CN102530871A - Modified borane ammoniate hydrogen storage material and preparation method thereof - Google Patents

Modified borane ammoniate hydrogen storage material and preparation method thereof Download PDF

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CN102530871A
CN102530871A CN2010106175919A CN201010617591A CN102530871A CN 102530871 A CN102530871 A CN 102530871A CN 2010106175919 A CN2010106175919 A CN 2010106175919A CN 201010617591 A CN201010617591 A CN 201010617591A CN 102530871 A CN102530871 A CN 102530871A
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dadb
hydrogen storage
ammonia borane
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王平
方占召
康向东
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Institute of Metal Research of CAS
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Abstract

The invention relates to the field of hydrogen storage materials, in particular to a modified borane ammoniate hydrogen storage material and a preparation method thereof, solving the problem that hydrogen storage application and the like are restricted by a large amount of volatile impurity gases produced in the pyrolysis process of a borane ammoniate (DADB (diamido-diborane)). The modified borane ammoniate hydrogen storage material consists of borane ammoniate and a modified additive, wherein the molar ratio of the borane ammoniate to the modified additive is (0.5-50):1. The preparation method comprises the following steps of: putting a mixture comprising the DADB and the modified additive into a ball-milling pot, and carrying out ball milling under an inertial gas protection atmosphere (the initial pressure is 1 atmosphere). Because the DADB and the modified additive are mixed and subjected to ball milling, impurity gases can be effectively prevented from being released, and the modified DADB material has the advantages of high hydrogen release capacity, low hydrogen release temperature, favorable hydrogen storage prospect and the like.

Description

A kind of modification ammonia borane compound hydrogen storage material and preparation method thereof
Affiliated technical field
The present invention relates to the hydrogen storage material field, be specially a kind of modification ammonia borane compound hydrogen storage material and preparation method thereof.
Background technology
Hydrogen Energy is the secondhand energy of a kind of efficient, cleaning, reproducible utilization, for solving global problems such as the energy, weather, environment ideal substitute energy mode is provided.But the mass-producing commercial applications that realizes Hydrogen Energy is faced with hydrogen manufacturing, storage/fortune hydrogen, with a series of technological challenge of links such as hydrogen, wherein efficient, safe hydrogen storage/fortune is the most outstanding because of the technological challenge that faces, and is acknowledged as " bottleneck " link that restricts the Hydrogen Energy utilization.In existing storage hydrogen mode, the solid-state storage hydrogen of material base significantly is superior to compressed hydrogen tank and low temperature liquid hydrogen at aspects such as processing safety, storage hydrogen volume density, thereby is regarded as the storage hydrogen mode of tool development prospect.In the known hydrogen storage material system, metal/alloy hydrogenate dynamic performance excellence and working temperature are low, but its weight hydrogen-storage density is lower than 2% more, are difficult to satisfy vehicle-mounted storage hydrogen application demand; Though the coordination metal hydride has high hydrogen storage capability, its reversible suction/hydrogen discharging temperature too high (being higher than 300 ℃).In view of above-mentioned present Research, development novel high-capacity chemical hydride becomes giving top priority to what is the most important of current storage hydrogen research field.
Ammonia borane compound molecule formula is [(NH 3) 2BH 2] (BH 4) (abbreviation: DADB), its hydrogen richness is up to 19.6wt%, and thermostability is moderate, is a kind of chemical hydride that has much storage hydrogen application potential.But DADB produces a large amount of volatile impunty gases in pyrolytic process, is one of its storage hydrogen application of restriction " bottleneck ".This shows that exploring advanced DADB modification technology is the key foundation that promotes its storage hydrogen applied research.
Summary of the invention
The object of the present invention is to provide a kind of modification ammonia borane compound hydrogen storage material and preparation method thereof, solve the DADB that exists in the prior art and in pyrolytic process, produce a large amount of volatile impunty gases, restrict problems such as its storage hydrogen application.
Technical scheme of the present invention is:
A kind of modification ammonia borane compound hydrogen storage material is made up of ammonia borane compound and property-modifying additive, and the mol ratio of ammonia borane compound and property-modifying additive is (0.5～50): 1, be preferably (1～10): 1.
Wherein, ammonia borane compound containing element is: boron (B), nitrogen (N), hydrogen (H); Its molecular formula is: [(NH 3) 2BH 2] (BH 4); Be abbreviated as: DADB.
The invention provides and can effectively suppress the property-modifying additive that DADB foreign gas discharges, property-modifying additive comprises: basic metal (Li, Na, K, Rb, Cs), earth alkali metal (Mg, Ca, Sr), Al, alkalimetal hydride (LiH, NaH, KH, RbH, CsH), alkaline earth metal hydride (MgH 2, CaH 2, SrH 2), AlH 3, metal halide (MgF 2, MgCl 2, MgBr 2, MgI 2, CaF 2, CaCl 2, CaBr 2, LiF, LiCl, LiI), metal nitride (Mg 3N 2, Ca 3N 2, Li 3N, Na 3N) a kind of in or several combination, the granularity of property-modifying additive is about 100～300 orders.
The invention provides a kind of preparation method of modification ammonia borane compound hydrogen storage material, promptly effectively suppress the novel method that DADB foreign gas discharges, specific as follows:
In the inert atmosphere glove box; The mol ratio of DADB and property-modifying additive is (0.5～50): 1; Be preferably (1～10): 1, the mixture of DADB and property-modifying additive is put into ball grinder, ball milling under inert protective atmosphere (initial pressure is 1 normal atmosphere); Ball material mass ratio was preferably (100～300): 1 greater than 20: 1; The ball milling time was preferably 0.5～5 hour greater than 0.2 hour.
Ammonia borane compound of the present invention (DADB) is with metal borohydride M (BH 4) xWith ammonium salt (NH 4) yL is that raw material makes.Metal M comprises: a kind of among basic metal (Li, Na, K, Rb, Cs), earth alkali metal (Mg, Ca, Sr), the Al or several combination; Acid ion L comprises: anaerobic acid group (F -, Cl -, Br -, I -, CN -, S 2-), oxygen acid root ((CO 3) 2-, (NO 3) -, (NO 2) -, (SO 4) 2-, (SO 3) 2-, (PO 4) 3-, (MnO 4) -, (ClO 3) -) in a kind of or several combination, metal borohydride M (BH 4) xAnd ammonium salt (NH 4) yThe granularity of L is about 100～300 orders.
Among the present invention, metal borohydride M (BH 4) xWith ammonium salt (NH 4) yThe mol ratio of L is y: x, y: x=(0.1～10): 1.
The preparation method of ammonia borane compound of the present invention (DADB) can adopt mechanical ball milling to combine the liquefied ammonia method of purification, and is specific as follows:
(1) with metal borohydride M (BH 4) xWith ammonium salt (NH 4) yThe mixture of L is a starting raw material, adopts the mechanical ball milling method, produces DADB and M yL xMixture.In the inert atmosphere glove box, (0.1～10) in molar ratio: 1 with metal borohydride M (BH 4) xWith ammonium salt (NH 4) yThe mixture of L is put into ball grinder, ball milling under inert protective atmosphere (initial pressure is 1 normal atmosphere); Ball material mass ratio was preferably (100～300): 1 greater than 20: 1; The ball milling time was preferably 0.5～5 hour greater than 0.2 hour.
(2) with DADB and M yL xMixture be starting raw material, adopt the liquefied ammonia solvent, through steps such as dissolving, filtration, deammoniations, remove by product M yL x, obtain pure DADB compound.Milled sample added fill in three mouthfuls of round-bottomed flasks of liquefied ammonia solvent, ultrasonic agitation and after leaving standstill is poured the upper strata clear solution into outer with filtering in saturated dry ice acetone solution (temperature is-73～-78 ℃) the refrigerative interlayer sand core funnel; At last filtrating is carried out vacuum distilling; After treating that the liquefied ammonia volatilization finishes, collect and obtain white DADB powdered sample, the DADB powder size is about 200～400 orders; Sample purity >=98%, productive rate >=95%.。
With metal borohydride and ammonium salt is starting raw material, adopts mechanical ball milling to combine follow-up liquefied ammonia method of purification to produce the DADB compound.Method is simple for this, low in raw material cost and nontoxic, but produced in high yields high purity DADB compound is suitable for macro preparation.
Advantage of the present invention and beneficial effect are:
1, DADB modification technology of the present invention is with DADB and modified materials mixing and ball milling, and the foreign gas that can effectively suppress in the DADB pyrolytic process discharges.DADB after modification has height and puts advantages such as hydrogen capacity, low hydrogen discharging temperature, possesses good storage hydrogen application prospect, the potentiality of especially using at vehicle-mounted storage hydrogen.
2, to put hydrogen capacity be 8.0wt%～11.0wt% to the DADB of the present invention after modification, and initial hydrogen discharging temperature is 80 ℃～90 ℃.
Description of drawings
Fig. 1: with NaBH 4+ NH 4F is a starting raw material, ball milling sample (a) and through the X ray diffracting spectrum of follow-up liquefied ammonia purification sample (b) after 3 hours.
Fig. 2: with NaBH 4+ NH 4F is a starting raw material, ball milling sample (a) and through the infrared spectrogram of follow-up liquefied ammonia purification sample (b) after 3 hours.
Fig. 3: ball milling is DADB+MgH after 30 minutes 2(red line) contrasts with the simultaneous thermal analysis-mass spectrum curve of pure DADB (black line) sample.Heating rate is 5 ℃/min.
Fig. 4: with LiBH 4+ NH 4Cl is a starting raw material, ball milling sample (a) and through the X ray diffracting spectrum of follow-up liquefied ammonia purification sample (b) after 1 hour.
Fig. 5: with LiBH 4+ NH 4Cl is a starting raw material, ball milling sample (a) and through the infrared spectrogram of follow-up liquefied ammonia purification sample (b) after 1 hour.
Fig. 6: the simultaneous thermal analysis of ball milling DADB+Mg (red line) and pure DADB (black line) sample after 30 minutes-mass spectrum curve contrast.Heating rate is 5 ℃/min.
Fig. 7: with 2LiBH 4+ (NH 4) 2SO 4Be starting raw material, ball milling sample (a) and through the X ray diffracting spectrum of follow-up liquefied ammonia purification sample (b) after 2 hours.
Fig. 8: with 2LiBH 4+ (NH 4) 2SO 4Be starting raw material, ball milling sample (a) and through the infrared spectrogram of follow-up liquefied ammonia purification sample (b) after 2 hours.
Fig. 9: ball milling is 3DADB+Mg after 30 minutes 3N 2(red line) contrasts with the simultaneous thermal analysis-mass spectrum curve of pure DADB (black line) sample.Heating rate is 5 ℃/min.
Embodiment
Embodiment 1
At first, with NaBH 4And NH 4F is a starting raw material, and mol ratio is 1: 1, adopts the mechanical ball milling legal system to be equipped with the mixture of DADB/2NaF; Be solvent with liquefied ammonia then,, remove the by product NaF in the milled sample, make white DADB powder through steps such as dissolving, filtration, deammoniations, specific as follows:
The employing raw material is: NaBH 4(purity 98% ,～200 orders), NH 4F (purity 98% ,～200 orders).
In the argon atmospher glove box with NaBH 4/ NH 4F mixture and Stainless Steel Ball are packed in the stainless steel jar mill, seal to be placed on Fritsch 7 planetary ball mills ball milling 3 hours.Milling atmosphere is high-purity argon gas (purity 99.9999%), and initial pressure is 1 normal atmosphere, and ball material mass ratio is about 100: 1.The milled sample adding is filled in three mouthfuls of round-bottomed flasks of liquefied ammonia solvent, and ultrasonic agitation left standstill after 30 minutes 5 minutes, then the upper strata clear solution was poured into outer with filtering in saturated dry ice acetone solution (temperature is-73～-78 ℃) the refrigerative interlayer sand core funnel; At last filtrating is carried out vacuum distilling; After treating that the liquefied ammonia volatilization finishes, collected powdered sample is the DADB compound, and its granularity is about 300 orders; Purity >=98%, productive rate >=95%.
X-ray diffraction testing apparatus and condition: Rigaku D/MAX-2500, Cu K α radiation.Fig. 1 has provided (a) NaBH 4/ NH 4F ball milling aspect article reach the X ray diffracting spectrum of the back DADB that (b) purifies.The result shows, NaBH 4/ NH 4The F mixture is in mechanical milling process, by the mixture of stoichiometric ratio complete reaction generation DADB and NaF, the X ray diffracting spectrum of DADB and bibliographical information result [document 1.S.G Shore and K.W.
Figure BDA0000042122040000041
Inorg.Chem.1964,3,914-915] unanimity; Adopt the liquefied ammonia method of purification can effectively remove by product NaF, finally obtain white DADB powdered sample.
Examination of infrared spectrum equipment and condition: Bruker TENSOR 27, DLaTGS detector, resolving power 4cm -1Fig. 2 has provided (a) NaBH 4/ NH 4F ball milling aspect article reach the infrared spectrogram of the back DADB that (b) purifies.The result shows, the The results of FT-IR of DADB and bibliographical information result [document 2.J.D.Carpenter and B.S.Ault, J.Phys.Chem.1991,95,3502-3506] unanimity.Comprehensive The above results, it is effective adopting mechanical ball milling provided by the invention and follow-up liquefied ammonia method of purification to prepare the DADB compound.
Secondly, with DADB and MgH 2Be starting raw material, adopt the mechanical ball milling legal system to be equipped with DADB/MgH 2The composite hydrogen storage material system.
The employing raw material is: DADB (purity>=98% ,～300 orders), MgH 2(purity 98% ,～200 orders).Material molar ratio is DADB: MgH 2=1: 1, the ball milling time is 30 minutes, and milling atmosphere is high-purity argon gas (purity 99.9999%), and initial pressure is 1 normal atmosphere, and ball material mass ratio is about 100: 1.
Simultaneous thermal analysis-mass spectrometric measurement equipment and condition: Netzsch STA 449C/QMS 403C; Heating rate with 5 ℃/min is heated to 400 ℃ from room temperature, and carrier gas is high-purity argon gas (purity 99.9999%).Fig. 3 has provided DADB/MgH 2With the simultaneous thermal analysis of DADB sample-(red line is DADB/MgH to the contrast of mass spectrum curve 2, black line is DADB).Test result shows: add MgH 2Can effectively suppress the DADB sample and put in heating and generate detrimental impurity gases such as borine, borazol, ammonia in the hydrogen process, significantly promote its potentiality as on-board hydrogen source; Material is put hydrogen since 90 ℃, is heated to 400 ℃ and puts hydrogen capacity and reach 8.2wt%.
Embodiment 2
At first, with LiBH 4And NH 4Cl is a starting raw material, and mol ratio is 1: 1, and the ball milling time is 1 hour, and all the other preparation conditions are identical with embodiment 1.
The employing raw material is: LiBH 4(purity 98% ,～200 orders), NH 4Cl (purity 98% ,～200 orders).
The X-ray diffraction test condition is with embodiment 1.Fig. 4 has provided (a) LiBH 4/ NH 4Cl ball milling aspect article reach the X ray diffracting spectrum of the back DADB that (b) purifies.The result shows, LiBH 4/ NH 4The Cl mixture is pressed the mixture that the stoichiometric ratio complete reaction generates DADB and LiCl, the X ray diffracting spectrum of DADB and bibliographical information result [document 1.S.G Shore and K.W. in mechanical milling process Inorg.Chem.1964,3,914-915] unanimity; Adopt the liquefied ammonia method of purification can effectively remove by product LiCl, finally obtain white DADB powdered sample, its granularity is about 300 orders, purity>=98%, productive rate>=95%.
The examination of infrared spectrum condition is with embodiment 1.Fig. 5 has provided (a) LiBH 4/ NH 4Cl ball milling aspect article reach the infrared spectrogram of the back DADB that (b) purifies.The result shows, the The results of FT-IR of DADB and bibliographical information [document 2.J.D.Carpenter and B.S.Ault, J.Phys.Chem.1991,95,3502-3506] unanimity.
Secondly, be starting raw material with DADB+Mg, adopt the mechanical ball milling legal system to be equipped with DADB/Mg composite hydrogen storage material system.
The employing raw material is: DADB (purity >=98% ,～300 orders), Mg (purity 98% ,～200 orders).Material molar ratio is DADB: Mg=1: 1, and the ball milling time is 30 minutes, and milling atmosphere is high-purity argon gas (purity 99.9999%), and initial pressure is 1 normal atmosphere, and ball material mass ratio is about 200: 1.
Simultaneous thermal analysis-mass spectrometric measurement condition is with embodiment 1.Fig. 6 has provided the simultaneous thermal analysis-mass spectrum curve contrast (red line is DADB/Mg, and black line is DADB) of DADB/Mg and DADB sample.Test result shows: add the Mg powder and can effectively suppress the DADB sample and put in heating and generate detrimental impurity gases such as borine, borazol, ammonia in the hydrogen process; Material is put hydrogen since 80 ℃, is heated to 400 ℃ and puts hydrogen capacity and reach 10.2wt%.
Embodiment 3
At first, with LiBH 4(NH 4) 2SO 4Be starting raw material, mol ratio is 2: 1, and the ball milling time is 2 hours, and all the other preparation conditions are identical with embodiment 1.
The employing raw material is: LiBH 4(purity 98% ,～200 orders), (NH 4) 2SO 4(purity 98% ,～200 orders).
The X-ray diffraction test condition is with embodiment 1.Fig. 7 has provided (a) 2LiBH 4/ (NH 4) 2SO 4Ball milling aspect article reach the X ray diffracting spectrum of the back DADB that (b) purifies.The result shows, 2LiBH 4/ (NH 4) 2SO 4Mixture generates DADB and Li by the stoichiometric ratio complete reaction in mechanical milling process 2SO 4Mixture, the X ray diffracting spectrum of DADB and bibliographical information result [document 1.S.G Shore and K.W. Inorg.Chem.1964,3,914-915] unanimity; Adopt the liquefied ammonia method of purification can effectively remove by product Li 2SO 4, finally obtaining white DADB powdered sample, its granularity is about 300 orders, purity>=98%, productive rate>=95%.
The examination of infrared spectrum condition is with embodiment 1.Fig. 8 has provided (a) 2LiBH 4/ (NH 4) 2SO 4Ball milling aspect article reach the infrared spectrogram of the back DADB that (b) purifies.The result shows, the The results of FT-IR of DADB and bibliographical information [document 2.J.D.Carpenter and B.S.Ault, J.Phys.Chem.1991,95,3502-3506] unanimity.
Secondly, with DADB+Mg 3N 2Be starting raw material, adopt the mechanical ball milling legal system to be equipped with DADB/Mg 3N 2The composite hydrogen storage material system.
The employing raw material is: DADB (purity>=98% ,～300 orders), Mg 3N 2(purity 98% ,～200 orders).Material molar ratio is DADB: Mg 3N 2=3: 1, the ball milling time is 30 minutes, and milling atmosphere is high-purity argon gas (purity 99.9999%), and initial pressure is 1 normal atmosphere, and ball material mass ratio is about 200: 1.
Simultaneous thermal analysis-mass spectrometric measurement condition is with embodiment 1.Fig. 9 has provided 3DADB/Mg 3N 2With the simultaneous thermal analysis of DADB sample-(red line is 3DADB/Mg to the contrast of mass spectrum curve 3N 2, black line is DADB).Test result shows: add Mg 3N 2Powder can effectively suppress the DADB sample to be put in heating and generates detrimental impurity gases such as borine, borazol, ammonia in the hydrogen process; Material is put hydrogen since 80 ℃, is heated to 200 ℃ and puts hydrogen capacity and reach 10.0wt%.
Embodiment 4
At first, with Mg (BH 4) 2And NH 4NO 3Be starting raw material, mol ratio is 1: 2, and the ball milling time is 5 hours, and all the other preparation conditions are identical with embodiment 1.
The employing raw material is: Mg (BH 4) 2(purity 98% ,～200 orders), NH 4NO 3(purity 98% ,～200 orders).
The X-ray diffraction test result shows, Mg (BH 4) 2/ 2NH 4NO 3Mixture can generate DADB and Mg (NO by the stoichiometric ratio complete reaction in mechanical milling process 3) 2Mixture, the X ray diffracting spectrum of DADB and bibliographical information result [document 1.S.G Shore and K.W.
Figure BDA0000042122040000071
Inorg.Chem.1964,3,914-915] unanimity; Adopt the liquefied ammonia method of purification can effectively remove by product Mg (NO 3) 2, finally obtaining white DADB powdered sample, its granularity is about 300 orders, purity>=98%, productive rate>=95%.
Examination of infrared spectrum is the result show, the The results of FT-IR of DADB and bibliographical information [document 2.J.D.Carpenter and B.S.Ault, J.Phys.Chem.1991,95,3502-3506] unanimity.
Secondly, with DADB+MgF 2Be starting raw material, adopt the mechanical ball milling legal system to be equipped with DADB/MgF 2The composite hydrogen storage material system.
The employing raw material is: DADB (purity>=98% ,～300 orders), MgF 2(purity 98% ,～200 orders).Material molar ratio is DADB: MgF 2=1: 1, the ball milling time is 3 hours, and milling atmosphere is high-purity argon gas (purity 99.9999%), and initial pressure is 1 normal atmosphere, and ball material mass ratio is about 200: 1.
Show through simultaneous thermal analysis-mass spectrometric measurement result: add MgF 2Powder can effectively suppress the DADB sample to be put in heating and generates detrimental impurity gases such as borine, borazol, ammonia in the hydrogen process; Material is put hydrogen since 80 ℃, is heated to 200 ℃ and puts hydrogen capacity and reach 9.3wt%.

Claims (8)

1. modification ammonia borane compound hydrogen storage material, it is characterized in that: be made up of ammonia borane compound and property-modifying additive, the mol ratio of ammonia borane compound and property-modifying additive is (0.5～50): 1.
2. according to the described modification ammonia borane of claim 1 compound hydrogen storage material, it is characterized in that: the mol ratio of ammonia borane compound and property-modifying additive is preferably (1～10): 1.
3. according to the described modification ammonia borane of claim 1 compound hydrogen storage material, it is characterized in that: ammonia borane compound containing element is: boron, nitrogen, hydrogen; Its molecular formula is: [(NH 3) 2BH 2] (BH 4).
4. according to the described modification ammonia borane of claim 1 compound hydrogen storage material, it is characterized in that: property-modifying additive comprises: a kind of in metal, metal hydride, metal halide, the metal nitride or several combination.
5. according to the described modification ammonia borane of claim 1 compound hydrogen storage material, it is characterized in that: property-modifying additive comprises: Li, Na, K, Rb, Cs, Al, Mg, Ca, Sr, LiH, NaH, KH, RbH, CsH, MgH 2, CaH 2, SrH 2, AlH 3, MgF 2, MgCl 2, MgBr 2, MgI 2, CaF 2, CaCl 2, CaBr 2, LiF, LiCl, LiI, Mg 3N 2, Ca 3N 2, Li 3N, Na 3A kind of among the N or several combination.
6. according to the described modification ammonia borane of claim 1 compound hydrogen storage material, it is characterized in that: the granularity of ammonia borane compound is 200～400 orders, and the granularity of property-modifying additive is 100～300 orders.
7. according to the preparation method of the described modification ammonia borane of claim 1 compound hydrogen storage material; It is characterized in that; Comprise the steps: in the inert atmosphere glove box; Mol ratio by ammonia borane compound and property-modifying additive is (1～50): 1, the mixture of ammonia borane compound and property-modifying additive is put into ball grinder, ball milling under inert protective atmosphere; Initial pressure is 1 normal atmosphere, and ball material mass ratio was greater than 20: 1, and the ball milling time was greater than 0.2 hour.
8. according to the preparation method of the described modification ammonia borane of claim 7 compound hydrogen storage material, it is characterized in that ball material mass ratio is preferably (100～300): 1, the ball milling time is preferably 0.5～5 hour.
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CN112110426A (en) * 2020-08-20 2020-12-22 浙江工业大学 Method for synthesizing amino lithium potassium by mechanical ball milling
CN112110428A (en) * 2020-08-25 2020-12-22 浙江工业大学 Method for synthesizing amino lithium potassium by solid-solid reaction
CN115159451A (en) * 2022-08-04 2022-10-11 华北电力大学（保定） Preparation method of aluminum hydride/magnesium borohydride @ MXene composite hydrogen storage material
WO2023050585A1 (en) * 2021-09-29 2023-04-06 中国科学院深圳先进技术研究院 Medical hydrogen storage material and preparation method therefor

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Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN112110426A (en) * 2020-08-20 2020-12-22 浙江工业大学 Method for synthesizing amino lithium potassium by mechanical ball milling
CN112110428A (en) * 2020-08-25 2020-12-22 浙江工业大学 Method for synthesizing amino lithium potassium by solid-solid reaction
WO2023050585A1 (en) * 2021-09-29 2023-04-06 中国科学院深圳先进技术研究院 Medical hydrogen storage material and preparation method therefor
CN115159451A (en) * 2022-08-04 2022-10-11 华北电力大学（保定） Preparation method of aluminum hydride/magnesium borohydride @ MXene composite hydrogen storage material
CN115159451B (en) * 2022-08-04 2023-04-07 华北电力大学（保定） Preparation method of aluminum hydride/magnesium borohydride @ MXene composite hydrogen storage material

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Application publication date: 20120704