CN114702006A - Method for synthesizing alkali metal aluminum coordination hydride - Google Patents
Method for synthesizing alkali metal aluminum coordination hydride Download PDFInfo
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- CN114702006A CN114702006A CN202210333008.4A CN202210333008A CN114702006A CN 114702006 A CN114702006 A CN 114702006A CN 202210333008 A CN202210333008 A CN 202210333008A CN 114702006 A CN114702006 A CN 114702006A
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- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 title claims abstract description 58
- 229910052782 aluminium Inorganic materials 0.000 title claims abstract description 58
- 229910052783 alkali metal Inorganic materials 0.000 title claims abstract description 33
- 150000001340 alkali metals Chemical class 0.000 title claims abstract description 33
- 150000004678 hydrides Chemical class 0.000 title claims abstract description 32
- 238000000034 method Methods 0.000 title claims abstract description 22
- 230000002194 synthesizing effect Effects 0.000 title claims description 14
- 238000000498 ball milling Methods 0.000 claims abstract description 52
- 239000001257 hydrogen Substances 0.000 claims abstract description 43
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 42
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims abstract description 36
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 claims abstract description 33
- 229910052751 metal Inorganic materials 0.000 claims abstract description 30
- 239000002184 metal Substances 0.000 claims abstract description 30
- 238000003786 synthesis reaction Methods 0.000 claims abstract description 16
- 238000006243 chemical reaction Methods 0.000 claims abstract description 15
- 230000015572 biosynthetic process Effects 0.000 claims abstract description 14
- 238000001308 synthesis method Methods 0.000 claims abstract description 12
- KEAYESYHFKHZAL-UHFFFAOYSA-N Sodium Chemical compound [Na] KEAYESYHFKHZAL-UHFFFAOYSA-N 0.000 claims abstract description 8
- 229910000103 lithium hydride Inorganic materials 0.000 claims abstract description 8
- 229910000104 sodium hydride Inorganic materials 0.000 claims abstract description 8
- 239000012312 sodium hydride Substances 0.000 claims abstract description 8
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims abstract 3
- 229910052700 potassium Inorganic materials 0.000 claims description 29
- 239000011591 potassium Substances 0.000 claims description 28
- 239000007787 solid Substances 0.000 claims description 22
- 229910000102 alkali metal hydride Inorganic materials 0.000 claims description 21
- 150000008046 alkali metal hydrides Chemical class 0.000 claims description 21
- 238000000926 separation method Methods 0.000 claims description 9
- 238000000227 grinding Methods 0.000 claims description 8
- AZDRQVAHHNSJOQ-UHFFFAOYSA-N alumane Chemical compound [AlH3] AZDRQVAHHNSJOQ-UHFFFAOYSA-N 0.000 claims description 3
- 239000003513 alkali Substances 0.000 claims description 2
- -1 hydrogen Chemical class 0.000 claims description 2
- 229910052744 lithium Inorganic materials 0.000 claims description 2
- 229910052708 sodium Inorganic materials 0.000 claims description 2
- 239000011734 sodium Substances 0.000 claims description 2
- 239000000126 substance Substances 0.000 claims 1
- 238000000746 purification Methods 0.000 abstract description 3
- 230000007613 environmental effect Effects 0.000 abstract description 2
- 238000002156 mixing Methods 0.000 abstract description 2
- 239000003960 organic solvent Substances 0.000 abstract description 2
- 238000011031 large-scale manufacturing process Methods 0.000 abstract 1
- 239000000843 powder Substances 0.000 description 16
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 12
- 239000000463 material Substances 0.000 description 9
- 238000003860 storage Methods 0.000 description 9
- 238000002441 X-ray diffraction Methods 0.000 description 8
- 238000012360 testing method Methods 0.000 description 8
- 150000002431 hydrogen Chemical class 0.000 description 7
- 238000011049 filling Methods 0.000 description 6
- 238000005516 engineering process Methods 0.000 description 5
- 238000010438 heat treatment Methods 0.000 description 5
- SIAPCJWMELPYOE-UHFFFAOYSA-N lithium hydride Chemical compound [LiH] SIAPCJWMELPYOE-UHFFFAOYSA-N 0.000 description 5
- 238000001914 filtration Methods 0.000 description 4
- 239000000203 mixture Substances 0.000 description 4
- 239000011232 storage material Substances 0.000 description 4
- 229910010084 LiAlH4 Inorganic materials 0.000 description 3
- 229910020828 NaAlH4 Inorganic materials 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- 239000000956 alloy Substances 0.000 description 3
- 229910045601 alloy Inorganic materials 0.000 description 3
- 239000003054 catalyst Substances 0.000 description 3
- 150000001875 compounds Chemical class 0.000 description 3
- 230000007547 defect Effects 0.000 description 3
- 238000005265 energy consumption Methods 0.000 description 3
- 239000012535 impurity Substances 0.000 description 3
- 239000012280 lithium aluminium hydride Substances 0.000 description 3
- 238000002360 preparation method Methods 0.000 description 3
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- WCUXLLCKKVVCTQ-UHFFFAOYSA-M Potassium chloride Chemical compound [Cl-].[K+] WCUXLLCKKVVCTQ-UHFFFAOYSA-M 0.000 description 2
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 2
- 239000003153 chemical reaction reagent Substances 0.000 description 2
- 238000002485 combustion reaction Methods 0.000 description 2
- 238000000354 decomposition reaction Methods 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 238000001704 evaporation Methods 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 229910000105 potassium hydride Inorganic materials 0.000 description 2
- NTTOTNSKUYCDAV-UHFFFAOYSA-N potassium hydride Chemical compound [KH] NTTOTNSKUYCDAV-UHFFFAOYSA-N 0.000 description 2
- 230000002441 reversible effect Effects 0.000 description 2
- 239000000243 solution Substances 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- 238000001291 vacuum drying Methods 0.000 description 2
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 229910052786 argon Inorganic materials 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000000919 ceramic Substances 0.000 description 1
- 238000012512 characterization method Methods 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- SBZXBUIDTXKZTM-UHFFFAOYSA-N diglyme Chemical compound COCCOCCOC SBZXBUIDTXKZTM-UHFFFAOYSA-N 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 239000001307 helium Substances 0.000 description 1
- 229910052734 helium Inorganic materials 0.000 description 1
- SWQJXJOGLNCZEY-UHFFFAOYSA-N helium atom Chemical compound [He] SWQJXJOGLNCZEY-UHFFFAOYSA-N 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 239000011259 mixed solution Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 235000011164 potassium chloride Nutrition 0.000 description 1
- 239000001103 potassium chloride Substances 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 238000004321 preservation Methods 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000012827 research and development Methods 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 1
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Classifications
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B6/00—Hydrides of metals including fully or partially hydrided metals, alloys or intermetallic compounds ; Compounds containing at least one metal-hydrogen bond, e.g. (GeH3)2S, SiH GeH; Monoborane or diborane; Addition complexes thereof
- C01B6/24—Hydrides containing at least two metals; Addition complexes thereof
- C01B6/243—Hydrides containing at least two metals; Addition complexes thereof containing only hydrogen, aluminium and alkali metals, e.g. Li(AlH4)
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2002/00—Crystal-structural characteristics
- C01P2002/70—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data
- C01P2002/72—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data by d-values or two theta-values, e.g. as X-ray diagram
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2006/00—Physical properties of inorganic compounds
- C01P2006/80—Compositional purity
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Inorganic Chemistry (AREA)
- Hydrogen, Water And Hydrids (AREA)
Abstract
The invention belongs to the technical field of chemical synthesis, and particularly relates to a synthesis method of alkali metal aluminum coordination hydride. The method is a method for preparing the alkali metal aluminum coordination hydride by mixing two or three of metal potassium, metal aluminum, sodium hydride and lithium hydride and ball milling for 6 to 72 hours in the atmosphere of hydrogen. Compared with the existing synthesis method under high temperature and high pressure, the method has the advantages of no use of organic solvent for purification, simple synthesis process, mild reaction conditions, high product purity, high yield, low cost, environmental friendliness, high safety factor and convenience for large-scale production. The synthesis method of the alkali metal aluminum coordination hydride is a green, novel, efficient and low-cost synthesis method.
Description
Technical Field
The invention belongs to the technical field of chemical synthesis, and particularly relates to a synthesis method of alkali metal aluminum coordination hydride.
Background
In the past decades, due to the world's pair being renewableThe demand of energy and green high-efficiency energy technology is continuously increased, and the search for a new environment-friendly energy conversion and storage material is widely concerned. Hydrogen energy is considered to be a renewable energy carrier which is expected to replace fossil energy due to its outstanding advantages of high combustion efficiency, clean combustion products, diversity of applications and the like. However, since hydrogen has a low density, it is difficult to store hydrogen at normal temperature and pressure, and a highly efficient and safe hydrogen storage technology becomes a key for hydrogen energy development. Wherein, the solid-state hydrogen storage technology has higher hydrogen storage capacity than the gaseous and liquid hydrogen storage technologies, can effectively improve the defects of the traditional hydrogen storage technology, and is expected to realize safe and efficient hydrogen storage [ Fichtner M.conversion materials for hydrogen storage and biochemical applications concentrations and silicon resources, journal of Alloys and Compounds 2011; 509S: S529e34.]. Of the numerous solid-state hydrogen storage materials, the alkali metal aluminum complex hydride is considered to be a very promising hydrogen storage material, including LiAlH4，NaAlH4，KAlH4And the like. By KAlH4For example, Morioka et al have shown that KAlH occurs at temperatures ranging from 250 to 340 deg.C4Can be reversibly dehydrogenated and rehydrogenated without any catalyst, and the theoretical hydrogen storage amount can reach 5.7 wt% [ H.Morioka, K.Kakizaki, S.C.Chung, A.Yamada, Reversible hydrogen decomposition of KAlH4.Journal of Alloys and Compounds2003；353:310-314.]Is a solid hydrogen storage compound which is very convenient for storing hydrogen.
Synthesis of alkali metal alanates KAlH known hitherto4The method comprises the following steps: (1) putting potassium hydride and metallic aluminum into a ball milling tank, ball milling for 30min at the rotating speed of 500rpm, putting the ball milled powder into a high-pressure reaction kettle, filling 135bar of hydrogen into the high-pressure reaction kettle, heating the reaction kettle to 135 ℃, and keeping the temperature for three days. Taking out the powder in the reaction kettle, dissolving the powder after reaction with diethyl ether, filtering to remove impurities, and evaporating at 34 deg.C to remove diethyl ether solvent to obtain KAlH4[H.Morioka,K.Kakizaki,S.C.Chung,A.Yamada,Reversible hydrogen decomposition of KAlH4.Journal of Alloys and Compounds 2003；353(1-2):310-314.]. (2) Mixing potassium chloride and NaAlH4Or LiAlH4Putting into a ball milling tank, and ball milling for 3h at the rotating speed of 500 rpm. And putting the obtained solid powder into a diglyme solution, stirring for 12 hours, putting the mixed solution into toluene for precipitation, filtering out, and putting the powder solid obtained by vacuum drying into a tetrahydrofuran solution for treatment for 12 hours. Filtering, vacuum drying to obtain KAlH4Powder [ B.Zibrowus, M.Felderhoff, On the preparation and NMR spectroscopic characterization of potassium aluminum tetrahydrate KAlH4.Phys Chem Phys 2019; 21(23):12576-12584.]. (3) Adding potassium hydride and metal aluminum into a ball milling tank, properly adding 5 wt% of catalyst, charging 85-120bar of hydrogen pressure, putting into a ball mill, and ball milling at 400rpm for 200min to obtain KAlH4And (3) powder. Dissolving the ball-milled sample powder with diethyl ether to remove catalyst and impurities, filtering out impurities, and evaporating diethyl ether solvent to obtain KAlH4Powder [ J.R.Ares, J.Zhang, T.Charpentier, F.Cuevas and M.Latroche, asymmetry Reaction Paths and Hydrogen absorption mechanization machinery in mechanical Chemistry-ceramic Ananate (KAlH4). The Journal of Physical Chemistry C2016; 120(38):21299-21308.]. The method for synthesizing the hydrogen storage material limits KAlH due to the defects of harsh preparation conditions, high cost of required raw materials, complex purification process, low product purity and the like4And large-scale application development. Thus, for the current preparation of KAlH4The problems exist, and the research and development of a green and economic synthesis method of the alkali metal aluminum complex hydride is of great significance.
Disclosure of Invention
The invention aims to provide a simple, economical, low-energy-consumption and green method for preparing alkali metal aluminum complex hydride aiming at the defects of the existing synthesis method. The technical scheme adopted by the invention for solving the technical problems is as follows:
a process for synthesizing the coordination hydride of alkali metal Al includes such steps as ball grinding of K, Al and MH in the presence of hydrogen to obtain the coordination hydride KxMAlHyX is more than or equal to 1 and less than or equal to 3, y is more than or equal to 4 and less than or equal to 6, and M is at least one of air, Na and Li; among them, potassium, aluminum and alkali metalsThe molar ratio of hydride is (1-3): 1: (0-1).
Preferably, the alkali metal hydride is at least one of sodium hydride and lithium hydride.
Preferably, the alkali metal aluminum complex hydride is KAlH4、K3AlH6、K2LiAlH6、K2NaAlH6At least one of (a).
Preferably, when the molar ratio of potassium to aluminum to alkali metal hydride is as follows, the alkali metal aluminum complex hydride is synthesized as follows:
the molar ratio of potassium to aluminum to alkali metal hydride is 1: 1: 0, Synthesis of KAlH4；
The molar ratio of potassium to aluminum to alkali metal hydride is 3: 1: 0, Synthesis K3AlH6；
The molar ratio of potassium to aluminum to alkali metal hydride is 2: 1: 1, the alkali metal hydride is lithium hydride, Synthesis of K2LiAlH6；
The molar ratio of potassium to aluminum to alkali metal hydride is 2: 1: 1, the alkali metal hydride is sodium hydride, Synthesis K2NaAlH6。
Preferably, the method specifically comprises the following steps:
(1) transferring a certain amount of metal potassium, metal aluminum, alkali metal hydride and grinding balls into a sealed ball-milling tank in an inert atmosphere, and replacing the atmosphere in the ball-milling tank with hydrogen;
(2) placing the ball milling tank on a ball mill to perform ball milling for a period of time under certain conditions; and after the ball milling is finished, carrying out post-treatment to obtain the alkali metal aluminum coordination hydride.
Preferably, in step (1), all samples are weighed and used in a glove box filled with an inert atmosphere.
Preferably, in the step (1), the molar ratio of the metal potassium to the metal aluminum to the alkali metal hydride is 1: 1: 0 then synthesizes KAlH4The molar ratio of metal potassium to metal aluminum to alkali metal hydride is 3: 1: 0 then synthesizing K3AlH6The molar ratio of the metal potassium to the metal aluminum to the metal lithium hydride is 2: 1: 1 then synthesis of K2LiAlH6The molar ratio of the metal potassium to the metal aluminum to the metal sodium hydride is 2: 1: 1 then synthesis of K2NaAlH6。
Preferably, in the step (1), the replacement of the atmosphere of hydrogen in the ball milling tank is carried out by vacuumizing the sealed ball milling tank and then filling hydrogen with a certain pressure; more preferably, the pressure of the hydrogen filled in the ball milling tank is 15-100bar, and the molar ratio of the metal potassium to the hydrogen is 1: (4-27).
Preferably, in the step (1), the ball-material ratio in the ball milling tank is (20-90): 1.
preferably, in the step (2), the ball milling rotation speed is (300-.
Preferably, in the step (2), the post-treatment is a conventional post-treatment operation, including but not limited to, carrying out gas-solid separation on the reaction system and then taking out the solid articles; more preferably, the post-treatment is: (3) after the ball milling is finished, separating gas from solid in the ball milling tank; (4) and taking out the solid sample in the ball milling tank under the inert atmosphere to obtain the alkali metal aluminum coordination hydride.
More preferably, the gas-solid separation is to evacuate the residual hydrogen in the ball milling tank and to evacuate the sealed ball milling tank.
More preferably, after gas-solid separation, the solid sample in the ball mill can be taken out under inert atmosphere, and the alkali metal aluminum coordination hydride is obtained.
Preferably, the inert atmosphere in the present invention is at least one of helium and argon.
Compared with the existing synthesis method, the invention has the following beneficial effects:
(1) the synthesis method has the advantages of simple synthesis process, low energy consumption, environmental protection and suitability for mass production.
(2) The synthesis method has mild conditions, does not need heating and heat preservation, does not need purification by using an organic solvent, and reduces the energy consumption of production.
(3) The synthesis method does not need to use expensive KH and NaAlH4、LiAlH4The alkali metal alanate with high yield and high purity can be directly synthesized only by using the metal potassium and the metal aluminum with lower price, and the method has a great rangeThe cost is reduced and the investment of equipment is reduced.
Drawings
Figure 1 is an XRD pattern of a ball milled product of an example of the invention,
figure 2 is an XRD pattern of an example three-ball milled product of the invention,
figure 3 is an XRD pattern of an example four-ball milled product of the invention,
figure 4 is an XRD pattern of an example five-ball milled product of the invention.
Detailed Description
The synthesis technical scheme of the present invention is further illustrated by the following specific examples in conjunction with the accompanying drawings, wherein the experimental methods in the examples are all conventional methods if no special provisions exist, and the involved experimental reagents and materials are all conventional biochemical reagents and materials if no special provisions exist, but it should be noted that the scope of the present invention is not limited thereto.
Example 1
In an inert atmosphere glove box, 1.1819g of potassium metal blocks (99%) and 0.8181g of aluminum metal (99%) were taken and transferred into a sealed ball mill jar and grinding balls were added at a ball to material ratio of 45: 1. The ball milling tank is firstly vacuumized and then filled with 60bar hydrogen, and ball milling is carried out for 48 hours at the rotating speed of 500 rpm. After gas-solid separation, taking out solid powder in an inert atmosphere glove box to obtain KAlH4The purity was 96% by hydrogen evolution test. XRD detection is carried out on the product after ball milling in the embodiment (figure 1), and figure 1 (lower) is the product after ball milling in the embodiment; in order to enhance the crystallinity of the sample, the product after ball milling is heated to 185 ℃ under vacuum and is subjected to heat treatment for 10 hours. FIG. 1 (top) is the XRD pattern of the product obtained after heat treatment of the ball-milled product of this example at a certain temperature, and KAlH as a product of heat treatment at 185 ℃ for 10 hours under vacuum4Has stronger XRD diffraction peak, and is consistent with the sample synthesized by ball milling.
Example 2
In an inert atmosphere glove box, 2.6590g of metal potassium block (99%) and 1.8410g of metal aluminum (99%) are taken, the mixture of metal potassium block and metal aluminum is moved into a ball milling tank, and grinding balls are added, wherein the ball material ratio is 20: 1, firstly vacuumizing the ball milling tank, then filling 100bar hydrogen, and rotating at 600 turnsAnd performing ball milling reaction for 72 hours at a rotating speed of/minute. After gas-solid separation, taking out solid powder in an inert atmosphere glove box to obtain KAlH4The purity was 95% by hydrogen evolution test.
Example 3
In an inert atmosphere glove box, 1.6250g of a metallic potassium block (99%) and 0.3750g of a metallic aluminum (99%) were taken, the metallic potassium block and metallic aluminum mixture were transferred into a ball mill jar, and grinding balls were added, the ball to material ratio was 45:1, firstly vacuumizing the ball milling tank, then filling 60bar of hydrogen, and carrying out ball milling reaction for 24 hours at the rotating speed of 500 revolutions per minute. After gas-solid separation, taking out solid powder in an inert atmosphere glove box to obtain K3AlH6The purity was 98% by hydrogen evolution test. XRD test is carried out on the product after ball milling in the embodiment, and figure 2 is an XRD pattern of the product after ball milling in the embodiment.
Example 4
In an inert atmosphere glove box, 1.2094g of metal potassium block (99%) and 0.4186g of metal aluminum (99%), 0.3720g of sodium hydride powder are taken, the metal potassium block, the metal aluminum and sodium hydride mixture are moved into a ball milling tank, and grinding balls are added, wherein the ball-to-material ratio is 45:1, firstly vacuumizing the ball milling tank, then filling 60bar of hydrogen, and carrying out ball milling reaction for 24 hours at the rotating speed of 500 revolutions per minute. After gas-solid separation, taking out solid powder in an inert atmosphere glove box to obtain K2NaAlH6The purity was 98% by hydrogen evolution test. XRD testing was performed on the ball-milled product of this example, and FIG. 3 is the XRD pattern of the ball-milled product of this example.
Example 5
In an inert atmosphere glove box, 1.3806g of metal potassium block (99%) and 0.4778g of metal aluminum (99%), 0.1416g of lithium hydride powder are taken, the metal potassium block, the metal aluminum and lithium hydride mixture are moved into a ball milling tank, and grinding balls are added, wherein the ball-to-material ratio is 45:1, firstly vacuumizing the ball milling tank, then filling 60bar of hydrogen, and carrying out ball milling reaction for 24 hours at the rotating speed of 500 revolutions per minute. After gas-solid separation, taking out solid powder in an inert atmosphere glove box to obtain K2LiAlH6The purity was 93% by hydrogen evolution test. XRD testing was performed on the ball-milled product of this example, and FIG. 4 is the XRD pattern of the ball-milled product of this example.
The above description is only a preferred embodiment of the present invention and should not be taken as limiting the invention, and any modification, replacement, or improvement made on the principle of the present invention should be included in the protection scope of the present invention.
Claims (10)
1. The synthesis method of the alkali metal aluminum complex hydride is characterized in that potassium K, aluminum Al and alkali metal hydride MH are synthesized into the alkali metal aluminum complex hydride K by ball milling in the presence of hydrogenxMAlHyX is more than or equal to 1 and less than or equal to 3, y is more than or equal to 4 and less than or equal to 6, and M is at least one of air, Na and Li; wherein the molar ratio of potassium to aluminum to alkali metal hydride is (1-3): 1: (0-1).
2. The method of synthesizing an alkali metal aluminum complex hydride according to claim 1, wherein said alkali metal hydride is at least one of sodium hydride and lithium hydride.
3. The method of synthesizing an alkali metal aluminum complex hydride as claimed in claim 1, wherein said alkali metal aluminum complex hydride is KAlH4、K3AlH6、K2LiAlH6、K2NaAlH6At least one of (1).
4. The method of synthesizing an alkali metal aluminum complex hydride according to claim 1, wherein when the molar ratio of potassium, aluminum and alkali metal hydride is as follows, the alkali metal aluminum complex hydride is synthesized as follows:
the molar ratio of potassium to aluminum to alkali metal hydride is 1: 1: 0, Synthesis of KAlH4；
The molar ratio of potassium to aluminum to alkali metal hydride is 3: 1: 0, Synthesis K3AlH6；
The molar ratio of potassium to aluminum to alkali metal hydride is 2: 1: 1, the alkali metal hydride is lithium hydride, Synthesis of K2LiAlH6；
The molar ratio of potassium to aluminum to alkali metal hydride is 2: 1: 1, alkali metal alkylationThe substance is sodium hydride, synthesis K2NaAlH6。
5. The method for synthesizing an alkali metal aluminum complex hydride according to any one of claims 1 to 4, which comprises the steps of:
(1) transferring a certain amount of metal potassium, metal aluminum, alkali metal hydride and grinding balls into a sealed ball-milling tank in an inert atmosphere, and replacing the atmosphere in the ball-milling tank with hydrogen;
(2) placing the ball milling tank on a ball mill to perform ball milling for a period of time under certain conditions; and after the ball milling is finished, carrying out post-treatment to obtain the alkali metal aluminum coordination hydride.
6. The method of synthesizing an alkali metal aluminum complex hydride according to claim 5, wherein in the step (1), all the samples are weighed and used in a glove box filled with an inert atmosphere.
7. The method of synthesizing an alkali metal aluminum complex hydride according to claim 5, wherein in the step (1), the pressure of hydrogen gas in the ball mill pot is 15 to 100 bar.
8. The process of synthesizing an alkali metal aluminum complex hydride according to claim 5, wherein in the step (1), the molar ratio of metal potassium to hydrogen is 1: (4-27).
9. The method for synthesizing an alkali metal aluminum complex hydride as claimed in claim 5, wherein in the step (2), the ball milling rotation speed is 300-600rpm and the ball milling time is 6-72 hours.
10. The method of synthesizing an alkali metal aluminum complex hydride according to claim 5, wherein the post-treatment is: after the ball milling is finished, carrying out gas-solid separation on a reaction system in the ball milling tank; and taking out a solid sample in the ball milling tank under an inert atmosphere to obtain the alkali metal aluminum coordination hydride.
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| WO2024103571A1 (en) * | 2022-11-17 | 2024-05-23 | 中国科学院大连化学物理研究所 | Alkali metal hydride, preparation method and use |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| US6251349B1 (en) * | 1997-10-10 | 2001-06-26 | Mcgill University | Method of fabrication of complex alkali metal hydrides |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6251349B1 (en) * | 1997-10-10 | 2001-06-26 | Mcgill University | Method of fabrication of complex alkali metal hydrides |
Non-Patent Citations (2)
| Title |
|---|
| D. PUKAZHSELVAN等: "One step high pressure mechanochemical synthesis of reversible alanates NaAlH4 and KAlH4" * |
| L.ELANSARI ET AL.: "Preparation of alkali metal hydrides by mechanical alloying" * |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2024103571A1 (en) * | 2022-11-17 | 2024-05-23 | 中国科学院大连化学物理研究所 | Alkali metal hydride, preparation method and use |
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