CN102491265A - Method for producing hydrogen by carrying out hydrolysis on magnesium-based material - Google Patents
Method for producing hydrogen by carrying out hydrolysis on magnesium-based material Download PDFInfo
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- CN102491265A CN102491265A CN2011104015623A CN201110401562A CN102491265A CN 102491265 A CN102491265 A CN 102491265A CN 2011104015623 A CN2011104015623 A CN 2011104015623A CN 201110401562 A CN201110401562 A CN 201110401562A CN 102491265 A CN102491265 A CN 102491265A
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
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- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/30—Hydrogen technology
- Y02E60/36—Hydrogen production from non-carbon containing sources, e.g. by water electrolysis
Abstract
The invention discloses a method for producing hydrogen by carrying out hydrolysis on magnesium-based material. According to the method disclosed by the invention, hydrolysis reaction is carried out between aqueous solution containing magnesium ions and halogen ions and magnesium metal, or magnesium-based alloy, or magnesium hydride or magnesium-based hydride composite material to produce hydrogen. By applying the hydrolysis method disclosed by the invention, efficiency of hydrogen production by utilizing the magnesium-based material is greatly improved, and the aqueous solution containing magnesium ions and halogen ions is easy to obtain with a low price and can be recycled, and no cation impurity except magnesium is introduced, thus separation operation is convenient to carry out; reaction byproduct is magnesium hydroxide which is safe and environmentally friendly; and the reaction byproduct can be recycled as an important chemical raw material.
Description
Technical field
The present invention relates to energy chemistry and chemical power source product technical field, be specifically related to the method that a kind of high-efficiency environment friendly utilizes the mg-based material hydrolytic hydrogen production.
Background technology
Hydrogen Energy is efficient because of it, environmental protection, advantage such as sustainable are used widely.Utilize in the process in Hydrogen Energy, it is prerequisite and the key that Hydrogen Energy is able to apply that cheap, convenient, safe hydrogen source is supplied with.Compared to traditional gaseous state high-pressure hydrogen storing and cryogenic liquefying storage hydrogen, it is big that solid-state hydrogen storage material has a hydrogen-storage amount, pollutes characteristics such as little, safe, mainly comprises nonmetal hydrogen storage material, metal hydrogen storage material, metal complex and organic liquid hydrogen storage material etc.Up to now, research is relatively more extensive and sophisticated to be metal hydrogen storage material, mainly comprises LaNi
5, TiFe, Mg
2Metallic compounds such as Ni for condition has been created in the utilization of Hydrogen Energy.
In numerous hydrogen storage alloys, Mg base hydrogen bearing alloy is because the high (MgH of hydrogen storage capability
2Theoretical hydrogen-storage amount is 7.6wt.%), advantage such as aboundresources, light weight and environmental pollution be little, be considered to promise to be most the hydrogen supply source of fuel cell.It is higher that but Magnuminium is inhaled hydrogen discharging temperature, and dynamic performance is not ideal enough, particularly hydrogen discharging temperature need reach usually 220 ℃～more than 340 ℃.Although through long-term extensive studies, adopt various means to reduce hydrogen discharging temperature, but still need just can put hydrogen more than 200 ℃, and effectively hydrogen desorption capacity is low, limits its practical application.
Adopt the hydrolytic hydrogen production technology to discharge the hydrogen that is stored in the alloy through simple chemical reaction; And can simultaneously the hydrogen ion in the water be transformed into hydrogen; If in conjunction with fuel cell technology, realize that the circulation of water transforms, system's hydrogen-storage amount will be up to 15.4wt.% (pressing magnesium hydride calculates).But magnesium-base hydrogen storage material can form the further contact reacts that one deck Marinco H passivation layer hinders water on the raw material surface in hydrolytic process, reduced hydrogen discharging rate and hydrogen manufacturing amount.At present mainly through with the alloying of salt, metal and metal hydride, add acidic solution, ultrasonic means such as peel off are accelerated hydrogen discharging rate; And then raising transformation efficiency (accumulative total in preset time; Amount to following 0 ℃ of condition of mark hydrogen manufacturing amount and the per-cent of theoretical hydrogen manufacturing amount down, the abbreviation transformation efficiency.The theoretical hydrogen manufacturing amount of simple substance magnesium and magnesium hydride is respectively 922mL/g and 1703mL/g), but also still fail satisfactoryly, theoretical hydrogen-storage amount descends, raw materials cost is high, hydrolysate is difficult to problems such as recycling but also exist.
Summary of the invention
The purpose of this invention is to provide a kind of method of utilizing the mg-based material hydrolytic hydrogen production.This method adopts and contains mg ion and the halide-ions aqueous solution as the reaction medium hydrogen manufacturing that is hydrolyzed, and ability realize high conversion within a short period of time.Wherein contain the mg ion and the halide-ions aqueous solution and do not introduce the impurity cationic beyond the demagging, be convenient to separate, reusable edible, and cheap and easy to get.
The objective of the invention is to realize through following scheme:
A kind of method of utilizing the mg-based material hydrolytic hydrogen production, 0 ℃～60 ℃ following hydrolysis reaction hydrogen manufacturing, in reaction process, the pH value of solution value is in 7.0～9.0 scopes with mg-based material and the aqueous solution that contains mg ion and halide-ions for this method; Magnesium ion concentration scope in the described aqueous solution that contains mg ion and halide-ions is 0.2mol/L～2mol/L; Ratio≤2 of halogen ion concentration and magnesium ion concentration; Preferred halogen ion concentration is 2 times of magnesium ion concentration, and halide-ions is preferably cl ions, most preferably MgCl
2Solution; Described mg-based material is MAGNESIUM METAL 99 or Magnuminium or magnesium hydride or magnesium-based hydride matrix material.Mg-based material and mg ion and halide-ions aqueous solution mass volume ratio are preferably 1: 10～1: in the 50g/mL scope.
Described mg-based material can also carry out ball milling before with the reactant aqueous solution that contains mg ion and halide-ions.The ball milling time is 0.3h～20h, rotating speed 200～500rpm, and the preferred spheres time consuming is 1h～10h, rotating speed 400rpm; Ball milling can adopt planetary high-energy ball mill.
Magnuminium of the present invention is an any mixture between 95wt.%～99wt.% magnesium nickel, magnesium iron or magnesium copper alloy or the three for the magnesium element content scope.
Magnesium hydride content is 80wt.%～99wt.% in the described magnesium-based hydride matrix material; This magnesium-based hydride matrix material can prepare through following method: adopt other hydrogenate or ball-milling additive and magnesium hydride to form matrix material; Metal hydride, magnesium, nickel, iron or the copper that described other hydrogenate is magnesium, nickel, iron or copper is with one or more mixtures in any multicomponent alloy hydrogenate than composition (the multicomponent alloy hydrogenate that preferably magnesium and nickel, iron or copper are formed), lithium hydride or the sodium hydride; Ball-milling additive is a kind of in blacking, the THF or it is multiple compound.Described blacking is preferably graphite, carbon nanotube, gac or Graphene.The magnesium-based hydride matrix material can also prepare through following method: took by weighing magnesium powder and nickel powder in 99: 1 in molar ratio; Mix under the condition that the back is 326K in temperature and dry, this mixture is placed in the synthetic furnace, hydrogen pressure is 2.0MPa in the stove; Be warmed up to 823K earlier; Under this temperature, be incubated 1h then, back naturally cooling is cooled to 623K, and under this temperature the insulation 10h after naturally cooling.
Below through experimentation to halogen ion concentration of the present invention and contain mg ion and the aqueous solution pH scope of halide-ions further specifies:
(1) about the selection of halogen ion concentration:
Experimental technique: the Mg base hydrogen bearing alloy hydrogenation burning of adopting inventor's patent (ZL2005100950255) to propose synthetic with the compound technology of preparing of mechanical ball milling (HCS+MM technology), concrete grammar took by weighing magnesium powder and nickel powder for 99: 1 in molar ratio, was with its oven dry in the baking oven of 326K in temperature after mixing; This mixture is placed in the synthetic furnace; Hydrogen pressure is 2.0MPa in the stove, is warmed up to 823K earlier, under this temperature, is incubated 1h then; Back naturally cooling is cooled to 623K; And naturally cooling to room temperature behind the insulation 10h under this temperature, and take out hydrogenation burning synthetic magnesium hydride matrix material, be kept in the argon atmospher.The magnesium base hydrogenation mixture 1g that aforesaid method is made contains the aqueous solution of mg ion and cl ions with 50ml down at 30 ℃, and (wherein magnesium ion concentration is 0.5M, and chlorine ion concentration is respectively 1.0M, 1.2M, 1.6M, 2.0M) hybrid reaction.Under the certain condition of magnesium ion concentration, chlorine ion concentration is big more in the solution, and the hydrolytic hydrogen production amount of 100min is respectively 1090mL/g, 1010mL/g, 950mL/g, 895mL/g.Under the certain condition of magnesium ion concentration, along with chlorine ion concentration increases, hydrogenate hydrolysis dynamics degradation is unfavorable for the hydrogen of putting of magnesium-base hydrogen storage material, shows as that hydrogen desorption capacity reduces in the unit time.Preferred chlorine ion concentration is the twice of magnesium ion concentration, if cl ions and magnesium ion concentration than greater than 2 reaction be difficult to carry out.
(2) about the selection of pH value:
Experimentation: took by weighing magnesium powder and nickel powder in 99: 1 in molar ratio, mixing the back is with its oven dry in the baking oven of 326K in temperature.This mixture is placed in the synthetic furnace; Hydrogen pressure is 2.0MPa in the stove, is warmed up to 823K earlier, under this temperature, is incubated 1h then; Back naturally cooling is cooled to 623K; And naturally cooling to room temperature behind the insulation 10h under this temperature, and take out hydrogenation burning synthetic magnesium hydride matrix material, be kept in the argon atmospher.
The magnesium hydride matrix material 1g that aforesaid method is made descends and the aqueous solution 50ml that contains mg ion and cl ions (wherein magnesium ion concentration is 0.5M, and chlorine ion concentration is respectively 1.0M) hybrid reaction at 30 ℃.In the hydrolysis reaction, the pH value of reaction soln fluctuates between 8.0～9.0, and behind reaction 30min, tends towards stability, and temperature fluctuation is in ± 1 ℃.Interpretation of result: the aqueous solution that contains Mg ion and halide-ions can be so that pH value of solution remains in 7～9 scopes always, and in this scope, hydrolysis is complete smoothly for mg-based material.And mg-based material is in pure water during hydrolysis, and the pH value of solution value can be climbed to 10.44, carries out thereby hinder reaction.
With prior art beneficial effect more of the present invention:
(1) the present invention adopts preparation of raw material cheap and easy to get to contain the aqueous solution of mg ion and halide-ions; With respect to traditional method for hydrolysis; Method described in the present invention can effectively improve mg-based material hydrolytic hydrogen production efficient, and is low to the envrionment temperature requirement, can be in sub-zero zero hydrogen manufacturing; And mg ion does not consume in hydrolytic process, and is reusable.
(2) method for hydrolysis described in the present invention can not introduced the impurity cationic except that mg ion, is convenient to separate, and the hydrolysate principal phase is a Marinco H, environmental friendliness, and can be used as the essential industry raw material and directly recycle.
(3) present method is low to the reaction raw materials requirement, is not only applicable to the hydrolytic hydrogen production of magnesiumalloy and composition thereof, also is applicable to the hydrolytic hydrogen production of magnesium-based hydride and mixture thereof.
(4) present method can realize high conversion within a short period of time, and made hydrogen purity is high, reaches for 99.9% (containing the minor amount of water steam), can directly apply to Proton Exchange Membrane Fuel Cells.
Description of drawings
Fig. 1 is that 30 ℃ of following 1g simple substance magnesium are at 0.5M MgCl
2With hydrolytic hydrogen production amount and transformation efficiency figure in the 1M NaCl solution.
Fig. 2 is that simple substance magnesium is at 0.5M MgCl
2Filter cake XRD figure after the hydrolysis fully in the solution.
Fig. 3 is equipped with magnesium-base hydrogen storage material at 0.5M MgCl for the HCS+MM legal system
2Hydrolysis output and transformation efficiency figure in the solution.
Fig. 4 is equipped with magnesium-base hydrogen storage material at 0.5M MgCl for the HCS+MM legal system
2Filter cake XRD figure after the hydrolysis fully in the solution.
Embodiment:
Further specify the present invention through instance below, but therefore do not limit content of the present invention.
Embodiment 1
With the undressed commercially available simple substance Mg of 1g respectively with 20mL 1.0mol/L (mol/L abbreviates M as, down with) NaCl solution and MgCl
2Solution (wherein magnesium ion concentration is 0.5M, and chlorine ion concentration is 1.0M) hybrid reaction, in reaction process, reacting solution pH value utilizes cmf record hydrogen manufacturing amount in 7.0～9.0 scopes.Under 30 ℃ of temperature of reaction, and contain MgCl
230 minutes hydrolytic hydrogen production amounts of solution hybrid reaction are 853mL, and hydrolysis conversion is that 92.5%, 60 minute hydrolytic hydrogen production amount is 906mL, and transformation efficiency is a complete reaction after 98.2%, 100 minute, and the hydrolytic hydrogen production amount is 922mL (result sees Fig. 1).Magnesium with contain MgCl
2Solution complete reaction after-filtration gets white mass; 70 ℃ of following vacuum-dryings get white powder after filtering three times with distilled water flushing, and (step-length is 0.02 °, and speed is 0.5 °/min to utilize XRD analysis; The result sees Fig. 2) white powder is Marinco H, do not see other impurity.
With the commercially available MgH of 1g
2(purity>=98wt.%) directly and 30mL MgCl
2Solution (wherein magnesium ion concentration is 0.5M, and chlorine ion concentration is 1.0M) hybrid reaction, in reaction process, reacting solution pH value is in 7.0～9.0 scopes, and under 30 ℃ of temperature of reaction, 60 minutes hydrogen desorption capacities are 1097mL, and transformation efficiency is 65.0%.
Embodiment 3
Took by weighing magnesium powder and nickel powder in 99: 1 in molar ratio, mixing the back is with its oven dry in the baking oven of 326K in temperature.This mixture is placed in the synthetic furnace; Hydrogen pressure is 2.0MPa in the stove, is warmed up to 823K earlier, under this temperature, is incubated 1h then; Back naturally cooling is cooled to 623K; And naturally cooling to room temperature behind the insulation 10h under this temperature, and take out hydrogenation burning synthetic magnesium hydride matrix material, be kept in the argon atmospher.
The hydrogenation burning synthetic magnesium hydride matrix material that 1g is made is unprocessed directly and 20mL MgCl
2Solution (wherein magnesium ion concentration is 0.5M, and chlorine ion concentration is 1.0M) hybrid reaction is in reaction process; Reacting solution pH value is in 7.0～9.0 scopes; Under 30 ℃ of temperature of reaction, 60 minutes hydrogen desorption capacities are 760mL, and transformation efficiency is 44.6%; 90 minutes hydrogen desorption capacities are 1069mL, and transformation efficiency is 62.8%.
Embodiment 4
Took by weighing magnesium powder and nickel powder in 99: 1 in molar ratio, mixing the back is with its oven dry in the baking oven of 326K in temperature.This mixture is placed in the synthetic furnace; Hydrogen pressure is 2.0MPa in the stove, is warmed up to 823K earlier, under this temperature, is incubated 1h then; Back naturally cooling is cooled to 623K; And naturally cooling to room temperature behind the insulation 10h under this temperature, and take out hydrogenation burning synthetic magnesium hydride matrix material, be kept in the argon atmospher.
The hydrogenation burning synthetic magnesium hydride matrix material that makes is carried out powerful ball milling 30min, rotating speed 400rpm with planetary high-energy ball mill.Get behind the ball milling magnesium base hydrogenation mixture 1g at 30 ℃ down and 20mL MgCl
2Solution (wherein magnesium ion concentration is 0.5M, and chlorine ion concentration is 1.0M) hybrid reaction is in reaction process; Reacting solution pH value is in 7.0～9.0 scopes, and 20 minutes hydrogen desorption capacities are 1347mL/g, and transformation efficiency is 79.1%; 60 minutes hydrogen desorption capacities are 1539mL/g; Transformation efficiency is 90.4%, this experiment repetition 3 times, and limit of error is (result sees Fig. 3) in ± 1%.Treat that the complete reaction after-filtration gets the pearl material, get pale powder 60 ℃ of following vacuum-dryings after filtering three times with distilled water flushing, utilizing the method described in the embodiment 1 to carry out XRD analysis (result sees Fig. 4) white powder is Marinco H.
Comparative Examples
To carry out powerful ball milling 0h, 1h, 5h, 10h, 20h, rotating speed 400rpm with planetary high-energy ball mill respectively according to embodiment 4 method hydrogenations burning synthetic magnesium hydride matrix material.Gained magnesium base hydrogenation mixture 1g is descended and 20mL deionized water hybrid reactions at 30 ℃.Wherein, the hydrogen manufacturing amount is maximum in the complex hydride unit time of ball milling 10h, and transformation efficiency is the highest: 20 minutes hydrogen manufacturing amounts are 670mL/g; Transformation efficiency is that 39.3%, 60 minute hydrogen manufacturing amount is 875mL/g, and transformation efficiency is 51.4%; 180 minutes hydrogen manufacturing amounts are 1080mL/g, and transformation efficiency is 63.4%.Ball milling 0h, 1h, 5h, 180 minutes hydrogen manufacturing amounts of magnesium base hydrogenation mixture of 20h are respectively 46mL/g, 440mL/g, 752mL/g, 1018mL/g.But reacting solution pH value is climbed to 10.4 along with reaction is carried out by 7.0.
Claims (10)
1. method of utilizing the mg-based material hydrolytic hydrogen production is characterized in that: 0 ℃～60 ℃ following hydrolysis reaction hydrogen manufacturing, in reaction process, the pH value of solution value is in 7.0～9.0 scopes with mg-based material and the aqueous solution that contains mg ion and halide-ions for this method; Magnesium ion concentration scope in the described aqueous solution that contains mg ion and halide-ions is 0.2mol/L～2mol/L, ratio≤2 of halogen ion concentration and magnesium ion concentration; Described mg-based material is MAGNESIUM METAL 99 or Magnuminium or magnesium hydride or magnesium-based hydride matrix material.
2. the method for hydrolytic hydrogen production according to claim 1 is characterized in that: contain that the ratio of halogen ion concentration and magnesium ion concentration is 2 in the aqueous solution of mg ion and halide-ions.
3. the method for hydrolytic hydrogen production according to claim 1 and 2 is characterized in that described halide-ions is a cl ions.
4. the method for hydrolytic hydrogen production according to claim 1 is characterized in that described mg-based material is carrying out ball milling before with the reactant aqueous solution that contains mg ion and halide-ions.
5. the method for hydrolytic hydrogen production according to claim 4 is characterized in that the described ball milling time is 0.3h～20h, rotating speed 200～500rpm.
6. the method for hydrolytic hydrogen production according to claim 5 is characterized in that the described ball milling time is 1h～10h, rotating speed 400rpm.
7. the method for hydrolytic hydrogen production according to claim 1, it is characterized in that: described Magnuminium is 95wt.%～99wt.% magnesium nickel, magnesium iron or magnesium copper alloy or three's any mixture for the magnesium element content scope.
8. the method for hydrolytic hydrogen production according to claim 1, it is characterized in that: magnesium hydride content is 80wt.%～99wt.% in the described magnesium-based hydride matrix material.
9. the method for hydrolytic hydrogen production according to claim 8, it is characterized in that: described magnesium-based hydride matrix material prepares through following method: adopt other hydrogenate or ball-milling additive and magnesium hydride to form matrix material; Described other hydrogenate is the metal hydride of magnesium, nickel, iron or copper, and magnesium, nickel, iron or copper are with any multicomponent alloy hydrogenate than composition, one or more mixtures in lithium hydride or the sodium hydride; Ball-milling additive is a kind of in blacking, the THF or it is multiple compound.
10. the method for hydrolytic hydrogen production according to claim 9, it is characterized in that: described blacking is graphite, carbon nanotube, gac, Graphene.
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Cited By (19)
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| CN102783691A (en) * | 2012-08-20 | 2012-11-21 | 李志林 | Calcium-magnesium hydrogen producing agent |
| CN103787276A (en) * | 2013-12-23 | 2014-05-14 | 浙江大学 | Composite material for preparing hydrogen through Mg-salt hydrolysis and preparation method of composite material |
| CN103964378A (en) * | 2014-05-16 | 2014-08-06 | 南开大学 | Method for hydrogen generation by hydrolysis of magnesium-based hydride MgH2 |
| DE102013211106A1 (en) | 2013-06-14 | 2014-12-18 | Fraunhofer-Gesellschaft zur Förderung der angewandten Forschung e.V. | Composite material, device and method for the hydrolytic production of hydrogen and apparatus for generating electrical energy and possible uses |
| DE102014211422A1 (en) | 2014-06-13 | 2015-12-17 | Fraunhofer-Gesellschaft zur Förderung der angewandten Forschung e.V. | Composite material for the hydrolytic production of hydrogen, apparatus for the hydrolytic production of hydrogen, methods for generating hydrogen, apparatus for generating electrical energy and possible uses |
| CN106629594A (en) * | 2016-11-15 | 2017-05-10 | 青岛大学 | High-performance magnesium hydride invertible hydrogen manufacturing system and hydrogen manufacturing method |
| CN107512701A (en) * | 2016-06-16 | 2017-12-26 | 常君辉 | The multi-electrode activation Catalytic processes of magnesium granules hydrolytic hydrogen production |
| CN109592637A (en) * | 2018-12-29 | 2019-04-09 | 杭州氢源素生物科技有限公司 | A kind of magnesium powder hydrogen manufacturing stick and preparation method thereof |
| CN110282602A (en) * | 2019-07-08 | 2019-09-27 | 陕西科技大学 | A kind of MoS2The nano combined rich magnesium hydrolysis of-EG concerted catalysis produces hydrogen material and preparation method thereof |
| CN111575487A (en) * | 2020-05-28 | 2020-08-25 | 哈尔滨工业大学（深圳） | Method for recovering products of hydrogen production by hydrolysis of aluminum-based materials |
| CN111634884A (en) * | 2020-07-04 | 2020-09-08 | 上海镁源动力科技有限公司 | Controllable hydrogen release material, preparation method thereof and hydrolysis hydrogen production method |
| CN111646429A (en) * | 2020-07-04 | 2020-09-11 | 上海镁源动力科技有限公司 | Magnesium-based hydrogen discharge material, preparation method thereof and hydrolysis hydrogen production method |
| CN111777036A (en) * | 2020-06-08 | 2020-10-16 | 复旦大学 | MgH improvement2Method for preparing hydrogen rate by hydrolyzing material |
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| CN112794283A (en) * | 2020-12-31 | 2021-05-14 | 河南中氢动力研究院有限公司 | Seawater hydrogen production and desalination integrated equipment |
| CN112850641A (en) * | 2021-02-06 | 2021-05-28 | 陕西科技大学 | Halogen anion hydrolysis medium greening regulation and control method for magnesium-based alloy hydrolysis hydrogen production |
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| CN111634884B (en) * | 2020-07-04 | 2022-08-16 | 上海镁源动力科技有限公司 | Controllable hydrogen release material, preparation method thereof and hydrolysis hydrogen production method |
| CN111646429A (en) * | 2020-07-04 | 2020-09-11 | 上海镁源动力科技有限公司 | Magnesium-based hydrogen discharge material, preparation method thereof and hydrolysis hydrogen production method |
| CN112250094A (en) * | 2020-10-13 | 2021-01-22 | 北京化工大学 | High-purity hydrotalcite and preparation method thereof |
| CN112250094B (en) * | 2020-10-13 | 2021-12-24 | 北京化工大学 | High-purity hydrotalcite and preparation method thereof |
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| CN112850641A (en) * | 2021-02-06 | 2021-05-28 | 陕西科技大学 | Halogen anion hydrolysis medium greening regulation and control method for magnesium-based alloy hydrolysis hydrogen production |
| CN114044491A (en) * | 2021-10-27 | 2022-02-15 | 世能氢电科技有限公司 | Preparation method of easily hydrolyzed composite magnesium hydride, composite magnesium hydride and battery |
| CN114455541A (en) * | 2021-12-24 | 2022-05-10 | 世能氢电科技有限公司 | Magnesium hydride AB material capable of controlling hydrolysis to produce hydrogen and preparation method thereof |
| CN114538372A (en) * | 2022-02-23 | 2022-05-27 | 氢华能源技术(武汉)有限公司 | Preparation method of hydrogen-rich water hydrogen source supply material |
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Inventor after: Li Liquan Inventor after: Liu Hu Inventor after: Zhu Yunfeng Inventor after: Zhao Zelun Inventor after: Sun Chencheng Inventor before: Li Liquan Inventor before: Zhao Zelun Inventor before: Zhu Yunfeng Inventor before: Liu Hu Inventor before: Sun Chencheng |
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