Patent Application
20210151796
This application claims priority to Korean Patent Application No. 10-2019-0149812, filed in the Korean Intellectual Property Office on Nov. 20, 2019, which application is hereby incorporated herein by reference.
The present invention relates to an electrolytic solution for lithium secondary batteries and a lithium secondary battery including the same.
A lithium secondary battery is an energy storage including a positive electrode configured to provide lithium during charging, a negative electrode configured to receive lithium during charging, an electrolyte serving as a lithium ion transfer medium, and a separator configured to separate the positive electrode and the negative electrode from each other. The lithium secondary battery generates and stores electric energy through a change in chemical potential when lithium ions are intercalated/deintercalated at the positive electrode and the negative electrode.
The lithium secondary battery is mainly used in portable electronic devices. In recent years, however, the lithium secondary battery has been used as an energy storage means of an electric vehicle (EV) and a hybrid electric vehicle (HEV) as the electric vehicle and the hybrid electric vehicle are commercialized.
Research to increase the energy density of the lithium secondary battery in order to increase the travel distance of the electric vehicle has been conducted. The energy density of the lithium secondary battery may be increased by increasing the capacity of the positive electrode.
The capacity of the positive electrode may be increased by using a Ni-rich method, which is a method of increasing the content of Ni of a Ni—Co—Mn oxide forming a positive electrode active material, or by increasing the positive electrode charging voltage.
However, the Ni-rich Ni—Co—Mn oxide has an unstable crystalline structure while exhibiting high interfacial reactivity, whereby degradation during cycles is accelerated and thus it is difficult to secure long-term performance of the lithium secondary battery.
The matters disclosed in this section are merely for enhancement of understanding of the general background of the invention and should not be taken as an acknowledgment or any form of suggestion that the matters form the related art already known to a person skilled in the art.
The present invention relates to an electrolytic solution for lithium secondary batteries and a lithium secondary battery including the same. Embodiments of the present invention address the above problems. Particular embodiments of the present invention provide an electrolytic solution for lithium secondary batteries capable of improving lifespan and output characteristics of lithium secondary batteries and a lithium secondary battery including the same.
In accordance with an embodiment of the present invention, the above and other objects can be accomplished by the provision of an electrolytic solution for lithium secondary batteries, the electrolytic solution including lithium salt, a solvent, and a functional additive, wherein the functional additive includes a high-voltage additive, 1-fluoroethyl methyl carbonate (FEMC), expressed by [Formula 1] below.
The high-voltage additive may be added so as to account for 1 to 3 wt % based on the weight of the electrolytic solution.
The functional additive may further include a negative electrode film additive, such as vinylene carbonate (VC).
The negative electrode film additive may be added so as to account for 0.5 to 3.0 wt % based on the weight of the electrolytic solution.
The lithium salt may be any one or a mixture of two or more selected from the group consisting of LiPF6, LiBF4, LiClO4, LiCl, LiBr, LiI, LiB10Cl10, LiCF3SO3, LiCF3CO2, LiAsF6, LiSbF6, LiAlCl4, CH3SO3Li, CF3SO3Li, LiN(SO2C2F5)2, Li(CF3SO2)2N, LiC4F9SO3, LiB(C6H5)4, Li(SO2F)2N(LiFSI), and (CF3SO2)2NLi.
The solvent may be any one or a mixture of two or more selected from the group consisting of a carbonate-based solvent, an ester-based solvent, an ether-based solvent, and a ketone-based solvent.
In accordance with another embodiment of the present invention, there is provided a lithium secondary battery including an electrolytic solution. The lithium secondary battery may further include a positive electrode including a positive electrode active material consisting of Ni, Co, and Mn, a negative electrode including one or more negative electrode active materials selected from among carbon (C)-based and silicon (Si)-based negative electrode active materials, and a separator interposed between the positive electrode and the negative electrode.
The content of Ni in the positive electrode may be 60 wt % or more.
The above and other objects, features and other advantages of the present invention will be more clearly understood from the following detailed description taken in conjunction with the accompanying drawings, in which:
Hereinafter, exemplary embodiments of the present invention will be described in detail with reference to the accompanying drawings. However, the present invention is not limited to the embodiments disclosed below and may be implemented in various different forms, and the embodiments herein are provided to make the disclosure of the present invention complete and to fully convey the scope of the invention to those skilled in the art.
An electrolytic solution for lithium secondary batteries according to an embodiment of the present invention is a material that forms an electrolyte applied to a lithium secondary battery, and includes lithium salt, a solvent, and a functional additive.
The lithium salt may be any one or a mixture of two or more selected from the group consisting of LiPF6, LiBF4, LiClO4, LiCl, LiBr, LiI, LiB10Cl10, LiCF3SO3, LiCF3CO2, LiAsF6, LiSbF6, LiAlCl4, CH3SO3Li, CF3SO3Li, LiN(SO2C2F5)2, Li(CF3SO2)2N, LiC4F9SO3, LiB(C6H5)4, Li(SO2F)2N(LiFSI), and (CF3SO2)2NLi.
The lithium salt may be present in the electrolytic solution such that the total amount of the lithium salt has a concentration of 0.1 to 1.2 moles.
Any one or a mixture of two or more selected from the group consisting of a carbonate-based solvent, an ester-based solvent, an ether-based solvent, and a ketone-based solvent may be used as the solvent.
Dimethyl carbonate (DMC), diethyl carbonate (DEC), dipropyl carbonate (DPC), methyl propyl carbonate (MPC), ethyl propyl carbonate (EPC), ethyl methyl carbonate (EMC), ethylene carbonate (EC), propylene carbonate (PC), butylene carbonate (BC), fluoroethylene carbonate (FEC), or vinylene carbonate (VC) may be used as the carbonate-based solvent. γ-butyrolactone (GBL), n-methyl acetate, n-ethyl acetate, or n-propyl acetate may be used as the ester-based solvent. Dibutyl ether may be used as the ether-based solvent. However, the present invention is not limited thereto.
In addition, the solvent may further include an aromatic hydrocarbon-based organic solvent. Concrete examples of the aromatic hydrocarbon-based organic solvent may include benzene, fluorobenzene, bromobenzene, chlorobenzene, cyclohexylbenzene, isopropylbenzene, n-butylbenzene, octylbenzene, toluene, xylene, and mesitylene, which may be used either alone or as a mixture of two or more.
Meanwhile, a high-voltage additive expressed by [Formula 1] below, such as 1-fluoroethyl methyl carbonate (FEMC), may be used as the functional additive added to the electrolytic solution according to an embodiment of the present invention.
The FEMC serves to improve oxidative stability of the electrolytic solution and to stabilize the interface between the electrolytic solution and a positive electrode, and may be added so as to account for 1 to 3 wt % based on the weight of the electrolytic solution.
In the case in which the content of the high-voltage additive is less than 1 wt %, it is difficult to sufficiently form a surface protective layer, whereby the expected effect is deficient. In the case in which the content of the high-voltage additive is greater than 3 wt %, the surface protective layer is excessively formed, whereby cell resistance is increased and thus battery output is reduced.
Meanwhile, a negative electrode film additive serving to form a film on a negative electrode may be further added as the functional additive. For example, vinylene carbonate (VC) may be used as the negative electrode film additive.
The negative electrode film additive may be added so as to account for preferably 0.5 to 3.0 wt %, more preferably 1.5 to 2.5 wt %, based on the weight of the electrolytic solution.
In the case in which the content of the negative electrode film additive is less than 0.5 wt %, the long-term lifespan characteristics of the cell are deteriorated. In the case in which the content of the negative electrode film additive is greater than 3.0 wt %, the surface protective layer is excessively formed, whereby cell resistance is increased and thus battery output is reduced.
As illustrated in
The positive electrode 104 includes an NCM-based positive electrode active material consisting of Ni, Co, and Mn. Particularly, in this embodiment, the positive electrode active material included in the positive electrode 104 may include only an NCM-based positive electrode active material containing 60 wt % or more of Ni.
The negative electrode 106 includes one or more negative electrode active materials selected from among carbon (C)-based and silicon (Si)-based negative electrode active materials.
At least one selected from the group consisting of artificial graphite, natural graphite, graphitized carbon fibers, graphitized mesocarbon mircobeads, fullerene, and amorphous carbon may be used as the carbon (C)-based negative electrode active materials.
The silicon (Si)-based negative electrode active materials include a silicon oxide, silicon particles, and silicon alloy particles.
Meanwhile, each of the positive electrode 104 and the negative electrode 106 is manufactured by mixing a conductive agent, a binder, and a solvent with the active material thereof to manufacture an electrode slurry and directly coating and drying the electrode slurry on a current collector. Aluminum (Al) may be used as the current collector. However, embodiments of the present invention are not limited thereto. An electrode manufacturing method is well known in the art to which the present invention pertains, and therefore a detailed description will be omitted from this specification.
The binder serves to properly attach active material particles to each other or to properly attach the active material particles to the current collector, and examples of the binder may include, but are not limited to, polyvinyl alcohol, carboxymethyl cellulose, hydroxypropyl cellulose, diacetyl cellulose, polyvinyl chloride, carboxylated polyvinyl chloride, polyvinyl fluoride, a polymer including an ethylene oxide, polyvinylpyrrolidone, polyurethane, polytetrafluoroethylene, polyvinylidene fluoride, polyethylene, polypropylene, styrene-butadiene rubber, acrylated styrene-butadiene rubber, an epoxy resin, and nylon.
In addition, the conductive agent is used to provide conductivity to an electrode, and any conductive agent may be used as long as the conductive agent does not cause a chemical change in a battery and is made of an electrically conductive material. For example, natural graphite, artificial graphite, carbon black, acetylene black, Ketjen black, carbon fiber, or metal powder or metal fiber, such as copper, nickel, aluminum, or silver may be used as the conductive agent. In addition, conductive materials, such as polyphenylene derivatives, may be used either alone or as a mixture of two or more.
The separator 108 prevents short circuit between the positive electrode 104 and the negative electrode 106, and provides a movement path for lithium ions. A polyolefin-based polymer film, such as polypropylene, polyethylene, polyethylene/polypropylene, polyethylene/polypropylene/polyethylene, or polypropylene/polyethylene/polypropylene, a multilayered film, a microporous film, woven fabric, or non-woven fabric may be used as the separator. In addition, a film obtained by coating a resin exhibiting high stability on a porous polyolefin film may be used.
Hereinafter, the present invention will be described based on Examples and Comparative Examples.
<Experiment 1> Experiment on Characteristics by Voltage at Room Temperature (25° C.) Based on Kind of Functional Additive (Half Cell)
In order to investigate characteristics by voltage based on the kind of the functional additive added to the electrolytic solution, initial capacities and capacity retentions at room temperature (25° C.) were measured while changing the kind of the functional additive and voltage, as shown in Table 1 below. The results are shown in Table 1 and
In order to manufacture the electrolytic solution, 0.5M LiPF6 and 0.5M LiFSI were used as the lithium salt, and a mixture of ethylene carbonate (EC):ethyl methyl carbonate (EMC):diethyl carbonate (DEC) in a ratio of 25:45:30 was used as the solvent.
NCM622 was used as the positive electrode, and Li metal was used as the negative electrode.
It can be seen from Table 1 and
In addition, it can be seen that, in the case in which the same functional additive was used, cell capacities increased through initial revelation of high capacities as voltage was increased and high capacity retentions were maintained at voltages ranging from 4.2 V to 4.5 V.
<Experiment 2> Experiment on Charge and Discharge Characteristics at High Temperature (45° C.) Based on Kind and Content of Functional Additive (Half Cell)
In order to investigate charge and discharge characteristics based on the kind and content of the functional additive added to the electrolytic solution, initial capacities and capacity retentions at high temperature (45° C.) were measured while changing the kind and content of the functional additive, as shown in Table 2 below. The results are shown in Table 2 and
It can be seen from Table 2 and
In addition, it can be seen that, in the case in which FEMC according to Examples was used as the functional additive, higher capacity retentions were maintained than in the case in which only VC, which is a conventional general functional additive, was used.
<Experiment 3> Experiment on Analysis of Surface of Positive Electrode Before and after Charge and Discharge by Kind of Functional Additive
Surfaces before and after charge and discharge experiments at high temperature (45° C.) in the case in which the electrolytic solutions according to No. 11 and No. 13 were used were observed, and the results are shown in
It can be seen from
However, it can be seen that, in the case of No. 13, in which FEMC, which is a functional additive according to the present invention, was used as the functional additive, no cracks were formed in the positive electrode.
As is apparent from the above description, according to embodiments of the present invention, an electrolytic solution including a high-voltage additive is used, whereby the long-term lifespan characteristics of a lithium secondary battery are improved.
In addition, in the case in which the electrolytic solution including the high-voltage additive is used, cell resistance of the lithium secondary battery is reduced, whereby the output characteristics of the lithium secondary battery are improved.
Although the preferred embodiments of the present invention have been described above with reference to the accompanying drawings, those skilled in the art will appreciate that the present invention can be implemented in various other embodiments without changing the technical ideas or features thereof.
| Number | Date | Country | Kind |
|---|---|---|---|
| 10-2019-0149812 | Nov 2019 | KR | national |
