Carbonate-based electrolyte system improving or supporting efficiency of electrochemical cells having lithium-containing anodes
A highly-concentrated electrolyte system for an electrochemical cell is provided, along with methods of making the electrolyte system. The electrolyte system includes a bound moiety having an ionization potential greater than an electron affinity and comprising one or more salts selected from the group consisting of: lithium bis(fluorosulfonyl)imide, sodium bis(fluorosulfonyl)imide, potassium bis(fluorosulfonyl)imide, and combinations thereof bound to a solvent comprising one or more solvents selected from the group consisting of: dimethyl carbonate, dimethyl dicarbonate, and combinations thereof. The salts have a concentration in the electrolyte system of greater than or equal to about 4 M. A molar ratio of the salts to the dimethyl carbonate is about 0.5. A molar ratio of the salts to the dimethyl dicarbonate is about 1. The salts binds to the dimethyl carbonate and/or dimethyl dicarbonate causing the electrolyte system to be substantially free of unbound dimethyl carbonate, unbound dimethyl dicarbonate, and unbound bis(fluorosulfonyl)imide.
1. A method of preparing an electrolyte system that improves or enhances the efficiency of an electrochemical cell comprising a positive electrode comprising a positive lithium-based electroactive material and having a maximum potential greater than or equal to about 5V and a negative electrode including a negative electroactive material comprising lithium, the method comprising:
mixing one or more salts selected from the group consisting of: lithium bis(fluorosulfonyl)imide (LiFSI), sodium bis(fluorosulfonyl)imide (NaFSI), potassium bis(fluorosulfonyl)imide (KFSI), and combinations thereof and a solvent comprising one or more solvents selected from the group consisting of: dimethyl carbonate (DMC), dimethyl dicarbonate (DMDC), and combinations thereof, forming a bound moiety having an ionization potential greater than an electron affinity to form an electrolyte system that is substantially free of unbound dimethyl carbonate (DMC), dimethyl dicarbonate (DMDC), and unbound bis(fluorosulfonyl)imide (FSI − ), wherein the one or more salts have a concentration in the electrolyte system of greater than or equal to about 4M.
2. The method of claim 1 , wherein the solvent comprises dimethyl carbonate (DMC) and a molar ratio of the one or more salts to the dimethyl carbonate (DMC) is about 0.5.
3. The method of claim 1 , wherein the solvent comprises dimethyl dicarbonate (DMDC) and a molar ratio of the one or more salts to the dimethyl dicarbonate (DMDC) is about 1.
4. The method of claim 1 , wherein the electrolyte system has a dynamic viscosity less than or equal to about 100 centipoise (cP) and the electrochemical cell has an energy density of greater than about 900 Wh/L.
5. The method of claim 1 , wherein the positive lithium-based electroactive material comprises elemental sulfur or a sulfur-containing active material.
6. The method of claim 1 , wherein the positive lithium-based electroactive material is selected from the group consisting of nickel-manganese-cobalt 811 (NMC811), nickel-manganese-cobalt 622 (NMC622); lithium cobalt oxide (LiCoO 2 ); lithium iron phosphate (LiFePO 4 ); high-energy nickel-manganese-cobalt-oxide (HENMC) (e.g., over-lithiated layered oxide cathode or lithium-rich NMC), lithium-manganese-nickel-oxide (LMNO); and combinations thereof.
7. A method of improving or optimizing anodic stability of an electrochemical cell that cycles lithium-ions and comprises a positive electrode comprising a positive lithium-based electroactive material having a maximum potential greater than or equal to about 5V and a negative electrode having a negative electroactive material comprising lithium, the method comprising:
introducing an electrolyte system into the electrochemical cell, the electrolyte system comprising a bound moiety having an ionization potential greater than an electron affinity and comprising one or more salts bound to a solvent, wherein the one or more salts has a concentration in the electrolyte system of greater than or equal to about 4M and is selected from the group consisting of: lithium bis(fluorosulfonyl)imide (LiFSI), sodium bis(fluorosulfonyl)imide (NaFSI), potassium bis(fluorosulfonyl)imide (KFSI), and combinations thereof and the solvent comprises one or more solvents selected from the group consisting of: dimethyl carbonate (DMC), dimethyl dicarbonate (DMDC), and combinations thereof, wherein when dimethyl carbonate (DMC) is present in the electrolyte system, a molar ratio of the one or more salts to the dimethyl carbonate (DMC) is about 0.5 and when dimethyl dicarbonate (DMDC) is present in the electrolyte system, a molar ratio of the one or more salts to the dimethyl dicarbonate (DMDC) is about 1, and the electrolyte system is substantially free of unbound dimethyl carbonate (DMC), unbound dimethyl dicarbonate (DMDC), and unbound bis(fluorosulfonyl)imide (FSI − ).
8. The method of claim 7 , wherein the electrolyte system has a viscosity less than or equal to about 100 centipoise (cP) and the electrochemical cell has an energy density of greater than about 900 Wh/L.
9. An electrochemical cell that cycles lithium-ions having improved or optimized efficiency comprising:
a positive electrode comprising a positive lithium-based electroactive material and having a maximum potential greater than or equal to about 5V;
a separator;
a negative electrode comprising a negative electroactive material comprising lithium; and
an electrolyte system comprising a bound moiety having an ionization potential greater than an electron affinity and comprising one or more salts bound to a solvent, wherein the one or more salts is selected from the group consisting of: lithium bis(fluorosulfonyl)imide (LiFSI), sodium bis(fluorosulfonyl)imide (NaFSI), potassium bis(fluorosulfonyl)imide (KFSI), and combinations thereof and the solvent comprises one or more solvents selected from the group consisting of: dimethyl carbonate (DMC), dimethyl dicarbonate (DMDC), and combinations thereof, wherein the one or more salts have a concentration in the electrolyte system of greater than or equal to about 4M, and wherein the electrolyte system is substantially free of unbound dimethyl carbonate (DMC), unbound dimethyl dicarbonate (DMDC), and unbound bis(fluorosulfonyl)imide (FSI − ).
10. The electrochemical cell of claim 9 , wherein the solvent comprises dimethyl carbonate (DMC) and a molar ratio of the one or more salts to the dimethyl carbonate (DMC) is about 0.5.
11. The electrochemical cell of claim 9 , wherein the solvent comprises dimethyl dicarbonate (DMDC) and a molar ratio of the one or more salts to the dimethyl dicarbonate (DMDC) is about 1.
12. The electrochemical cell of claim 9 , wherein the electrolyte system has a dynamic viscosity less than or equal to about 100 centipoise (cP) and the electrochemical cell has an energy density of greater than about 900 Wh/L.
13. The electrochemical cell of claim 9 , wherein the positive lithium-based electroactive material includes elemental sulfur or a sulfur-containing active material.
14. The electrochemical cell of claim 9 , wherein the positive lithium-based electroactive material is selected from the group consisting of nickel-manganese-cobalt 811 (NMC811); nickel-manganese-cobalt 622 (NMC622); lithium cobalt oxide (LiCoO 2 ); lithium iron phosphate (LiFePO 4 ); high-energy nickel-manganese-cobalt-oxide (HENMC) (e.g., over-lithiated layered oxide cathode or lithium-rich NMC); lithium-manganese-nickel-oxide (LMNO); and combinations thereof.