CN107021864A - A kind of metal hydride in-situ polymerization coats passivating method - Google Patents
A kind of metal hydride in-situ polymerization coats passivating method Download PDFInfo
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Abstract
Passivating method is coated the invention discloses a kind of metal hydride in-situ polymerization, it is characterised in that：Comprise the following steps：(1) take the copolyether and curing agent of 3,3 two azido-methyl oxygen fourth rings and tetrahydrofuran to be dissolved in anhydrous ethyl acetate, be configured to weak solution；(2) metal hydride is taken to be placed in weak solution, ultrasonic disperse forms suspension；(3) stirring is warming up to 40 DEG C~60 DEG C simultaneously, and solvent ethyl acetate is evaporated recovery by stirring reaction, reaction after terminating；(4) solidification is dried in the product after solvent evaporated in an oven, produces the insensitiveness metal hydride of cladding.A kind of metal hydride in-situ polymerization cladding passivating method that the present invention is provided, carries out in-situ polymerization cladding to metal hydride using BAMO THF copolyethers, handles obtained metal hydride to the moisture insensitiveness in air.While being passivated to metal hydride, ensure that metal hydride energy response itself is unaffected.
Description
Technical field
Passivating method is coated the present invention relates to a kind of metal hydride in-situ polymerization, energetic material security protection is particularly belonged to
Technical field.
Background technology
The binary chemical combination that metal hydride, also known as salt form hydride are active alkali metal and the direct chemical combination of hydrogen and are generated
Thing, chemical general formula is MH, and wherein M is any one in the alkali metals such as Li, Na, Al.Metal hydride and other hydrogen storages
Mode is compared, and has the advantages that hydrogen-storage density is high, pressure is steady and it is simple to be flushed with hydrogen, unit volume hydride hydrogen-storing it is close
1000 times of Gaseous Hydrogen under the reachable mutually synthermal, pressure condition of degree.Because metal hydride has the advantages that hydrogen-storage density is high, because
This, which is used as high energy additive, is used to further improve propellant energy specific impulse in rocket solid propellant, with important military affairs
Application value.
Because metal hydride has the H element in the special construction of binary compound, metal hydride with -1 valency
Electron valence state is present, therefore most metals hydride has very strong reproducibility.When it exposes in atmosphere, meeting and air
In moisture occur redox reaction release heat and hydrogen, making the purity of metal hydride reduces, compatible with other materials
Property be deteriorated, and then cause metal hydride when as propellant high energy additive energy reduce, danger coefficient increase.
One kind is described in Chinese patent application publication number CN105565262 A with bicyclic diene (DCPD) for polymerisation
Monomer, by home position polymerization reaction, the homopolymer or copolymer of polydicyclopentadiene (pDCPD) are formed on metal hydride surface
Clad, so as to realize the passivating method of the insulation blocking to metal hydride.Clad used in this method contains to be non-
Energy class clad, is passivated processing to metal hydride, although play and metal hydride is entered with such non-clad containing energy
The purpose of row passivation, but high energy flow characteristic when also reducing metal hydride simultaneously as high energy additive.
In addition, rarely seen metal hydride relevant passivation handling process report, above-mentioned patented method is primarily focused on pair
The passivation protection of metal hydride, influence of the non-clad containing energy to metal hydride energy response itself is not considered.How
While being passivated to metal hydride, it is ensured that metal hydride is not reduced as the energy response of high energy additive in itself,
It is urgent problem to be solved in terms of current metal hydride passivation protection.
The content of the invention
To solve the deficiencies in the prior art, it is an object of the invention to provide a kind of metal hydride in-situ polymerization cladding is blunt
Change method, while being passivated to metal hydride, ensures that itself energy response is not reduced.
In order to realize above-mentioned target, the present invention is adopted the following technical scheme that：
A kind of metal hydride in-situ polymerization coats passivating method, comprises the following steps：(1) the azido-methyl oxygen of 3,3- bis- is taken
The copolyether (BAMO-THF copolyethers) and curing agent of fourth ring and tetrahydrofuran are dissolved in anhydrous ethyl acetate, are configured to weak solution；
(2) metal hydride is taken to be placed in weak solution, ultrasonic disperse forms suspension；(3) warming while stirring is to 40 DEG C~60 DEG C,
Stirring reaction, reaction, which evaporates solvent ethyl acetate after terminating, reclaims；(4) product after solvent evaporated is dried in an oven
Solidification, produces the insensitiveness metal hydride of cladding.
Further, aforementioned metal hydride in-situ polymerization cladding passivating method, comprises the following steps：(1) 3,3- bis- is taken
The copolyether and curing agent of azido-methyl oxygen fourth ring and tetrahydrofuran are dissolved in anhydrous ethyl acetate, are configured to weak solution；(2) gold is taken
Category hydride particle is placed in weak solution, and ultrasonic disperse 0.3h~1h forms milk-white coloured suspension；(3) warming while stirring is extremely
30 DEG C~75 DEG C, 2~4h of stirring reaction, reaction, which evaporates solvent ethyl acetate after terminating, reclaims；(4) product after solvent evaporated
3~5h of solidification is dried in 45 DEG C~90 DEG C baking ovens, the insensitiveness metal hydride of cladding is produced.
Preferably, aforementioned metal hydride in-situ polymerization cladding passivating method, comprises the following steps：(1) 3,3- bis- is taken to fold
The copolyether and curing agent of N-methyl oxygen fourth ring and tetrahydrofuran are dissolved in anhydrous ethyl acetate, are configured to weak solution；(2) metal is taken
Hydride particle is placed in weak solution, 0.5~0.8h of ultrasonic disperse, forms milk-white coloured suspension；(3) warming while stirring is to 35
DEG C~50 DEG C, 2~4h of stirring reaction, reaction, which evaporates solvent ethyl acetate after terminating, reclaims；(4) product after solvent evaporated exists
3~5h of solidification is dried in 65 DEG C~85 DEG C baking ovens, the insensitiveness metal hydride of cladding is produced.
In aforementioned metal hydride in-situ polymerization cladding passivating method, 3,3- bis- azido-methyl oxygen fourth rings and tetrahydrofuran
The number-average molecular weight of copolyether is the mol ratio of the azido-methyl oxygen fourth rings of 3,3- bis- and tetrahydrofuran in 3000~6000, copolyether
For 0.8~1.4 ︰ 1.2.The characteristics of BAMO-THF copolyethers have high energy and good adhesive property, with the BAMO-THF copolymerization containing energy
The non-adhesive containing energy of ether substitution tradition can significantly improve mechanical properties of propellant and energy level.BAMO-THF copolyethers are inherently
The adhesive containing energy is may be used as to be applied in solid propellant, therefore the gold after the cladding passivation of BAMO-THF copolyethers in-situ polymerization
Category hydride possesses good compatibility after being applied in solid propellant with other components.
Aforementioned metal hydride in-situ polymerization is coated in passivating method, the weak solution of step (1), 3,3- bis- azido-methyl oxygen
The mass volume ratio of the copolyether and anhydrous ethyl acetate of fourth ring and tetrahydrofuran is 1~3g ︰ 100mL, curing agent and anhydrous second
The mass volume ratio of acetoacetic ester is 0.3~0.9g ︰ 100mL.
Aforementioned metal hydride in-situ polymerization is coated in passivating method, step (2), the quality of metal hydride and weak solution
Volume ratio is：100~120mL of 100g ︰.
In aforementioned metal hydride in-situ polymerization cladding passivating method, curing agent is IPDI, toluene
Diisocyanate or 4,4- diphenylmethyl baked diisocyanate.
In aforementioned metal hydride in-situ polymerization cladding passivating method, metal hydride is AlH3, CeH3-4, LiH or NaH.
The cladding of traditional hydrogenation thing is coated using the non-adhesive analog containing energy, because energy level itself is low, institute
So that hydride average energy can be reduced after being coated to hydride.The azido-methyl oxygen fourth rings of 3,3- bis- and tetrahydrochysene are used in the present invention
The copolyether (BAMO-THF copolyethers) of furans is coated under curing agent effect to hydride, and BAMO-THF is used as energy value
The very high copolyether containing energy, uses in explosive and propellant as the adhesive containing energy, uses the BAMO- of high energy at present
THF copolyethers are coated to hydride, will not reduce the average energy of coated hydride.After cladding, hydride has
Effect content can be controlled in 98%, and hydrogen and oxidation will not be seted off certainly in atmosphere by putting, and activity degree is >=97%.
From the BAMO-THF copolyethers that number-average molecular weight is 3000~6000 in the present invention.The molecular weight of copolyether is got over
Low, the molecular motion of copolyether is more active, is difficult to stick to hydride surface, and need multiple crosslinking curing to be formed
Network molecular structure is coated to hydride；When copolyether molecular weight is excessive, dispersed meeting of the copolyether in ethyl acetate
It is affected.Therefore, the BAMO-THF copolyethers that final choice number-average molecular weight is 3000~6000 are considered.
In the present invention, the consumption of curing agent is related to the consumption of BAMO-THF copolyethers, and BAMO-THF copolyethers make
Consumption is related to the thickness of clad.Addition is very few, it is difficult to form coating film；Addition is excessive, and clad is blocked up, influence production
The reactivity worth of product.Therefore, after considering, the mass volume ratio of selection copolyether and anhydrous ethyl acetate is 1~3g ︰
The mass volume ratio of 100mL, curing agent and anhydrous ethyl acetate is 0.3~0.9g ︰ 100mL.Using consumption in the range of this, both shapes
Into effective cladding, the reactivity worth of product has also been ensured.
The present invention is advantageous in that：A kind of metal hydride in-situ polymerization cladding passivating method that the present invention is provided,
In-situ polymerization cladding is carried out to metal hydride using BAMO-THF copolyethers, obtained metal hydride is handled in air
Moisture insensitiveness.The inventive method has ensured metal hydride energy response itself while being passivated to metal hydride
It is unaffected.After cladding, the effective content of hydride can be controlled in 98%, and hydrogen and oxidation will not be seted off certainly in atmosphere by putting, living
Property degree be >=97%.The method of the present invention directly forms polymerization clad on metal hydride surface, compared to other physics cladding
Passivating method, with more preferable stability.In-stiu coating is carried out using BAMO-THF copolyethers, due to BAMO-THF copolyether sheets
Body can be used as the adhesive containing energy to be applied in solid propellant, so that the metal hydride after cladding passivation is applied to admittedly
When in body propellant, compatibility is more preferable between other components.
Embodiment
The present invention is further introduced below in conjunction with specific embodiment.
Agents useful for same is commercially available prod in the present invention.
Embodiment 1
A kind of metal hydride in-situ polymerization coats passivating method, and metal hydride is AlH3, CeH3-4, LiH or NaH, bag
Include following steps：(1) copolyether (BAMO-THF copolyethers) and the solidification of the azido-methyl oxygen fourth rings of 3,3- bis- and tetrahydrofuran are taken
Agent is dissolved in anhydrous ethyl acetate, is configured to weak solution；Wherein, curing agent is IPDI, BAMO-THF copolymerization
The number-average molecular weight of ether is that the mol ratio of the azido-methyl oxygen fourth rings of 3,3- bis- and tetrahydrofuran in 3000, BAMO-THF copolyethers is
The mass volume ratio of 0.8 ︰ 1.2, BAMO-THF copolyethers and anhydrous ethyl acetate is 1.5g ︰ 100mL, curing agent and anhydrous acetic acid
The mass volume ratio of ethyl ester is 0.4g ︰ 100mL；(2) take metal hydride particle to be placed in weak solution, metal hydride with it is dilute molten
The mass volume ratio of liquid is：100g ︰ 100mL, ultrasonic disperse 0.3h, form milk-white coloured suspension；(3) warming while stirring is to 30
DEG C, stirring reaction 4h, reaction, which evaporates solvent ethyl acetate after terminating, reclaims；(4) product after solvent evaporated is in 45 DEG C of progress
Dry solidification 5h, produces the insensitiveness metal hydride of cladding.
Embodiment 2
A kind of metal hydride in-situ polymerization coats passivating method, and metal hydride is AlH3, CeH3-4, LiH or NaH, bag
Include following steps：(1) copolyether (BAMO-THF copolyethers) and the solidification of the azido-methyl oxygen fourth rings of 3,3- bis- and tetrahydrofuran are taken
Agent is dissolved in anhydrous ethyl acetate, is configured to weak solution；Wherein, curing agent is toluene di-isocyanate(TDI), BAMO-THF copolyethers
Number-average molecular weight is that the mol ratio of the azido-methyl oxygen fourth rings of 3,3- bis- and tetrahydrofuran in 6000, BAMO-THF copolyethers is 1.4 ︰
The mass volume ratio of 1.2, BAMO-THF copolyethers and anhydrous ethyl acetate is 3g ︰ 100mL, curing agent and anhydrous ethyl acetate
Mass volume ratio is 0.9g ︰ 100mL；(2) metal hydride particle is taken to be placed in weak solution, the matter of metal hydride and weak solution
Measuring volume ratio is：100g ︰ 120mL, ultrasonic disperse 1h, form milk-white coloured suspension；(3) warming while stirring is to 75 DEG C, stirring
2h is reacted, reaction, which evaporates solvent ethyl acetate after terminating, reclaims；(4) solidification is dried at 90 DEG C in the product after solvent evaporated
3h, produces the insensitiveness metal hydride of cladding.
Embodiment 3
A kind of metal hydride in-situ polymerization coats passivating method, and metal hydride is AlH3, CeH3-4, LiH or NaH, bag
Include following steps：(1) copolyether and curing agent of the azido-methyl oxygen fourth rings of 3,3- bis- and tetrahydrofuran is taken to be dissolved in anhydrous acetic acid second
Ester, is configured to weak solution；Wherein, curing agent is 4,4- diphenylmethyl baked diisocyanate, and the number of BAMO-THF copolyethers is divided equally
Son amount is that the mol ratio of the azido-methyl oxygen fourth rings of 3,3- bis- and tetrahydrofuran in 4000, BAMO-THF copolyethers is 1 ︰ 1.2,
The mass volume ratio of BAMO-THF copolyethers and anhydrous ethyl acetate is 2.5g ︰ 100mL, curing agent and anhydrous ethyl acetate matter
Amount volume ratio is 0.6g ︰ 100mL；(2) metal hydride particle is taken to be placed in weak solution, the quality of metal hydride and weak solution
Volume ratio is：100g ︰ 110mL, ultrasonic disperse 0.5h, form milk-white coloured suspension；(3) warming while stirring is to 40 DEG C, stirring
3h is reacted, reaction, which evaporates solvent ethyl acetate after terminating, reclaims；(4) solidification is dried at 75 DEG C in the product after solvent evaporated
4h, produces the insensitiveness metal hydride of cladding.
Embodiment 4
A kind of metal hydride in-situ polymerization coats passivating method, and metal hydride is AlH3, comprise the following steps：(1)
The copolyether (BAMO-THF copolyethers) and curing agent of the azido-methyl oxygen fourth rings of 3,3- bis- and tetrahydrofuran is taken to be dissolved in anhydrous acetic acid
Ethyl ester, is configured to weak solution；Wherein, curing agent is IPDI, the number-average molecular weight of BAMO-THF copolyethers
It is 1.2 ︰ 1.2, BAMO- for the mol ratio of the azido-methyl oxygen fourth rings of 3,3- in 5000, BAMO-THF copolyethers bis- and tetrahydrofuran
The mass volume ratio of THF copolyethers and anhydrous ethyl acetate is 2g ︰ 100mL, curing agent and anhydrous ethyl acetate quality volume
Than for 0.5g ︰ 100mL；(2) metal hydride particle is taken to be placed in weak solution, the mass volume ratio of metal hydride and weak solution
For：100g ︰ 115mL, ultrasonic disperse 0.8h, form milk-white coloured suspension；(3) warming while stirring is to 50 DEG C, stirring reaction
2.5h, reaction, which evaporates solvent ethyl acetate after terminating, reclaims；(4) solidification is dried at 65 DEG C in the product after solvent evaporated
4.5h, produces the insensitiveness metal hydride of cladding.Weight is 101.7g, effective AlH3Content is 98.3%.
Embodiment 5
A kind of metal hydride in-situ polymerization coats passivating method, and metal hydride is CeH3-4, comprise the following steps：(1)
The copolyether (BAMO-THF copolyethers) and curing agent of the azido-methyl oxygen fourth rings of 3,3- bis- and tetrahydrofuran is taken to be dissolved in anhydrous acetic acid
Ethyl ester, is configured to weak solution；Wherein, curing agent is toluene di-isocyanate(TDI), and the number-average molecular weight of BAMO-THF copolyethers is
The mol ratio of the azido-methyl oxygen fourth rings of 3,3- bis- and tetrahydrofuran is 1.1 ︰ 1.2 in 3000~6000, BAMO-THF copolyether,
The mass volume ratio of BAMO-THF copolyethers and anhydrous ethyl acetate is 1g ︰ 100mL, curing agent and anhydrous ethyl acetate quality
Volume ratio is 0.3g ︰ 100mL；(2) metal hydride particle is taken to be placed in weak solution, the mass body of metal hydride and weak solution
Accumulating ratio is：100g ︰ 105mL, ultrasonic disperse 0.6h, form milk-white coloured suspension；(3) warming while stirring is to 35 DEG C, and stirring is anti-
Answer 3.5h, reaction to evaporate solvent ethyl acetate after terminating to reclaim；(4) solidification is dried at 85 DEG C in the product after solvent evaporated
3.5h, produces the insensitiveness metal hydride of cladding.Weight is 100.9g, effective CeH3-4Content is 99.1%.
Embodiment 6
A kind of metal hydride in-situ polymerization coats passivating method, and metal hydride is LiH, is comprised the following steps：(1) take
The copolyether (BAMO-THF copolyethers) and curing agent of the azido-methyl oxygen fourth rings of 3,3- bis- and tetrahydrofuran are dissolved in anhydrous acetic acid second
Ester, is configured to weak solution；Wherein, curing agent is 4,4- diphenylmethyl baked diisocyanate, and the number of BAMO-THF copolyethers is divided equally
Son amount is that the mol ratio of the azido-methyl oxygen fourth rings of 3,3- bis- and tetrahydrofuran in 5500, BAMO-THF copolyethers is 0.9 ︰ 1.2,
The mass volume ratio of BAMO-THF copolyethers and anhydrous ethyl acetate is 3g ︰ 100mL, curing agent and anhydrous ethyl acetate quality
Volume ratio is 0.9g ︰ 100mL；(2) metal hydride particle is taken to be placed in weak solution, the mass body of metal hydride and weak solution
Accumulating ratio is：100g ︰ 100mL, ultrasonic disperse 0.7h, form milk-white coloured suspension；(3) warming while stirring is to 60 DEG C, and stirring is anti-
Answer 2.6h, reaction to evaporate solvent ethyl acetate after terminating to reclaim；(4) solidification is dried at 50 DEG C in the product after solvent evaporated
4h, produces the insensitiveness metal hydride of cladding.Weight is 102.6g, and effective LiH contents are 97.4%.
Embodiment 7
A kind of metal hydride in-situ polymerization coats passivating method, and metal hydride is NaH, is comprised the following steps：(1) take
The copolyether (BAMO-THF copolyethers) and curing agent of the azido-methyl oxygen fourth rings of 3,3- bis- and tetrahydrofuran are dissolved in anhydrous acetic acid second
Ester, is configured to weak solution；Wherein, curing agent is 4,4- diphenylmethyl baked diisocyanate, and the number of BAMO-THF copolyethers is divided equally
Son amount is that the mol ratio of the azido-methyl oxygen fourth rings of 3,3- bis- and tetrahydrofuran in 3000~6000, BAMO-THF copolyethers is 1.3 ︰
The mass volume ratio of 1.2, BAMO-THF copolyethers and anhydrous ethyl acetate is 2g ︰ 100mL, curing agent and anhydrous ethyl acetate
Mass volume ratio is 0.7g ︰ 100mL；(2) metal hydride particle is taken to be placed in weak solution, the matter of metal hydride and weak solution
Measuring volume ratio is：100g ︰ 120mL, ultrasonic disperse 0.4h, form milk-white coloured suspension；(3) warming while stirring is stirred to 70 DEG C
Reaction 2.2h is mixed, reaction, which evaporates solvent ethyl acetate after terminating, reclaims；(4) product after solvent evaporated is dried at 80 DEG C
Solidify 3.2h, produce the insensitiveness metal hydride of cladding.Quality is 101.7g, and effective NaH contents are 98.3%.
Claims (8)
1. a kind of metal hydride in-situ polymerization coats passivating method, it is characterised in that：Comprise the following steps：(1) 3,3- bis- is taken
The copolyether and curing agent of azido-methyl oxygen fourth ring and tetrahydrofuran are dissolved in anhydrous ethyl acetate, are configured to weak solution；(2) gold is taken
Category hydride is placed in weak solution, and ultrasonic disperse forms suspension；(3) warming while stirring is to 40 DEG C~60 DEG C, and stirring is anti-
Should, reaction, which evaporates solvent ethyl acetate after terminating, reclaims；(4) dry solidification in an oven of the product after solvent evaporated, is produced
The insensitiveness metal hydride of cladding.
2. metal hydride in-situ polymerization according to claim 1 coats passivating method, it is characterised in that：Including following step
Suddenly：(1) take the copolyether and curing agent of the azido-methyl oxygen fourth rings of 3,3- bis- and tetrahydrofuran to be dissolved in anhydrous ethyl acetate, be configured to
Weak solution；(2) metal hydride particle is taken to be placed in weak solution, ultrasonic disperse 0.3h~1h forms milk-white coloured suspension；(3)
Warming while stirring is to 30 DEG C~75 DEG C, and solvent ethyl acetate is evaporated recovery by 2~4h of stirring reaction, reaction after terminating；(4) steam
3~5h of solidification is dried in 45 DEG C~90 DEG C baking ovens in product after dry solvent, produces the insensitiveness metal hydride of cladding.
3. metal hydride in-situ polymerization according to claim 2 coats passivating method, it is characterised in that：Including following step
Suddenly：(1) take the copolyether and curing agent of the azido-methyl oxygen fourth rings of 3,3- bis- and tetrahydrofuran to be dissolved in anhydrous ethyl acetate, be configured to
Weak solution；(2) metal hydride particle is taken to be placed in weak solution, 0.5~0.8h of ultrasonic disperse forms milk-white coloured suspension；(3)
Warming while stirring is to 35 DEG C~50 DEG C, and solvent ethyl acetate is evaporated recovery by 2~4h of stirring reaction, reaction after terminating；(4) steam
3~5h of solidification is dried in 65 DEG C~85 DEG C baking ovens in product after dry solvent, produces the insensitiveness metal hydride of cladding.
4. the metal hydride in-situ polymerization cladding passivating method according to any one of claims 1 to 3, it is characterised in that：
The number-average molecular weight of the copolyether of the azido-methyl oxygen fourth rings of 3,3- bis- and tetrahydrofuran is 3000~6000,3 in copolyether,
The mol ratio of the azido-methyl oxygen fourth rings of 3- bis- and tetrahydrofuran is 0.8~1.4 ︰ 1.2.
5. the metal hydride in-situ polymerization cladding passivating method according to any one of claims 1 to 3, it is characterised in that：
In the weak solution of the step (1), the copolyether and anhydrous ethyl acetate of 3,3- bis- azido-methyl oxygen fourth rings and tetrahydrofuran
Mass volume ratio is 1~3g ︰ 100mL, and the mass volume ratio of curing agent and anhydrous ethyl acetate is 0.3~0.9g ︰ 100mL.
6. the metal hydride in-situ polymerization cladding passivating method according to any one of claims 1 to 3, it is characterised in that：
In the step (2), the mass volume ratio of metal hydride and weak solution is：100~120mL of 100g ︰.
7. the metal hydride in-situ polymerization cladding passivating method according to any one of claims 1 to 3, it is characterised in that：
The curing agent is IPDI, toluene di-isocyanate(TDI) or 4,4- diphenylmethyl baked diisocyanate.
8. the metal hydride in-situ polymerization cladding passivating method according to any one of claims 1 to 3, it is characterised in that：
The metal hydride is AlH3, CeH3-4, LiH or NaH.
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| CN110981659A (en) * | 2019-12-11 | 2020-04-10 | 湖北航天化学技术研究所 | Method for coating metal hydride by solvent-nonsolvent method |
| CN111892468A (en) * | 2020-07-24 | 2020-11-06 | 西安近代化学研究所 | alpha-AlH3/Al2O3/C60Double-shell structure compound, synthesis method and application |
| CN115259978A (en) * | 2022-08-12 | 2022-11-01 | 南京理工大学 | Polydopamine-coated aluminum trihydride compound with core-shell structure and preparation method thereof |
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| CN111892468A (en) * | 2020-07-24 | 2020-11-06 | 西安近代化学研究所 | alpha-AlH3/Al2O3/C60Double-shell structure compound, synthesis method and application |
| CN115259978A (en) * | 2022-08-12 | 2022-11-01 | 南京理工大学 | Polydopamine-coated aluminum trihydride compound with core-shell structure and preparation method thereof |
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