Compounds and methods for preparing aluminates

Abstract

The methods of the present disclosure include the development of low temperature, solvent assisted synthesis of aluminate salts, such as lithium tetraiodo aluminate (LiAlI4). The present disclosure comprises a process for preparing a compound of formula (I): [M + q] [Al (X) 3I] q.

Description

Technical Field

[0001] The present disclosure relates to the field of chemistry. More specifically, the present disclosure relates to compounds and methods for preparing aluminates. Background Art

[0002] Ball milling can be used to blend solid particles into a blended fine powder. Summary of the invention

[0003] Methods for preparing aluminates, such as LiAlI4, are limited in part due to hazards associated with the synthesis process (e.g., reagent toxicity) or extreme preparation conditions (i.e., high temperature reactions (e.g., reactions at temperatures exceeding 200°C)). One example includes heating a mixture of AlI3 and LiI contained in CS2. Potential disadvantages of the methods include the toxicity of CS2. Some of the methods include intense heating reactions, such as intense heating with a Bunsen burner. A method for preparing LiAlI4 involves heating AlI3 and LiI together in the solid state at high temperatures (e.g., temperatures exceeding 200°C). Some preparation methods include ball milling the solid reactants at 200 rpm and room temperature.

[0004] In contrast, the methods of the present disclosure involve the development of a low temperature, solvent-assisted synthesis of aluminates, such as lithium tetraiodoaluminate (LiAlI4). The methods of the present disclosure do not require high temperatures (e.g., greater than ~200°C). The methods of the present disclosure also do not require solid reactions via ball milling or melting. The present disclosure does not require ball milling because the reactants can be in solution (e.g., a slurry). In addition, the present disclosure does not require toxic polar solvents to completely dissolve the reactants (that is, the starting materials).

[0005] In some aspects, the technology described herein relates to a method comprising: reacting an aluminum (Al) reactant with a reactant M in a solvent at a temperature not greater than 200° C. to form a compound of formula (I): [M +q ][Al(X)3I] q (I), wherein: M is selected from (i) selected from Li + 、Na + , K + , Rb + and Cs + (ii) a Group 1 metal cation selected from Mg 2+ , Ca 2+ , Sr 2+ And Ba 2+(iii) ammonium, C1-C6 alkylammonium or benzylammonium cation; and (iii) ammonium, C1-C6 alkylammonium or benzylammonium cation; q is the valence of M and is 1 or 2; and X is chlorine, bromine or iodine.

[0006] In some aspects, the technology described herein relates to a method in which M +q It's Li + .

[0007] In some aspects, the technology described herein relates to a method wherein q is 1.

[0008] In some aspects, the technology described herein relates to a method wherein X is iodine.

[0009] In some aspects, the technology described herein relates to a method wherein the compound of formula (I) is LiAlI4.

[0010] In some aspects, the technology described herein relates to a method, wherein reacting the aluminum (Al) reactant with the reactant M comprises: (i) reacting AlX3 with M +q X q reaction; or (ii) making Al 0 , I2 and M +q X q reaction.

[0011] In some aspects, the technology described herein relates to a method in which Al 0 , I2 and M +q X q The reaction involves firstly making Al 0 React with I2 in a solvent to generate AlI3 in situ.

[0012] In some aspects, the technology described herein relates to a method that further comprises reacting the in-situ generated AlI 3 with LiI.

[0013] In some aspects, the technology described herein relates to a method in which AlX3 is reacted with M +q X q The reaction comprises reacting AlI3 with LiI.

[0014] In some aspects, the technology described herein relates to a method wherein reacting AlI 3 with LiI comprises reacting AlI 3 with LiI in a 1:1 molar equivalent.

[0015] In some aspects, the technology described herein relates to a method wherein reacting AlI 3 with LiI comprises reacting AlI 3 with LiI at a temperature of less than 150° C.

[0016] In some aspects, the technology described herein relates to a method wherein the compound of formula (I) is generated in situ.

[0017] In some aspects, the technology described herein relates to a method wherein the aluminum (Al) reactant is AlI 3 .

[0018] In some aspects, the technology described herein relates to a method wherein the reactant M is LiI.

[0019] In some aspects, the technology described herein relates to a method wherein the solvent is an aromatic hydrocarbon.

[0020] In some aspects, the technology described herein relates to a method wherein the aromatic hydrocarbon is toluene, xylene, benzene, or chlorobenzene.

[0021] In some aspects, the technology described herein relates to a method, wherein preparing the compound of formula (I) comprises preparing the compound of formula (I) at a temperature of less than 50°C.

[0022] In some aspects, the technology described herein relates to a method, wherein preparing the compound of formula (I) comprises preparing the compound of formula (I) at a temperature of less than 40°C.

[0023] In some aspects, the technology described herein relates to a method wherein the reaction of the aluminum (Al) reactant with the reactant M is performed in a solution at a temperature of 30° C. or higher.

[0024] In some aspects, the technology described herein relates to a method wherein the reaction of the aluminum (Al) reactant with the reactant M is performed in a slurry at a temperature of 30° C. or higher. BRIEF DESCRIPTION OF THE DRAWINGS

[0025] Some embodiments of the present disclosure are described with reference to the accompanying drawings by way of example only. With specific reference to the details of the accompanying drawings, it should be emphasized that the embodiments shown are by way of example and for the purpose of illustrative discussion of the embodiments of the present disclosure. In this respect, this description is similar to the accompanying drawings. Figure 1 It will make it apparent to those skilled in the art how the embodiments of the present disclosure can be implemented.

[0026] Figure 1 Non-limiting examples of two reaction schemes of the present disclosure are depicted in accordance with at least some embodiments of the present disclosure.

[0027] Figure 2 Depicting lithium (Li) nuclear magnetic resonance (NMR) spectra ( 7 Li-NMR spectrum).

[0028] Figure 3 Depicted is a Fourier transform infrared spectroscopy (FTIR) spectrum of LiAlI4 formed in toluene according to some embodiments of the present disclosure.

[0029] Figure 4 Depicted is a differential scanning calorimetry (DSC) comparison of AlI3 and LiAlI4 according to some embodiments of the present disclosure. DETAILED DESCRIPTION

[0030] Among those benefits and improvements disclosed, other objects and advantages of the present disclosure will become apparent from the following description in conjunction with the accompanying drawings. Detailed embodiments of the present disclosure are disclosed herein; however, it should be understood that the disclosed embodiments are merely illustrative of the present disclosure that can be embodied in various forms. In addition, the examples given of various embodiments of the present disclosure are intended to be illustrative rather than limiting.

[0031] All prior patents and publications cited herein are incorporated by reference in their entirety.

[0032] Throughout this specification and claims, unless the context clearly dictates otherwise, the following terms have the meanings clearly associated with them herein. 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 be the same embodiment. In addition, as used herein, the phrases "in another embodiment" and "in some other embodiments" do not necessarily refer to different embodiments, but may be different embodiments. All embodiments of the present disclosure are intended to be combined without departing from the scope or spirit of the present disclosure.

[0033] As used herein, the term "based on" is not exclusive and allows for being based on additional factors not described, unless the context clearly dictates otherwise. In addition, throughout this specification, the meanings of "a", "an", and "the" include plural referents. The meaning of "in..." includes "in..." and "on...".

[0034] As used herein, the term "between" does not necessarily require being directly adjacent to other elements. Generally speaking, the term refers to a configuration in which something is sandwiched between two or more other things. At the same time, the term "between" can describe something that is directly adjacent to two opposing things. Therefore, in any one or more of the embodiments disclosed herein, a specific structural component that is disposed between two other structural elements may be:

[0035] being disposed directly between two other structural elements so that the specific structural component is in direct contact with both of the two other structural elements;

[0036] being disposed directly adjacent to only one of the two other structural elements such that the particular structural component is in direct contact with only one of the two other structural elements;

[0037] being disposed not directly adjacent to only one of the two other structural elements, such that the particular structural component is not directly in contact with only one of the two other structural elements, and there is another element juxtaposing the particular structural component with one of the two other structural elements;

[0038] is arranged not directly between two other structural elements, so that the specific structural component does not directly contact the two other structural elements, and other features can be arranged therebetween; or

[0039] Any combination thereof.

[0040] As used herein, "embedded" means that a first material is distributed in a second material.

[0041] The methods of the present disclosure include the development of a low temperature, solvent-assisted synthesis of aluminates such as lithium tetraiodoaluminate (LiAlI4). The methods of the present disclosure do not require high temperatures (e.g., greater than ~200°C). The methods of the present disclosure also do not require ball milling because the reactants can be in solution (e.g., a slurry).

[0042] The present disclosure includes methods for preparing compounds of formula (I):

[0043] [M +q ][Al(X)3I] q

[0044] (I).

[0045] The method comprises reacting an aluminum (Al) reactant with a reactant M to form a compound of formula (I). M is selected from (i) + 、Na + , K + , Rb + and Cs + A Group 1 metal cation, (ii) selected from Mg 2+ , Ca 2+ , Sr 2+ And Ba 2+and (iii) an ammonium, C1-C6 alkylammonium, or benzylammonium cation; q is the valence of M and is 1 or 2; and X is chlorine, bromine, or iodine. In some embodiments, the reactant M is a metal or behaves like a metal (e.g., ammonium, C1-C6 alkylammonium, and / or benzylammonium cation).

[0046] In some embodiments, the compound of formula (I) comprises 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.

[0047] In some embodiments, M is selected from, for example, (CH3)4N + 、(CH3CH2)4N + 、(CH3CH2CH2)4N + and (CH3CH2CH2CH2)4N + of cations.

[0048] In some embodiments, the compound of formula (I) may be referred to as an aluminate and may be generated by reacting the reactants in a solution using a 1:1 molar ratio (or 2:1 in the case of a divalent Group 2 metal cation). For example, LiAl(I)4 aluminate may be prepared by mixing LiI and Al(I)3 in a solution (when combined in a 1:1 molar ratio). In some embodiments, gentle heating may be used while mixing the reactants. Gentle heating may include raising the temperature to a maximum of the boiling point of the solvent of the solution.

[0049] 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 may be toluene. The boiling point of toluene is 115°C. In some embodiments, when the solvent comprises toluene, the method may include heating to 115°C. In some embodiments, the solvent may be benzene. The boiling point of benzene is 80°C. In some embodiments, when the solvent comprises benzene, the method may include heating to 80°C. In some embodiments, the solvent may be chlorobenzene. The boiling point of chlorobenzene is 132°C. In some embodiments, when the solvent comprises chlorobenzene, the method may include heating to 132°C. In some embodiments, the solvent may be xylene. The boiling points of xylene isomers include 139°C for meta-xylene, 144°C for o-xylene, and 138.4°C for p-xylene. In some embodiments, when the solvent comprises xylene isomers, the method may include heating to 138.4°C, 139°C, or 144°C. In some embodiments, gentle heating can comprise raising the temperature to a maximum of the boiling point of the solvent of the solution (as described herein).

[0050] Alternatively, the in-situ formation of LiAlI4 can be accomplished via Al 0 +I2 is prepared by reaction in a solvent followed by addition of LiI.

[0051] In some embodiments, the aluminum (Al) reactant is aluminum triiodide. In some embodiments, the displacement reaction occurs in the presence of aluminum triiodide alone; this aluminum triiodide can be directly used as the aluminum (Al) reactant or can be generated in situ by the reaction of metallic aluminum with iodine.

[0052] In some embodiments, Al(X)3 in formula (I), when X is chlorine, bromine or (iodine), can be used in combination with an iodide of Group 1 or Group 2. In these cases, the aluminate species can be generated in situ by reacting, for example, AlCl3 with MgI2, which can be formed in situ by reacting metallic magnesium with iodine.

[0053] In some embodiments, reacting the aluminum (Al) reactant with the reactant M comprises:

[0054] (i) Make AlX3 and M +q X q reaction; or

[0055] (ii) Make Al 0 , I2 and M +q X q reaction.

[0056] In some embodiments, Al 0 , I2 and M+q X q The reaction involves firstly making Al 0 and reacting with I2 in a solvent to generate AlI3 in situ. The method further comprises subsequently reacting the in situ generated AlI3 with LiI.

[0057] In some embodiments, AlX3 and M +q X q The reaction comprises reacting AlI 3 with LiI. In some embodiments, reacting AlI 3 with LiI comprises reacting AlI 3 with LiI in a 1:1 molar equivalent.

[0058] Figure 1 Depicting non-limiting examples of two reaction schemes of the present disclosure in accordance with at least some embodiments of the present disclosure. Figure 1 In the separation pathway, (i) AlX3 and M +q X q One embodiment of the present disclosure of the reaction mechanism of the reaction: AlI3 reacts with LiI. Figure 1 There is no separation pathway showing that (ii) makes Al 0 , I2 and M +q X q One embodiment of the present disclosure of the reaction mechanism of the reaction: First, Al 0 Reaction with I2 and then Al 0 And the product of I2 (the product is AlI3) reacts with LiI.

[0059] In some embodiments, when reacting AlI3 with LiI, the methods of the present disclosure include heating AlI3 and LiI to a temperature less than 150° C. In some embodiments, the methods of the present disclosure include heating to a maximum temperature equal to the boiling point of the solvent.

[0060] In some embodiments, the compound of formula (I) is generated in situ. In some embodiments, the aluminum (Al) reactant is AlI3. In some embodiments, the reactant M is LiI. In some embodiments, reacting the aluminum (Al) reactant with the reactant M comprises reacting the aluminum (Al) reactant with the reactant M in a solvent.

[0061] In some embodiments, preparing the compound of formula (I) comprises reacting an aluminum (Al) reactant with a reactant M at a temperature of 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 the compound of formula (I) is the boiling point of the solvent.

[0062] In some embodiments, the reaction of the aluminum (Al) reactant with the reactant M occurs at a temperature of 30°C or higher and in a solution or slurry. In some embodiments, the reaction of the aluminum (Al) reactant with the reactant M occurs at a temperature of less than about 150°C and in a solution or slurry. In some embodiments, the reaction of the aluminum (Al) reactant with the reactant M occurs at a temperature of less than about 50°C and in a solution or slurry. In some embodiments, the reaction of the aluminum (Al) reactant with the reactant M occurs at a temperature from about 30°C to about 150°C and in a solution or slurry. In some embodiments, the reaction of the aluminum (Al) reactant with the reactant M occurs at a temperature from about 40°C to about 60°C and in a solution or slurry. In some embodiments, the reaction of the aluminum (Al) reactant with the reactant M occurs at a temperature of less than about 60°C and in a solution or slurry.

[0063] Examples

[0064] Example 1

[0065] Figure 2 Describes some embodiments of the present disclosure 7 Li-NMR spectrum. More specifically, Figure 2 Plotted on a tetrahydrofuran (THF) solution of LiAlI4 synthesized using the solvothermal method 7 Li-NMR spectrum. The reaction took place in toluene.

[0066] The THF solution of LiAlI4 synthesized in this way was 7 Li-NMR experiments were consistent with the consumption of LiI (3.5 ppm) and the generation of LiAlI4 (2.8 ppm). In addition, AlI3 reacted with THF.

[0067] Figure 3 Fourier transform infrared (FTIR) spectrum depicting the formation of LiAlI4 in toluene according to some embodiments of the present disclosure.

[0068] FTIR experiments on solid-state samples of LiAlI4 produced by the solvothermal synthesis described previously showed that the -1 There are new vibrations, so AlI3 (~400cm -1 ). Taken together, these data are consistent with the consumption of AlI3 and the generation of LiAlI4.

[0069] Example 2

[0070] Figure 4 Depicted is a differential scanning calorimetry (DSC) comparison of AlI3 and LiAlI4 according to some embodiments of the present disclosure.

[0071] The melting points of AlI3 (189.5°C) and LiAlI4 (235.2°C) determined by DSC are in good agreement with previously reported literature values ​​(235.9°C for LiAlI4).

[0072] The DSC analysis revealed that the reaction product obtained from combining AlI3 and LiI in toluene did not contain AlI3 and was consistent with the consumption of AlI3 and the formation of LiAlI4.

[0073] Example 3

[0074] Solvothermal Synthesis of LiAlI4

[0075] In a nitrogen-filled glove box, AlI3 (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 turbid light yellow solution, which was stirred at room temperature for 3.5 hours. At this time, the solvent was removed under reduced pressure to produce LiAlI4 as an off-white solid in quantitative yield. The melting point of the product (235.2 ° C) was obtained via differential scanning calorimetry (DSC) and is consistent with that reported in the literature. 7 Li-NMR (155MHz, THF, 298K): 2.874ppm; 27 Al-NMR (104MHz, C7D8, 298K); -20.0ppm. FTIR (diamond grade); 340cm -1 .

[0076] aspect

[0077] A number of aspects are described below. It should be appreciated that any one or more of the features listed in the following aspects may be combined with any one or more other aspects.

[0078] Aspect 1. A method comprising: reacting an aluminum (Al) reactant with a reactant M in a solvent at a temperature not greater than 200° C. to form a compound of formula (I): [M +q ][Al(X)3I] q (I), wherein: M is selected from (i) selected from 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) ammonium, C1-C6 alkylammonium or benzylammonium cation; and (iii) ammonium, C1-C6 alkylammonium or benzylammonium cation; q is the valence of M and is 1 or 2; and X is chlorine, bromine or iodine.

[0079] Aspect 2. The method according to aspect 1, wherein M +q It's Li + .

[0080] Aspect 3. The method according to aspect 1 or 2, wherein q is 1.

[0081] Aspect 4. The method according to any one of the preceding aspects, wherein X is iodine.

[0082] Aspect 5. The method according to any one of the preceding aspects, wherein the compound of formula (I) is LiAlI4.

[0083] Aspect 6. The method according to any one of the preceding aspects, wherein reacting the aluminum (Al) reactant with the reactant M comprises: (i) reacting AlX3 with M +q X q reaction; or (ii) making Al 0 , I2 and M +q X q reaction.

[0084] Aspect 7. The method according to aspect 6, wherein Al 0 , I2 and M +q X q The reaction involves firstly making Al 0 React with I2 in a solvent to generate AlI3 in situ.

[0085] Aspect 8. The method according to aspect 7, further comprising reacting the in-situ generated AlI3 with LiI.

[0086] Aspect 9. The method according to aspect 6, wherein AlX3 and M +q X q The reaction comprises reacting AlI3 with LiI.

[0087] Aspect 10. The method according to aspect 9, wherein reacting AlI 3 with LiI comprises reacting AlI 3 and LiI in a 1:1 molar equivalent.

[0088] Aspect 11. The method according to aspect 9, wherein reacting AlI 3 with LiI comprises reacting AlI 3 with LiI at a temperature of less than 150° C.

[0089] Aspect 12. The method according to any one of the preceding aspects, wherein the compound of formula (I) is generated in situ.

[0090] Aspect 13. A method according to any of the preceding aspects, wherein the aluminum (Al) reactant is AlI3.

[0091] Aspect 14. The method according to any one of the preceding aspects, wherein the reactant M is LiI.

[0092] Aspect 15. The method according to any one of the preceding aspects, wherein the solvent is an aromatic hydrocarbon.

[0093] Aspect 16. The method according to aspect 15, wherein the aromatic hydrocarbon is toluene, xylene, benzene or chlorobenzene.

[0094] Aspect 17. The method according to any one of the preceding aspects, wherein preparing the compound of formula (I) comprises preparing the compound of formula (I) at a temperature of less than 50°C.

[0095] Aspect 18. The method according to any one of the preceding aspects, wherein preparing the compound of formula (I) comprises preparing the compound of formula (I) at a temperature of less than 40°C.

[0096] Aspect 19. The method according to any one of the preceding aspects, wherein the reaction of the aluminum (Al) reactant with the reactant M is carried out in a solution at a temperature of 30° C. or higher.

[0097] Aspect 20. The method according to any one of the preceding aspects, wherein the reaction of the aluminum (Al) reactant with the reactant M is performed in a slurry at a temperature of 30° C. or higher.

[0098] It is understood that changes may be made in detail, particularly in the construction materials used and in the shape, size and arrangement of parts without departing from the scope of the present disclosure. This specification and described embodiments are examples, with the true scope and spirit of the present disclosure being indicated by the following claims.

Claims

1. A method comprising: Aluminum (Al) reactant is reacted with reactant M in a solvent at a temperature not greater than 200° C. to form a compound of formula (I): <h2 style=";text-align:left;direction:ltr">[M<h2 style=";text-align:left;direction:ltr"> +q <h2 style=";text-align:left;direction:ltr"> ][Al(X)3I]<h2 style=";text-align:left;direction:ltr"> q <h2 style=";text-align:left;direction:ltr"> (I) in: M is selected from (i) selected from Li + 、Na + , K + , Rb + and Cs + A Group 1 metal cation, (ii) selected from Mg 2+ , Ca 2+ , Sr 2+ And Ba 2+ and (iii) an ammonium, C1-C6 alkylammonium or benzylammonium cation; q is the valence of M and is 1 or 2; and X is chlorine, bromine or iodine.

2. The method according to claim 1, wherein M +q It's Li + . The method according to claim 1 , wherein q is 1.

4. The method according to claim 1, wherein X is iodine.

5. The method according to claim 1, wherein the compound of formula (I) is LiAlI4.

6. The method of claim 1, wherein reacting the aluminum (Al) reactant with the reactant M comprises: (i) Make AlX3 and M +q X q reaction; or (ii) Make Al 0 , I2 and M +q X q reaction.

7. The method according to claim 6, wherein Al 0 , I2 and M +q X q The reaction involves firstly making Al 0 React with I2 in a solvent to generate AlI3 in situ.

8. The method of claim 7, further comprising reacting the in-situ generated AlI3 with LiI.

9. The method according to claim 6, wherein the AlX3 and M +q X q The reaction comprises reacting AlI3 with LiI.

10. The method of claim 9, wherein reacting the AlI3 with LiI comprises reacting AlI3 with LiI in a 1:1 molar equivalent.

11. The method of claim 9, wherein reacting the AlI3 with LiI comprises reacting AlI3 with LiI at a temperature less than 150°C.

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

13. The method of claim 1, wherein the aluminum (Al) reactant is AlI3.

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

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

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

17. 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. 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. The method of claim 1, wherein the reaction of the aluminum (Al) reactant with the reactant M is performed in a solution at a temperature of 30°C or higher.

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

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