/TiO2, minus 178 mV on FeSe2/NF and minus 180 mV on NiCo2N/NF. That indicated a fairly high efficiency of the catalysts obtained in this work, but also the need to continue research to achieve even greater efficiency.
01.03.02. Obtaining of finely dispersed composite powders with a predictable structural and phase state based on LaNi5 for metal hydride applications by alloying A1, V, etc.
The stage supervisor is Mukhamedova N.M. PhD, Laboratory Head at IAE Branch
As part of implementing the project tasks by scanning electron microscopy of mechanically synthesized powder mixtures based on LaNi5 in the mode of topographic and compositional contrast under the identical conditions, it was revealed that the ratio of grinding balls to the powder had a significant effect on the result of the process. When estimating the particle sizes obtained as a result of the synthesis of mixtures, it was found that an increase in the number of grinding balls relative to the amount of powder lead to the formation of a more finely dispersed mixture. The teardrop-shaped particles obtained using a 1:20 ratio of balls to the powder had the shape of an “irregular” ball: oval or flattened. The mixture was characterized by a more uniform particle distribution. The size of the crystallites in all samples varied from 15.35 to 83.44 nm, which corresponded to a small size. Such small crystallites can contribute to the deformation of the crystal lattice, since the expansion of peaks is associated with a less ordered structure in small-sized crystallites. The phase composition of the samples was based on hydroxide and oxide phases (La(OH)3, La2O3), which was mainly related to the oxidation process of the samples. An inhomogeneous multiphase structure without pores and with minor cracks was observed in all samples obtained by the SPS method of mechanically synthesized powder mixtures. The studies showed that, depending on the chemical composition, the distribution of elements and the structure morphology were of diverse character, in particular, the formation of secondary phases such as LaNi5, NiV, Ni happened in various modifications. All samples were characterized by the lanthanum oxide phase, which had a cubic crystal lattice (Ia-3spatial group), the lattice parameter was a=b=c=1.1418 nm. However, there was a decrease in the intensity of diffraction lines. The peaks with high intensities belonged to nickel (Ni) with a cubic crystal lattice (Fm-3m space group), the lattice parameter was a=b=c=0.3523 nm, as well as in the samples after MS.
01.04.01. Hydrogen accumulating properties of mechanically alloyed composite hydrogen storage systems based on LaNi5
The stage supervisor is Mukhamedova N.M. PhD, Laboratory Head at IAE Branch
As a result of the analysis, the processes of adsorption and desorption depending on pressure at a temperature of 50 °C were studied. The amount of the adsorbed gas increased with increasing the pressure and reached a maximum value 3.5 cm3/g. The graph showed the presence of a hysteresis effect between the adsorption and desorption curves. This phenomenon indicated the material porosity and the features of gas binding to the adsorbent. The presence of hysteresis could also indicate that a certain number of gas molecules remained in the material after desorption. A linear relationship between the adsorption and pressure was observed in the graph initial section. This indicated that the adsorption went on under the equilibrium conditions at low pressures. The sorption kinetic curve showed that the hydrogen content increased with the saturation time increasing. According to the results obtained at the beginning of the tests, during the first 7-8 minutes, hydrogen absorption practically did not occur, and with increasing the time, the absorption intensity increased until the equilibrium was reached. It took about 60 minutes to reach the equilibrium at a temperature of 50 °C and a pressure of 20 Bar. The kinetic desorption curve showed that the hydrogen content began to decrease from the first minutes. It should be noted that with the addition of Al, the kinetic curves of both sorption and desorption had a more uniform character. It took about 60 minutes to reach the equilibrium at a temperature of 75 °C and a pressure of 25 Bar. A similar nature of the hydrogen kinetics during the saturation could be associated with the oxidation of the surface of the materials under study. The oxidation of the LaNi5-based MH surface with a hexagonal and cubic structure was facilitated by an increased duration (more than 60 minutes) of sorption/desorption processes.
01.05.02. Development of a method for obtaining hydrogen-intensive polymer-carbon composite materials: copolymerization of cellulose microwaves based on AAm and PAAm monomers. Determination of the effective mass fraction of cellulose nanofibers providing the mechanical strength
The stage supervisor is Mukhamedova N.M. PhD, Laboratory Head at IAE Branch
As part of the Project, a method for obtaining polymer-carbon composite materials was developed, a 3D microporous hydrogen condenser based on micro- and nanocrystalline cellulose was developed, the diffusion doping of walls between silicon pores was studied, the resistivity of porous silicon was evaluated, and mesoporous silicon with high electron resistance was developed and studied to isolate the anode and cathode the membrane-electrode unit. The surface of silicon mesopores was modified with a material with ionic conductivity in order to obtain a reinforced solid electrolyte. The gas tightness of a proton-conducting membrane based on porous silicon was studied. A method for obtaining polymer-carbon composite materials with hydrogen capacity by copolymerization of cellulose microfibers with acrylamide and polyacrylamide monomers was developed. According to the obtained results, the microcrystalline cellulose and polyacrylamide were effective as an effective copolymerizing monomer. In addition, during the copolymerization with the polyacrylamide, the effective concentration of microcrystalline cellulose was 3%; it was also found that the mechanical strength in this case could withstand the pressure up to 132 kPa and underwent further deformation. A 3D microporous hydrogen condenser based on micro- and nanocrystalline cellulose from plant raw materials and graphene-like materials was developed. Their physical and chemical characteristics, optimal conditions of hydrogen capacity and physical factors affecting the sorption/desorption process were determined. According to the research results, the addition of carbon materials, such as graphene oxide, did not adversely affect the chemical structure and thermal stability of the cellulose-based composite.
01.05.03. Development of a 3D microporous hydrogen condenser based on micro- and nanocrystalline cellulose from plant raw materials and graphene-like materials, determination of their physical and chemical characteristics, optimal conditions of hydrogen capacity and physical factors affecting the sorption/desorption process. Immobilization of the graphene-like materials (unreduced and reduced) into the volume of a 3D mesoporous hydrogen condenser by in-situ method
The stage supervisor is Miniyazov A.Zh. PhD, Director at IAE Branch Center
By modifying the graphene-like materials, the samples of a 3D mesoporous hydrogen condenser with improved sorption characteristics were obtained, the optimal type, amount, and ratio of the modifier were established, and physical and chemical properties were studied. Their physical and chemical characteristics, optimal conditions of hydrogen capacity and physical factors affecting the sorption/desorption process were determined. According to the results of the conducted research, it was found that the addition of carbon materials, such as graphene oxide, did not adversely affect the chemical structure and thermal stability of the cellulose-based composite. It was found that the mechanical strength of aerogel immobilized with the carbon material, such as graphene oxide with a content of 1%, 3% and 5%, could withstand a pressure of 140 kPa and underwent further deformation. However, the aerogels with the carbon material such as 5% graphene oxide were found to have 1.5 and 1.2 times longer stability under the pressure compared to 1% and 3%.
Based on the obtained results, it could be concluded that a 3D material based on micro- and nanocrystalline cellulose immobilized by a carbon material such as graphene oxide had significant potential to be used as a hydrogen-sorbing material.
01.06.03. Studying the diffusion doping of walls between the silicon pores, assessment of the macroporous silicon resistivity
The stage supervisor is Miniyazov A.Zh. PhD, Director at IAE Branch Center
A study of porous silicon as a fuel cell membrane was conducted. For this purpose, the experimental work was carried out on the chemical etching of the pores on the initial silicon wafers by a step-by-step process: the application of a silver catalyst from silver nitrate salts; pore growth in a solution of hydrofluoric acid with hydrogen peroxide; removal of silver nanoparticles by etching in nitric acid. The obtained composite sample based on a matrix of porous silicon and the filler, a gel proton–conducting electrolyte, made it possible to form mechanically more stable structures. The electrolyte encapsulation into the porous silicon matrix structure significantly increased the membrane mechanical strength, and also demonstrated the possibilities for using proton ionic liquids as proton donors in the proton-conducting membranes.
The properties of specific macroporous silicon were determined. The properties of the structures such as “porous silicon/deposited Me” could vary widely due to the ability to change both the modes of electrochemical deposition of metals, as well as the metals themselves and the structure of porous silicon itself.
A comparative analysis of the silicon samples with Me and gel electrolyte according to the resistivity data showed that a silicon sample with the gel electrolyte had lower resistance, which made it more attractive from the point of view of the effectiveness to be used in MEU FR.
The combination of all the properties of the studied samples determined their possible choice for the use as a fuel cell membrane.
01.06.04. Development and study of mesoporous silicon with high electron resistance for isolating the anode and cathode of the MEUFR membrane-electrode unit. The modification of the surface/filling of the silicon mesopores with an ionic conductive material in order to obtain a reinforced solid electrolyte. Study of the gas tightness properties of a proton-conducting membrane
The stage supervisor is Miniyazov A.Zh. PhD, Director at IAE Branch Center
The solid electrolyte material and data on its properties were obtained as part of the implementation of the project objectives. The experimental work was carried out on the chemical etching of pores on the initial silicon wafers by a step-by-step process: application of a silver catalyst from silver nitrate salts; pore growth in a solution of hydrofluoric acid with hydrogen peroxide; removal of silver nanoparticles by etching in nitric acid. As a result, the samples of porous silicon with a thickness of 0.2-0.4 mm were obtained for the research and modification. The structure was characterized by a network of channels inside the silicon matrix, the pores were pronounced with clear edges and protruding formations, the surface was homogeneous, and the pores were evenly distributed over the surface, the structure demonstrated a fairly high level of porosity.
Porous silicon was studied by the method of adsorption porometry. The measurements were carried out after preliminary vacuuming for the degassing of the samples, followed by the processing of experimental data with the BET (measurement of specific surface area using the Brunauer-Emmett-Teller method) and BJH (distribution of total volume and pore size determined by the Barrett-Joyner-Halend method along the desorption isotherm curve) methods. The obtained data were segmented into micropores (0.35–2 nm), mesopores (2-10 nm) and pores (10-50 nm, 50-200 nm). At the same time, the pores with a size of 10-50 nm occupied the largest proportion of the pore volume (81.38%), and pores with a size of 2-10 nm accounted for 15.91% of the total pore volume, respectively, the pores with a size of 50-200 nm had a small proportion, which was 2.71% of the total volume. The pore surface area was represented by the following results: mesopores (2-10 nm) occupied the largest pore surface area (74.43%), the pores of 10-50 nm occupied 25.39% of the surface area, and the macropores (50-200 nm) occupied only 0.18% of the area. The deposition of Me could lead to a change in the porous silicon properties, therefore, the proton conductivity of the obtained samples was measured and compared with the proton conductivity of a porous silicon sample with the addition of a DEMA/TfO gel conducting electrolyte.
According to the analysis results, it was found that a sample of porous silicon with the gel filler with a sensory response of 27% had reduced gas permeability, which allowed us to conclude that it was not sufficiently suitable as a gas permeable FR membrane, but it could be useful if high mechanical stability was required. A sample with a filler (DEMA/TO) with a response of 43% had sufficient gas permeability and channel density. A porous Si sample with a gel filler (DEMA/TO) was the best choice for the FR membrane, as it had a sufficiently high gas permeability and balanced channel density and diameter characteristics, which could ensure efficient FR operation.
01.07.02 Selection of the optimal carrier based on the activated carbon, and development of a method for their modification
The stage supervisor is Miniyazov A.Zh. PhD, Director at IAE Branch Center
Rice husks, soybean husks and sunflower husks collected in Kyzylorda and the East Kazakhstan region were used as materials for fabricating the activated carbon. The activation process included chemical treatment with various reagents such as KOH, NaOH, HSO₄ (5% and 15%), HCl (5%), NaCl (5%) and HPO₄ (15%), which improved the adsorption properties of carbon. To increase the efficiency of the carbon carrier, a heat treatment method (carbonation) was applied at temperatures of 300-700 °C for removing the volatile substances. The characteristics of the obtained activated carbon were compared with the commercial analogues, which made it possible to assess its suitability for the use in low-temperature fuel rods. The results showed that the activated carbon obtained from agricultural bio-waste had higher adsorption capacity and environmental value, which made it a promising and stable carrier for the catalysts.
01.07.03 Synthesis of nanoparticles of transition metals (Cu, Fe, Pd). Development of a method for applying nanoparticles to the volume of the modified carbon carriers. Studying the physical and chemical characteristics of the catalysts. Doping of commercial and synthesized AC with glucose and studying their physical and chemical properties
The stage supervisor is Miniyazov A.Zh. PhD, Director at IAE Branch Center
The AC samples for deposition of transition metal nanoparticles and their physical and chemical characteristics were obtained. Monometallic (10Pd/ACm, 10Cu/ACm, 10Fe/ACm) and bimetallic (3Pd-7Cu/ACm, 3Pd-7Fe/ACm) catalysts were synthesized by wet impregnation of the carbon carriers followed by the reduction of metal ions using NaBH4. Doping of industrial and synthesized activated carbon by adding the glucose was used to modify the structure of carbon materials and increase their sorption capacity. The analysis of textural characteristics showed an increase in the specific surface area and pore volume, which significantly improved the sorption of metals The IR spectroscopy study confirmed the formation of chemical bonds between metal nanoparticles and functional groups of the carbon carrier, which contributed to an increase in catalytic activity. The microscopic analysis revealed the particle sizes: 5-15 nm for palladium, 8-19 nm for copper, and 30-34 nm for bimetallic systems. The developed methods ensured a uniform distribution of metals on the carrier and the stability of the physical and chemical characteristics of the catalysts.
01.08.03. Selection of additive components and development of an electrode preparation technology that meets the requirements of high reversibility, power and phase stability
The stage supervisor is Miniyazov A.Zh. PhD, Director at IAE Branch Center
The LaNi5 electrode material was obtained by self-igniting synthesis, and the technology for preparing an electrode based on it, used for nickel metal hydride (Ni-MeH) batteries, was developed.
For the self-igniting synthesis from salt solutions, 5 mmol of La(NO3)3•6H2O, 25 mmol of Ni(NO3)3•6H2O and 36 mmol of glycine dissolved in 50 ml of water were used. The resulting solution was evaporated at 100 °C to form a gel, which then self-ignited with a subsequent increase in temperature to 600 °C in a muffle furnace (10 °C/min) and exposed for 2 hours. The obtained black powder was then mixed with CaH2 and LiCl in a mass ratio of 1:2:0.9 in an inert argon atmosphere in a glove box and transferred to a pipe furnace. The furnace was heated from room temperature to 600 °C at a rate of 5 °C/min and kept at this temperature for 5 hours. The material was reduced in an atmosphere of Ar/H2 mixture (95:5) with a flow rate of 200 ml/min. The resulting product after washing was analyzed by the X-ray diffractometry and scanning electron microscopy.
The fabrication of an electrode composite based on LaNi5 was carried out in three different ways to compare and optimize the process of their creation. Based on the obtained data, PTFE was selected as the optimal binding material for further research. In the future, all materials will be made using PTFE.
01.08.04. Reducing the temperature dependence of the electrochemical characteristics of metal hydride electrodes for increasing the stability and reducing self-discharge
The stage supervisor is Miniyazov A.Zh. PhD, Director at IAE Branch Center
A study was conducted on the effect of various hydroxide electrolytes on the battery operation at low temperatures, including the following compounds: NaOH, KOH, RbOH, CsOH. Various salt additives and anions were used as additives: CO32-, PO43-, F-, NO3- and I-. All solutions had a concentration of 6 M. The test temperature was 20 °C, 10 °C, 0 °C, -10 °C, -20 °C. Before the experiments, the electrodes were activated in several cycles to stabilize their characteristics. At the end of the tests, the capacitance of the electrodes was also measured at room temperature to assess whether the initial capacitance parameters were restored.
The study showed that the KOH-based electrolyte was the most effective for LaNi5-based batteries to operate at low temperatures. It was found that anions such as CO32-, PO43-, and F- improved the electrochemical behavior, while others, such as NO3- and I-, showed poor efficiency. It was assumed that the main mechanism of the effect of salt additives was to change the nature of hydrogen bonds and chemical interactions on the surface of the electrodes. As an example, the addition of salt additives such as Cs2CO3 significantly improved the battery operation at low temperatures.
OUTCOMES FOR 2025:
Section 1.
The work was carried out to study the characteristics and properties of solid products of the methane pyrolysis reaction in a microwave discharge. The results showed that the change in power had a significant effect on the morphology, structural characteristics and porosity of the obtained carbon materials (Protocol No. 14-250-02/98 dated 19.09.2025).
The data on the economic efficiency of using 2D materials as catalysts for the electrochemical hydrogen generation were obtained (Final Research Report, reg. No. 0123RK01187, inv. No. 0225RK00958 dated 14.10.2025).
Section 2.
The samples of finely dispersed effective hydrogen-absorbing materials based on LaNi5+Mex for reversible storage of hydrogen by alloying Ti, Mn, and Co were obtained and their properties were studied depending on the obtaining modes (Act 14-250-02/67 of 17.03.2025, Protocol No. 14-250-02/94 dated 29.08.2025).
The comprehensive studies of the cyclic stability of finely dispersed composite hydrogen storage systems based on LaNi5Mex in hydrogenation/dehydrogenation cycles of up to 500 cycles were carried out. The patterns of the structural-phase state degradation under the cyclic effects. The microstructural features and mechanisms of functional degradation of the sorption properties in the studied hydrides were studied (Act No. 14-250-02/123 dated 10.11.2025).
The data on the sorption capacity, hydrogen retention time, sorption/desorption rate, working cycle of the condenser, as well as the factors affecting the process of hydrogen sorption/desorption, including: temperature, pressure, time were obtained (Act No. 14-250-02/77 dated 14.05.2025, Final Research Report reg. No. 0123RK01187, inv. No. 0225RK00958 dated 14.10.2025).
Section 3.
The experimental samples of the composite silicon electrode structures and a membrane electrode unit of a fuel rod were obtained. An electrode material based on porous silicon was developed and tested, there a formed local dimensional structure with the possibility of introducing nanoscale catalytic particles into the pore structure was created (Act No. 14-250-02/54a dated 09.01.2025, Final Research Report, reg. No. 0123RK01187, inv. No. 0225RK00958 dated 14.10.2025).
The results of a study on the testing of electrode materials and a membrane electrode unit were obtained. MEU tests showed that the conductivity was low and stable with the moisture absorption of up to 20-30%, and a sharp increase in conductivity was observed with an increase in moisture absorption above 30%, and the conductivity stabilizes when a moisture saturation of about 80% was reached. The tests to determine the current-voltage characteristics and calculate the specific power of the MSU sample showed that when the current density increased, a voltage drop was observed and maximum power was reached in the range of 200-300 MW/cm2 (Protocol No. 14-250-02/71a dated 03.04.2025, Final Research Report, reg. No. 0123RK01187, inv. No. 0225RK00958 dated 14.10.2025).
The samples of Cu, Fe, and Pd nanoparticles and their size and optical characteristics were obtained. The monometallic catalysts 5Pd/ACm, 10Cu/ACm, and 10Fe/ACm were obtained by wet impregnation. The aqueous solutions of salts of FeCl₃•6H₂O, Cu(NO₃)co₂•3H₂O and PdCl₂ at a concentration of 0.001 mol/l were prepared for the application of ions of iron, palladium and copper on the activated carbon (ACm) (Act No. 14-250-02/78 dated 14.05.2025, Final Research Report, reg. No. 0123RK01187, inv. No. 0225RK00958 dated 14.10.2025).
An experimental model of a low-temperature fuel rod with improved or new catalytic systems for converting hydrogen energy into electrical energy was developed. A full-size Ni-MH battery layout in the “pouch cell” format based on the developed composite materials was assembled and tested. The prototype demonstrated the stable operation with a discharge plateau of about 1.25 V, a high initial specific capacity of ~230 mAh/g and good initial cycling (maintaining 85% capacity after 25 cycles), (Final Research Report, reg. No. 0123RK01187, inv. No. 0225RK00958 dated 14.10.2025).
01.01.03. Materials science studies of solid products of the methane pyrolysis reaction in the microwave discharge
The stage supervisor is Tulenbergenov T.R., a Department Head at NNC RK
The materials science studies of solid products of the methane pyrolysis reaction in the microwave discharge using a transmission electron microscope (TEM) were carried out. The object of the study was carbon powders obtained as a result of the methane pyrolysis at the PM-6 installation. The analyses were performed on a JEOL JEM-1400Plus microscope at an accelerating voltage of 80 kV. A comparative analysis confirmed that the structure of the carbon material under study corresponded to the characteristics of turbostratic graphite, which indicated similar mechanisms for the inner structure formation. The TEM analysis of the carbon samples synthesized at various capacities (C-1, C-2, and C-3) revealed the features of their morphology and microstructure. The samples showed a porous structure with signs of layering characteristic of graphene-like and turbostratic carbon nanomaterials. The C-1 sample mainly consisted of loose amorphous clusters of particles with the pronounced porosity. In the C-2 sample, the regions with local ordering and the presence of graphene-like fragments, including spherical structures with a turbostrate structure, were observed. The C-3 sample showed a more pronounced crystallinity, including the domains with a regular lattice and defects characteristic of partially ordered turbostratic systems.
01.02.03. Assessment of the economic efficiency of using catalysts based on 2D materials in the processes of electrochemical hydrogen release
The stage supervisor is Tulenbergenov T.R., a Department Head at NNC RK
The analysis of composite materials based on MXene, including the noble metal atoms or nanoparticles, various morphologies of cobalt phosphides, layered transition metal hydroxides, certain organometallic frameworks and carbon nanotubes integrated into the MXene structure, was carried out, and an economic justification for the choice of cathode materials was made. There were some active variants among the transition metal-based hydrogen release catalysts, but their common problem was a low specific surface area due to the aggregation of the nanoparticles. The MXene layered materials were an excellent matrix for creating the composite catalysts due to their unique combination of high electrical conductivity, good chemical and mechanical stability, as well as a developed surface and ability to functionalize. The analysis of the reviewed studies showed that the best catalytic characteristics among the MXene-based composite materials were shown by the systems including the noble metal atoms or nanoparticles, various morphologies of cobalt phosphides, layered transition metal hydroxides, certain organometallic frameworks and carbon nanotubes integrated into the MXene structure.
In addition to the catalytic activity, the economic efficiency of the catalysts was important. The purpose of analyzing the synthesis costs of the materials considered in this part of the work was to compare and correlate them with RVV overvoltage parameters, as well as to identify the common trends and the most cost-effective catalysts. The best price/efficiency combinations were shown by: MWCNT@V2CTx ($7/synthesis, 27 mV), Ru@Ti3C2Tx-VC ($14.1/synthesis, 35 mV) and Ru/Ti3C2Tx/NF ($21.3/synthesis, 37 mV). It was also found that rare expensive precursors, in particular platinum acetylacetonate, hexachlorobenzene and the Pluronics P-123 block copolymer, as well as the cost of MAX phases and the choice of a leaching agent for the production of MXene, have the greatest impact on the increase in the costs.
01.03.03. Obtaining of finely dispersed composite powders with a predictable structural and phase state based on LaNi5 for metal hydride applications by alloying Ni, Mn, Ti
The stage supervisor is Mukhamedova N.M. PhD, Laboratory Head at IAE Branch
As part of the Project, the samples of finely dispersed effective hydrogen-absorbing materials based on LaNi5+Mex for the reversible hydrogen storage by alloying Ti, Mn, and Co were obtained. The particle sizes of the powder mixtures of the LNT series with the addition of titanium, the LNM series with the addition of manganese, and the LNC series with the addition of cobalt were determined. The results of the microscopic analysis showed that the average size of the 36%La-64%Ni-15%Ti mixture with 350, 400 revolutions with the ratio of 1:20, 1:30 was 6.15 µm, 36%La-64%Ni-15%Mn with 350, 400 revolutions with the ratio of 1:20, 1:30 was 2.29 µm, while the particle size of 36%La-64%Ni-15%Co with 350, 400 revolutions with a ratio of 1:20, 1:30 was 1.55 µm. The LNT series samples were characterized by the formation of LaNi5 and TiNi intermetallic phases, as well as the by-product oxide phases of La2O3 and TiO2. Among them, the most preferred characteristics were demonstrated by the LNT-1 sample, which has the highest intensity of the diffraction peaks of the target phases, as well as their high values of the average crystallite size (LaNi5 – 86.31 nm; TiNi – 63.28 nm), which indicates the best crystallinity degree. The presence of LaNi5, LaNi4Mn, LaNi3Mn2 and oxide LaMnO3 phases were found in the LNM series. The LNM 1 sample demonstrated the most pronounced characteristics of the target phases (in terms of the number, intensity of peaks, and size of crystallites), which made it the most promising for the further research in the field of hydrogen absorption. The average crystallite size of the target phases in this sample reached: LaNi5 – 90.23 nm; LaNi4Mn – 87.61 nm; LaNi3Mn2 – 87.85 nm. There was a decrease in the number and intensity of reflexes of the target phases, as well as a decrease in the size of crystallites in the LNM-4 sample, which may indicate a partial violation of the crystalline order. In the LNC series samples, the main phases are LaNi4Co and LaNi5, accompanied by La2O3 oxide compounds and residual metallic Ni. The main phases LaNi4Co and LaNi5, accompanied by La2O3 oxide compounds and residual metallic Ni were in the LNC samples. The LaNi4Co phase was revealed in all samples, most intensively in LNC-1 (crystallite size was 89.31 nm), but the degree of its crystallinity was limited there. At the same time, the LNC-4 sample, despite the smaller size of LaNi4Co and LaNi5 crystallites, demonstrated the highest content of target phases and a more pronounced crystalline ordering, which made it possible to consider it as the most suitable candidate for the hydrogen storage.
01.04.02. Cyclic stability of LaNi5 hydrides under close to the operating conditions
The stage supervisor is Mukhamedova N.M. PhD, Laboratory Head at IAE Branch
The LaNi5-based materials modified with Ti and Mn showed the increased cyclic stability due to improved hydrogen dissociation, facilitated diffusion of the H atom, and reduced energy barriers. The multicomponent phases and recrystallization contributed to the structure stabilization and more uniform operation of the sorption sites, which generally improved the kinetics and durability of hydride systems during the multiple hydrogenation/dehydrogenation cycles. The surface activation/catalytic processes – the adsorption rate depended on the surface chemical activity (the additive catalytic properties). Ti often acted as a catalyst for the H₂ dissociation and facilitated the penetration of H atoms into the lattice. Ti and its oxides/intermetallic phases often improved the H₂ dissociation on the surface, created favorable boundary states, and titanium also caused a slight expansion of the Lani₅ crystal lattice, increasing the H placement and facilitating its migration. Mn could be part of phases less prone to the formation of hydrides, or create the transition zones with a high energy barrier. The presence of multiple phases/recrystallized areas increased the distribution of energy barriers, which visually gave a “blurred” plateau and slow kinetics. Mn more often formed the oxides/phosphates on the surface, which could interfere with adsorption/desorption.
01.05.04. Development of a 3D microporous hydrogen condenser based on micro- and nanocrystalline cellulose from the plant raw materials and graphene-like materials, determination of their physical and chemical characteristics, optimal conditions of hydrogen capacity and physical factors affecting the sorption/desorption process. Study of the sorption and desorption properties of a 3D mesoporous hydrogen condenser
The stage supervisor is Mukhamedova N.M. PhD, Laboratory Head at IAE Branch
As part of the implementation of the Project objectives, a 3D microporous hydrogen condenser based on micro- and nanocrystalline cellulose from the plant raw materials and graphene-like materials was developed. Their physical and chemical characteristics, optimal conditions of the hydrogen capacity and physical factors affecting the sorption/desorption process were determined. The hydrogen absorption properties of 3%MCC/PAm-3%CNF aerogel with a surface area of 3000 cm2/g were studied. According to the obtained results, starting from the low pressure, the hydrogen sorption process was active. At a pressure of 1 bar, the sorption capacity of aerogel was 0.8%. The studies showed that the hydrogen-intensive properties of the materials directly depended on their surface area.
The study of the hydrogen sorption kinetics by 3%MCC/PAm-3%CNF-5%GO aerogel showed that the sorption process at the initial stage was characterized by rapid growth, after which it gradually reached the saturation state. In the low-pressure range (0-200 mbar), there was a sharp increase in the hydrogen sorption, which was associated with the presence of a large number of free active centers and light gas adsorption. In the average the pressure range (200-600 mbar), the sorption rate slowed down, but the growth still continued. The sorption value stabilized and tended to the saturation in the high pressure range (600-1000 mbar). The maximum sorption capacity was about 4 wt.%, which was 4 times higher than for 3%MCC/PAm-3%CNF. The hydrogen sorption process was replicated on a single sample for up to 21 cycles. According to the obtained results of studying the dependence of hydrogen desorption in 3%MCC/PAm-3%CNF-5%GO aerogel on the temperature, the mass fraction of hydrogen remained almost constant (≈4 wt.%) in the low-temperature range (25-100 °C). That indicated that the hydrogen was in a bound state on the material surface or in the volume and a significant desorption did not occur. In the range of the average temperatures (100-150 °C), the desorption process began. According to the diagram, the mass fraction of hydrogen decreased sharply. This indicated that the energy of hydrogen binding in the material had an average value. The main desorption process took place precisely in this temperature range. In the high-temperature range (150-200 °C), the mass fraction of hydrogen tended to zero. This meant that at a given temperature, most of the hydrogen was completely desorbed from the material.
01.06.05. Test of electrode materials and the MEU block, comparative analysis
The stage supervisor is Miniyazov A.Zh. PhD, Deputy Director at IAE Branch
As part of the implementation of the Project objectives, a membrane was obtained by impregnating porous silicon with a solution of PVA–H₃po₄ (20:80 wt.%), followed by drying at 60 °C to a stable mass, Pt–Co (cathode) and Pd–Cu (anode) electrodes deposited on a Vulcan XC72 carbon carrier were hermetically attached to both sides of the membrane. The MEU was assembled in a pressed test casing using the graphite gaskets and current collectors (the electrodes were pre-clipped over the reactor core area of 1 cm2, the membrane and electrodes in the press were combined with graphite current collectors and gaskets, and the assembly was compressed in a press cell with a force of 50-80 N for the contact between the layers).
According to the data obtained from the tests of porous silicon electrodes to determine the physical and chemical and mechanical properties, the specific surface area was 105-180 m2/g, the pore volume was 0.1–0.2 cm3/g, the average pore diameter was ~18-22 nm, the surface energy was 45-55 MJ/m2, the hydrophobicity was 72-84°C, the chemical stability was at pH 3-10, the Si content was ≥ 98.5wt.%, the corrosion resistance in HSO₄ was > 72 h at 60 °C, Vickers microhardness was 0.3–0.6 GPa, the bending strength was ~20-30 MPa, the modulus of elasticity was 2.8–4.5 GPa, the thermal stability of TGA/DTA was up to 250°C. As can be seen from the obtained data, the porous silicon had a number of physico-mechanical and thermal properties that ensured its suitability as an effective material for the electrodes of low-temperature fuel rods. It combined the sufficient mechanical strength, resistance to temperature effects and high compatibility with the catalysts. The presented physical and chemical properties showed the possibility of its use as a universal “template substrate”.
01.06.06. Assessment of the operability of sorbent materials and the possibility of application in the electrochemical and metal hydride method of hydrogen accumulation
The stage supervisor is Miniyazov A.Zh. PhD, Deputy Director at IAE Branch
To test the MEU FR based on the porous silicon, a membrane material was developed and fabricated, and a composite sample was obtained based on a matrix of porous silicon and a filler, the PVA/H₃po₄ proton-conducting electrolyte (85:15 wt.% 350-400 µm thick). The temperature dependence of the ionic conductivity of the “porous silicon/PVA–H₃po₄” composite showed that at 25 °C the ionic conductivity was about 1.2 mS/cm, which corresponds to the lower limit of the applicability in the low-temperature FR. With an increase in temperature to 75 °C, a monotonous increase in the conductivity up to ~5.4 mS/cm was observed. That growth was due to the increased proton mobility and intensification of hydrogen conduction in the PVA-H₃po₄ gel-like matrix. Temperature-dependent conductivity was particularly effective at high humidity and temperature, making it suitable for conditions with variable humidity and moderate heating.
The MEU sample based on a porous silicon/PVA–H₃po₄ composite membrane at 25 °C and humidity below 20% had a low ~10⁻⁴ mS/cm conductivity, the growth after 30-45%, and at 85-95% saturation, a level of ~1.2×10-1 mS/cm was reached. In the studied MEU sample with a PVA–H₃po₄ membrane at 50 °C, an increase in ionic mobility was observed, and the conductivity increased by almost 1.8 times over the entire range. The same sample showed the highest level of conductivity up to ~3.4×10-1 mS/cm at 95% RH at 75 °C, which indicated a high potential of such MEU. When compared with the known data, for example, with Nafion, it had higher basic conductivity at 25 °C ~2.5×10-1 mS/cm at 90% RH, however, as the temperature increases, PVA–H₃po₄ approaches it. The tests to determine the voltage characteristics and calculate the specific power of the MEU sample (membrane – “porous silicon/PVA–H₃po₄”, where the content of PVA–H₃po₄ was 20:80 wt.% /cathode - Pt–Co-carbon carrier/ anode - Pd–Cu- carbon carrier) showed that with the current density increasing there was a voltage drop and the maximum power was reached in the range of 200-300 MW/cm2.
01.07.04. Synthesis of nanoparticles of transition metals (Cu, Fe, Pd). Development of a method for applying the nanoparticles to the volume of modified carbon carriers. The study of their physical and chemical and electrochemical properties and the electrochemical stability of catalytic systems. Study of their dimensional and optical characteristics
The stage supervisor is Miniyazov A.Zh. PhD, Deputy Director at IAE Branch
As part of the implementation of the Project objectives, the 5Pd/ACm, 10Cu/ACm, and 10Fe/ACm monometallic catalysts were obtained by wet impregnation. For the application of the ions of iron, palladium and copper on activated carbon (ACm) the aqueous solutions of salts of FeCl₃•6H₂O, Cu(NO₃)co₂•3H₂O and PdCl₂ at a concentration of 0.001 mol/L were prepared. The obtained solutions were added to ACm while mixing, they were mixed for 10 minutes, and then left at room temperature for 4 hours for complete sorption of metal ions. Next, the material was dried at 150 °C for 2 hours to remove moisture, and then it was dried at 300 °C for 4 hours to fix the metal ions. After drying, the samples were cooled to room temperature.
The 3Pd–7Cu/ACm and 3Pd–7Fe/ACm bimetallic systems were also obtained by wet impregnation. For that purpose, Cu(no₃)₂•3H₂O salts were dissolved in distilled water, and PdCl₂ was dissolved in an aqueous alcohol solution (90% ethanol: water = 30:70 ml/ml). 1 g of ACm was added to the mixture, mixed for 10 minutes and exposed at room temperature for 4 hours for the sorption of metal ions. The washing, moisture removal and drying procedures were carried out in a similar manner of the 5Pd/ACm obtaining process. Then 0.5 g of Cu(NO₃)₂•3H₂O or 0.8 g of FeCl₃•6H₂O, previously dissolved in 5 ml of water, were added to 5Pd/ACm. The mixture was heated to 55-60 ° C, mixed for 30 minutes, after which the washing and drying were carried out by analogy with the synthesis of 10Cu/ACm.
NABH₄ solution was used for the reduction of metal ions in the pores of the ACm carrier, 1.6 g of NABH₄ was dissolved in 20 ml of water. Each of the catalytic systems (10Cu/ACm, 10Fe/ACm, 5Pd/ACm, 3Pd–7Cu/ACm, and 3Pd–7Fe/ACm) was individually placed in 50 ml of water, maintaining a pH of > 7 by adding 1 ml of 5 M NaOH. The NABH₄ solution was introduced slowly until hydrogen was released, the mixture was mixed for 3 hours. The resulting material was dried at 150 °C for 2 hours, after that it was exposed at 300 ° C for 4 hours to fix the metals. After drying, the samples were cooled to room temperature in a desiccator.
It was found that the specific pore surface of the synthesized catalysts was in the range of 2296.101-2672.132 m2/g and was within the SW index of the AСm. carrier.
In all catalyst samples, a decrease in the total volume of pores, the values of which were 36.627, 73.948, 64.932, 65.636 and 53.652 ml/g for 5Pd/AFm, 10Cu/AFm, 10Fe/ACm and 3Pd-7Cu/AFm, 3Pd-7Fe/ACm, was observed respectively. This indicated that the porous structure of the catalysts was well developed, and that phenomenon was typical for a palladium catalyst. That indicated an increase in the number of adsorption sites. In the course of the study, it was found that the modification of activated carbon electrodes with oxide, Fe and Pd nanoparticles significantly increased their electrochemical activity and stability during the oxygen reduction. The Fe-based catalyst was characterized by a maximum current density and minimal charge transfer resistance, whereas the Pd-based catalyst was characterized by a low reaction initiation potential and by stable operation. The copper (Cu)-based catalyst also showed the activity, but its efficiency was lower compared to other metals.
The cyclic voltammetric studies in the K3[Fe(CN)₆]³⁻/⁴⁻ system showed the differences in the ability of the catalysts to the electron exchange and in their surface conductivity. The EIS results made it possible to compare the charge transfer resistance: the iron (Fe) modification provided the lowest impedance value. The results of chronopotentiostatic tests showed that the metal-modified electrodes were able to maintain a stable potential for a long time, which confirmed their suitability for the long-term use. The ACNaOH/Fe and ACNaOH/Pd samples showed particularly high stability. The obtained results allowed considering the activated carbon modified with FE and Pd nanoparticles as promising, stable and effective materials for the oxygen reduction processes.
01.08.05 Selection of the battery cathode, optimization of its operation and carrying out a complex of electrochemical tests for the stability, self-discharge and temperature dependence of the characteristics
The stage supervisor is Miniyazov A.Zh. PhD, Deputy Director at IAE Branch
Composite Ni(OH)2/C cathode material was synthesized and comprehensively studied by chemical co-deposition. It was proved that the material was significantly superior to its analogues, possessing a set of improved characteristics: high specific capacity (~265 mAh/g), excellent cyclic stability (preservation of ~87% after 100 cycles), excellent rate (~225mAh/g at 10C) and high resistance to low temperatures (preservation of ~85% capacity at -10 °C).
As part of the implementation of the program for 2023-2025, the following was published:
– 9 articles in peer-reviewed scientific publications in the scientific field of the program, including those in the 1st (first), 2nd (second) and/or 3rd (third) quartile of impact factor in the Web of Science database and/or having a CiteScore percentile in the Scopus database of at least 50 (fifty);
– 15 articles in journals recommended by SHEQACMSHE
– 3 monographs of Kazakhstani publishers;
– 5 intellectual property objects (patents) registered at the National Institute of Intellectual Property of the Republic of Kazakhstan.