Superconcentrated electrolytes, also known as water-in-salt or solvent-in-salt liquids, usually refer to chemical systems, which are liquid near room temperature and consist of a solvent-to-dissoved salt in a molar ratio near or smaller than ca. 4-8, i.e. where all solvent molecules are coordinated to cations, and no free solvent molecules remain. [1] Since ca. 2010 such liquid electrolytes found several applications, primarily for batteries. In the case of lithium metal batteries and lithium-ion batteries most commonly used anions for superconcentrated electrolytes are those, that are large, asymmetric and rotationally-vibrationally flexible, such as bis(trifluoromethanesulfonyl)amide and bis(fluorosulfonyl)amide. Noteworthy, lithium chloride and sodium perchlorate also form water-in-salt solutions. [2]
Superconcentrated electrolytes demonstrate the following advantages: [3]
(1) Many show a good oxidative stability. [1] In particular, some can suppress oxidative corrosion of an Al current collector without a source of fluoride ion (such as hexafluorophosphate) and enable the use of 5 V lithium-ion battery cathode materials. [3]
(2) Some are resistant to electrochemical reduction. It is believed, that some sulfonimides (e.g., those with S-F and F-(H)C-N fragments, form a solid electrolyte interface similar to that formed by some organic carbonate solvents. [4] Properties #1 and #2 are responsible for very large (4-5 volt) voltage window, which is useful for advanced batteries.
(3) Related to #2 is the ability of some superconcentrated electrolytes to allow for reversible intercalation of Li+ ions into graphite in the absence of ethylene carbonate solvent, [5] therefore enabling a new class of safer lithium-ion batteries.
(4) Solvent vapor pressure is lower, thermal stability is higher, and flammability is absent, [1] which contributes to a better battery safety. [3]
(5) The concentration of charge-carrying ion is larger, which translates into smaller ion travelling distances. [3]
(6) In some cases, and contrary to expectations, faster rates of electrode reactions are observed, than in conventional low-salt-concentration electrolytes. [3]
(7) Polysulfide dissolution is sometimes suppressed, which enables cycling of such batteries as lithium-sulfur. [3]
(8) Some studies report, that Li+ transference number in such liquids is close to one, which means, that Li+ concentration gradient between anode and cathode does not develop during the battery's charge and discharge. [3]
(9) Electrodeposition of lithium metal from superconcentrated electrolytes is often nodular (without dendrites) and reversible. [3]
At the same time, highly concentrated electrolytes are not without disadvantages: [3]
(1) Their ionic conductivity is generally lower than that of corresponding dilute (~1 M) electrolytes. [3]
(2) Their viscosity is higher than that of conventional electrolytes. [3]
(3) Their cost is usually higher, because manufacturing of some anions, such as sulfonimides, requires several low-yield synthetic steps. [3]
The exact mechanism of high-voltage stability of superconcentrated electrolytes have not been established as of 2023. The two main proposed mechanisms are: [6]
(1) a decrease of water molecules' thermodynamic activity, when all water molecules are coordinated to cations, such as Li+.
(2) decomposition of an anion with the formation of a solid electrolyte interface.
Most recent studies suggest, that the anion decomposition mechanism (2) dominates in a majority of cases.