Patent Application
20250006979
This disclosure relates to liquid electrolyte formulations for lithium-ion batteries having a functionalized additive containing silicon for a stable cathode-electrolyte-interface (CEI).
A conventional electrolyte formulation for a lithium-ion battery will include a lithium salt such as LiPF6 and a carbonate-based solvent. When a small amount of water is naturally introduced to the battery, the water reacts with the salt, forming hydrogen fluoride, which reacts with the transition metals in the cathode active material. This is particularly pervasive when the cathode active material includes nickel. The nickel is pulled into the electrolyte, decreasing the cell capacity.
Although nickel-rich cathode active materials are of interest owing to their high specific capacities, nickel-rich cathode active material faces other challenges. It is challenging to stabilize the nickel-rich cathode interface over long-term cycling, due in part to parasitic reactions, including electrolyte permeation, which results in the growth of impedance and capacity decay.
Disclosed herein are implementations of lithium-ion batteries that incorporate one or more electrolyte additives that are specifically functionalized with a five member ring with a silicon heteroatom to organically create a physical barrier on the cathode surface. The physical barrier is a protective, uniform film that improves the interface stability, inhibits the decomposition of the electrolyte, inhibits the side reactions at the interface, scavenges hydrogen fluoride and/or water, with hydrogen fluoride quenching preferred, and oxidizes before the electrolyte solvents.
One implementation of a lithium-ion battery as disclosed has anode active material, nickel-based cathode active material, and an electrolyte. The electrolyte has the following formulation: a carbonate-based solvent; LiPF6; vinylene carbonate; and an additive that satisfies the following: less than or equal to nine carbons; at least one unsaturated bond; a predicted oxidation potential Vox of 2.0<Vox<4.5; and a five membered ring with a silicon heteroatom.
Another implementation of a lithium-ion battery as disclosed herein has anode active material, nickel-based cathode active material, and an electrolyte. The electrolyte has a solvent, a lithium salt, vinylene carbonate, and one or more additives. Each additive has: less than or equal to nine carbons; at least one unsaturated bond; a predicted oxidation potential Vox of 2.0<Vox<4.5; and atoms selected from the group consisting of: C; H; O; N; S and Si.
Also disclosed is a liquid electrolyte for a lithium-ion battery, comprising one or more additives selected from the group consisting of:
The disclosure is best understood from the following detailed description when read in conjunction with the accompanying drawings. It is emphasized that, according to common practice, the various features of the drawings are not to-scale. On the contrary, the dimensions of the various features are arbitrarily expanded or reduced for clarity.
A conventional electrolyte formulation for a lithium-ion battery will include a lithium salt such as LiPF6 and a carbonate-based solvent. When a small amount of water is naturally introduced to the battery, the LiPF6 may undergo a series of side reactions:
LiPF6LiF+PF5
LiPF6+H2O→LiF+HF+POF3
PF5+H2O→POF3+2HF
POF3+H2O→HPO2F2+HF
The hydrogen fluoride reacts with the cathode active material, releasing the transition metals into the electrolyte. Additives that scavenge hydrogen fluoride alone do not eliminate the problem, but rather reduce the hydrogen fluoride's negative impact.
High energy batteries will increasingly depend on layered oxides, with the amount of nickel in the layered oxides growing. Due to the cost and depleting reserves of cobalt, cathode active materials with diminished mole ratios of cobalt, or no cobalt altogether, have been developed. Nickel-rich NMC cathode active materials often have the formula LiNixM1-xO2, where x≥0.6 and M=Mn, Co, and sometimes Al. Manganese and aluminum are essentially inactive, providing stability to the properties of the battery. The more nickel used, the greater the amount of lithium that can be cycled in and out of the cathode.
However, nickel-rich cathode active materials face challenges. Nickel-rich cathode active materials are particularly susceptible to the hydrogen fluoride scavenging, resulting in dramatically decreased cell capacity. It is challenging to stabilize the nickel-rich cathode interface over long-term cycling, due in part to parasitic reactions, including electrolyte permeation, which results in the growth of impedance and capacity decay. Providing a stable CEI interface can suppress the electrolyte decomposition, improve the interface stability, and alleviate transition metal ion dissolution.
There are conventional electrolyte additives that are used to address one or more of these issues. Often, multiple additives are used in a formulation, each selected for a particular role but having a limited impact. With each cathode additive needed in the formulation, issues with compatibility with the other electrolyte components such as solvents and anode additives, as well as compatibility with the anode material, may present a new set of problems.
The electrolyte formulations disclosed herein contain an electrolyte additive specifically functionalized to organically create a physical barrier on the cathode surface. The physical barrier is a protective, uniform film that improves the interface stability, inhibits the decomposition of the electrolyte, inhibits the side reactions at the interface, scavenges hydrogen fluoride and/or water, with hydrogen fluoride quenching preferred, and oxidizes before the electrolyte solvents.
The disclosed electrolyte additives are specifically formulated to improve the performance of nickel-based cathode active materials. Nickel-based cathode active materials include, but are not limited to, LiNiO2, Li(Ni0.5Mn0.5)O2, LiNixCoyMn2O2, LiNi0.5Co0.5PO4, and LiNi0.8Co0.15Al0.05O2. The nickel-based cathode active material can have the formula LiNixM1-xO2, where x≥0.6, and more particularly x≥0.8, and M=Mn, Co, and Al. As needed, the cathode active material can contain an electroconductive material, a binder, etc.
The disclosed electrolyte additives are also specifically formulated for lithium-ion batteries having an anode active material that is graphite or an anode active material that is a silicon-based material. The silicon-based material is not limited except to include some form of silicon or silicon alloy. Non-limiting examples of silicon-based anode material include Si, SiOx, and Si/SiOx composites. A conducting agent may be used. Further, one or more of a binder and a solvent may be used to prepare a slurry that is applied to a current collector, for example.
The electrolytes disclosed herein have the following formulation: a solvent; a lithium salt; vinylene carbonate (VC); and an additive that satisfies the following: less than or equal to nine carbons; at least one unsaturated bond; a predicted oxidation potential Vox of 2.0<Vox<4.5; and a five member ring with a silicon heteroatom. The additive will only have atoms selected from the group consisting of: C; H; O; N; S and Si. The electrolytes may only have one of the disclosed additives or may have more than one of the disclosed additives.
The term “formulation” as used herein indicates that the formulation consists of the named components. However, it is contemplated herein that the electrolytes disclosed herein may comprise additional components.
The electrolyte additives are formulated to work with a carbonate-based solvent and lithium hexafluorophosphate (LiPF6) as the lithium salt. In particular, the carbonate-based solvent can be one or more of ethylene carbonate (EC), diethyl carbonate (DEC), and fluoroethylene carbonate (FEC). The LiPF6 has a molar concentration of 0.5M to 3.0M.
The electrolyte additives disclosed herein have also been found to create the physical CEI barrier when used with one or both of dioxolane (DOL) and dimethoxyethane (DME) with one or both of lithium bis(fluorosulfonyl)imide (LiFSI) and lithium bis(trifluoromethanesulfonyl)imide (LiTFSI). The total lithium salt has a molar concentration of 0.5M to 3.0M.
The electrolyte additives disclosed herein work with the VC, an anode-directed additive, to enhance the durability of the battery while operating in a voltage range of 2.0 V to 5.0 V. The VC can be 0.5 wt % to 3.0 wt % of the electrolyte. VC has been shown to have a positive impact on the capacity retention and coulombic efficiency of anodes in lithium-ion batteries, particularly with silicon-based anode active material.
The electrolyte additive or additives are between 0.1 wt % and 10.0 wt % of the electrolyte, and more particularly between 0.5 wt % and 5.0 wt % of the electrolyte.
The electrolyte additives disclosed herein have a predicted oxidation potential of between 2.0 and 4.5, which falls within the typical battery operating voltage range. The electrolyte additives oxidize in the operating voltage range, with the oxidation products participating in the CEI formation. The electrolyte additives may have a lower oxidation potential than the electrolyte as a whole.
The electrolyte additives disclosed herein can be described as having the following composition, wherein R1-6 can be H or a C group optionally containing one or more of H, O, N and S:
The five member ring having the silicon heteroatom quenches hydrogen fluoride (HF) with the following reactions:
The electrolyte additive with the five member ring with the silicon heteroatom forms the CEI protective barrier by polymerizing the ethylene carbonate as shown below.
The attack on the carbonyl carbon occurs, with further polymerization by the Si—O center.
The electrolytes with the electrolyte additive formulations disclosed herein form a CEI during the first few cycles (i.e., less than 10) of the battery that is between 1 nm and 100 nm with very poor electron conductivity (i.e., less than 10-9 mS/cm). The CEI formed from polymerization of the electrolyte additives allows lithium ion penetration while preventing nickel dissolution and electrolyte oxidation. Hydrogen fluoride and/or water is scavenged, preventing HF attack.
Table 1 is a list of electrolyte additives.
A lithium-ion battery cell 100 is illustrated schematically in cross-section in
The cathode current collector 108 can be, for example, an aluminum sheet or foil. The anode current collector 110 can be a copper or nickel sheet or foil, as a non-limiting example. Examples of the separator are porous films of polyolefin such as polyethylene and polypropylene.
While the disclosure has been described in connection with certain embodiments, it is to be understood that the disclosure is not to be limited to the disclosed embodiments but, on the contrary, is intended to cover various modifications and equivalent arrangements included within the scope of the appended claims, which scope is to be accorded the broadest interpretation so as to encompass all such modifications and equivalent structures as is permitted under the law.
