Compounds and methods for the preparation of aluminates

Abstract

The method of the present disclosure involves the development of a low-temperature, solvent-assisted synthesis of aluminates such as lithium tetraiodoaluminate (LiAlI). +q ][Al(X)I] q The present invention also includes a method for preparing the compound of formula (I).

Description

[Technical Field]

[0001] The present disclosure relates to the field of chemistry. More particularly, the present disclosure relates to compounds and methods for the preparation of aluminates. [Background technology]

[0002] Ball milling can be used to mix the solid particles into a mixed fine powder. Summary of the Invention

[0003] Methods for preparing aluminates, such as LiAlI, are limited in part by the dangers associated with the synthetic procedures (e.g., toxicity of the reagents) or extreme preparative conditions (i.e., high-temperature reactions (e.g., reactions at temperatures above 200°C)). One example involves heating a mixture of AlI and LiI in CS. Potential drawbacks of this method include the toxicity of CS. Some methods involve intense heating of the reactants, for example, with a Bunsen burner. One method for preparing LiAlI involves heating AlI and LiI together in the solid state at high temperatures (e.g., temperatures above 200°C). Some preparative methods involve ball milling the solid reactants at 200 rpm and room temperature.

[0004] In contrast, the disclosed method involves the development of a low-temperature, solvent-assisted synthesis of aluminates, such as lithium tetraiodoaluminate (LiAlI4). The disclosed method does not require high temperatures (e.g., above about 200°C). The disclosed method also does not require solid-state reaction by ball milling or melting. The disclosed method does not require ball milling because the reactants can be in solution, e.g., in a slurry. Additionally, the disclosed method does not require toxic polar solvents to fully solubilize the reactants (i.e., starting materials).

[0005] In some aspects, the techniques described herein comprise a method comprising: Formula (I) [M +q ][Al(X)I]q (I), wherein M is (i) Li + , Na + , K. + , Rb + , and Cs + (ii) a Group 1 metal cation selected from Mg 2+ , Ca 2+ , Sr 2+ , and Ba 2+ and (iii) an ammonium, C1-C6 alkylammonium, or benzylammonium cation; and (iii) an ammonium, C1-C6 alkylammonium, or benzylammonium cation; q is the valence of M and is 1 or 2; The present invention relates to a process comprising reacting an aluminum (Al) reactant with a reactant M in a solvent at a temperature of 200° C. or less to form a compound of formula (I), wherein X is chloro, bromo, or iodo.

[0006] In some aspects, the techniques described herein include +q Li + This relates to a method.

[0007] In some embodiments, the techniques described herein relate to methods where q is 1.

[0008] In some embodiments, the techniques described herein relate to methods where X is iodo.

[0009] In some embodiments, the techniques described herein relate to methods wherein the compound of formula (I) is LiAlI4.

[0010] In some embodiments, the techniques described herein may further comprise reacting an aluminum (Al) reactant with a reactant M to (i) convert AlX3 to M +q X q or (ii) reacting with Al 0 , I2, and M +q X qThe present invention relates to a method comprising reacting

[0011] In some aspects, the techniques described herein include Al 0 , I2, and M +q X q The reaction is carried out by first reacting Al 0 with I2 to produce AlI3 in situ.

[0012] In some embodiments, the techniques described herein relate to methods that further include reacting the in situ generated AlI with LiI.

[0013] In some embodiments, the techniques described herein may be used to convert AlX3 to M +q X q comprises reacting AlI with LiI.

[0014] In some embodiments, the techniques described herein relate to methods in which reacting AlI3 with LiI comprises reacting AlI3 with LiI in a 1:1 molar equivalent.

[0015] In some embodiments, techniques described herein relate to methods in which reacting AlI3 with LiI includes reacting AlI3 with LiI at a temperature less than 150°C.

[0016] In some aspects, the techniques described herein relate to methods by which compounds of formula (I) are produced in situ.

[0017] In some embodiments, the techniques described herein relate to methods in which the aluminum (Al) reactant is AlI3.

[0018] In some embodiments, the techniques described herein relate to methods in which reactant M is LiI.

[0019] In some aspects, the techniques described herein relate to methods in which the solvent is an aromatic hydrocarbon.

[0020] In some aspects, the techniques described herein relate to methods where the aromatic hydrocarbon is toluene, xylene, benzene, or chlorobenzene.

[0021] In some embodiments, the techniques described herein relate to methods wherein preparing a compound of formula (I) comprises preparing a compound of formula (I) at a temperature of less than 50°C.

[0022] In some embodiments, the techniques described herein relate to methods where preparing a compound of formula (I) comprises preparing a compound of formula (I) at a temperature of less than 40°C.

[0023] In some embodiments, the techniques described herein relate to methods in which the reaction between an aluminum (Al) reactant and a reactant M proceeds in solution at a temperature of 30° C. or greater.

[0024] In some embodiments, the techniques described herein relate to methods in which the reaction between an aluminum (Al) reactant and reactant M proceeds in a slurry at a temperature of 30° C. or greater.

[0025] Some embodiments of the present disclosure are herein described, by way of example only, with reference to the accompanying drawings. With particular reference now to the drawings in detail, it is emphasized that the illustrated embodiments are by way of example and for illustrative purposes of illustrating embodiments of the present disclosure. In this regard, the description made with the drawings will make apparent to those skilled in the art how embodiments of the present disclosure may be practiced. [Brief explanation of the drawings]

[0026] [Figure 1] FIG. 1 shows non-limiting embodiments of two reaction schemes of the present disclosure, according to at least some embodiments of the present disclosure. [Figure 2] FIG. 1 shows a lithium (Li) nuclear magnetic resonance (NMR) spectrum (7Li-NMR spectrum) according to some embodiments of the present disclosure. [Figure 3] FIG. 1 shows a Fourier transform infrared spectroscopy (FTIR) of the formation of LiAlI4 in toluene according to some embodiments of the present disclosure. [Figure 4] FIG. 1 shows a differential scanning calorimetry (DSC) comparison of AlI3 and LiAlI4 according to some embodiments of the present disclosure. DETAILED DESCRIPTION OF THE INVENTION

[0027] Among these disclosed benefits and improvements, other objects and advantages of the present disclosure will become apparent from the following description taken in conjunction with the accompanying drawings. While detailed embodiments of the present disclosure are disclosed herein, it should be understood that the disclosed embodiments are merely exemplary of the present disclosure, which may be embodied in various forms. Moreover, each of the examples provided with respect to various embodiments of the present disclosure is intended to be illustrative and not limiting.

[0028] All prior patents and publications referenced herein are incorporated by reference in their entirety.

[0029] Throughout the specification and claims, the following terms take the meanings expressly associated therewith herein, unless the context clearly dictates otherwise. As used herein, the phrases "in one embodiment," "in an embodiment," and "in some embodiments" do not necessarily refer to the same embodiment, but may. Additionally, as used herein, the phrases "in another embodiment" and "in some other embodiments" do not necessarily refer to different embodiments, but may. It is intended that all embodiments of the present disclosure be combinable without departing from the scope or spirit of the disclosure.

[0030] As used herein, the term "based on" is not exclusive and allows for based on additional factors not listed unless the context clearly dictates otherwise. Additionally, throughout this specification, the meanings of "a," "an," and "the" include plural references. The meaning of "in" includes "in" and "on."

[0031] As used herein, the term "between" does not necessarily require placement immediately adjacent to another element. Generally, the term refers to a configuration in which an item is sandwiched between two or more other items. At the same time, the term "between" can describe an item that is immediately adjacent to two opposing items. Thus, in any one or more of the embodiments disclosed herein, a particular structural component that is positioned between two other structural elements may be: A particular structural component may be placed directly between two other structural elements, such that the structural component is in direct contact with both of the two other structural elements; A particular structural component can be placed directly next to only one of two other structural elements, such that it is in direct contact with only one of the two other structural elements; A particular structural element may be indirectly adjacent to only one of the two other structural elements, such that the particular structural element is not in direct contact with only one of the two other structural elements, but there is another element that juxtaposes the particular structural element and one of the two other structural elements; or A particular structural component may be indirectly disposed between two other structural elements, such that the structural component does not directly contact both of the two other structural elements, but other features may be disposed between the structural elements; or It can be any combination thereof.

[0032] As used herein, "embedded" means that a first material is distributed throughout a second material.

[0033] The disclosed method involves the development of a low-temperature, solvent-assisted synthesis of aluminates, such as lithium tetraiodoaluminate (LiAlI4). The disclosed method does not require high temperatures (e.g., above about 200°C). The disclosed method also does not require ball milling, as the reactants can be in solution, e.g., in a slurry.

[0034] The present disclosure provides a compound of formula (I): [M +q ][Al(X)I] q The present invention also includes a method for preparing a compound of formula (I).

[0035] The method includes reacting an aluminum (Al) reactant with a reactant M to form a compound of formula (I), where M is (i) Li + , Na + , K. + , Rb + , and Cs + (ii) a Group 1 metal cation selected from Mg 2+ , Ca 2+ , Sr 2+ , and Ba 2+ and (iii) an ammonium, C1-C6 alkylammonium, or benzylammonium cation, where q is the valence of M and is 1 or 2, and X is chloro, bromo, or iodo. In some embodiments, reactant M is a metal or behaves like a metal (e.g., an ammonium, C1-C6 alkylammonium, and / or benzylammonium cation).

[0036] In some embodiments, the compound of formula (I) is LiAl(I)4, NaAl(I)4, KAl(I)4, Mg[Al(I)4]2, Ca[Al(I)4]2, LiAl(Cl)3I, LiAlCl(I)3, NaAl(Cl)3I, NaAlCl(I)3, KAl(Cl) 3I, KAlCl(I)3, Mg[Al(Cl)3I]2, Mg[Al(Cl)(I)3]2, Ca[Al(Cl)3I]2, Ca[Al(Cl)(I)3]2, NH4Al(I)4, NH4Al(Cl)3I, NH4Al(Cl)(I)3, NaAl2I7, NaAl3I 10, and Al(I)3.

[0037] In some embodiments, M is a cation, e.g., (CH3)4N + , (CH3CH2)4N + , (CH3CH2CH2)4N + , and (CH3CH2CH2CH2)4N + is selected from.

[0038] In some embodiments, compounds of Formula (I) can be referred to as aluminates and can be produced by reaction in solution using a 1:1 molar ratio of reactants (or 2:1 for divalent Group 2 metal cations). As an example, LiAl(I)4 aluminate can be prepared by mixing LiI and Al(I)3 in solution when combined in a 1:1 molar ratio. In some embodiments, gentle heating can be used while mixing the reactants. Gentle heating can include raising the temperature to the maximum boiling point of the solvent for the solution.

[0039] In some embodiments, the solvent is an aromatic hydrocarbon. In some embodiments, the aromatic hydrocarbon is toluene, xylene, benzene, chlorobenzene, or a combination thereof. In some embodiments, the solvent can be toluene. The boiling point of toluene is 115°C. In some embodiments, when the solvent comprises toluene, the method can include heating to 115°C. In some embodiments, the solvent can be benzene. The boiling point of benzene is 80°C. In some embodiments, when the solvent comprises benzene, the method can include heating to 80°C. In some embodiments, the solvent can be chlorobenzene. The boiling point of chlorobenzene is 132°C. In some embodiments, when the solvent comprises chlorobenzene, the method can include heating to 132°C. In some embodiments, the solvent can be xylene. Boiling points of xylene isomers include 139°C for meta-xylene, 144°C for ortho-xylene, and 138.4°C for para-xylene. In some embodiments, when the solvent comprises xylene isomers, the method can include heating to 138.4°C, 139°C, or 144°C. In some embodiments, mild heating may include raising the temperature to the maximum boiling point of the solvent (as described herein) for the solution.

[0040] Alternatively, the in situ formation of LiAlI4 can be achieved by the addition of Al 0 It can be prepared by the reaction of +I2 followed by the addition of LiI.

[0041] In some embodiments, the aluminum (Al) reactant is aluminum triiodide. In some embodiments, the substitution reaction occurs in the presence of aluminum triiodide alone. Such aluminum triiodide can be used directly as the aluminum (Al) reactant or can be generated in situ by reaction of aluminum metal with iodine.

[0042] In some embodiments, when X is chloro, bromo (or iodo), Al(X) from formula (I) can be utilized in combination with a Group I or Group II iodide. In such cases, the aluminate species can be generated in situ, for example, by reacting AlCl with MgI, which can be formed in situ by the reaction of magnesium metal with iodine.

[0043] In some embodiments, reacting the aluminum (Al) reactant with the reactant M comprises: (i) AlX3 to M +q X q reacting with, or (ii) Al 0 , I2, and M +q X q This includes reacting

[0044] In some embodiments, Al 0 , I2, and M +q X q The reaction is carried out by first reacting Al 0 with I2 to generate AlI3 in situ. The method further comprises subsequently reacting the in situ generated AlI3 with LiI.

[0045] In some embodiments, AlX3 is M +q X q Reacting with comprises reacting AlI with LiI. In some embodiments, reacting AlI with LiI comprises reacting AlI with LiI in a 1:1 molar equivalent.

[0046] 1 illustrates non-limiting embodiments of two reaction schemes of the present disclosure, according to at least some embodiments of the present disclosure. In FIG. 1, the route with isolation involves (i) converting AlX to M +q X qIn FIG. 1, the non-isolation pathway is shown as (ii) Al 0 , I2, and M +q X q react, i.e., first Al 0 and I2, and then Al 0 1 illustrates one embodiment of the present disclosure for a reaction mechanism for reacting the product of I and I (which product is AlI) with LiI.

[0047] In some embodiments, while reacting AlI with LiI, the disclosed methods include heating AlI and LiI to a temperature less than 150° C. In some embodiments, the disclosed methods include heating to a maximum temperature equal to the boiling point of the solvent.

[0048] In some embodiments, the compound of Formula (I) is generated in situ. In some embodiments, the aluminum (Al) reactant is AlI. In some embodiments, reactant M is LiI. In some embodiments, reacting the aluminum (Al) reactant with reactant M includes reacting the aluminum (Al) reactant with reactant M in a solvent.

[0049] In some embodiments, preparing a compound of Formula (I) comprises reacting an aluminum (Al) reactant with reactant M at a temperature less than 150° C., less than 100° C., less than 90° C., less than 80° C., less than 70° C., less than 60° C., less than 50° C., less than 45° C., less than 40° C., or less than 30° C. In some embodiments, the maximum temperature for preparing a compound of Formula (I) is the boiling point of the solvent.

[0050] In some embodiments, the reaction of the aluminum (Al) reactant with reactant M occurs at a temperature of 30° C. or greater and is in solution or slurry. In some embodiments, the reaction of the aluminum (Al) reactant with reactant M occurs at a temperature of less than about 150° C. and is in solution or slurry. In some embodiments, the reaction of the aluminum (Al) reactant with reactant M occurs at a temperature of less than about 50° C. and is in solution or slurry. In some embodiments, the reaction of the aluminum (Al) reactant with reactant M occurs at a temperature of about 30° C. to about 150° C. and is in solution or slurry. In some embodiments, the reaction of the aluminum (Al) reactant with reactant M occurs at a temperature of about 40° C. to about 60° C. and is in solution or slurry. In some embodiments, the reaction of the aluminum (Al) reactant with reactant M occurs at a temperature of less than about 60° C. and is in solution or slurry. [Example]

[0051] Example 1 FIG. 2 illustrates a block diagram of a network according to some embodiments of the present disclosure. 7 2 shows the Li-NMR spectrum. More specifically, FIG. 2 shows the Li-NMR spectrum recorded in tetrahydrofuran (THF) solution of LiAlI4 synthesized using the solvothermal method described. 7 The Li-NMR spectrum is shown. The reaction took place in toluene.

[0052] was performed on a THF solution of as-synthesized LiAlI4. 7 Li-NMR experiments are consistent with the consumption of LiI (3.5 ppm) and the production of LiAlI4 (2.8 ppm). Furthermore, AlI3 is reactive with THF.

[0053] FIG. 3 shows a Fourier transform infrared spectroscopy (FTIR) of the formation of LiAlI4 in toluene according to some embodiments of the present disclosure.

[0054] FTIR experiments performed on a solid-state sample of LiAlI4 produced from the aforementioned solvothermal synthesis showed a peak at approximately 340 cm -1It shows a new vibration at about 400 cm -1 ) has not been observed. Taken together, these data are consistent with the consumption of AlI3 and the production of LiAlI4.

[0055] Example 2 FIG. 4 shows a differential scanning calorimetry (DSC) comparison of AlI3 and LiAlI4 according to some embodiments of the present disclosure.

[0056] The melting points of AlI3 (189.5 °C) and LiAlI4 (235.2 °C) established using DSC correspond well to previously reported literature values ​​(235.9 °C for LiAlI4).

[0057] The reaction product obtained from the combination of AlI3 and LiI in toluene was free of AlI3 by DSC analysis, consistent with the consumption of AlI3 and the formation of LiAlI4.

[0058] Example 3 Solvothermal synthesis of LiAlI4 In a nitrogen-filled glovebox, AlI (0.300 g, 0.736 mmol) and LiI (0.0984 g, 0.736 mmol) were placed in a 40 mL vial equipped with a magnetic stir bar and diluted with toluene (8 mL) to form a slightly cloudy, pale yellow solution, which was stirred at room temperature for 3.5 h. At this point, the solvent was removed under reduced pressure to give LiAlI as an off-white solid in quantitative yield. The melting point of the product (235.2 °C) was obtained by differential scanning calorimetry (DSC) and was consistent with that reported in the literature. 7 Li-NMR (155MHz, THF, 298K): 2.874ppm, 27 Al-NMR (104 MHz, C7D8, 298 K): -20.0 ppm. FTIR (diamond stage): 340 cm -1 .

[0059] Aspects Various aspects are described below. It should be understood that any one or more of the features listed in the following aspects can be combined with any one or more other aspects.

[0060] Aspect 1. A method comprising: Formula (I) [M +q ][Al(X)I] q (I), wherein M is (i) Li + , Na + , K. + , Rb + , and Cs + (ii) a Group 1 metal cation selected from Mg 2+ , Ca 2+ , Sr 2+ , and Ba 2+ and (iii) an ammonium, C1-C6 alkylammonium, or benzylammonium cation; and (iii) an ammonium, C1-C6 alkylammonium, or benzylammonium cation; q is the valence of M and is 1 or 2; 1. A method comprising reacting an aluminum (Al) reactant with a reactant M in a solvent at a temperature of 200° C. or less to form a compound of formula (I), wherein X is chloro, bromo, or iodo.

[0061] Aspect 2M +q Li + 2. The method of embodiment 1, wherein

[0062] The method of embodiment 1 or 2, wherein embodiment 3q is 1.

[0063] Embodiment 4 The method of any one of embodiments 1 to 3, wherein X is iodine.

[0064] Embodiment 5. The method of any one of embodiments 1 to 4, wherein the compound of formula (I) is LiAlI4.

[0065] Aspect 6 Reacting an aluminum (Al) reactant with a reactant M comprises (i) converting AlX3 to M +q X q or (ii) reacting with Al 0 , I2, and M +q X q 6. The method of any one of embodiments 1 to 5, comprising reacting

[0066] Aspect 7A1 0 , I2, and M +q X q The reaction is carried out by first reacting Al 0 7. The method of embodiment 6, comprising reacting with I to generate AlI in situ.

[0067] Embodiment 8. The method of embodiment 7, further comprising reacting the in situ generated AlI with LiI.

[0068] Aspect 9AlX3 is M +q X q 7. The method of embodiment 6, wherein reacting with comprises reacting AlI with LiI.

[0069] Embodiment 10. The method of embodiment 9, wherein reacting AlI3 with LiI comprises reacting AlI3 with LiI in a 1:1 molar equivalent.

[0070] Embodiment 11 The method of embodiment 9, wherein reacting AlI3 with LiI comprises reacting AlI3 with LiI at a temperature less than 150°C.

[0071] Embodiment 12. The method of any one of embodiments 1 to 11, wherein the compound of formula (I) is generated in situ.

[0072] Embodiment 13. The method of any one of embodiments 1 to 12, wherein the aluminum (Al) reactant is AlI.

[0073] Embodiment 14 The method of any one of embodiments 1 to 13, wherein reactant M is LiI.

[0074] Embodiment 15. The method of any one of embodiments 1 to 14, wherein the solvent is an aromatic hydrocarbon.

[0075] Aspect 16. The method of aspect 15, wherein the aromatic hydrocarbon is toluene, xylene, benzene, or chlorobenzene.

[0076] Embodiment 17 The method of any one of embodiments 1 to 16, wherein preparing the compound of Formula (I) comprises preparing the compound of Formula (I) at a temperature of less than 50°C.

[0077] Embodiment 18. The method of any one of embodiments 1 to 17, wherein preparing the compound of formula (I) comprises preparing the compound of formula (I) at a temperature of less than 40°C.

[0078] Embodiment 19. The method of any one of embodiments 1 to 18, wherein the reaction of the aluminum (Al) reactant with reactant M proceeds in solution at a temperature of 30° C. or greater.

[0079] Embodiment 20. The method of any one of embodiments 1 to 19, wherein the reaction of the aluminum (Al) reactant with reactant M proceeds in a slurry at a temperature of 30° C. or greater.

[0080] It is understood that changes in detail may be made, particularly to the materials of construction utilized, and to the shape, size, and arrangement of parts, without departing from the scope of the present disclosure. The specification and described embodiments are examples, with the true scope and spirit of the present disclosure being indicated by the following claims.

Claims

1. 1. A method comprising: Formula (I) [M ＋ｑ ][Al(X) ３ I] ｑ (I) wherein M is (i) Li ＋ , Na ＋ , K. ＋ , Rb ＋ , and Cs ＋ (ii) a Group 1 metal cation selected from Mg ２＋ , Ca ２＋ , Sr ２＋ , and Ba ２＋ and (iii) a Group 2 metal cation selected from ammonium, C １ ~C ６ selected from alkylammonium or benzylammonium cations, q is the valence of M and is 1 or 2; X is chloro, bromo, or iodo; A process comprising reacting an aluminum (Al) reactant with a reactant M in a solvent at a temperature of 200° C. or less to form a compound of formula (I).

2. M ＋ｑ Li ＋ The method of claim 1, wherein

3. The method of claim 1 , wherein q is 1.

4. 10. The method of claim 1, wherein X is iodo.

5. The compound of formula (I) is LiAlI ４ The method of claim 1, wherein

6. reacting an aluminum (Al) reactant with a reactant M, (i) AlX ３ M ＋ｑ X ｑ reacting with, or (ii) Al ０ , I ２ , and M ＋ｑ X ｑ 10. The method of claim 1, comprising reacting

7. Al ０ , I ２ , and M ＋ｑ X ｑ is reacted by first reacting Al ０ I ２ to react with AlI in situ ３ The method of claim 6, comprising generating:

8. In situ generated AlI ３ 8. The method of claim 7, further comprising reacting with LiI.

9. AlX ３ M ＋ｑ X ｑ Reacting with AlI ３ 7. The method of claim 6, comprising reacting with LiI.

10. All I ３ Reacting with LiI gives AlI ３ 10. The method of claim 9, comprising reacting with LiI in a 1:1 molar equivalent.

11. All I ３ with LiI at a temperature below 150° C. ３ 10. The method of claim 9, comprising reacting with LiI.

12. 10. The method of claim 1, wherein the compound of formula (I) is produced in situ.

13. The aluminum (Al) reactant is AlI ３ The method of claim 1, wherein

14. The method of claim 1 , wherein reactant M is LiI.

15. 10. The method of claim 1, wherein the solvent is an aromatic hydrocarbon.

16. 16. The method of claim 15, wherein the aromatic hydrocarbon is toluene, xylene, benzene, or chlorobenzene.

17. 10. The method of claim 1, wherein preparing the compound of formula (I) comprises preparing the compound of formula (I) at a temperature of less than 50°C.

18. 10. The method of claim 1, wherein preparing the compound of formula (I) comprises preparing the compound of formula (I) at a temperature of less than 40°C.

19. 10. The method of claim 1, wherein the reaction of the aluminum (Al) reactant with reactant M proceeds in solution at a temperature of 30°C or greater.

20. 10. The method of claim 1, wherein the reaction of the aluminum (Al) reactant with reactant M proceeds in the slurry at a temperature of 30°C or greater.

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