Patent Application
20230395861
The present disclosure relates to salts of magnesium. Additionally, the present disclosure relates to a method of making the magnesium salts, and the use of the magnesium salts as electrolytes in a cell or battery.
The drive to increase power densities of rechargeable batteries past those currently accessible in established lithium-ion cells for portable electronics has brought about increased interest in developing multivalent battery systems with superior theoretical energy densities. In particular, considerable research focus has been placed on magnesium-ion cells owing to the high theoretical volumetric energy density of magnesium metal anodes as well as potential safety, cost, and environmental benefits. Lithium-ion cells can also form dendrite growths, which have been found to cause short circuiting and dangerous thermal runaway. Magnesium does not readily form dendrites over multiple charge cycles. Furthermore, magnesium is highly earth-abundant and has a lower costs of production than lithium, and magnesium metal can be used directly as an anode material.
Despite being an attractive alternative to lithium-ion technology, development of magnesium-ion systems continues to be limited by a lack of electrolyte systems that are stable at both the magnesium anode and cathode materials that operate at potentials greater than 3.5 V. Many established magnesium-ion electrolyte systems gradually decompose at the electrode surfaces and result in magnesium-impermeable layers that passivate the electrodes. Additionally, many high-voltage electrolytes (stable to at least 3.4 V) are chloride-containing and are thought to result in the corrosion of common battery components such as stainless steel. Accordingly, new directions in magnesium-ion electrolyte development have focused on the synthesis and use of chloride-free salts.
In some embodiments, the present disclosure provides a method of making a salt of the formula:
Mg[Al(R)4]2
wherein R represents a compound selected from a deprotonated alcohol or thiol; an amine; or a mixture thereof; the method comprising: combining a Mg(AlH4)2 precursor with the deprotonated alcohol or thiol; or amine; or a mixture thereof to create a reaction liquor containing Mg[A(R)4]2, and washing the reaction liquor in an organic solvent.
The term salt used throughout the specification is intended to cover complex magnesium salts that fall within the general formula given above. The choice of R group may allow for a more stable reaction mixture in the synthesis of the magnesium aluminate salt.
Previous synthetic methodologies to manufacture magnesium aluminate salts require the use of sufficiently nucleophilic reagents, thus limiting the number of candidate magnesium aluminates. However, the presently defined method allows for a broader range of reagents such that the electrochemical screening and identification of promising electrolyte candidates is not as limited.
In addition, the presently defined method relies on the use of a common Mg(AlH4)2 precursor, which can be used to synthesise a wide range of magnesium aluminate salts. The single precursor allows for rapid access to a range of relatively stable aluminate derivatives without the need to tune the reactivity of reagents or the solubility of the resulting products.
The method may comprise a further final step of filtering the washed reaction liquor under an inert atmosphere. The additional step of washing of the reaction products allows for the removal of insoluble impurities, such Aluminium-containing by-products.
The Mg(AlH4)2 precursor may be formed by a one-step ball milling process of NaAlH4 and MgCl2. A ball milling process is low cost and effective. A reasonable yield of the Mg(AlH4)2 precursor can be achieved via the relatively uncomplicated synthetic route.
The deprotonated alcohol or thiol; or amine may be aliphatic or aromatic. That is to say that the deprotonated alcohol or thiol; or amine may be part of a simple aromatic system, or a heterocyclic system, or be partially or fully saturated. The oxygen, nitrogen or sulphur aryl groups provide a different steric profile and electron donating ability, leading to compounds of varying stability.
The deprotonated alcohol or thiol; or amine may be fluorinated. Fluorination of the alcohol, thiol or amine increases the species reactivity and therefore increase yield of the magnesium aluminate salt and can increase the stability of the organic fragment. Based on the above, the organic moiety of the deprotonated alcohol or thiol; or amine may be based on; tert-butyl, perfluoro-tert-butyl, hexafluoro-iso-propyl, phenyl, or pentafluorophenyl.
The organic solvent may be dry DME, 2-methyl-THF, diglyme, triglyme, tetraglyme or THF. These donor solvents provide a high yield of magnesium aluminate salt. Furthermore, these solvents readily interact with the magnesium aluminate structure and can increase stability of the salt.
In some embodiments, an electrolyte comprising a salt in accordance with the above Formula (i) is included. The electrolyte may comprise the salt as an additive to a conventional electrolyte, or the salt may be used in a pure solution to form, with an appropriate solvent, an electrolyte by itself. The electrolyte may further comprises an Mg(PF6)2 additive.
In some embodiments, provided is a cell or battery comprising an electrolyte in accordance with the above Formula (i). The salts of the present disclosure do not suffer from some of the same disadvantages observed with the use of lithium salts in electrochemical cells or batteries. In addition, the salts of the present disclosure can be used in electrolytes in a number of cell or battery systems. More specifically, the cell or battery can be, for example, a lithium cell or a lithium-ion cell. However, the cell or battery using the salts of the present disclosure may be more generally described as a metal based, or a metal-ion based cell or battery. Examples of other metal or metal-ion based cells or batteries may include magnesium, calcium or aluminium metals or ions. When using the salt of the present disclosure in an electrolyte in metal cell or battery, metals such as magnesium, calcium or aluminum may be used as the metal anode without the risk of the salt decomposing.
In order that the present disclosure may be more readily understood, an embodiment of the disclosure will now be described, by way of example, with reference to the accompanying Figures, in which:
The present disclosure will now be illustrated with reference to the following examples.
A mixture of sodium aluminium hydride from Acros Organics and magnesium chloride from Alfa Aesar in a ratio of 2:1 was ball-milled for an hour to produce a mixture of magnesium aluminium hydride and sodium chloride, containing a theoretical 42.5 wt % of magnesium aluminium hydride (scheme below).
The resulting magnesium aluminium hydride mixture offers a general platform for the synthesis of magnesium aluminates, as will be shown by the following examples.
Magnesium aluminates were synthesized by treating magnesium aluminium hydride with various fluorinated/non-fluorinated alkyl and aryl alcohols in dry THF or DME (Scheme below).
These reactions were followed by filtration under inert atmosphere to remove insoluble impurities (i.e. sodium chloride and aluminium-containing by-products). The resulting magnesium aluminates were retrieved, typically as THF or DME solvates, in moderate to high yields (77-94%). The particular alcohols that were used in the synthesis were (1) tert-butanol (Sigma-Aldrich); (2) perfluoro-tert-butanol (Alfa Aesar); (3) hexafluoro-iso-propanol (Fluorochem); (4) phenol (Sigma-Aldrich); (5) pentafluorophenol (Fluorochem).
All cyclic voltammetry (CV) and linear sweep voltammetry (LSV) experiments reported below were performed in a glovebox (MBraun) under an atmosphere of dry argon using dry solvents. Cyclic voltammetry and linear sweep voltammetry were performed using an IVIUM CompactS tat.
A solution of each of the magnesium aluminates (1)-(5) in dry organic solvent was prepared at a concentration of 0.25 M. A solution of magnesium tert-butoxyaluminate (1) in THF was found to exhibit poor oxidative stability on stainless steel (ss-316), aluminium, copper, gold, and platinum electrodes, with the onset of oxidation occurring at around 1 V vs magnesium on each electrode, as shown in
In contrast to magnesium tertbutoxyaluminate (1), magnesium aluminates 2-5 are soluble in DME. The solution of magnesium perfluoro-tert-butoxyaluminate (2) in DME exhibits an extended stability window on the five electrodes tested above, exhibiting onsets of oxidation between 1.9 V (copper) and 2.6 V (platinum) vs magnesium, as shown in
A 0.25 M solution of magnesium hexafluoro-iso-propoxyaluminate (3) made by the presently claimed method exhibits an onset of oxidation of around 2.2 V, 2.5 V, and 2.9 V vs magnesium on copper, aluminium, and gold, respectively, as shown in
A solution of magnesium phenoxyaluminate (4) in DME exhibits moderate oxidative stability with the electrodes that were tested, showing onsets of oxidation between 1.5 V (aluminium, gold and platinum) and 2.2 V ss-316 vs magnesium, as shown in
The solution of magnesium perfluorophenoxyaluminate (5) in DME exhibits an onset of oxidation below 2 V vs magnesium on all electrodes tested, with ss-316 and aluminium exhibiting the lowest onset, as shown in
CV was used to examine the ability of these 0.25 M magnesium aluminate solutions to facilitate magnesium plating and stripping using a platinum working electrode.
CV measurements of magnesium aluminate (1) in THF as well as magnesium aluminates (3) and (5) in DME did not show evidence of magnesium plating/stripping behaviour between −0.5 V and 1 V vs Mg.
CV of magnesium aluminate (2) in DME shows that this solution facilitates plating and stripping of magnesium using a platinum working electrode over fifty cycles between −0.55 V and 1 V vs magnesium, as shown in
CV of magnesium aluminate (4) in DME shows clear plating and stripping behaviour on platinum between −0.5 V and 1 V vs magnesium over 50 voltammetric cycles, as shown in
The electrochemical behaviour of 0.25 M DME solutions of magnesium aluminates (2)-(5) was further examined in magnesium full cells constructed using Chevrel phase (Mo6S8) cathodes, magnesium ribbon anodes, and stainless steel current collectors both at room temperature and 55° C.
Generally, the magnesium aluminate electrolytes exhibited better reversibility, maintained higher capacities over more charge-discharge cycles, and could be cycled at higher rates at 55° C. than at room temperature, as shown in
Full cells containing magnesium aluminate (5) exhibited very poor charge-discharge behaviour and significant capacity fade within five cycles at room temperature and 55° C. The full cell performance of magnesium aluminate (5) in DME is consistent with its apparent instability as observed by LSV measurements. Without wishing to be bound by theory, the low stability of the magnesium pentafluorophenyl aluminate (5) may result from the stability of the pentafluorophenoxy anion, which could render it more labile and more easily removed from aluminium.
| Number | Date | Country | Kind |
|---|---|---|---|
| 1714770.3 | Sep 2017 | GB | national |
This application is a national stage application under 35 U.S.C. 371 of International Application No. PCT/GB2018/052537, filed Sep. 7, 2018, which claims the priority of United Kingdom Application No. 1714770.3, filed Sep. 14, 2017, the entire contents of each of which are incorporated herein by reference.
| Number | Date | Country | |
|---|---|---|---|
| Parent | 16647468 | Mar 2020 | US |
| Child | 18235306 | US |
