Patent Application
20180342776
The present application claims priority to Korean Patent Application No. 10-2017-0063848 filed May 24, 2017, the entire contents of which is incorporated herein for all purposes by this reference.
The present invention relates to a sodium-air battery comprising a high-concentration electrolyte which can increase the chemical stability of a battery material and a discharge product in the sodium-air battery.
A lithium-air battery, which is receiving attention as a next-generation high-capacity battery, exhibits high energy density due to its use of oxygen which is lightweight. However, current lithium-air batteries have the low efficiency and reversibility thereof.
As an alternative thereto, Korean Patent Application Publication No. 10-2014-0144245 discloses a sodium-air battery. Unlike a lithium-air battery, a sodium-air battery produces a discharge product in the form of superoxide and has considerably low charge overvoltage, high efficiency and large capacity.
The sodium-air battery forms discharge products that are different than those initially reported. This may be due to the chemical sensitivity of a battery system. Since this has resulted in low efficiency, such sodium-air batteries have failed to meet expectations. Specifically, in recent theories, sodium superoxide, which is a discharge product of a sodium-air battery, may dissolve and dissociate in a liquid electrolyte and thus generate a sodium ion and an oxygen radical anion. The generated oxygen radical anion manifests high reactivity with the liquid electrolyte in the battery, like active oxygen, and consequently, side reactions in the battery may occur, thus forming byproducts. Such byproducts need high overvoltage upon charging compared to sodium superoxide, which is an initial discharge product. This is an undesirable for a sodium-air battery.
Thus, techniques for preventing the dissolution of sodium superoxide, which is a discharge product, and increasing chemical stability sodium superoxide to thus minimize side reactions in the battery are urgently needed.
The information disclosed in this Background of the Invention section is only for enhancement of understanding of the general background of the invention and may not be taken as an acknowledgement or any form of suggestion that this information forms the prior art already known to a person skilled in the art.
Various aspects of the present invention are directed to providing a sodium-air battery, which may prevent the dissolution and dissociation of a discharge product in a liquid electrolyte to thus exhibit superior chemical stability and high efficiency.
The aspect of the present invention is not limited to the foregoing, and will be able to be clearly understood through the following description and to be realized by the means described in the claims and combinations thereof.
Various aspects of the present invention are directed to providing a sodium-air battery, as described below.
The sodium-air battery according to an exemplary embodiment of the present invention comprises an anode comprising sodium, a cathode, and a liquid electrolyte. In various exemplary embodiments, the liquid electrolyte comprises an ether-based solvent and a sodium salt having a concentration of about 4 M or less but exceeding about 0.5 M (e.g., about 0.5 M, about 0.6 M, about 0.7 M, about 0.8 M, about 0.9 M, about 1 M, about 1.1 M, about 1.2 M, about 1.3 M, about 1.3 M, about 1.5 M, about 1.6 M, about 1.7 M, about 1.8 M, about 1.9 M, about 2 M, about 2.1 M, about 2.2 M, about 2.3 M, about 2.3 M, about 2.5 M, about 2.6 M, about 2.7 M, about 2.8 M, about 2.9 M, about 3 M, about 3.1 M, about 3.2 M, about 3.3 M, about 3.3 M, about 3.5 M, about 3.6 M, about 3.7 M, about 3.8 M, about 3.9 M, or about 4M.
In various exemplary embodiments of the present invention, the liquid electrolyte may include a sodium salt having a concentration from about 3 M to about 4 M (e.g., about 3 M, about 3.1 M, about 3.2 M, about 3.3 M, about 3.3 M, about 3.5 M, about 3.6 M, about 3.7 M, about 3.8 M, about 3.9 M, or about 4M).
In various exemplary embodiments of the present invention, the ether-based solvent may be selected from the group consisting of diethyleneglycol dimethylether (DEGDME), tetraethyleneglycol dimethylether (TEGDME), dimethoxyethane (DME) and combinations thereof.
In other exemplary embodiments of the present invention, the sodium salt may be selected from the group consisting of NaPF6, NaBF4, NaClO4, NaAsF6, NaCF3SO3, NaN(SO2F)2, Na2SiF6, NaSbF6, NaAlCl4 and combinations thereof.
In various exemplary embodiments of the present invention, the anode may be a sodium metal.
In various exemplary embodiments of the present invention, the cathode may comprise a carbon material, a binder, and a porous current collector.
In various exemplary embodiments of the present invention, the sodium-air battery may further comprise a separator interposed between the cathode and the anode to separate the cathode and the anode from each other.
The sodium-air battery according to an exemplary embodiment of the present invention may be a battery in which a discharge product, sodium superoxide (NaO2), is formed on the cathode upon discharging.
The sodium-air battery according to an exemplary embodiment of the present invention may be a battery in which a discharge product, sodium superoxide (NaO2), remains on the cathode for about 60 hr when the battery is allowed to stand in a discharged state.
The sodium-air battery according to an exemplary embodiment of the present invention may be a battery in which a byproduct, sodium peroxide dihydrate (Na2O2.2H2O), is not formed on the cathode upon discharging.
According to an exemplary embodiment of the present invention, a sodium-air battery can prevent sodium superoxide, which is a discharge product, from dissolving and dissociating in an electrolyte, whereby side reactions do not occur, thus realizing superior chemical stability and high efficiency.
Also, according to an exemplary embodiment of the present invention, a sodium-air battery can suppress side reactions, whereby the stability of an anode including sodium is improved, and shorting of the battery due to dendrites does not occur.
The effects of the present invention are not limited to the foregoing, and should be understood to incorporate all effects that can be reasonably inferred from the following description.
The methods and apparatuses of the present invention have other features and advantages which will be apparent from or are set forth in more detail in the accompanying drawings, which are incorporated herein, and the following Detailed Description, which together serve to explain certain principles of the present invention.
It may be understood that the appended drawings are not necessarily to scale, presenting a somewhat simplified representation of various features illustrative of the basic principles of the invention. The specific design features of the present invention as disclosed herein, including, for example, specific dimensions, orientations, locations, and shapes will be determined in part by the particularly intended application and use environment.
In the figures, reference numbers refer to the same or equivalent parts of the present invention throughout the several figures of the drawing.
It may be understood that the appended drawings are not necessarily to scale, presenting a somewhat simplified representation of various features illustrative of the basic principles of the invention. The specific design features of the present invention as disclosed herein, including, for example, specific dimensions, orientations, locations, and shapes will be determined in part by the particularly intended application and use environment.
In the figures, reference numbers refer to the same or equivalent parts of the present invention throughout the several figures of the drawing.
Hereinafter, a detailed description will be given of embodiments of the present invention. The embodiments of the present invention may be variously modified without changing the gist thereof, but are not to be construed as limiting the scope of the present invention.
In the following description of the present invention, it is to be noted that a detailed description of related known functions or constructions will be omitted when it would make the gist of the present invention unclear. As used herein, the term “includes” means that it may further include other components unless otherwise mentioned.
Upon charging and discharging of the sodium-air battery, reduction and oxidation of sodium at the anode 10 and the oxidation and reduction of oxygen introduced from the outside at the cathode 20 occur.
Specifically, upon discharging of the sodium-air battery, sodium is oxidized at the anode 10 to thus produce a sodium ion and an electron, as represented in Reaction Scheme 1 below.
Na→Na++e− [Reaction Scheme 1]
The sodium ion and the electron are transferred to the cathode 20 via the liquid electrolyte and the outer conductor or current collector, respectively. The cathode 20 is porous and thus external air is introduced thereto. Here, oxygen contained in the external air is reduced by the electron and reacts with the sodium ion, thereby forming sodium superoxide (NaO2), which is a discharge product, at the cathode 20, as shown in Reaction Scheme 2 below.
Na++O2+e−→NaO2 [Reaction Scheme 2]
The charging reaction proceeds in the opposite direction. Specifically, sodium superoxide (NaO2), which is a discharge product, is decomposed to thus produce a sodium ion and an electron.
The present inventors have identified the reaction mechanism of the sodium-air battery as mentioned above, and have also ascertained that a sodium ion and an oxygen radical anion are produced due to the dissolution and dissociation of a discharge product, sodium superoxide (NaO2), in a liquid electrolyte, and a byproduct such as sodium peroxide dihydrate (Na2O2.2H2O) is formed, attributable to a side reaction in the battery involving the oxygen radical anion.
Sodium peroxide dihydrate (Na2O2.2H2O) requires high overvoltage upon charging compared to sodium superoxide (NaO2), thus deteriorating the energy efficiency and lifetime of the battery.
Accordingly, the present inventors have repeated studies to solve the above problems and have ascertained that when a liquid electrolyte containing a sodium salt at a high concentration is used, the dissolution and dissociation of sodium superoxide (NaO2), which is a discharge product, in the liquid electrolyte, may be prevented, and the chemical stability of an organic solvent in the electrolyte is also increased to thus prevent side reactions from occurring.
The technical features of the present invention may be more clearly understood through the specific description and embodiments of the present invention.
According to an exemplary embodiment of the present invention, the liquid electrolyte of the sodium-air battery includes an ether-based solvent and a sodium salt that is dissolved at a high concentration of 4 M or less but exceeding 0.5 M in the ether-based solvent.
The ether-based solvent may be a non-aqueous solvent, which facilitates the dissociation of a sodium salt because of the high dielectric constant thereof and enables the efficient transfer of a sodium ion due to the low viscosity thereof. Specifically, the ether-based solvent may be a non-aqueous solvent selected from the group consisting of diethyleneglycol dimethylether (DEGDME), tetraethyleneglycol dimethylether (TEGDME), dimethoxyethane (DME), and combinations thereof.
The sodium salt may be selected from the group consisting of NaPF6, NaBF4, NaClO4, NaAsF6, NaCF3SO3, NaN(SO2F)2, Na2SiF6, NaSbF6, NaAlCl4 and combinations thereof.
The liquid electrolyte contains the sodium salt at a high concentration of 4 M or less but exceeding 0.5 M, and particularly of 3 M to 4 M. When the concentration of the sodium salt exceeds 0.5 M, dissolution and dissociation of the sodium superoxide (NaO2), which is a discharge product, in the liquid electrolyte, may be sufficiently suppressed. If the concentration of the sodium salt is too high, the viscosity of the liquid electrolyte may increase and thus the mobility of the sodium ion may decrease. Hence, the upper limit of the concentration thereof is preferably 4 M.
A better understanding of the present invention will be given through the following Examples, which are merely set forth to illustrate, but are not to be construed as limiting the scope of the present invention.
A sodium-air battery was manufactured using a liquid electrolyte containing a sodium salt having a concentration of 4 M through the following procedures.
The anode was a sodium metal having a thickness of 500 μm and a diameter of ½ inch (available from Sigma Aldrich), and a glass fiber filter (GF/A, available from Whatman) was used as a separator.
A carbon material, Ketjen black carbon, and a binder, polytetrafluoroethylene (PTFE), were mixed and applied on a nickel mesh current collector, which was then used as a cathode (oxygen electrode).
The liquid electrolyte was prepared by dissolving the sodium salt, NaClO4, at a concentration of 4 M in diethyleneglycol dimethylether (DEGDME), which is an ether-based solvent.
A Swagelok-type sodium-air battery was manufactured using the anode, the separator, the cathode and the liquid electrolyte.
A sodium-air battery was manufactured in the same configuration and manner as in Example 1, with the exception that the concentration of the sodium salt of the liquid electrolyte was changed to 3 M.
A sodium-air battery was manufactured in the same configuration and manner as in Example 1, with the exception that the concentration of the sodium salt of the liquid electrolyte was changed to 0.1 M.
According to an exemplary embodiment of the present invention, when the sodium-air battery is manufactured using the liquid electrolyte including the ether-based solvent and the sodium salt at a concentration of 4 M or less but exceeding 0.5 M, and particularly, 3 M to 4 M, the chemical stability of the battery can be significantly increased, thus maximizing battery efficiency and improving anode stability, thereby making it possible to perform stable charging without shorting of the battery.
Therefore, the present invention is technically significant in that it identifies the charge-discharge mechanism of the sodium-air battery, which is receiving attention as a next-generation battery, and also in that it completely overcomes the drawbacks thereof.
As described hereinbefore, the present invention has been described in detail with respect to experimental examples and embodiments. However, the scope of the present invention is not limited to the above-described experimental examples and examples, and various modifications and improved modes of the present invention using the basic concept of the present invention defined in the accompanying claims are also incorporated in the scope of the present invention.
The foregoing descriptions of specific exemplary embodiments of the present invention have been presented for purposes of illustration and description. They are not intended to be exhaustive or to limit the invention to the precise forms disclosed, and obviously many modifications and variations are possible in light of the above teachings. The exemplary embodiments were chosen and described in order to explain certain principles of the invention and their practical application, to enable others skilled in the art to make and utilize various exemplary embodiments of the present invention, as well as various alternatives and modifications thereof. It is intended that the scope of the invention be defined by the Claims appended hereto and their equivalents.
| Number | Date | Country | Kind |
|---|---|---|---|
| 10-2017-0063848 | May 2017 | KR | national |
