Ambient temperature superionic conducting salt including metal cation and borate anion or carborate anion and process for making ambient temperature superionic conducting salt

• US 10,553,897 B2
• Filed: 06/03/2016
• Issued: 02/04/2020
• Est. Priority Date: 06/16/2015
• Status: Active Grant

• Current Assignee: THE GOVERNMENT OF THE UNITED STATES OF AMERICA, AS REPRESENTED BY THE SECRETARY OF COMMERCE
• Original Assignee: Governement of The United States of America As Represented By The Secretary of Agriculture
• Inventors: Udovic, Terrence John
• Primary Examiner(s): Cullen, Sean P
• Application Number:
  US15/172,641
• Publication Number:
  US 20160372786A1
• Time in Patent Office: 1,341 Days
• Field of Search: 429322
• CPC Class Codes: C01B 35/026 Higher boron hydrides, i.e. containing at least three boron atoms
• CPC Class Codes: H01M 10/052 Li-accumulators
• CPC Class Codes: H01M 10/054 Accumulators with insertion or intercalation of metals other than lithium, e.g. with magnesium or aluminium
• CPC Class Codes: H01M 10/0562 Solid materials
• CPC Class Codes: H01M 2300/0068 inorganic
• CPC Class Codes: H01M 2300/0091 in the form of mixtures
• CPC Class Codes: Y02E 60/10 Energy storage using batteries

Abstract

A process for making a superionic conducting salt includes: combining a primary salt and an impact member, the primary salt including an ordered phase and being an ionic conductor; impacting the primary salt with the impact member; and converting the primary salt to the superionic conducting salt in response to impacting the primary salt with the impact member at a conversion temperature to make the superionic conducting salt, the conversion temperature optionally being less than a thermally activated transition temperature that thermally converts the primary salt to the superionic conducting salt in an absence of the impacting the primary salt, and the superionic conducting salt including a superionic conductive phase in a solid state at less than the thermally activated transition temperature.

Claims

1. A superionic conducting salt comprising:

a plurality of salt cations;

a plurality of salt anions the salt anions comprising;

a closo-borate anion of formula B_nH<sub>(n−

z)</sub>R_z²⁻

, wherein n is an integer greater than or equal to 10;

z is an integer from 0 to n; and

each R independently comprises a hydrocarbon substituent, a halogenated-hydrocarbon substituent, a halogen, an amine, a cyano, a hydroxyl, a thiol, a carbonyl, a carboxylate, a carboxylic acid, an epoxide, an ester, an amide, an ether, or a combination comprising at least one of the foregoing groups;

a closo-carborate anion of formula CB_nH<sub>(n+1)−

z</sub>R_z<sup>−

1</sup>, wherein n is an integer greater than or equal to 9;

z is an integer from 0 to n; and

each R independently comprises a hydrocarbon substituent, a halogenated-hydrocarbon substituent, a halogen, an amine, a cyano, a hydroxyl, a thiol, a carbonyl, a carboxylate, a carboxylic acid, an epoxide, an ester, an amide, an ether, or a combination comprising at least one of the foregoing groups;

a closo-dicarborate anion of formula C₂B_nH<sub>(n+3)−

z</sub>R_z¹⁻

, wherein n is an integer greater than or equal to 9;

z is an integer from 0 to n; and

each R independently comprises a hydrocarbon substituent, a halogenated-hydrocarbon substituent, a halogen, an amine, a cyano, a hydroxyl, a thiol, a carbonyl, a carboxylate, a carboxylic acid, an epoxide, an ester, an amide, an ether, or a combination comprising at least one of the foregoing groups;

a carborate anion of formula CB_nH<sub>(n+3)−

z</sub>R_z¹⁻

, wherein n is an integer greater than or equal to 9;

z is an integer from 0 to n; and

each R independently comprises a hydrocarbon substituent, a halogenated-hydrocarbon substituent, a halogen, an amine, a cyano, a hydroxyl, a thiol, a carbonyl, a carboxylate, a carboxylic acid, an epoxide, an ester, an amide, an ether, or a combination comprising at least one of the foregoing groups;

a borate of formula B₁₁H<sub>(14−

z)</sub>R_z<sup>−

1</sup>, wherein z is an integer from 0 to 11; and

each R independently comprises a hydrocarbon substituent, a halogenated-hydrocarbon substituent, a halogen, an amine, a cyano, a hydroxyl, a thiol, a carbonyl, a carboxylate, a carboxylic acid, an epoxide, an ester, an amide, an ether, or a combination comprising at least one of the foregoing groups;

a closo-ammonioborate anion of formula ((R′

R″

R′

″

)NB_nZ<sub>n−

1</sub>)¹⁻

, wherein n is an integer greater than or equal to 10, N is bonded to B; and

R′

, R″

, R′

″

, and Z independently comprise a hydrogen, a hydrocarbon substituent, a halogenated-hydrocarbon substituent, a halogen, an amine, a cyano, a hydroxyl, a thiol, a carbonyl, a carboxylate, a carboxylic acid, an epoxide, an ester, an amide, an ether, or a combination comprising at least one of the foregoing groups;

or a combination comprising at least one of the foregoing salt anions; and

a superionic conductive phase that is present in a solid state at ambient temperature,

the superionic conducting salt being a mechanical milling product of a primary salt or a drying product of a drying composition comprising the primary salt.

2. The superionic conducting salt of claim 1, wherein that salt cations comprise:

a cation of an alkali metal, an alkaline earth metal, a transition metal, a rare earth metal, or a combination comprising at least one of the foregoing metals.

3. The superionic conducting salt of claim 2, wherein the salt anions comprise:

a plurality of first salt anions; and

a plurality of second salt anions.

4. A battery comprising:

an electrolyte composition comprising;

a superionic conducting salt that comprises;

a plurality of salt cations;

a plurality of salt anions, the salt anions comprising;

a closo-borate anion of formula B_nH<sub>(n−

z)</sub>R_z²⁻

, wherein n is an integer greater than or equal to 10;

z is an integer from 0 to n; and

each R independently comprises a hydrocarbon substituent, a halogenated-hydrocarbon substituent, a halogen, an amine, a cyano, a hydroxyl, a thiol, a carbonyl, a carboxylate, a carboxylic acid, an epoxide, an ester, an amide, an ether, or a combination comprising at least one of the foregoing groups;

a closo-carborate anion of formula CB_nH<sub>(n+1)−

z</sub>R_z¹⁻

, wherein n is an integer greater than or equal to 9;

z is an integer from 0 to n; and

each R independently comprises a hydrocarbon substituent, a halogenated-hydrocarbon substituent, a halogen, an amine, a cyano, a hydroxyl, a thiol, a carbonyl, a carboxylate, a carboxylic acid, an epoxide, an ester, an amide, an ether, or a combination comprising at least one of the foregoing groups;

a closo-dicarborate anion of formula C₂B_nH<sub>(n+3)−

z</sub>R_z¹⁻

, wherein n is an integer greater than or equal to 9;

z is an integer from 0 to n; and

each R independently comprises a hydrocarbon substituent, a halogenated-hydrocarbon substituent, a halogen, an amine, a cyano, a hydroxyl, a thiol, a carbonyl, a carboxylate, a carboxylic acid, an epoxide, an ester, an amide, an ether, or a combination comprising at least one of the foregoing groups;

a carborate anion of formula CB_nH<sub>(n+3)−

z</sub>R_z¹⁻

, wherein n is an integer greater than or equal to 9;

z is an integer from 0 to n; and

each R independently comprises a hydrocarbon substituent, a halogenated-hydrocarbon substituent, a halogen, an amine, a cyano, a hydroxyl, a thiol, a carbonyl, a carboxylate, a carboxylic acid, an epoxide, an ester, an amide, an ether, or a combination comprising at least one of the foregoing groups;

a borate of formula B₁₁H<sub>(14−

z)</sub>R_z¹⁻

, wherein z is an integer from 0 to 11; and

each R independently comprises a hydrocarbon substituent, a halogenated-hydrocarbon substituent, a halogen, an amine, a cyano, a hydroxyl, a thiol, a carbonyl, a carboxylate, a carboxylic acid, an epoxide, an ester, an amide, an ether, or a combination comprising at least one of the foregoing groups;

a closo-ammonioborate anion of formula ((R′

R″

R′

″

)NB_nZ<sub>n−

1</sub>)¹⁻

, wherein n is an integer greater than or equal to 10, N is bonded to B; and

R′

, R″

, R′

″

, and Z independently comprise a hydrogen, a hydrocarbon substituent, a halogenated-hydrocarbon substituent, a halogen, an amine, a cyano, a hydroxyl, a thiol, a carbonyl, a carboxylate, a carboxylic acid, an epoxide, an ester, an amide, an ether, or a combination comprising at least one of the foregoing groups;

or a combination comprising at least one of the foregoing salt anions; and

a superionic conductive phase that is present in a solid state at ambient temperature; and

optionally, a binder in which the superionic conducting salt is disposed;

a first electrode; and

a second electrode separated from the first electrode by interposition of the electrolyte composition.

5. The battery of claim 4, wherein the salt cations comprise:

a cation of an alkali metal, an alkaline earth metal, a transition metal, a rare earth metal, or a combination comprising at least one of the foregoing metals.

6. The battery of claim 5, wherein the salt anions comprise:

a plurality of first salt anions; and

a plurality of second salt anions.

7. A process for making a superionic conducting salt, the process comprising:

combining a primary salt and an impact member,

the primary salt comprising an ordered phase and being an ionic conductor;

impacting the primary salt with the impact member; and

converting the primary salt to the superionic conducting salt in response to impacting the primary salt with the impact member at a conversion temperature to make the superionic conducting salt,

the conversion temperature optionally being less than a thermally activated transition temperature that thermally converts the primary salt to the superionic conducting salt in an absence of the impacting the primary salt, and

the superionic conducting salt comprising a superionic conductive phase in a solid state at less than the thermally activated transition temperature,

wherein the superionic conducting salt comprises;

a plurality of salt cations;

a plurality of salt anions, the salt anions comprising;

a closo-borate anion of formula B_nH<sub>(n−

z)</sub>R_z²⁻

, wherein n is an integer greater than or equal to 10;

z is an integer from 0 to n; and

each R independently comprises a hydrocarbon substituent, a halogenated-hydrocarbon substituent, a halogen, an amine, a cyano, a hydroxyl, a thiol, a carbonyl, a carboxylate, a carboxylic acid, an epoxide, an ester, an amide, an ether, or a combination comprising at least one of the foregoing groups;

a closo-carborate anion of formula CB_nH<sub>(n+1)−

z</sub>R_z¹⁻

, wherein n is an integer greater than or equal to 9;

z is an integer from 0 to n; and

each R independently comprises a hydrocarbon substituent, a halogenated-hydrocarbon substituent, a halogen, an amine, a cyano, a hydroxyl, a thiol, a carbonyl, a carboxylate, a carboxylic acid, an epoxide, an ester, an amide, an ether, or a combination comprising at least one of the foregoing groups;

a closo-dicarborate anion of formula C₂B_nH<sub>(n+3)−

z</sub>R_z¹⁻

, wherein n is an integer greater than or equal to 9;

z is an integer from 0 to n; and

each R independently comprises a hydrocarbon substituent, a halogenated-hydrocarbon substituent, a halogen, an amine, a cyano, a hydroxyl, a thiol, a carbonyl, a carboxylate, a carboxylic acid, an epoxide, an ester, an amide, an ether, or a combination comprising at least one of the foregoing groups;

a carborate anion of formula CB_nH<sub>(n+3)−

z</sub>R_z¹⁻

, wherein n is an integer greater than or equal to 9;

z is an integer from 0 to n; and

each R independently comprises a hydrocarbon substituent, a halogenated-hydrocarbon substituent, a halogen, an amine, a cyano, a hydroxyl, a thiol, a carbonyl, a carboxylate, a carboxylic acid, an epoxide, an ester, an amide, an ether, or a combination comprising at least one of the foregoing groups;

a borate of the formula B₁₁H<sub>(14−

z)</sub>R_z¹⁻

, wherein z is an integer from 0 to 11; and

each R independently comprises a hydrocarbon substituent, a halogenated-hydrocarbon substituent, a halogen, an amine, a cyano, a hydroxyl, a thiol, a carbonyl, a carboxylate, a carboxylic acid, an epoxide, an ester, an amide, an ether, or a combination comprising at least one of the foregoing groups;

a closo-ammonioborate anion of formula ((R′

R″

R′

″

)NB_NZ<sub>n−

1</sub>)¹⁻

, wherein n is an integer greater than or equal to 10, N is bonded to B; and

R′

, R″

, R′

″

, and Z independently comprise a hydrogen, a hydrocarbon substituent, a halogenated-hydrocarbon substituent, a halogen, an amine, a cyano, a hydroxyl, a thiol, a carbonyl, a carboxylate, a carboxylic acid, an epoxide, an ester, an amide, an ether, or a combination comprising at least one of the foregoing groups;

or

a combination comprising at least one of the foregoing salt anions; and

the superionic conductive phase is present in a solid state at ambient temperature.

8. The process of claim 7, wherein impacting the primary salt with the impact member comprises milling the primary salt with the impact member.

9. The process of claim 8, wherein the primary salt comprises:

a plurality of primary cations that comprise a cation of an alkali metal, an alkaline earth metal, a transition metal, a rare earth metal, or a combination comprising at least one of the foregoing metals; and

a plurality of primary anions.

10. The process of claim 9, wherein the primary anions comprise:

a closo-borate anion of formula B_nH<sub>(n−

z)</sub>R_z²⁻

, wherein n is an integer greater than or equal to 10;

z is an integer from 0 to n; and

each R independently comprises a hydrocarbon substituent, a halogenated-hydrocarbon substituent, a halogen, an amine, a cyano, a hydroxyl, a thiol, a carbonyl, a carboxylate, a carboxylic acid, an epoxide, an ester, an amide, an ether, or a combination comprising at least one of the foregoing groups;

a closo-carborate anion of formula CB_nH<sub>(n+1)−

z</sub>R_z¹⁻

, wherein n is an integer greater than or equal to 9;

z is an integer from 0 to n; and

each R independently comprises a hydrocarbon substituent, a halogenated-hydrocarbon substituent, a halogen, an amine, a cyano, a hydroxyl, a thiol, a carbonyl, a carboxylate, a carboxylic acid, an epoxide, an ester, an amide, an ether, or a combination comprising at least one of the foregoing groups;

a closo-dicarborate anion of formula C₂B_nH<sub>(n+3)−

z</sub>R_z¹⁻

, wherein n is an integer greater than or equal to 9;

z is an integer from 0 to n; and

each R independently comprises a hydrocarbon substituent, a halogenated-hydrocarbon substituent, a halogen, an amine, a cyano, a hydroxyl, a thiol, a carbonyl, a carboxylate, a carboxylic acid, an epoxide, an ester, an amide, an ether, or a combination comprising at least one of the foregoing groups;

a carborate anion of formula CB_nH<sub>(n+3)−

z</sub>R_z¹⁻

, wherein n is an integer greater than or equal to 9;

z is an integer from 0 to n; and

each R independently comprises a hydrocarbon substituent, a halogenated-hydrocarbon substituent, a halogen, an amine, a cyano, a hydroxyl, a thiol, a carbonyl, a carboxylate, a carboxylic acid, an epoxide, an ester, an amide, an ether, or a combination comprising at least one of the foregoing groups;

a borate of the formula B₁₁H<sub>(14−

z)</sub>R_z¹⁻

, wherein z is an integer from 0 to 11; and

each R independently comprises a hydrocarbon substituent, a halogenated-hydrocarbon substituent, a halogen, an amine, a cyano, a hydroxyl, a thiol, a carbonyl, a carboxylate, a carboxylic acid, an epoxide, an ester, an amide, an ether, or a combination comprising at least one of the foregoing groups;

a closo-ammonioborate anion of formula ((R′

R″

R′

″

)NB_nZ<sub>n−

1</sub>)¹⁻

, wherein n is an integer greater than or equal to 10, N is bonded to B; and

R′

, R″

, R′

″

, and Z independently comprise a hydrogen, a hydrocarbon substituent, a halogenated-hydrocarbon substituent, a halogen, an amine, a cyano, a hydroxyl, a thiol, a carbonyl, a carboxylate, a carboxylic acid, an epoxide, an ester, an amide, an ether, or a combination comprising at least one of the foregoing groups;

or

a combination comprising at least one of the foregoing primary anions.

11. The process of claim 10, wherein the salt cations comprises:

a cation of an alkali metal, an alkaline earth metal, a transition metal, a rare earth metal, or a combination comprising at least one of the foregoing metals.

12. The process of claim 11, wherein the impact member comprises a ball for a ball mill, a secondary salt, or a combination comprising at least one of the foregoing impact members.

13. The process of claim 12, wherein the impact member is the ball and impacting the primary salt comprises ball milling the primary salt to make the superionic conducting salt.

14. The process of claim 12, wherein the impact member is the secondary salt that comprises:

a plurality of secondary cations that comprise;

a cation of an alkali metal, an alkaline earth metal, a transition metal, a rare-earth metal, a polyatomic cation, or a combination comprising at least one of the foregoing; and

a plurality of secondary anions.

15. The process of claim 14, wherein the secondary anions comprise:

a closo-borate anion of formula B_nH<sub>(n−

z)</sub>R_z²⁻

, wherein n is an integer greater than or equal to 10;

z is an integer from 0 to n; and

each R independently comprises a hydrocarbon substituent, a halogenated-hydrocarbon substituent, a halogen, an amine, a cyano, a hydroxyl, a thiol, a carbonyl, a carboxylate, a carboxylic acid, an epoxide, an ester, an amide, an ether, or a combination comprising at least one of the foregoing groups;

a closo-carborate anion of formula CB_nH<sub>(n+1)−

z</sub>R_z¹⁻

, wherein n is an integer greater than or equal to 9;

z is an integer from 0 to n; and

each R independently comprises a hydrocarbon substituent, a halogenated-hydrocarbon substituent, a halogen, an amine, a cyano, a hydroxyl, a thiol, a carbonyl, a carboxylate, a carboxylic acid, an epoxide, an ester, an amide, an ether, or a combination comprising at least one of the foregoing groups;

a closo-dicarborate anion of formula C₂B_nH<sub>(n+3)−

z</sub>R_z¹⁻

, wherein n is an integer greater than or equal to 9;

z is an integer from 0 to n; and

each R independently comprises a hydrocarbon substituent, a halogenated-hydrocarbon substituent, a halogen, an amine, a cyano, a hydroxyl, a thiol, a carbonyl, a carboxylate, a carboxylic acid, an epoxide, an ester, an amide, an ether, or a combination comprising at least one of the foregoing groups;

a carborate anion of formula CB_nH<sub>(n+3)−

z</sub>R_z¹⁻

, wherein n is an integer greater than or equal to 9;

z is an integer from 0 to n; and

each R independently comprises a hydrocarbon substituent, a halogenated-hydrocarbon substituent, a halogen, an amine, a cyano, a hydroxyl, a thiol, a carbonyl, a carboxylate, a carboxylic acid, an epoxide, an ester, an amide, an ether, or a combination comprising at least one of the foregoing groups;

a borate of the formula B₁₁H<sub>(14−

z)</sub>R_z¹⁻

, wherein z is an integer from 0 to 11; and

each R independently comprises a hydrocarbon substituent, a halogenated-hydrocarbon substituent, a halogen, an amine, a cyano, a hydroxyl, a thiol, a carbonyl, a carboxylate, a carboxylic acid, an epoxide, an ester, an amide, an ether, or a combination comprising at least one of the foregoing groups;

a closo-ammonioborate anion of formula ((R′

R″

R′

″

)NB_nZ<sub>n−

1</sub>)¹⁻

, wherein n is an integer greater than or equal to 10, N is bonded to B; and

R′

, R″

, R′

″

, and Z independently comprise a hydrogen, a hydrocarbon substituent, a halogenated-hydrocarbon substituent, a halogen, an amine, a cyano, a hydroxyl, a thiol, a carbonyl, a carboxylate, a carboxylic acid, an epoxide, an ester, an amide, an ether, or a combination comprising at least one of the foregoing groups;

a monoatomic anion;

a polyatomic anion;

a halide;

or

a combination comprising at least one of the foregoing secondary anions.

16. A process for making a superionic conducting salt, the process comprising:

combining a primary salt and a secondary salt to form a drying composition that is a fluid and that comprises the primary salt and the secondary salt,

the primary salt comprising an ordered phase and being an ionic conductor;

drying the drying composition; and

converting the primary salt to the superionic conducting salt in response to drying the drying composition at a conversion temperature to make the superionic conducting salt,

the conversion temperature optionally being less than a thermally activated transition temperature that thermally converts the primary salt to the superionic conducting salt in an absence of the secondary salt, and

the superionic conducting salt comprising a superionic conducting phase in a solid state at less than the thermally activated transition temperature,

wherein the superionic conducting salt comprises;

a plurality of salt cations;

a plurality of salt anions, the salt anions comprising;

a closo-borate anion of formula B_nH<sub>(n−

z)</sub>R_z²⁻

, wherein n is an integer greater than or equal to 10;

z is an integer from 0 to n; and

each R independently comprises a hydrocarbon substituent, a halogenated-hydrocarbon substituent, a halogen, an amine, a cyano, a hydroxyl, a thiol, a carbonyl, a carboxylate, a carboxylic acid, an epoxide, an ester, an amide, an ether, or a combination comprising at least one of the foregoing groups;

a closo-carborate anion of formula CB_nH<sub>(n+1)−

z</sub>R_z¹⁻

, wherein n is an integer greater than or equal to 9;

z is an integer from 0 to n; and

each R independently comprises a hydrocarbon substituent, a halogenated-hydrocarbon substituent, a halogen, an amine, a cyano, a hydroxyl, a thiol, a carbonyl, a carboxylate, a carboxylic acid, an epoxide, an ester, an amide, an ether, or a combination comprising at least one of the foregoing groups;

a closo-dicarborate anion of formula C₂B_nH<sub>(n+3)−

z</sub>R_z¹⁻

, wherein n is an integer greater than or equal to 9;

z is an integer from 0 to n; and

each R independently comprises a hydrocarbon substituent, a halogenated-hydrocarbon substituent, a halogen, an amine, a cyano, a hydroxyl, a thiol, a carbonyl, a carboxylate, a carboxylic acid, an epoxide, an ester, an amide, an ether, or a combination comprising at least one of the foregoing groups;

a carborate anion of formula CB_nH<sub>(n+3)−

z</sub>R_z¹⁻

, wherein n is an integer greater than or equal to 9;

z is an integer from 0 to n; and

each R independently comprises a hydrocarbon substituent, a halogenated-hydrocarbon substituent, a halogen, an amine, a cyano, a hydroxyl, a thiol, a carbonyl, a carboxylate, a carboxylic acid, an epoxide, an ester, an amide, an ether, or a combination comprising at least one of the foregoing groups;

a borate of the formula B₁₁H<sub>(14−

z)</sub>R_z¹⁻

, wherein z is an integer from 0 to 11; and

each R independently comprises a hydrocarbon substituent, a halogenated-hydrocarbon substituent, a halogen, an amine, a cyano, a hydroxyl, a thiol, a carbonyl, a carboxylate, a carboxylic acid, an epoxide, an ester, an amide, an ether, or a combination comprising at least one of the foregoing groups;

a closo-ammonioborate anion of formula ((R′

R″

R′

″

)NB_nZ<sub>n−

1</sub>)¹⁻

, wherein n is an integer greater than or equal to 10, N is bonded to B; and

R′

, R″

, R′

″

, and Z independently comprise a hydrogen, a hydrocarbon substituent, a halogenated-hydrocarbon substituent, a halogen, an amine, a cyano, a hydroxyl, a thiol, a carbonyl, a carboxylate, a carboxylic acid, an epoxide, an ester, an amide, an ether, or a combination comprising at least one of the foregoing groups;

or

a combination comprising at least one of the foregoing salt anions; and

the superionic conductive phase is present in a solid state at ambient temperature.

17. The process of claim 16, wherein the drying composition further comprises a solvent.

18. The process of claim 16, wherein the salt cations comprises:

a cation of an alkali metal, an alkaline earth metal, a transition metal, a rare earth metal, or a combination comprising at least one of the foregoing metals.

19. The process of claim 16, wherein the primary salt comprises:

a plurality of primary cations that comprise a cation of an alkali metal, an alkaline earth metal, a transition metal, a rare earth metal, or a combination comprising at least one of the foregoing metals; and

a plurality of primary anions.

20. The process of claim 19, wherein the primary anions comprise:

a closo-borate anion of formula B_nH<sub>(n−

z)</sub>R_z²⁻

, wherein n is an integer greater than or equal to 10;

z is an integer from 0 to n; and

each R independently comprises a hydrocarbon substituent, a halogenated-hydrocarbon substituent, a halogen, an amine, a cyano, a hydroxyl, a thiol, a carbonyl, a carboxylate, a carboxylic acid, an epoxide, an ester, an amide, an ether, or a combination comprising at least one of the foregoing groups;

a closo-carborate anion of formula CB_nH<sub>(n+1)−

z</sub>R_z¹⁻

, wherein n is an integer greater than or equal to 9;

z is an integer from 0 to n; and

each R independently comprises a hydrocarbon substituent, a halogenated-hydrocarbon substituent, a halogen, an amine, a cyano, a hydroxyl, a thiol, a carbonyl, a carboxylate, a carboxylic acid, an epoxide, an ester, an amide, an ether, or a combination comprising at least one of the foregoing groups;

a closo-dicarborate anion of formula C₂B_nH<sub>(n+3)−

z</sub>R_z¹⁻

, wherein n is an integer greater than or equal to 9;

z is an integer from 0 to n; and

each R independently comprises a hydrocarbon substituent, a halogenated-hydrocarbon substituent, a halogen, an amine, a cyano, a hydroxyl, a thiol, a carbonyl, a carboxylate, a carboxylic acid, an epoxide, an ester, an amide, an ether, or a combination comprising at least one of the foregoing groups;

a carborate anion of formula CB_nH<sub>(n+3)−

z</sub>R_z¹⁻

, wherein n is an integer greater than or equal to 9;

z is an integer from 0 to n; and

each R independently comprises a hydrocarbon substituent, a halogenated-hydrocarbon substituent, a halogen, an amine, a cyano, a hydroxyl, a thiol, a carbonyl, a carboxylate, a carboxylic acid, an epoxide, an ester, an amide, an ether, or a combination comprising at least one of the foregoing groups;

a borate of the formula B₁₁H<sub>(14−

z)</sub>R_z¹⁻

, wherein z is an integer from 0 to 11; and

each R independently comprises a hydrocarbon substituent, a halogenated-hydrocarbon substituent, a halogen, an amine, a cyano, a hydroxyl, a thiol, a carbonyl, a carboxylate, a carboxylic acid, an epoxide, an ester, an amide, an ether, or a combination comprising at least one of the foregoing groups;

a closo-ammonioborate anion of formula ((R′

R″

R′

″

)NB_nZ<sub>n−

1</sub>)¹⁻

, wherein n is an integer greater than or equal to 10, N is bonded to B; and

R′

, R″

, R′

″

, and Z independently comprise a hydrogen, a hydrocarbon substituent, a halogenated-hydrocarbon substituent, a halogen, an amine, a cyano, a hydroxyl, a thiol, a carbonyl, a carboxylate, a carboxylic acid, an epoxide, an ester, an amide, an ether, or a combination comprising at least one of the foregoing groups;

or

a combination comprising at least one of the foregoing primary anions.

21. The process of claim 16, wherein the secondary salt comprises:

a plurality of secondary cations that comprise a cation of an alkali metal, an alkaline earth metal, a transition metal, a rare-earth metal, a polyatomic cation, or a combination comprising at least one of the foregoing; and

a plurality of secondary anions.

22. The process of claim 21, wherein the secondary anions comprise:

a closo-borate anion of formula B_nH<sub>(n−

z)</sub>R_z²⁻

, wherein n is an integer greater than or equal to 10;

z is an integer from 0 to n; and

each R independently comprises a hydrocarbon substituent, a halogenated-hydrocarbon substituent, a halogen, an amine, a cyano, a hydroxyl, a thiol, a carbonyl, a carboxylate, a carboxylic acid, an epoxide, an ester, an amide, an ether, or a combination comprising at least one of the foregoing groups;

a closo-carborate anion of formula CB_nH<sub>(n+1)−

z</sub>R_z¹⁻

, wherein n is an integer greater than or equal to 9;

z is an integer from 0 to n; and

each R independently comprises a hydrocarbon substituent, a halogenated-hydrocarbon substituent, a halogen, an amine, a cyano, a hydroxyl, a thiol, a carbonyl, a carboxylate, a carboxylic acid, an epoxide, an ester, an amide, an ether, or a combination comprising at least one of the foregoing groups;

a closo-dicarborate anion of formula C₂B_nH<sub>(n+3)−

z</sub>R_z¹⁻

, wherein n is an integer greater than or equal to 9;

z is an integer from 0 to n; and

each R independently comprises a hydrocarbon substituent, a halogenated-hydrocarbon substituent, a halogen, an amine, a cyano, a hydroxyl, a thiol, a carbonyl, a carboxylate, a carboxylic acid, an epoxide, an ester, an amide, an ether, or a combination comprising at least one of the foregoing groups;

a carborate anion of formula CB_nH<sub>(n+3)−

z</sub>R_z¹⁻

, wherein n is an integer greater than or equal to 9;

z is an integer from 0 to n; and

each R independently comprises a hydrocarbon substituent, a halogenated-hydrocarbon substituent, a halogen, an amine, a cyano, a hydroxyl, a thiol, a carbonyl, a carboxylate, a carboxylic acid, an epoxide, an ester, an amide, an ether, or a combination comprising at least one of the foregoing groups;

a borate of the formula B₁₁H<sub>(14−

z)</sub>R_z¹⁻

, wherein z is an integer from 0 to 11;

and each R independently comprises a hydrocarbon substituent, a halogenated-hydrocarbon substituent, a halogen, an amine, a cyano, a hydroxyl, a thiol, a carbonyl, a carboxylate, a carboxylic acid, an epoxide, an ester, an amide, an ether, or a combination comprising at least one of the foregoing groups;

a closo-ammonioborate anion of formula ((R′

R″

R′

″

)NB_nZ<sub>n−

1</sub>)¹⁻

, wherein n is an integer greater than or equal to 10, N is bonded to B; and

R′

, R″

, R′

″

, and Z independently comprise a hydrogen, a hydrocarbon substituent, a halogenated-hydrocarbon substituent, a halogen, an amine, a cyano, a hydroxyl, a thiol, a carbonyl, a carboxylate, a carboxylic acid, an epoxide, an ester, an amide, an ether, or a combination comprising at least one of the foregoing groups;

a monoatomic anion;

a polyatomic anion;

a halide;

or

a combination comprising at least one of the foregoing secondary anions.