Patent Application
20150056488
With the increasing demand, the escalating supply issues, the higher prices, and the environmental concerns associated with fossil fuels, electrical-energy generating devices and energy storage devices (e.g., fuel cells, batteries, and capacitors) with substantially higher energy and power densities and faster recharge times are urgently needed in almost all applications, including, mobile, transportation, and grid applications. The state-of-the-art batteries, including lithium-ion batteries, for mobile electronic devices in the present commercial market cannot meet the requirements. Lithium metal batteries are very attractive due to the use of high capacity lithium metal as anodes. However, even the use of most polymer electrolytes still cannot prevent the lithium dendrite penetration through the polymer electrolytes. Thus, solving or reducing the safety problem of dendrite formation, of battery cyclability and safety, and of low Coulombic efficiency of metal deposition will enable the practical use of rechargeable metal polymer batteries and accelerate the commercialization of high-energy and high-power metal-ion and metal batteries for commercial applications, including commercial electronics, electrical vehicles, and grid energy storages.
Therefore, a need for improved dendrite-free metal polymer energy storage devices with high Coulombic efficiency and/or fewer safety hazards exists.
Disclosed herein is an energy storage device comprising an anode and a first metal (M1) electrodeposited on the anode during operation of the device, the energy storage device characterized by an electrolyte composition comprising a polymer, cations of M1 and by a surface-smoothing additive comprising a metal (M2), cations of M2 having an effective electrochemical reduction potential in solution or in polymer lower than that of the cations of M1.
Also disclosed herein is an energy storage device comprising an anode and lithium metal electrodeposited on the anode during operation of the device, the energy storage device characterized by an electrolyte composition comprising a polymer, lithium cations and a surface-smoothing additive comprising a metal (M2), cations of M2 having a concentration in solution less than 30% of that of the lithium cations and having an effective electrochemical reduction potential in solution lower than that of the lithium cations.
Further disclosed herein is an electrolyte composition for enhancing surface smoothness during electrodeposition of a metal (M1) on an anode that occurs when operating an energy storage device, the electrolyte composition characterized by a polymer, cations of M1 and by a surface-smoothing additive comprising a metal (M2), cations of M2 having an effective electrochemical reduction potential in solution or polymer lower than that of the cations of M1.
The foregoing will become more apparent from the following detailed description, which proceeds with reference to the accompanying figures.
This invention describes polymer electrolyte compositions, which can suppress dendrite growth, retain high Coulombic efficiency of metal deposition/stripping, and/or reduce device flammability. The electrolyte composition comprises a mixture of appropriate polymers or by adding appropriate SEI formation additives to form high quality SEI layers on the metal anode surface and to limit reactions between the metal and the electrolyte constituents. The electrolyte composition further comprises self-healing electrostatic shield (SHES) additives to prevent dendrite formation and growth on the metal or graphite anodes during long-term charge/discharge processes and other extreme charging conditions.
The SHES mechanism is illustrated in U.S. Application Publication US 2013/0202956 A1 and in Journal of the American Chemical Society, 2013, 135(11), pp4450-4456, both of which are incorporated herein by reference. In general, M1 cations can be any cations that have an effective electrochemical reduction potential less than those of selected M2 cations, which SHES additives comprise. In one embodiment, the M1 cation comprises lithium cations (e.g., Li+) and the SHES additive can comprise an additive metal (M2) salt containing M2 cations that are not substantially reactive with anodes and cathode through intercalation, alloying, or conversion reactions. The M2 cations of the additive salt can be preferentially adsorbed, but cannot be deposited on the protruded region of the lithium anode surface and, can form a positively charged SHES layer that covers the protruded region. During the charging process, the Li+ ions will be prevented from depositing in the protruded region of the anode by the SHES effect; instead, they will be preferentially deposited onto the non-protruded region. This self-smoothing process will effectively improve the smoothness of the deposited lithium film. In addition, by choosing appropriate polymers and/or additives for forming good solid electrolyte interphase (SEI) layers, and by optimizing the electrolyte formulations, high Coulombic efficiency of lithium metal deposition/stripping can be achieved. Thus practical rechargeable lithium metal batteries with significantly improved safety and long-term cycle life can be realized.
SHES additive salts can comprise M2 cations that include, but are not limited to Cs, Rb, K, Ba, Sr, Ca, Li, Na, Mg, Al, La, and Eu. The preferred cation is Cs. The salts can comprise anions that include, but are not limited to PF6−, AsF6−, BF4−, AlF4−, N(SO2CF3)2− (TFSI−), N(SO2F)2− (FSI−), CF3SO3− (TO , ClO4−, bis(oxalate)borate (BOB−), difluoro oxalato borate (DFOB−), F−, Cl−, Br−, I−, and combinations thereof.
The selected polymer electrolytes have much less side reaction in contact with Li metal and can significantly diminish the flammability problem common to lithium energy storage devices. Examples of appropriate polymers include, but are not limited to, hexafluopropylene (PVdF-co-HFP), polyethylene glycol (PEG), polyethylene oxide (PEO), poly(methyl methacrylate) (PMMA), poly(acrylonitrile) (PAN), copolymers such as poly(ethylene oxide-propylene oxide) (PEO-co-PPO), vinylidene fluoride and hexafluopropylene (PVdF-co-HFP), and block copolymers such as poly(methyl methacrylate)-b-poly(oligo(oxyethylene) methacrylate) (PMMA-b-POEM), poly(ethylene oxide) and polystyrene (PS) (PEO-b-PS). The electrolyte composition can alternatively comprise gel polymers. Examples of gel polymers include, but are not limited to, combinations of liquid electrolytes and polymers, copolymers, or block polymers. In certain embodiments, the gel polymer has a liquid electrolyte solution soaked in a material selected from the group consisting of polyethylene glycol (PEG), polyethylene oxide (PEO), poly(methyl methacrylate) (PMMA), poly(acrylonitrile) (PAN), copolymers, block copolymers, and combinations thereof. “Soaked” means that the liquid electrolyte is confined inside the polymer, and the liquid does not flow freely thus avoiding leakage of the liquid electrolyte. The solvent and solute of the liquid electrolyte are described, for example, in US 2013/0202956 A1, which is incorporated herein by reference. Further still, the addition of SEI formation additives can help to form high quality SEI layers on the lithium anode surface. Examples of SEI formation additives include, but are not limited to vinylene carbonate, fluoroethylene carbonate, vinyl ethylene carbonate, 4-methylene ethylene carbonate, water, and combinations thereof. In certain embodiments the SEI formation additive is water.
The preferable amount of polymer is 5-95% by weight, more preferably 20-80 wt%, and most preferably 40-70 wt%, based on the total weight of the electrolyte composition. The preferable amount of M1 salt is 5-50 wt%, more preferably 10-40 wt%, and most preferably 15-30 wt%, based on the total weight of the electrolyte composition. The SHES additive is preferably 1-30 wt%, more preferably 2-20 wt%, and most preferably 3-10 wt%, based on the total weight of the electrolyte composition. The SEI formation additive (except for water) is preferably 1-20 wt%, more preferably 2-15 wt%, and most preferably 3-10 wt%, based on the total weight of the electrolyte composition.
In the case where water is used as the SEI formation additive, the water amount is up to 100 ppm in the electrolyte composition.
The electrolyte composition may also include an aprotic solvent. Illustrative aprotic solvents include carbonates, carboxylates, ethers, lactones, sulfones, phosphates, phosphites, nitriles, and combinations thereof.
Protrusions or dendrites 6 of M1 will form, but they will be smoothed as described above.
For use as a control sample, 0.8 g PEO (Mw, 160,000) and 0.3 g LiTFSI were mixed in 25 ml acetonitrile. No surface-smoothing additive was used. After dissolution, the homogeneous solution was poured into a PTFE disk. The solvent acetonitrile was vaporized overnight at room temperature, followed by vacuum drying at 110° C., resulting in a thin polymer electrolyte film with thickness approximately equal to 200 μm. The Li salt concentration was 27.3% by weight, or [Li+]/[EO]=1/17.3 by molar ratio where EO is the repeating ethyleneoxy unit in PEO. All processes were carried out in a glove box filled with purified argon and with a moisture and oxygen content less than 1 ppm.
Li symmetric cells were assembled in an argon-filled glove box and Li deposition and stripping were measured at 80° C. with current density of 0.5 mA/cm2. The time for each deposition or stripping process was 1 hour and the voltage versus time was measured.
In a first embodiment, 0.8g PEO (Mw, 160,000) and 0.3g LiTFSI and 0.03g CsTFSI was mixed in 25 ml acetonitrile. After dissolution, the homogeneous solution was poured into a PTFE disk. The solvent acetonitrile was vaporized overnight at room temperature, followed by vacuum drying at 110° C., resulting in a thin polymer electrolyte film with thickness approximately equal to 200 pm. The Li salt concentration was 26.5% by weight and Cs salt concentration was 2.7% by weight, or [Li+]/[EO]=1/17.3 by molar ratio where EO is the repeating ethyleneoxy unit in PEO and the weight ratio of Cs salt and Li salt was 1:10. All processes were carried out in a glove box filled with purified argon and with a moisture and oxygen content less than 1 ppm.
Li symmetric cells were assembled in an argon-filled glove box and lithium deposition and stripping were conducted at 80° C. with current density of 0.5 mA/cm2. The time for each deposition or stripping was 1 hour and the voltage versus time was measured.
Compared to liquid electrolytes, polymer electrolytes can be thermodynamically more stable with fresh lithium according to embodiments described herein. In other words, during lithium deposition and stripping, a liquid electrolyte such as ethylene carbonate (EC), propylene carbonate (PC), dimethyl carbonate (DMC), ethyl methyl carbonate (EMC), or diethyl carbonate (DEC) can react with fresh lithium to form an SEI (solid electrolyte interface) that consumes both liquid electrolyte and lithium metal, leading to relatively low Coulombic efficiency. In contrast, polymers such as PEO can be stable with fresh lithium. There is little or no interfacial reaction during lithium deposition and stripping. Therefore, lithium dendrite-free deposition with high Coulombic efficiency (which are basic requirements for long-cycle-life battery using lithium metal as anodes) can be obtained from polymer electrolyte containing M2 additive, as described herein, to effectively suppress lithium dendrite formation and growth.
The purpose of the foregoing description is to enable the United States Patent and Trademark Office and the public generally, especially the scientists, engineers, and practitioners in the art who are not familiar with patent or legal terms or phraseology, to determine quickly from a cursory inspection the nature and essence of the technical disclosure of the application. The summary is neither intended to define the invention of the application, which is measured by the claims, nor is it intended to be limiting as to the scope of the invention in any way.
Various advantages and novel features of the present invention are described herein and will become further readily apparent to those skilled in this art from the following detailed description. In the preceding descriptions, the various embodiments, including the preferred embodiments, have been shown and described. Included herein is a description of the best mode contemplated for carrying out the invention. As will be realized, the invention is capable of modification in various respects without departing from the invention. Accordingly, the drawings and description of the preferred embodiments set forth are to be regarded as illustrative in nature, and not as restrictive.
While a number of embodiments of the present invention have been shown and described, it will be apparent to those skilled in the art that many changes and modifications may be made without departing from the invention in its broader aspects. The appended claims, therefore, are intended to cover all such changes and modifications as they fall within the true spirit and scope of the invention.
This application claims the benefit of U.S. Provisional Patent Application No. 61/856,932, filed Jul. 22, 2013, which is hereby incorporated by reference.
This invention was made with government support under Contract DE-AC0576RLO1830 awarded by the U.S. Department of Energy. The government has certain rights in the invention.
| Number | Date | Country | |
|---|---|---|---|
| 61856932 | Jul 2013 | US |
