• Korean Chemical Engineering Research
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• v.54 no.5
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• pp.587-592
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• 2016

Sodium borohydride, $NaBH_4$, shows a number of advantages as hydrogen source for portable proton exchange membrane fuel cells (PEMFCs). Properties of $NaBH_4$ hydrolysis reaction using unsupported Co-P-B Co-B, catalyst at high concentration $NaBH_4$ solution were studied. In order to enhance the hydrogen generation yield at high concentration of $NaBH_4$, the effect of catalyst type, $NaBH_4$ concentration and recovery of condensing water on the hydrogen yield were measured. The yield of hydrogen evolution increased as the boron ratio increased in preparation process of Co-P-B catalyst. The hydrogen yield decreased as the concentration increased from 20 wt% to 25 wt% in $NaBH_4$ solution during hydrolysis reaction using 1:5 Co-P-B catalyst. Maximum hydrogen yield of 96.4% obtained by recovery of condensing water and thinning of catalyst pack thickness in reactor using Co-P-B with Co-B catalyst and 25 wt% $NaBH_4$ solution.

• 한국전기화학회:학술대회논문집
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• 2005.07a
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• pp.373-378
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• 2005

[ $Zn(BH_4)_2$ ] ($8.4\;wt\%$ theoretical hydrogen storage capacity) powders have been successfully synthesized by mechanochemical reaction from mixtures of $ZnCl_2$ and $NaBH_4$ powders in a 1:2 molar ratio in different times. $$ZnCl_2\;+\;2NaBH_4\rightarrow\;Zn(BH_4)_2\;+\;2NaCl\;(1)$$ $Zn(BH_4)_2$ powders were characterized by X-ray diffractometry(XRD), and Furier Transform Infrared spectrometry(FT-IR). The thermal stabilities of $Zn(BH_4)_2$ powders were studied by Differential scanning calorimetry(DSC), Thermogravimetry analysis(TGA), and Mass spectrometry(MS). $Zn(BH_4)_2$ can be tested for hydrogen evolution without further purification. The reaction to yield hydrogen is irreversible, the other products being compounds of Zn, and borane. $Zn(BH_4)_2$ thermally decomposes to release borane and hydrogen gas between about 85 and $150^{\circ}C$.

• Korean Chemical Engineering Research
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• v.48 no.3
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• pp.322-326
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• 2010

Stability of sodium borohydride solution during storage was studied. In order to enhance the $NaBH_4$ stability, NaOH and KOH were added to the $NaBH_4$ solution. The effect of concentration of the borohydride and alkaline solution, temperature and materials of storage vessels on the rate of borohydride hydrolysis was investigated. The rate of hydrogen evolution decreased as the concentration of alkaline increased due to increase of $NaBH_4$ stability in the solution. The stability of $NaBH_4$ solution decreased when the borohydride concentration raised from 10 to 15 wt% and then increased when the $NaBH_4$ concentration increased above 15 wt% due to increase in the pH of the concentrated solution. The activity coefficient of hydrolysis of $NaBH_4$ solution(NaOH 3.0 wt%, $NaBH_4$ 25 wt%) was 115.1 kJ/mol and this value was 1.5~4.0 times higher than that of hydrolysis of $NaBH_4$ solution with catalyst. The borohydride solutions in glass and stainless-steel vessel were more stable than the solution in plastic(PE) vessel.

• Korean Journal of Materials Research
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• v.25 no.1
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• pp.43-47
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• 2015

$Zn(BH_4)_2$ was prepared by milling $ZnCl_2$ and $NaBH_4$ in a planetary ball mill in an Ar atmosphere, and XRD analysis, SEM observation, FT-IR analysis, DTA, and TGA were performed for synthesized $Zn(BH_4)_2$ samples. 90 wt% $MgH_2$+1.67 wt% $Zn(BH_4)_2(+NaCl)$+5 wt% Ni+1.67 wt% Ti+1.67 wt% Fe (named $90MgH_2+1.67Zn(BH_4)_2(+NaCl)$+5Ni+1.67Ti+1.67Fe) samples were also prepared by milling in a planetary ball mill in an $H_2$ atmosphere. The gas absorption and release properties of the $Zn(BH_4)_2(+NaCl)$ and $90MgH_2+1.67Zn(BH_4)_2(+NaCl)_2(+NaCl)$+5Ni+1.67Ti+1.67Fe samples were investigated. An FT-IR analysis showed that $Zn(BH_4)_2$ formed in the $Zn(BH_4)_2(+NaCl)$ samples prepared by milling $ZnCl_2$ and $NaBH_4$. At the first cycle at $320^{\circ}C$, $90MgH_2+1.67Zn(BH_4)_2(+NaCl)$+5Ni+1.67Ti+1.67Fe absorbed 2.95 wt% H for 2.5 min and 4.93 wt% H for 60 min under 12 bar $H_2$, and released 1.46 wt% H for 10 min and 4.57 wt% H for 60 min under 1.0 bar $H_2$.

• Korean Chemical Engineering Research
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• v.59 no.4
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• pp.503-507
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• 2021

Sodium borohydride, NaBH₄, has many advantages as hydrogen source for portable proton exchange membrane fuel cells (PEMFC). When PEMFC is used outdoors as a transport type, it is economical to hydrolyze NaBH₄ using fresh water instead of distilled water. Therefore, in this study, hydrogen was generated using fresh water instead of distilled water during the NaBH₄ hydrolysis process. The properties of NaBH₄ hydrolysis were studied using an activated carbon-supported Co-P-B/C catalyst. Fresh water did not generate tetrahydrate during the NaBH₄ hydrolysis process, and distilled water produced tetrahydrate by-products, which consumed a lot of water during the hydrolysis process, indicating that at the end of the reaction at a high concentration of 25% or more of NaBH₄, dry by-products and unreacted NaBH₄ remained. As a result, when fresh water was used, the hydrogen yield and hydrogen generation rate were higher than that of distilled water at a high concentration of 25% or more of NaBH₄, indicating that it is suitable for use in transport-type fuel cells such as unmanned aerial vehicles.

• Korean Chemical Engineering Research
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• v.53 no.6
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• pp.677-681
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• 2015

Aluminum alloy was examined as a material of low weight reactor for hydrolysis of $NaBH_4$. Aluminum is dissolved with alkali, but there is NaOH as a stabilizer in $NaBH_4$ solution. To decrease corrosion rate of aluminum, decrease NaOH concentration and this result in loss of $NaBH_4$ during storage of $NaBH_4$ solution. Therefore stability of $NaBH_4$ and corrosion of aluminum should be considered in determining the optimum NaOH concentration. $NaBH_4$ stability and corrosion rate of aluminum were measured by hydrogen evolution rate. $NaBH_4$ stability was tested at $20{\sim}50^{\circ}C$ and aluminum corrosion was measured at $60{\sim}90^{\circ}C$. The optimum concentration of NaOH was 0.3 wt%, considering both $NaBH_4$ stability and aluminun corrosion. $NaBH_4$ hydrolysis reaction continued 200min in aluminum No 6061 alloy reactor with 0.3 wt% NaOH at $80{\sim}90^{\circ}C$.

• Journal of the Korean Society for Aeronautical & Space Sciences
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• v.39 no.9
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• pp.858-865
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• 2011

This paper describes the characteristics of hydrogen generation from solid-state $NaBH_4$ and fuel cell operation for fuel cell aircraft. The solid-state $NaBH_4$ was used for a high hydrogen storage density, and was reacted with hydrochloric acid to generate hydrogen. The hydrogen generation rate for the solid-state $NaBH_4$ reaction was measured at various conditions. As a result, the hydrogen generation rate was increased with the feed rate and concentration of hydrochloric acid, while not be affected by the reaction temperature. A fuel cell was connected with the solid-state $NaBH_4$ hydrogen generator. The stable power output was obtained at the gradual and sudden increases of electric loads.

• Journal of Hydrogen and New Energy
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• v.16 no.3
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• pp.262-268
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• 2005

[ $Zn(BH_4)_2$ ](8.4 wt% theoretical hydrogen storage capacity powders have been successfully synthesized by mechanochemical reaction from mixtures of $ZnCl_2$ and $NaBH_4$ powders in a 1:2 molar ratio in different times. $$ZnCl_2+2NaBH_4{\rightarrow}Zn(BH_4)_2+2NaCl$$ (1) $Zn(BH_4)_2$ powders were characterized by X-ray diffractometry(XRD), and Furier Transform Infrared spectrometry(FT-IR). The thermal stabilities of $Zn(BH_4)_2$ powders were studied by Differential scanning calorimetry(DSC), Thermogravimetry analysis(TGA), and Mass spectrometry(MS). $Zn(BH_4)_2$ can be tested for hydrogen evolution without further purification. The reaction to yield hydrogen is irreversible, the other products being compounds of Zn, and borane. $Zn(BH_4)_2$ thermally decomposes to release borane and hydrogen gas between about 85 and 150$^{\circ}C$.

• Journal of the Korean Society for Aeronautical & Space Sciences
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• v.40 no.10
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• pp.901-909
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• 2012

This paper describes characteristics of solid-state $NaBH_4$ hydrogen generation and supply system for fuel cell UAV. Flow rate and pressure of the generated hydrogen were dramatically changed during $NaBH_4$ decomposition using acid. Hydrogen supply was stabilized by a self-pressurized reactor, and hydrogen stabilization method was introduced. For hydrogen generation in below zero-temperature, hydrochloric acid was diluted by propylene glycol-water mixtures. Solid-state $NaBH_4$hydrogen generation and supply system was designed. Basic operation experiments was performed to reveal the characteristics of this hydrogen generation system.

• Korean Chemical Engineering Research
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• v.57 no.6
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• pp.758-762
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• 2019

Sodium borohydride,$NaBH_4$, has many advantages as hydrogen source for portable proton exchange membrane fuel cells (PEMFC). When PEMFC is used for marine use, $NaBH_4$ hydrolysis using seawater is economical. Therefore, in this study, hydrogen was generated by using seawater instead of distilled water in the process of hydrolysis of $NaBH_4$. Properties of $NaBH_4$ hydrolysis reaction using activated carbon supported Co-B/C catalyst were studied. The yield of hydrogen decreased as $NaBH_4$ concentration and NaOH concentration were increased during $NaBH_4$ hydrolysis using sea water. At higher concentrations of $NaBH_4$ and NaOH, byproducts adhered to the surface of the catalyst after hydrolysis reaction using sea water, reduced hydrogen yield compared to distilled water. The activation energy of $NaBH_4$ hydrolysis is 59.3, 74.4 kJ/mol for distilled water and sea water, respectively. In order to increase the hydrogen generation rate in seawater as high as distilled water, the reaction temperature has to be increased by $80^{\circ}C$ or more.