PATENT DOCUMENT

Publication Number: US-11908998-B2
Application Number: US-202016922332-A
Country: US
Kind Code: B2

Title: Liquid electrolyte for lithium metal battery

Abstract:
Liquid electrolytes for a lithium metal battery comprise an aprotic solvent, an ionic liquid, a lithium salt, 8 mol % to 30 mol % hydrofluoroether and up to 5 mol % additives. A molar ratio of the hydrofluoroether to the lithium salt is 0.22:1 to 0.83:1. The liquid electrolytes achieve at least a 50% improvement in cycle life over conventional electrolytes, extend capacity retention and delay increases in internal resistance.

Claims:
What is claimed is: 
     
       1. A liquid electrolyte for a lithium metal battery, having the following composition:
 LiF SI; 
 PYR 13 FSI; 
 DMC; and 
 13 mol %-21 mol % BTFE, wherein a molar ratio of BTFE to LiFSI is 0.22:1 to 0.83:1, a molar ratio of BTFE to DMC is 0.1:1 to 1:1, and a molar ratio of BTFE to a total of DMC and PYR 13 FSI is 0.15:1 to 0.5:1. 
 
     
     
       2. The liquid electrolyte of  claim 1 , having the following composition:
   30 mol % LiFSI+8 mol % PYR 13 FSI+45 mol % DMC+17 mol % BTFE. 
 
     
     
       3. The liquid electrolyte of  claim 1 , wherein the LiFSI is 29 mol % of the liquid electrolyte. 
     
     
       4. The liquid electrolyte of  claim 1 , wherein the PYR 13 FSI is 8 mol % of the liquid electrolyte. 
     
     
       5. The liquid electrolyte of  claim 1 , wherein the DMC is 44 mol % of the liquid electrolyte. 
     
     
       6. The liquid electrolyte of  claim 1 , wherein the BTFE is 19 mol % of the liquid electrolyte. 
     
     
       7. The liquid electrolyte of  claim 1 , having the following composition:
   29 mol % LiFSI+7 mol % PYR 13 FSI+44 mol % DMC+20 mol % BTFE. 
 
     
     
       8. The liquid electrolyte of  claim 1 , having the following composition:
   31 mol % LiFSI+9 mol % PYR 13 FSI+46 mol % DMC+14 mol % BTFE. 
 
     
     
       9. The liquid electrolyte of  claim 1 , wherein the molar ratio of the BTFE to the LiFSI is 0.22:1 to 0.7:1. 
     
     
       10. A lithium metal battery, comprising:
 a cathode having a cathode current collector and a cathode active material comprising a lithium transition metal oxide; 
 an anode having an anode current collector and an anode active material comprising lithium metal; and 
 the liquid electrolyte of  claim 1 .

Description:
CROSS-REFERENCE TO RELATED APPLICATION 
     This application claims priority to Provisional Application Ser. No. 62/901,982, filed on Sep. 18, 2019, the entirety of which is hereby incorporated by reference. 
    
    
     TECHNICAL FIELD 
     This application generally relates to a liquid-based electrolyte for lithium metal batteries comprising both ionic liquid and a hydrofluoroether, resulting in improved cell performance. 
     BACKGROUND 
     Lithium metal batteries have received significant attention as advanced high-performance next generation batteries. However, these high voltage rechargeable batteries can face performance obstacles due at least in part to high reactivity between the battery components and traditional electrolytes. For example, the thermodynamic instability of lithium metal can cause irreversible and continuous reactions between lithium metal and the electrolyte that generate thick solid electrolyte interphase (SEI) layers on the lithium metal surface, consume lithium and electrolyte, and increase the internal resistance, thus shortening cycle life. Large volumetric changes can occur in the lithium metal anode during repeated cycling, but the aforementioned SEI films can be too frail to fully suppress such significant changes in the lithium metal electrode. The resulting structural instability limits the applications of these batteries. 
     SUMMARY 
     The disclosed embodiments provide a liquid electrolyte for a lithium metal battery. One embodiment of a liquid electrolyte for a lithium metal battery comprises an aprotic solvent, an ionic liquid, a lithium salt, 8 mol % to 30 mol % hydrofluoroether and up to 5 mol % additives. A ratio of the hydrofluoroether to the lithium salt is 0.22:1 to 0.83:1. 
     In some embodiments, the ratio of the hydrofluoroether to the lithium salt is 0.22:1 to 0.7:1. 
     In some embodiments, a ratio of the hydrofluoroether to the aprotic solvent is 0.1:1 to 1:1. 
     In some embodiments, the ratio of the hydrofluoroether to solvent is 0.15:1 to 0.5:1, wherein the solvent is the aprotic solvent and the ionic liquid. 
     In some embodiments, a ratio of hydrofluoroether to the ionic liquid is 0.5:1 to 10:1. 
     The aprotic solvent can be a linear carbonate, a cyclic carbonate, or a linear ether selected from the group consisting of monoglyme, diglyme, triglyme, tetraglyme, a cyclic ether or a cyclic acetal. 
     In some embodiments, the aprotic solvent is dimethyl carbonate (DMC). 
     The hydrofluoroether can be 1,1,2,2-tetrafluoroethyl-2,2,3,3-tetrafluoropropyl ether (TTE), bis(2,2,2-trifluoroethyl) ether (BTFE), 1,1,2,2-tetrafluoroethyl-2,2,2-trifluoroethyl ether (TFTFE), tris(hexafluoroisopropyl) phosphate, tris(2,2,2-trifluoroethyl) borate, or any combination thereof. 
     In some embodiments, the hydrofluoroether is BTFE. 
     The ionic liquid can be N-propyl-N-methylpyrrolidinium bis(fluorosulfonyl)imide (PYR 13 FSI), N-butyl-N-methylpyrrolidinium bis(fluorosulfonyl)imide (PYR 14 FSI); N-propyl-N-methylpyrrolidinium bis(trifluoromethanesulfonyl)imide (PYR 13 TFSI); or N-butyl-N-methylpyrrolidinium bis(trifluoromethanesulfonyl)imide (PYR 14 TFSI), as well as other lithium compatible ionic liquids. 
     The lithium salt can be lithium bis(fluorosulfonyl)imide (LiFSI), lithium bis(trifluoromethanesulfonyl)imide (LiTFSI), and lithium bis(pentafluoroethanesulfonyl)imide (LiBETI). 
     In one embodiment, the aprotic solvent is DMC, the ionic liquid is PYR 13 FSI, the lithium salt is LiFSI, and the hydrofluoroether is BTFE, the liquid electrolyte having the following composition: 29 mol % LiFSI+7 mol % PYR 13 FSI+44 mol % DMC+20 mol % BTFE. 
     Also disclosed is a lithium metal battery having a cathode, an anode and the liquid electrolytes disclosed herein. 
    
    
     
       BRIEF DESCRIPTION OF THE DRAWINGS 
         FIG.  1 A  is a graph of the discharge capacity versus number of cycles comparing a cell using a liquid electrolyte without a hydrofluoroether and cells using liquid electrolytes with hydrofluoroether. 
         FIG.  1 B  is a graph of the direct current internal resistance (DCIR) versus number of cycles comparing the cell using the liquid electrolyte without a hydrofluoroether and the cells using the liquid electrolytes with hydrofluoroether. 
         FIG.  2    is a cross-section view of a lithium metal battery as disclosed herein. 
     
    
    
     DETAILED DESCRIPTION 
     Liquid electrolytes for lithium metal batteries should be chemically compatible with metallic lithium, allow for cell reversibility utilizing a suitable cathode material, be thermodynamically stable at high voltage, and be non-flammable. However, conventional liquid electrolytes fail to provide one or more of these requirements. In some cases, high reactivity between the battery components and traditional electrolytes results in structural instability and cathode/electrolyte interface degradation. Transition metal cathode materials, for example, can have catalytically active surfaces that promote the decomposition of conventional electrolytes, resulting in corrosive species that structurally degrade the cathode material. 
     Conventional organic solvent electrolytes, for example, are not thermodynamically stable at high voltages. Ether electrolytes may decompose at the cathode above 4V and carbonate electrolytes can be unstable with the lithium anode material at any voltage. Organic solvent electrolytes can also have low flash points. As an example, 1,2-dimethyoxyethane (DME) has a flash point of −2° C. and dimethyl carbonate (DMC) has a flash point of 17° C. The flash points of organic solvents improve when lithium salt is added, but still do not reach non-flammable ratings. As examples, DME with 10 mol % LiFSI has a flash point of less than 25° C. and DME with 40 mol % LiFSI has a flash point of less than 40° C. 
     Disclosed herein are liquid electrolytes for lithium metal batteries that are chemically compatible with the anode material, are non-flammable, are thermodynamically stable at voltages over 4V, suppress the instability of the cathode material and suppress the decomposition of the electrolyte. The liquid electrolytes disclosed herein achieve at least a 50% improvement in cycle life over known electrolytes, extend capacity retention and delay increases in internal resistance. 
     One embodiment of a liquid electrolyte for a lithium metal battery comprises an aprotic solvent, an ionic liquid compatible with lithium metal, a lithium salt, 8 mol % to 30 mol % hydrofluoroether and up to 5 mol % additives. A molar ratio of the hydrofluoroether to the lithium salt is 0.22:1 to 0.83:1, and more particularly, 0.22:1 to 0.7:1. All ranges disclosed herein are inclusive. 
     The molar ratio of the hydrofluoroether to the aprotic solvent can be 0.1:1 to 1:1, more particularly 0.15:1 to 0.8:1, and even more particularly 0.15:1 to 0.5:1. In some embodiments, the molar ratio of the hydrofluoroether to solvent can be 0.1:1 to 0.8:1, and more particularly 0.15:1 to 0.5:1. “Solvent” here refers to the total of both the aprotic solvent and the ionic liquid. In some embodiments, a molar ratio of hydrofluoroether to the ionic liquid is 0.5:1 to 10:1. 
     The lithium ion, its anion, the ionic liquid cation, and its anion are solvated to form a complex such that the aprotic solvent is bound in the mixture, resulting in high flash points even when aprotic solvents with low flash points are used. The ionic liquid is a salt, yet already molten. The ionic liquid and the aprotic solvent are very miscible with each other, resulting in their particular solvation interaction. The cell reversibility is significantly improved with these electrolytes due to the ability of the mixture to solvate unusually high salt content. The ionic liquid, which is typically non-flammable and chemically compatible with lithium metal, increases the flash point of the electrolyte while improving the cell stability. Although ionic liquids have limited transport properties, the large amount of lithium salt in the electrolyte negates these limited properties. As the lithium salt content increases, the viscosity of the ionic liquid increases and cell wetting decreases. The mixture of the ionic liquid and the aprotic solvent balances out the viscosity. 
     The addition of the hydrofluoroether, in part, improves the wettability of the liquid electrolyte as the lithium salt is not very soluble in the hydrofluoroether. It is believed that the relationship between the high molarity lithium salt component and the low molarity hydrofluoroether component, in combination with the stabilizing ionic liquid and the aprotic solvent, is the key to the improved performance metrics realized in test cells using the liquid electrolyte. The performance metrics fall off when the hydrofluoroether:lithium salt ratio falls outside of the 0.22:1 to 0.83:1 range, and more particularly, outside of the 0.22:1 to 0.7:1 range. 
     The hydrofluoroether can be, but is not limited to, 1,1,2,2-tetrafluoroethyl-2,2,3,3-tetrafluoropropyl ether (TTE), bis(2,2,2-trifluoroethyl) ether (BTFE), 1,1,2,2-tetrafluoroethyl-2,2,2-trifluoroethyl ether (TFTFE), and any combination thereof. As used herein, the term hydrofluoroether also includes tris(hexafluoroisopropyl) phosphate, tris(2,2,2-trifluoroethyl) borate and other like heteroatom-centered hydrofluoroether functionalized compounds. 
     The aprotic solvent can be one or more of a linear carbonate, a cyclic carbonate, or a linear ether selected from the group consisting of monoglyme, diglyme, triglyme and tetraglyme, a cyclic ether such as dioxane (DIOX) or a cyclic acetal such as dioxolane (DOL). As non-limiting examples, DME, ethyl methyl carbonate (EMC), DMC, and diethyl carbonate (DEC) are suitable aprotic organic solvents. 
     The ionic liquid should be compatible with the lithium anode. Examples include N-ethyl-N-methylpyrrolidinium bis(fluorosulfonyl)imide (PYR 12 FSI), N-propyl-N-methylpyrrolidinium bis(fluorosulfonyl)imide (PYR 13 FSI), N-butyl-N-methylpyrrolidinium bis(fluorosulfonyl)imide (PYR 14 FSI); N-propyl-N-methylpyrrolidinium bis(trifluoromethanesulfonyl)imide (PYR 13 TFSI); or N-butyl-N-methylpyrrolidinium bis(trifluoromethanesulfonyl)imide (PYR 14 TFSI). Other ionic liquids compatible with lithium can also be used, such as, but not limited to, tetrafluoroborate (BF 4 ), hexafluorophosphate (PF 6 ), triflate (OTf) and bis(pentafluoroethanesulfonyl)imide (BETI) and phosphonium or ammonium cations. Ionic liquids such as imidazolium are not compatible with the lithium anode. 
     The lithium salt should not be sensitive to moisture so that it does not break down. The lithium salt should have weakly coordinating anions and be hydrolytically stable. Non-limiting examples of the lithium salt is lithium bis(fluorosulfonyl)imide (LiFSI), lithium bis(trifluoromethanesulfonyl)imide (LiTFSI), and lithium bis(pentafluoroethanesulfonyl)imide (LiBETI). One or a combination of lithium salts can be used. 
     The additives are those known to the skilled artisan that may be used to improve electrolyte performance by improving, for example, the electrolyte conductivity or thermal stability. Non-limiting examples include vinylene carbonate, vinyl ethylene carbonate and lithium salts such as LiF and LiNO 3 . 
     In some embodiments, the aprotic solvent is DMC, the ionic liquid is PYR 13 FSI, the lithium salt is LiFSI, and the hydrofluoroether is BTFE, the liquid electrolytes having the following compositions:
 
30 mol % LiFSI+8 mol % PYR 13 FSI+45 mol % DMC+17 mol % BTFE;
 
31 mol % LiFSI+9 mol % PYR 13 FSI+46 mol % DMC+14 mol % BTFE;
 
29 mol % LiFSI+7 mol % PYR 13 FSI+44 mol % DMC+20 mol % BTFE.
 
     Some other embodiments have BTFE between 13 mol % and 21 mol %, inclusive, with the other elements adjusting to accommodate while maintaining the molar ratios of hydrofluoroether to lithium salt of 0.22:1 to 0.83:1; hydrofluoroether to aprotic solvent of 0.1:1 to 1:1; and hydrofluoroether to solvent of 0.15:1 to 0.5:1. 
     The liquid electrolytes disclosed herein can improve the cycle life of a battery cell by 50% or more, can extend capacity retention and can delay DCIR increase.  FIGS.  1 A and  1 B  are graphs illustrating the improved cell performance.  FIGS.  1 A and  1 B  compare performance of a cell using a liquid electrolyte without a hydrofluoroether to cells using liquid electrolytes as disclosed herein. In particular, the two liquid electrolytes used to achieve the cell performance shown in  FIGS.  1 A and  1 B  have the following compositions. The electrolyte with 14 mol % BTFE has the following composition:
 
31 mol % LiFSI+9 mol % PYR 13 FSI+46 mol % DMC+14 mol % BTFE.
 
The molar ratio of hydrofluoroether to lithium salt is 0.45:1. The ratio of hydrofluoroether to aprotic solvent is 0.30. The ratio of hydrofluoroether to total solvent is 0.25. The ratio of hydrofluoroether to ionic liquid is 1.56. The electrolyte with 20 mol % BTFE has the following composition:
 
29 mol % LiFSI+7 mol % PYR 13 FSI+44 mol % DMC+20 mol % BTFE.
 
The molar ratio of hydrofluoroether to lithium salt is 0.69:1. The ratio of hydrofluoroether to aprotic solvent is 0.46:1. The ratio of hydrofluoroether to total solvent is 0.39. The ratio of hydrofluoroether to ionic liquid is 2.86. The 12 cm 2  cell used a 10 μm lithium metal anode, 14 μm ceramic coated polyethylene and 39 μm LiCoO 2  cathode. The cycle test was performed at 4.25-3.0V; C/5 discharge in cycles 1, 10, 30, 50, 70, etc.; C/10 discharge in cycles 20, 40, 60, 80, etc.; C/2 discharge in all other cycles; and C/7 charge for all cycles.
 
       FIG.  1 A  graphs discharge capacity against number of cycles. The cell using the liquid electrolyte without the hydrofluoroether only achieved about 360 cycles with 80% capacity retention or higher while the cell using the liquid electrolyte with 14% hydrofluoroether as disclosed herein achieved about 630 cycles with 80% capacity retention or higher and the cell using the liquid electrolyte with 20% hydrofluoroether as disclosed herein achieved about 900 cycles with 80% capacity retention or higher. 
       FIG.  1 B  graphs DCIR against number of cycles. The cell using the liquid electrolyte without the hydrofluoroether saw a DCIR increase (above 2.5 ohms) at about 340 cycles while the cell using the liquid electrolyte with 14% hydrofluoroether as disclosed herein did not see the DCIR increase to over 2.5 ohms until about 600 cycles and the cell using the liquid electrolyte with 20% hydrofluoroether as disclosed herein did not see the DCIR increase to over 2.5 ohms until about 800 cycles. 
     An aspect of the disclosed embodiments is a lithium metal battery  200 , the layers of which are shown in cross-section in  FIG.  2   . The lithium metal battery  200  has an anode  202  with an anode current collector  204  and an anode active material  206  disposed on the anode current collector  204 . The lithium metal battery  200  also has a cathode  208  with a cathode current collector  210  and a cathode active material  212  disposed over the cathode current collector  210 . The cathode  208  and the anode  202  are separated by a separator  214  and the liquid electrolyte disclosed herein. 
     The cathode current collector  210  can be, for example, an aluminum sheet or foil. Cathode active materials  212  can include one or more lithium transition metal oxides which can be bonded together using binders and optionally conductive fillers such as carbon black. Lithium transition metal oxides can include, but are not limited to, LiCoO 2 , LiNiO 2 , LiNi 0.8 Co 0.15 Al 0.05 O 2 , LiMnO 2 , Li(Ni 0.5 Mn 0.5 )O 2 , LiNi x Co y Mn 2 O 2 , Spinel Li 2 Mn 2 O 4 , LiFePO 4  and other polyanion compounds, and other olivine structures including LiMnPO 4 , LiCoPO 4 , LiNi 0.5 Co 0.5 PO 4 , and LiMn 0.33 Fe 0.33 Co 0.33 PO 4 . As needed, the cathode active material  212  can contain an electroconductive material, a binder, etc. 
     The anode active material  206  can comprise at least one selected from the group consisting of a metal material, an alloy material and a carbonaceous material. The anode active material  206  is not particularly limited, and can comprise lithium metals, lithium alloys, lithium-containing metal oxides, lithium-containing metal sulfides, lithium-containing metal nitrides, carbonaceous materials such as graphite, etc. The anode current collector  204  can be a copper or nickel sheet or foil, as a non-limiting example. 
     The separator  214  may be a single layer or multi-layer of polyethylene, polypropylene, and polyvinylidene fluoride, as non-limiting examples. 
     The foregoing descriptions of various embodiments have been presented only for purposes of illustration and description. They are not intended to be exhaustive or to limit the present invention to the forms disclosed. Accordingly, many modifications and variations will be apparent to practitioners skilled in the art.

Metadata:
Filing Date: 20200707
Publication Date: 20240220
Grant Date: 20240220
Priority Date: 20190918
Inventors: RITCHIE, ALAN A.
NEUDECKER, Bernd Jurgen
BROWN, KARL M.
BASILE, Andrew
Assignee: APPLE INC
CPC Classifications: [{"code": "H01M10/0567", "inventive": true, "first": true, "tree": "[]"}, {"code": "H01M4/382", "inventive": true, "first": false, "tree": "[]"}, {"code": "H01M4/485", "inventive": true, "first": false, "tree": "[]"}, {"code": "H01M10/052", "inventive": true, "first": false, "tree": "[]"}, {"code": "H01M10/0568", "inventive": true, "first": false, "tree": "[]"}, {"code": "H01M10/0569", "inventive": true, "first": false, "tree": "[]"}, {"code": "H01M2300/0025", "inventive": false, "first": false, "tree": "[]"}, {"code": "H01M10/0567", "inventive": true, "first": true, "tree": "[]"}, {"code": "H01M10/0567", "inventive": true, "first": true, "tree": "[]"}, {"code": "H01M10/0568", "inventive": true, "first": false, "tree": "[]"}, {"code": "H01M10/0569", "inventive": true, "first": false, "tree": "[]"}, {"code": "H01M10/052", "inventive": true, "first": false, "tree": "[]"}, {"code": "H01M2300/0028", "inventive": false, "first": false, "tree": "[]"}, {"code": "H01M2300/0045", "inventive": false, "first": false, "tree": "[]"}, {"code": "Y02E60/10", "inventive": false, "first": false, "tree": "[]"}, {"code": "H01M10/0569", "inventive": true, "first": false, "tree": "[]"}, {"code": "H01M10/052", "inventive": true, "first": false, "tree": "[]"}, {"code": "H01M2300/0025", "inventive": false, "first": false, "tree": "[]"}, {"code": "H01M4/485", "inventive": true, "first": false, "tree": "[]"}, {"code": "H01M10/0568", "inventive": true, "first": false, "tree": "[]"}, {"code": "H01M4/382", "inventive": true, "first": false, "tree": "[]"}]
Family ID: 74868096