ADDITIVE CONTAINING ELECTROLYTES FOR HIGH ENERGY RECHARGEABLE METAL ANODE BATTERIES
Electrolytes for use in commercially viable, rechargeable lithium metal batteries are described. The electrolytes contain one or more lithium salts, one or more organic solvents, and one or more additives. The electrolytes allow for reversible deposition and dissolution of lithium metal. Specific additives or additive combinations dramatically improved cycle life, decrease cell swelling, and/or lower cell impedance.
1 . A rechargeable electrochemical cell having a non-aqueous fluid electrolyte solution, comprising:
a negative electrode comprising lithium metal in part in direct physical contact with said non-aqueous fluid electrolyte;
a positive electrode in direct physical contact with said non-aqueous fluid electrolyte;
an electronically insulating separator configured to separate said negative electrode and said positive electrode;
said non-aqueous fluid electrolyte comprising:
at least one organic solvent;
at least one electrolytically active, soluble, lithium (Li) salt other than LiPF 6 or LiAsF 6 or LiClO 4 ; and
at least one additive from the following: pyrrolidones, sulfonimides, carbodimides, sulfonylfluorides, nitriles, isocyanates, fluoroacetates, silanes, triflate, halides, or organo-borates.
2 . The rechargeable electrochemical cell of claim 1 , wherein at least one electrolytically active lithium salt is selected from the group of salts consisting of lithium bis(perfluoroalkylsulfonyl)imide, lithium bis(fluorosulfonyl)imide, lithium bis(trifluoromethanesulfonyl)imide, lithium bis(perfluoroethylsulfonyl)imide, lithium dicyanamide, lithium tricyanomethide, lithium tetracyanoborate, lithium bis(oxalato)borate, lithium difluoro(oxalato)borate, lithium difluoro(malonato)borate, lithium tetrafluoroborate, lithium bis(benzenesulfonyl)imide, lithium triflate, lithium bis(perfluoropinacolato)borate, lithium bis(salicylato)borate, lithium perfluorobutanesulfonate, lithium thiocyanate, lithium triflinate, and lithium nitrate.
3 . The rechargeable electrochemical cell of claim 2 , comprising at least two electrolytically active lithium salts.
4 . The rechargeable electrochemical cell of claim 1 , wherein at least one additive is selected from the group of chemicals consisting of 1-ethyl-2-pyrrolidone, carbon dioxide, N-fluorobenzenesulfonimide, allyl trifluoroacetate, vinyltrimethylsilane, tetra(isocyanato)silane, lithium bis(salicylato)borate, lithium triflate, lithium fluoride, perfluorobutanesulfonyl fluoride, lithium perfluoro-1-butanesulfonate, lithium vinyltrifluoroborate, lithium halide, benzonitriles, 4-fluorobenzonitrile, 4-trifluoromethyl benzonitrile, benzonitrile, aryl isocyanates, 4-methoxyphenyl isocyanate, 1,3-phenylene diisocyanate, 1,4-phenylene diisocyanate, 3,5-bis(trifluoromethyl)phenyl isocyanate, 2-trifluoromethoxyphenyl isocyanate, alkyl isocyanates, ethyl isocyanate, pentyl isocyanate, octyl isocyanate, dodecyl isocyanate, 4-fluorobenzyl isocyanate bis(trimethylsilyl)carbodiimide, 1-phenylpyrrolidine, N-nitrosopyrrolidine, Disuccinimidyl carbonate, lithium trifluoroacetate, methyl difluoroacetate, ethyl difluoroacetate, Ethyl 4,4,4-trifluoro(aceto)acetate, Methyl 2,2-difluoro-2-(fluorosulfonyl)acetate, Lithium nonafluorobutanesulfonate, Lithium 1,1,2,2,3,3-Hexafluoropropane-1,3-disulfonimide, N-fluorobenzenesulfonimide, methyl Cyanoacetate, chlorosulfonyl isocyanate.
5 . The rechargeable electrochemical cell of claim 4 , comprising at least two additives selected from the group of chemicals listed in claim 4 .
6 . The rechargeable electrochemical cell of claim 1 , wherein each additive comprises greater than zero and less than ten percent by mass of the total electrolyte mass.
7 . The rechargeable electrochemical cell of claim 1 , wherein an anode polarization between electrodeposition and electrodissolution is less than 500 mV at 25 degrees Celsius.
8 . The rechargeable electrochemical cell of claim 1 , wherein the cell Coulombic efficiency is greater than 99.35% at 25 degrees Celsius.
9 . The rechargeable electrochemical cell of claim 1 , wherein the electrolyte solution comprises one or more liquid-infused polymers or gels.
10 . The rechargeable electrochemical cell of claim 1 , wherein said negative electrode and said positive electrode are configured such that a capacity of said negative electrode is strictly less than a capacity of said positive electrode.
11 . The rechargeable electrochemical cell of claim 1 , wherein a ratio of reversible capacity between said negative electrode and said positive electrode is such that Q (negative electrode)/Q (positive electrode)<0.9.
12 . The rechargeable electrochemical cell of claim 1 , configured to charge to greater than or equal to 4.3 V.
13 . The rechargeable electrochemical cell of claim 1 , configured to discharge to −2.5 V.
14 . The rechargeable electrochemical cell of claim 1 , configured to charge and discharge at ≦10 C-rate of rated capacity.
15 . The rechargeable electrochemical cell of claim 1 , configured to discharge and charge at temperatures in the range of −20° C. and 200° C.
16 . The rechargeable electrochemical cell of claim 1 , configured to provide at least 80% of initial capacity for greater than 30 charging and discharging cycles.
17 . The rechargeable electrochemical cell of claim 1 , wherein said negative electrode is configured to provide >1000 mAh/cc.
18 . The rechargeable electrochemical cell of claim 1 , wherein the active cation is lithium.
19 . The rechargeable electrochemical cell of claim 15 , wherein an anode Coulombic efficiency is greater than 99.35% at 25 degrees Celsius.
20 . The rechargeable electrochemical cell of claim 1 , wherein said non-aqueous electrolyte comprises a salt, or combination of salts in a concentration in the range of 0.5 M to saturated.
21 . The rechargeable electrochemical cell of claim 1 , wherein at least one of said negative electrode or positive electrode comprises one of a metal, an alloy, and an intermetallic compound.
22 . The rechargeable electrochemical cell of claim 1 , wherein at least one of said negative electrode or positive electrode comprises a material configured to undergo a reaction selected from the group of reactions consisting of an insertion reaction, an alloying, an intercalation, a disproportionation, a conversion reaction, or a combination thereof.
23 . The rechargeable electrochemical cell of claim 1 , wherein a pressure perpendicular to the interface of the positive and negative electrodes is greater than 0.06 MPa.
24 . The rechargeable electrochemical cell of claim 1 , further comprising at least one gate electrode having a gate electrode electrical terminal, said gate electrode in communication with said non-aqueous fluid electrolyte and permeable to at least one mobile species which is redox-active at at least one of said positive electrode or said negative electrode, said gate electrode situated between said positive electrode and said negative electrode.
25 . The rechargeable electrochemical cell of claim 1 , comprising lithium metal which is configured to plate onto a negative electrode current collector during charging.