Patent Application
20200052335
This disclosure relates to a lithium secondary battery.
A portable information device such as a cell phone, a laptop, smart phone, and the like or an electric vehicle has used a lithium secondary battery having high energy density and easy portability as a driving power source.
In general, a lithium secondary battery is manufactured by using materials capable of reversibly intercalating and deintercalating lithium ions as a positive active material and a negative active material and filling an electrolyte between the positive electrode and the negative electrode.
Lithium-transition metal oxides are used as the positive active material of the lithium secondary battery, various types of carbon-based materials are used as the negative active material, and lithium salts dissolved in the non-aqueous organic solvent are used as an electrolyte.
In particular, as a lithium secondary battery exhibits battery characteristics by complex reactions such as those between a positive electrode and an electrolyte, a negative electrode and an electrolyte, and the like, the use of a suitable electrolyte is one of important parameters for improving the performance of a lithium secondary battery.
Embodiments provide a lithium secondary battery exhibiting good battery performance.
In one aspect, the present disclosure provides a lithium secondary battery including a positive electrode including a positive active material layer, the positive active material layer including a positive active material and a carbonaceous nanostructure; a negative electrode including a negative active material; and a non-aqueous organic solvent, a lithium salt, and an additive including a compound represented by Chemical Formula 1, wherein the amount of the carbonaceous nanostructure is about 0.5 wt % or more and less than 4 wt % (e.g., from 0.5 wt % to less than 4 wt %) based on 100 wt % of the total amount (e.g., total weight) of the positive active material layer.
In Chemical Formula 1, A is a substituted or unsubstituted aliphatic chain or (—C2H4—O—C2H4-)n, and n is an integer from 1 to 10.
According to the embodiments, the impregnation of an electrolyte may be improved so that a lithium secondary battery exhibiting improved cycle-life characteristics and storage characteristics at high temperatures may be provided.
Hereinafter, the present disclosure will be described more fully hereinafter with reference to the accompanying drawings, in which exemplary embodiments of the invention are shown. However, this disclosure may be embodied in many different forms and is not construed as limited to the example embodiments set forth herein.
In order to clearly illustrate the present invention, parts that are not related to the description are omitted, and the same or similar components are denoted by the same reference numerals throughout the specification.
Sizes and thicknesses of components in the drawings are arbitrarily expressed for convenience of description and, thus, the present invention is not limited by the drawings.
In addition, unless explicitly described to the contrary, the word “comprise” and variations such as “comprises” or “comprising,” will be understood to imply the inclusion of stated elements but not the exclusion of any other elements.
A lithium secondary battery according to one embodiment includes a positive electrode including a positive active material layer, the positive active material layer including a positive active material and a carbonaceous nanostructure; a negative electrode including a negative active material; and an electrolyte including a non-aqueous organic solvent, a lithium salt, and an additive including a compound represented by Chemical Formula 1. The amount of the carbonaceous nanostructure may be about 0.5 wt % or more and less than 4 wt % based on 100 wt % of the total amount of the positive active material layer.
In Chemical Formula 1, A is a substituted or unsubstituted aliphatic chain or (—C2H4—O—C2H4-)n, and n is an integer from 1 to 10.
An electrolyte of a lithium secondary battery may be generally an organic solvent in which a lithium salt is dissolved. In particular, non-aqueous organic solvents having a high ionic conductivity and dielectric constant and a low viscosity may be used.
In lithium secondary battery using a carbonate-based solvent of such a non-aqueous organic solvent, an irreversible side reaction may occur between the electrolyte and the positive electrode, and between the electrolyte and the negative electrode at a high temperature and a high pressure.
The decomposition products produced by such a side reaction form a thick passivation film which acts as a resistance on the surface of the electrode and decrease a cycle life and capacity of the lithium secondary battery. Also, due to the decomposition of a carbonate-based organic solvent, gas is generated inside the battery which causes a swelling phenomenon and it may lead to battery explosion.
Accordingly, the inventors of the present invention have conducted studies to develop an electrolyte composition for a lithium secondary battery that prevents the swelling phenomenon of a lithium secondary battery and has excellent stability and cycle-life characteristics and as a result, it has been found that the above object may be achieved by using a compound represented by Chemical Formula 1.
That is, the electrolyte for a lithium secondary battery according to the present disclosure comprises a non-aqueous organic solvent, a lithium salt, and an additive including a compound represented by Chemical Formula 1.
In Chemical Formula 1, A is a substituted or unsubstituted aliphatic chain or (—C2H4—O—C2H4-)n, and n is an integer from 1 to 10.
In Chemical Formula 1, A may be a C2 to C20 hydrocarbon chain or (—C2H4—O—C2H4-)n, and n may be an integer from 1 to 5.
In addition, the compound represented by Chemical Formula 1 may be a compound represented by Chemical Formula 1-1.
When the electrolyte including an additive including the compound represented by Chemical Formula 1 is applied to a lithium secondary battery, the cycle-life characteristics of the lithium secondary battery may be improved and the generation of gas at a high temperature may be greatly reduced.
The compound represented by Chemical Formula 1 includes a difluorophosphite (—OPF2) group having excellent electrochemical reactivity at both terminals.
During the initial charge of a lithium secondary battery, lithium ions, which are released from the lithium-transition metal oxide, i.e., the positive electrode, are transported into a carbon electrode which is a negative electrode and intercalated thereinto. Because of its high reactivity, lithium reacts with the carbon electrode to produce Li2CO3, LiO, LiOH, etc., thereby forming a thin film on the surface of the negative electrode. This thin film is referred to as a solid electrolyte interface (SEI) film. The SEI thin film formed during the initial charge prevents the reaction between lithium ions and carbon negative electrode or other materials during charge and discharge. In addition, it also acts as an ion tunnel, allowing the passage of only lithium ions. The ion tunnel prevents disintegration of the structure of the carbon negative electrode, which is caused by co-intercalation of organic solvents of the electrolyte, having a high molecular weight along with solvated lithium ions into the carbon negative electrode. Once the SEI thin film is formed, lithium ions do not react again with the carbon negative electrode or other materials, such that the amount of lithium ions is reversibly maintained. Therefore, in order to improve the high-temperature cycle characteristics and the low-temperature output of the lithium secondary battery, a rigid SEI thin film must be always formed on the negative electrode of the lithium secondary battery.
However, when the additive including the compound represented by Chemical Formula 1 is included like (e.g., as in) the electrolyte for a lithium secondary battery according to the present disclosure, a rigid SEI film having good ion conductivity is formed on the surface of the negative electrode, and thereby it is possible to suppress a decomposition of the surface of the negative electrode during high temperature cycle operation and to prevent an oxidation reaction of the electrolyte solution.
When the compound represented by Chemical Formula 1 is decomposed, a difluorophosphite (—OPF2) group and an ethylene dioxide fragment may be formed.
The difluorophosphite (—OPF2) group may form a donor-acceptor bond with transition metal oxide that is exposed on the surface of the positive active material due to excellent electrochemical reactivity and thus a protective layer in a form of a composite may be formed.
In addition, the difluorophosphite (—OPF2) adhered to the transition metal oxide at the initial charge of the lithium secondary battery may be oxidized to a plurality of fluorophosphates, and thus more stable inactive layer having excellent ion conductivity may be formed on a positive electrode. Therefore, it is possible to prevent other components of the electrolyte from being oxidation-decomposed, and as a result, the cycle-life performance of the lithium secondary battery may be improved and a swelling phenomenon may be prevented from occurring.
Further, the compound represented by Chemical Formula 1 and its oxide participate in the electrochemical reaction with the components of the SEI thin film to make the SEI thin film more rigid and to improve stability of other components included in the electrolyte by oxidative decomposition.
In addition, the compound represented by Chemical Formula 1 forms a composite with LiPF6 and thus undesirable side reactions may be prevented from occurring, and it is possible to improve cycle-life characteristics of the lithium secondary battery and to prevent the generation of gas in the lithium secondary battery, thereby significantly reducing an occurrence rate of defects due to a swelling phenomenon.
On the other hand, the additive including the compound represented by Chemical Formula 1 may be included in an amount of 0.1 wt % or more and less than 3 wt % based on a total amount of the electrolyte for a lithium secondary battery. More specifically, the amount of the compound represented by Chemical Formula 1 may be 0.1 wt % to 3 wt % or 0.1 wt % to 1 wt %. When the amount of the additive satisfies the above ranges, a resistance increase may be prevented and thus a lithium secondary battery having improved cycle-life characteristics may be realized.
The additive for a lithium secondary battery of this disclosure may further include an additional additive. The additional additive may be, for example, at least one selected from the group consisting of fluoroethylene carbonate, vinylethylene carbonate, vinylene carbonate, succinonitrile, hexane tricyanide, lithium tetrafluoroborate, and propane sultone, but is not limited thereto.
Herein, an amount of the additional additive may be 0.1 wt % to 20 wt % based on a total amount of the electrolyte for a lithium secondary battery. More specifically, the amount of the additional additive may be 0.1 wt % to 15 wt %. When the amount of the additional additive satisfies the above ranges, battery resistance may be effectively suppressed and a lithium secondary battery having cycle-life characteristics may be realized.
On the other hand, the non-aqueous organic solvent serves as a medium for transporting ions taking part in the electrochemical reaction of a lithium secondary battery.
The non-aqueous organic solvent may include a carbonate-based, ester-based, ether-based, ketone-based, alcohol-based, or aprotic solvent.
The carbonate-based solvent may include dimethyl carbonate (DMC), diethyl carbonate (DEC), dipropyl carbonate (DPC), methylpropyl carbonate (MPC), ethylpropyl carbonate (EPC), methylethyl carbonate (MEC), ethylene carbonate (EC), propylene carbonate (PC), butylene carbonate (BC), and/or the like. The ester-based solvent may include methyl acetate, ethyl acetate, n-propyl acetate, dimethylacetate, methylpropionate, ethyl propionate, propyl propionate, γ-butyrolactone, decanolide, valerolactone, mevalonolactone, caprolactone, and/or the like.
The ether-based solvent may include dibutyl ether, tetraglyme, diglyme, dimethoxyethane, 2-methyltetrahydrofuran, tetrahydrofuran, and/or the like, and the ketone-based solvent may include cyclohexanone, and/or the like.
The alcohol-based solvent may include ethanol, isopropyl alcohol, and/or the like, and the aprotic solvent may include nitriles such as T-CN (wherein T is a hydrocarbon group having a C2 to C20 linear, branched, or cyclic structure and may include a double bond, an aromatic ring, or an ether bond), and/or the like, dioxolanes such as 1,3-dioxolane, and/or the like, sulfolanes, and/or the like.
The non-aqueous organic solvent may be used alone or in a mixture. When the organic solvent is used in a mixture, the mixture ratio may be controlled in accordance with a desirable battery performance.
The carbonate-based solvent is prepared by mixing a cyclic carbonate and a linear carbonate. When the cyclic carbonate and linear carbonate are mixed together in a volume ratio of 1:1 to 1:9, an electrolyte performance may be improved.
The non-aqueous organic solvent may further include an aromatic hydrocarbon-based organic solvent in addition to the carbonate-based solvent. Herein, the carbonate-based solvent and the aromatic hydrocarbon-based organic solvent may be mixed in a volume ratio of 1:1 to 30:1.
The aromatic hydrocarbon-based organic solvent may be an aromatic hydrocarbon-based compound of Chemical Formula 2.
In Chemical Formula 2, R1 to R6 are the same or different and are each independently selected from the group consisting of hydrogen, halogen, C1 to C10 alkyl group, haloalkyl group, and a combination thereof.
Specific examples of the aromatic hydrocarbon-based organic solvent may be selected from benzene, fluorobenzene, 1,2-difluorobenzene, 1,3-difluorobenzene, 1,4-difluorobenzene, 1,2,3-trifluorobenzene, 1,2,4-trifluorobenzene, chlorobenzene, 1,2-dichlorobenzene, 1,3-dichlorobenzene, 1,4-dichlorobenzene, 1,2,3-trichlorobenzene, 1,2,4-trichlorobenzene, iodobenzene, 1,2-diiodobenzene, 1,3-diiodobenzene, 1,4-diiodobenzene, 1,2,3-triiodobenzene, 1,2,4-triiodobenzene, toluene, fluorotoluene, 2,3-difluorotoluene, 2,4-difluorotoluene, 2,5-difluorotoluene, 2,3,4-trifluorotoluene, 2,3,5-trifluorotoluene, chlorotoluene, 2,3-dichlorotoluene, 2,4-dichlorotoluene, 2,5-dichlorotoluene, 2,3,4-trichlorotoluene, 2,3,5-trichlorotoluene, iodotoluene, 2,3-diiodotoluene, 2,4-diiodotoluene, 2,5-diiodotoluene, 2,3,4-triiodotoluene, 2,3,5-triiodotoluene, xylene, and a combination thereof.
The electrolyte of a lithium secondary battery may further include vinylethyl carbonate, vinylene carbonate, an ethylene carbonate-based compound represented by Chemical Formula 3 or a combination thereof in order to improve cycle life of a battery.
In Chemical Formula 3, R7 and R8 are each independently selected from hydrogen, a halogen, a cyano group (CN), a nitro group (NO2), and a fluorinated C1 to C5 alkyl group, provided that at least one of R7 and R8 is selected from a halogen, a cyano group (CN), a nitro group (NO2), and a fluorinated C1 to C5 alkyl group, and R7 and R8 are not simultaneously hydrogen.
Examples of the ethylene carbonate-based compound may be difluoro ethylenecarbonate, chloroethylene carbonate, dichloroethylene carbonate, bromoethylene carbonate, dibromoethylene carbonate, nitroethylene carbonate, cyanoethylene carbonate, fluoroethylene carbonate, and the like. The amount of the additive for improving cycle life may be used within an appropriate range.
The lithium salt dissolved in the non-aqueous solvent supplies lithium ions in a battery, enables a basic operation of a lithium secondary battery, and improves transportation of the lithium ions between positive and negative electrodes. Examples of the lithium salt include at least one supporting salt selected from LiPF6, LiSbF6, LiAsF6, LiN(SO2C2F6)2, Li(CF3SO2)2N, LiN(SO3C2F5)2, LiC4F9SO3, LiClO4, LiAlO2, LiAlCl4, LiN(CxF2x+1SO2)(CyF2y+1SO2) (wherein x and y are natural numbers, for example, an integer from 0 to 20), LiCl, LiI, LiB(C2O4)2 (lithium bis(oxalato) borate, LiBOB), LiDFOP (lithium difluoro bis(oxalato)phosphate), LiDFOB (lithium difluoro(oxalato) borate), and LiPO2F2 (lithium difluorophosphate). The lithium salt may be used in a concentration from 0.1 M to 2.0 M. When the lithium salt is included at the above concentration range, an electrolyte may have excellent performance and lithium ion mobility due to optimal electrolyte conductivity and viscosity.
Hereinafter, a lithium secondary battery according to another embodiment of the present disclosure is described.
Referring to
The electrode assembly 40 includes a positive electrode 10 including a positive active material, a negative electrode 20 including a negative active material, and a separator 30 disposed between the positive electrode 10 and the negative electrode 20. The positive electrode 10, the negative electrode 20, and the separator 30 may be impregnated in the aforementioned electrolyte solution (not shown) according to the present disclosure.
The positive electrode 10 includes a current collector and a positive active material layer disposed on the current collector and including a positive active material.
In one embodiment, the positive active material layer includes a positive active material and a carbonaceous nanostructure, and the amount of the carbonaceous nanostructure may be 0.5 wt % or more and less than 4 wt % (e.g., from 0.5 wt % to less than 4 wt %) based on 100 wt % of the total amount (e.g., weight) of the positive active material layer. In another embodiment, the amount of the carbonaceous nanostructure may be 1 wt % to 3 wt % based on 100 wt % of the total amount of the positive active material layer.
As such, the lithium secondary battery according to one embodiment includes the electrolyte including the additive represented by Chemical Formula 1 and the positive electrode including the carbonaceous nanostructure at the specific amount, i.e., 0.5 wt % or more and less than 4 wt % based on 100 wt % of the total amount of the positive active material layer, so that the impregnation of the electrolyte may be further improved and the cycle-life characteristics, especially the high-temperature cycle-life characteristics may be further improved, and the resistance increase during storage at high temperatures may be effectively suppressed.
Even if the positive electrode includes the carbonaceous nanostructure, the desired effects may not be obtained, if the electrolyte includes no (e.g., if the electrolyte does not include the) additive of Chemical Formula 1. In addition, even if the electrolyte includes the additive of Chemical Formula 1, the effects may be insufficiently obtained, if the amount of the carbonaceous nanostructure is out of the above range.
The carbonaceous nanostructure may have a one-dimensional carbonaceous nanostructure, a two-dimensional carbonaceous nanostructure, or a combination thereof. The carbonaceous nanostructure may be carbon nanotubes (CNT), carbon nanofibers, graphene, graphene nanosheets, hollow carbon, porous carbon, mesoporous carbon, or a combination thereof. The carbon nanotubes may be single-wall carbon nanotubes, double-wall carbon nanotubes, multi-wall carbon nanotubes, or a combination thereof.
The carbonaceous nanostructure may have a length (e.g., an average length) of more than about 1 μm and less than 200 μm, and in one embodiment, 5 μm to 100 μm. When the length of the carbonaceous nanostructure is within the above ranges, the improvements in the impregnation of the electrolyte may be further enhanced, the high-temperature cycle-life characteristics may be surprisingly improved, and the resistance increase during storage at high temperatures may be more effectively suppressed. The term “length of the carbonaceous nanostructure” as used herein refers to a maximum value of a distance between opposite ends of a carbonaceous nanostructure. The term “average length” of the carbonaceous nanostructures as used herein refers to a calculated average of the lengths of a plurality of carbonaceous nanostructures.
In the positive active material layer, the positive active material may include a compound (lithiated intercalation compound) being capable of intercalating and deintercallating lithium and specifically at least one composite oxide of lithium and a metal of cobalt, manganese, nickel, and a combination thereof may be used. Specific examples thereof may be a compound represented by one of the following chemical formulae. LiaA1−bXbD2 (0.90≤a≤1.8, 0≤b≤0.5); LiaA1−bXbO2−cDc (0.90≤a≤1.8, 0≤b≤0.5, 0≤c≤0.05); LiaE1−bXbO2−cDc (0.90≤a≤1.8, 0≤b≤0.5, 0≤c≤0.05); LiaE2−bXbO4−cDc (0.90≤a≤1.8, 0≤b≤0.5, 0≤c≤0.05); LiaNi1−b−cCobXcDa (0.90≤a≤1.8, 0≤b≤0.5, 0≤c≤0.5, 0<α≤2); LiaNi1−b−cCobXcO2−αTα (0.90≤a≤1.8, 0≤b≤0.5, 0≤c≤0.05, 0<α<2); LiaNi1−b−cCobXcO2−αT2 (0.90≤a≤1.8, 0≤b≤0.5, 0≤c≤0.05, 0<α<2); LiaNi1−b−cMnbXcDa (0.90≤a≤1.8, 0≤b≤0.5, 0≤c≤0.05, 0<α≤2); LiaNi1−b−cMnbXcO2−αTα (0.90≤a≤1.8, 0≤b≤0.5, 0≤c≤0.05, 0<α<2); LiaNi1−b−cMnbXcO2−αT2 (0.90≤a≤1.8, 0≤b≤0.5, 0≤c≤0.05, 0<α<2); LiaNibEcGdO2 (0.90≤a≤1.8, 0≤b≤0.9, 0≤c≤0.5, 0.001≤d≤0.1); LiaNibCocMndGeO2 (0.90≤a≤1.8, 0≤b≤0.9, 0≤c≤0.5, 0≤d≤0.5, 0.001≤e≤0.1); LiaNiGbO2 (0.90≤a≤1.8, 0.001≤b≤0.1); LiaCoGbO2 (0.90≤a≤1.8, 0.001≤b≤0.1); LiaMn1−bGbO2 (0.90≤a≤1.8, 0.001≤b≤0.1); LiaMn2GbO4 (0.90≤a≤1.8, 0.001≤b≤0.1); LiaMn1−gGgPO4 (0.90≤a≤1.8, 0≤g≤0.5); QO2; QS2; LiQS2; V2O5; LiV2O5; LiZO2; LiNiVO4; Li(3−f)J2(PO4)3 (0≤f≤2); Li(3−f)Fe2(PO4)3 (0≤f≤2); and LiaFePO4 (0.90≤a≤1.8)
In the chemical formulae, A is selected from Ni, Co, Mn, and a combination thereof; X is selected from Al, Ni, Co, Mn, Cr, Fe, Mg, Sr, V, a rare earth element, and a combination thereof; D is selected from O, F, S, P, and a combination thereof; E is selected from Co, Mn, and a combination thereof; T is selected from F, S, P, and a combination thereof; G is selected from Al, Cr, Mn, Fe, Mg, La, Ce, Sr, V, and a combination thereof; Q is selected from Ti, Mo, Mn, and a combination thereof; Z is selected from Cr, V, Fe, Sc, Y, and a combination thereof; and J is selected from V, Cr, Mn, Co, Ni, Cu, and a combination thereof.
The lithium metal oxide may have a coating layer on the surface, or may be mixed with another lithium metal oxide having a coating layer. The coating layer may include at least one coating element compound selected from an oxide of a coating element, a hydroxide of a coating element, an oxyhydroxide of a coating element, an oxycarbonate of a coating element, and a hydroxy carbonate of a coating element. The compound for the coating layer may be amorphous or crystalline. The coating element included in the coating layer may include Mg, Al, Co, K, Na, Ca, Si, Ti, V, Sn, Ge, Ga, B, As, Zr, or a mixture thereof. The coating layer may be disposed by a method having no adverse influence on properties of a positive active material by using these elements in the compound, (e.g., the method may include any coating method (e.g., spray coating, dipping, etc.)), but is not illustrated in more detail since it is well-known to those skilled in the related field.
In the positive electrode, the positive active material may be included in an amount of 90 wt % to 98 wt % based on a total weight of the positive active material layer.
In an embodiment, the positive active material layer may include a binder and a conductive material. Herein, the binder and the conductive material may be included in an amount of 1 wt % to 5 wt %, respectively, based on the total amount of the positive active material layer.
The binder serves to adhere the positive active material particles with one another and to adhere the positive active material to a current collector and examples thereof may be polyvinyl alcohol, carboxylmethyl cellulose, hydroxypropyl cellulose, diacetyl cellulose, polyvinylchloride, carboxylated polyvinylchloride, polyvinylfluoride, an ethylene oxide-containing polymer, polyvinylpyrrolidone, polyurethane, polytetrafluoroethylene, polyvinylidene fluoride, polyethylene, polypropylene, a styrene-butadiene rubber, an acrylated styrene-butadiene rubber, an epoxy resin, nylon, and the like, but are not limited thereto.
The conductive material is included to provide conductivity to the electrode and any electrically conductive material may be used as a conductive material unless it causes a chemical change. Examples of the conductive material may include a carbon-based material such as natural graphite, artificial graphite, carbon black, acetylene black, ketjen black, carbon fiber, and the like; a metal-based material of a metal powder or a metal fiber including copper, nickel, aluminum, silver, and the like; a conductive polymer such as a polyphenylene derivative; or a mixture thereof.
The current collector may be an aluminum foil, a nickel foil, or a combination thereof, but is not limited thereto.
The negative electrode 20 includes a current collector and a negative active material layer disposed on the current collector and including a negative active material.
The negative active material may include a material that reversibly intercalates/deintercalates lithium ions, a lithium metal, a lithium metal alloy, a material capable of doping/dedoping lithium, or a transition metal oxide.
The material that reversibly intercalates/deintercalates lithium ions may include for example, a carbon material, and i.e., the carbon material which may be a generally-used carbon-based negative active material in a lithium secondary battery. Examples of the carbon-based negative active material may include crystalline carbon, amorphous carbon, or mixtures thereof. The crystalline carbon may be unspecified shaped, or sheet, flake, spherical, or fiber shaped natural graphite or artificial graphite. The amorphous carbon may be a soft carbon, a hard carbon, a mesophase pitch carbonization product, fired coke, and the like.
The lithium metal alloy includes an alloy of lithium and at least one additional metal selected from Na, K, Rb, Cs, Fr, Be, Mg, Ca, Sr, Si, Sb, Pb, In, Zn, Ba, Ra, Ge, Al, and Sn.
The material being capable of doping/dedoping lithium may be Si, SiOx (0<x<2), a Si-Q alloy (wherein Q is an element selected from an alkali metal, an alkaline-earth metal, a Group 13 element, a Group 14 element, a Group 15 element, a Group 16 element, a transition metal, a rare earth element, and a combination thereof, and not Si), a Si-carbon composite, Sn, SnO2, Sn—R (wherein R is an element selected from an alkali metal, an alkaline-earth metal, a Group 13 element, a Group 14 element, a Group 15 element, a Group 16 element, a transition metal, a rare earth element, and a combination thereof, and not Sn), a Sn-carbon composite, and the like. At least one of these materials may be mixed with SiO2. The elements Q and R may be selected from Mg, Ca, Sr, Ba, Ra, Sc, Y, Ti, Zr, Hf, Rf, V, Nb, Ta, Db, Cr, Mo, W, Sg, Tc, Re, Bh, Fe, Pb, Ru, Os, Hs, Rh, Ir, Pd, Pt, Cu, Ag, Au, Zn, Cd, B, Al, Ga, Sn, In, Ge, P, As, Sb, Bi, S, Se, Te, Po, and a combination thereof.
The transition metal oxide may include lithium titanium oxide.
The negative active material layer includes a negative active material and a binder, and optionally a conductive material.
In the negative active material layer, the negative active material may be included in an amount of 95 wt % to 99 wt % based on the total weight of the negative active material layer. In the negative active material layer, a content of the binder may be 1 wt % to 5 wt % based on a total weight of the negative active material layer. When the negative active material layer includes a conductive material, the negative active material layer includes 90 wt % to 98 wt % of the negative active material, 1 wt % to 5 wt % of the binder, and 1 wt % to 5 wt % of the conductive material.
The binder improves binding properties of negative active material particles with one another and with a current collector. The binder may use a non-water-soluble binder, a water-soluble binder, or a combination thereof.
The non-water-soluble binder may be polyvinylchloride, carboxylated polyvinylchloride, polyvinylfluoride, an ethylene oxide-containing polymer, polyvinylpyrrolidone, polyurethane, polytetrafluoroethylene, polyvinylidene fluoride, polyethylene, polypropylene, polyamideimide, polyimide, or a combination thereof.
The water-soluble binder may be a styrene-butadiene rubber, an acrylated styrene-butadiene rubber, polyvinyl alcohol, sodium polyacrylate, a copolymer of propylene and a C2 to C8 olefin, a copolymer of (meth)acrylic acid and (meth)acrylic acid alkyl ester, or a combination thereof.
When the water-soluble binder is used as a negative electrode binder, a cellulose-based compound may be further used to provide viscosity as a thickener. The cellulose-based compound includes one or more of carboxymethyl cellulose, hydroxypropylmethyl cellulose, methyl cellulose, or alkali metal salts thereof. The alkali metals may be Na, K, or Li. The thickener may be included in an amount of 0.1 parts by weight to 3 parts by weight based on 100 parts by weight of the negative active material.
The conductive material is included to provide electrode conductivity, and any electrically conductive material may be used as a conductive material unless it causes a chemical change. Examples of the conductive material include a carbon-based material such as natural graphite, artificial graphite, carbon black, acetylene black, ketjen black, denka black, a carbon fiber, and the like; a metal-based material of a metal powder or a metal fiber including copper, nickel, aluminum silver, and the like; a conductive polymer such as a polyphenylene derivative; or a mixture thereof.
The current collector may include one selected from a copper foil, a nickel foil, a stainless steel foil, a titanium foil, a nickel foam, a copper foam, a polymer substrate coated with a conductive metal, and a combination thereof.
The positive active material layer and the negative active material layer are formed by mixing an active material, a binder and optionally a conductive material in a solvent to prepare an active material composition, and coating the active material composition on a current collector. The formation method of the active material layer is well known, and thus is not described in detail in the present disclosure. The solvent includes N-methylpyrrolidone and the like, but is not limited thereto. When a water-soluble binder is used in the negative active material layer, a solvent used for preparing the negative active material composition may be water.
The separator 30 may include polyethylene, polypropylene, polyvinylidene fluoride, and multi-layers thereof such as a polyethylene/polypropylene double-layered separator, a polyethylene/polypropylene/polyethylene triple-layered separator, or a polypropylene/polyethylene/polypropylene triple-layered separator.
Hereinafter, the disclosure (e.g., the subject matters of the disclosure) will be specifically examined (e.g., illustrated) through Examples.
(1) Positive Electrode and Negative Electrode
97.3 wt % of LiCoO2 as a positive active material, 1.4 wt % of polyvinylidene fluoride as a binder, and 1.3 wt % of ketjen black as a conductive material were mixed and then, dispersed in N-methylpyrrolidone to prepare positive active material slurry. The positive active material slurry was coated on an aluminum foil and then, dried and compressed to manufacture a positive electrode.
98 wt % of graphite as a negative active material, 1 wt % of polyvinylidene fluoride as a binder, and 1 wt % of ketjen black as a conductive material were mixed and then, dispersed in N-methylpyrrolidone to prepare a negative active material layer composition, and the negative active material layer composition was coated on a copper foil and dried to manufacture a negative electrode.
(2) Preparation of Electrolyte
0.95 M LiPF6 was added to a mixed solution of ethylene carbonate (EC):diethyl carbonate (DEC):ethylpropionate (EP) mixed in a volume ratio of 30:50:20 to prepare a non-aqueous mixed solution.
1.0 wt % of a compound represented by Chemical Formula 1-1 based on an amount of the non-aqueous mixed solution was added thereto to manufacture an electrolyte for a lithium secondary battery.
(3) Manufacture of Lithium Secondary Battery Cell
The positive and negative electrodes manufactured according to the (1) and the electrolyte prepared according to the (2) were used to manufacture a lithium secondary battery cell.
(1) Manufacture of Positive Electrode and Negative Electrode
A positive electrode and a negative electrode were manufactured in the same method as Example 1.
(2) Manufacture of Electrolyte
0.95 M LiPF6 was added to a first mixed solution of ethylene carbonate (EC):ethylmethyl carbonate (EMC):ethylpropionate (EP):γ-butyrolactone (GBL) used in a volume ratio of 27:50:20:3 to prepare a second mixed solution.
6 wt % of fluoroethylene carbonate (FEC), 0.5 wt % of vinylethylene carbonate (VEC), 0.2 wt % of lithium tetrafluoroborate (LiBF4), 5 wt % of succinonitrile (SN), 2 wt % of hexane tri-cyanide (HTCN), and 0.5 wt % of a compound represented by Chemical Formula 1-1 based on an amount of the second mixed solution were added thereto to prepare an electrolyte for a lithium secondary battery.
(3) Manufacture of Lithium Secondary Battery Cell
A prismatic lithium secondary battery was manufactured by housing the positive and negative electrodes and a polypropylene separator in a container and injecting the prepared electrolyte thereinto.
A lithium secondary battery cell was manufactured according to the same method as Example 2 except that 0.25 wt % of the compound represented by Chemical Formula 1-1 was added to prepare an electrolyte.
A lithium secondary battery cell was manufactured according to the same method as Example 2 except that 1 wt % of the compound represented by Chemical Formula 1-1 was added to prepare an electrolyte.
A lithium secondary battery cell was manufactured according to the same method as Example 2 except that 2 wt % of the compound represented by Chemical Formula 1-1 was added to prepare an electrolyte.
(1) Manufacture of Positive Electrode and Negative Electrode
A positive electrode and a negative electrode were manufactured according to the same method as Example 1.
(2) Manufacture of Electrolyte
0.95 M LiPF6 was added to a mixed solution of ethylene carbonate (EC):diethyl carbonate (DEC):ethylpropionate (EP) used in a volume ratio of 30:50:20 to prepare a non-aqueous mixed solution.
(3) Manufacture of Lithium Secondary Battery Cell
A prismatic lithium secondary battery cell was manufactured by housing the positive and negative electrodes manufactured in the above (1) and the electrolyte prepared in the above (2).
(1) Manufacture of Positive Electrode and Negative Electrode
A positive electrode and a negative electrode were manufactured according to the same method as Example 1.
(2) Manufacture of Electrolyte
An electrolyte for a lithium secondary battery cell was manufactured according to the same method as Example 2 except that the compound represented by Chemical Formula 1-1 was not added thereto.
(3) Manufacture of Lithium Secondary Battery Cell
A lithium secondary battery cell was manufactured according to the same method as Example 2.
Experimental Example 1—CV Characteristics Evaluation
Cyclic voltammetry (CV) characteristics of the half-cells according to Example 1 and Comparative Example 1 were evaluated. The result of
Example 1 is shown in
In
Referring to
Experimental Example 2—Evaluation of LSV Characteristics
The electrolytes of Example 1 and Comparative Example 1 were evaluated regarding oxidation electrode decomposition at 25° C. using a linear sweep voltammetry (LSV) method. In this evaluation, a three-electrode electrochemical cell using a Pt electrode as a working electrode, a counter electrode, and Li as a reference electrode was used. Herein, a scan was performed in a range of 3.0 V to 7.0 V at a rate of 1 mV/sec, and the results are shown in
Referring to
The lithium secondary battery cells according to Example 2 and Comparative Example 2 were constant current charged at current density of 1 C until a voltage reached 4.45 V. After measuring thicknesses of the cells after the charge, their thickness variation ratios (%) were measured every seven day, while stored at 60° C. for 28 days. The thickness variation ratios measured at the 28th day were shown in Table 1.
Referring to Table 1 and
The lithium secondary battery cells according to Example 2 and Comparative Example 2 were constant current charged at current density of 1 C at 45° C. until a voltage reached 4.45 V. Subsequently, the lithium secondary battery cells were allowed to stand for 10 minutes and then, discharged at constant current of 1 C, until the voltage reached 3 V, and this charge and discharge as one cycle was 250 times repeated. The results are shown in
Referring to
(1) Positive Electrode and Negative Electrode
96.3 wt % of LiNi0.8Co0.1Al0.1O2 as a positive active material, 1 wt % of multi-wall carbon nanotubes (CNT) having a length (e.g., an average length) of 50 μm, 1.4 wt % of polyvinylidene fluoride as a binder, and 1.3 wt % of ketjen black as a conductive material were mixed, and then dispersed in N-methylpyrrolidone to prepare a positive active material slurry. The positive active material slurry was coated on an aluminum foil, and then dried and compressed to manufacture a positive electrode.
98 wt % of graphite as a negative active material, 1 wt % of polyvinylidene fluoride as a binder, and 1 wt % of ketjen black as a conductive material were mixed and then dispersed in N-methylpyrrolidone to prepare a negative active material slurry. The negative active material slurry was coated on a copper foil, and then dried and compressed to manufacture a negative electrode.
(2) Preparation of Electrolyte
1.15 M LiPF6 was added to a mixed solution of ethylene carbonate (EC):ethyl methyl carbonate (EMC):dimethyl carbonate (DMC) mixed in a volume ratio of 20:40:40 to prepare a non-aqueous mixed solution.
1 wt % of vinylene carbonate and 1 wt % of a compound represented by Chemical Formula 1-1 based on 100 wt % of the non-aqueous mixed solution were added thereto to manufacture an electrolyte for a lithium secondary battery.
(3) Manufacture of Lithium Secondary Battery Cell
The positive and negative electrodes manufactured according to (1), the electrolyte prepared according to (2), and a polypropylene separator were used to manufacture a lithium secondary battery cell.
(1) Manufacture of Positive Electrode and Negative Electrode
A positive electrode and a negative electrode were manufactured according to the same method as Example 6.
(2) Preparation of Electrolyte
1.15 M LiPF6 was added to a mixed solution of ethylene carbonate (EC):ethyl methyl carbonate (EMC):dimethyl carbonate (DMC) mixed in a volume ratio of 20:40:40 to prepare a non-aqueous mixed solution.
1 wt % of vinylene carbonate based on 100 wt % of the non-aqueous mixed solution was added thereto to manufacture an electrolyte for a lithium secondary battery.
(3) Manufacture of Lithium Secondary Battery Cell
The positive and negative electrodes manufactured according to (1), the electrolyte prepared according to (2), and a polypropylene separator were used to manufacture a lithium secondary battery cell.
(1) Positive Electrode and Negative Electrode
96.8 wt % of LiNi0.8Co0.1Al0.1O2 as a positive active material, 0.5 wt % of multi-wall carbon nanotubes (CNT) having a length (e.g., an average length) of 50 μm, 1.4 wt % of polyvinylidene fluoride as a binder, and 1.3 wt % of ketjen black as a conductive material were mixed, and then dispersed in N-methylpyrrolidone to prepare a positive active material slurry. The positive active material slurry was coated on an aluminum foil, and then dried and compressed to manufacture a positive electrode.
A negative electrode was manufactured according to the same method as Example 6.
(2) Preparation of Electrolyte
The electrolyte was manufactured according to the same method as Example 6.
(3) Manufacture of Lithium Secondary Battery Cell
The positive and negative electrodes manufactured according to (1), the electrolyte prepared according to (2), and a polypropylene separator were used to manufacture a lithium secondary battery cell.
(1) Positive Electrode and Negative Electrode
95.3 wt % of LiNi0.8Co0.1Al0.1O2 as a positive active material, 2 wt % of multi-wall carbon nanotubes (CNT) having a length (e.g., an average length) of 50 μm, 1.4 wt % of polyvinylidene fluoride as a binder, and 1.3 wt % of ketjen black as a conductive material were mixed, and then dispersed in N-methylpyrrolidone to prepare a positive active material slurry. The positive active material slurry was coated on an aluminum foil, and then dried and compressed to manufacture a positive electrode.
A negative electrode was manufactured according to the same method as Example 6.
(2) Preparation of Electrolyte
The electrolyte was manufactured according to the same method as Example 6.
(3) Manufacture of Lithium Secondary Battery Cell
The positive and negative electrodes manufactured according to (1), the electrolyte prepared according to (2), and a polypropylene separator were used to manufacture a lithium secondary battery cell.
(1) Positive Electrode and Negative Electrode
94.3 wt % of LiNi0.8Co0.1Al0.1O2 as a positive active material, 3 wt % of multi-wall carbon nanotubes (CNT) having a length (e.g., an average length) of 50 μm, 1.4 wt % of polyvinylidene fluoride as a binder, and 1.3 wt % of ketjen black as a conductive material were mixed, and then dispersed in N-methylpyrrolidone to prepare a positive active material slurry. The positive active material slurry was coated on an aluminum foil, and then dried and compressed to manufacture a positive electrode.
A negative electrode was manufactured according to the same method as Example 6.
(2) Preparation of Electrolyte
The electrolyte was manufactured according to the same method as Example 6.
(3) Manufacture of Lithium Secondary Battery Cell
The positive and negative electrodes manufactured according to the (1), the electrolyte prepared according to the (2), and a polypropylene separator were used to manufacture a lithium secondary battery cell.
(1) Positive Electrode and Negative Electrode
97.2 wt % of LiNi0.8Co0.1Al0.1O2 as a positive active material, 0.1 wt % of multi-wall carbon nanotube (CNT) having a length (e.g., an average length) of 50 μm, 1.4 wt % of polyvinylidene fluoride as a binder, and 1.3 wt % of ketjen black as a conductive material were mixed, and then dispersed in N-methylpyrrolidone to prepare a positive active material slurry. The positive active material slurry was coated on an aluminum foil, and then dried and compressed to manufacture a positive electrode.
A negative electrode was manufactured according to the same method as Example 6.
(2) Preparation of Electrolyte
The electrolyte was manufactured according to the same method as Example 6.
(3) Manufacture of Lithium Secondary Battery Cell
The positive and negative electrodes manufactured according to the (1), the electrolyte prepared according to the (2), and a polypropylene separator were used to manufacture a lithium secondary battery cell.
(1) Positive Electrode and Negative Electrode
93.3 wt % of LiNi0.8Co0.1Al0.1O2 as a positive active material, 4 wt % of multi-wall carbon nanotubes (CNT) having a length (e.g., an average length) of 50 μm, 1.4 wt % of polyvinylidene fluoride as a binder, and 1.3 wt % of ketjen black as a conductive material were mixed, and then dispersed in N-methylpyrrolidone to prepare a positive active material slurry. The positive active material slurry was coated on an aluminum foil, and then dried and compressed to manufacture a positive electrode.
A negative electrode was manufactured according to the same method as Example 6.
(2) Preparation of Electrolyte
The electrolyte was manufactured according to the same method as Example 6.
(3) Manufacture of Lithium Secondary Battery Cell
The positive and negative electrodes manufactured according to the (1), the electrolyte prepared according to the (2), and a polypropylene separator were used to manufacture a lithium secondary battery cell.
(1) Positive Electrode and Negative Electrode
A positive electrode and a negative electrode were manufactured according to the same method as Example 6.
(2) Preparation of Electrolyte
1.15 M LiPF6 was added to a mixed solution of ethylene carbonate (EC):ethylmethyl carbonate (EMC):dimethyl carbonate (DMC) mixed in a volume ratio of 20:40:40 to prepare a non-aqueous mixed solution.
1 wt % of vinylene carbonate and 0.5 wt % of a compound represented by Chemical Formula 1-1 based on 100 wt % of the non-aqueous mixed solution were added thereto to manufacture an electrolyte for a lithium secondary battery.
(3) Manufacture of Lithium Secondary Battery Cell
The positive and negative electrodes manufactured according to the (1), the electrolyte prepared according to the (2), and a polypropylene separator were used to manufacture a lithium secondary battery cell.
(1) Positive Electrode and Negative Electrode
A positive electrode and a negative electrode were manufactured according to the same method as Example 6.
(2) Preparation of Electrolyte
1.15 M LiPF6 was added to a mixed solution of ethylene carbonate (EC):ethyl methyl carbonate (EMC):dimethyl carbonate (DMC) mixed in a volume ratio of 20:40:40 to prepare a non-aqueous mixed solution.
1 wt % of vinylene carbonate and 2 wt % of a compound represented by Chemical Formula 1-1 based on 100 wt % of the non-aqueous mixed solution were added thereto to manufacture an electrolyte for a lithium secondary battery.
(3) Manufacture of Lithium Secondary Battery Cell
The positive and negative electrodes manufactured according to the (1), the electrolyte prepared according to the (2), and a polypropylene separator were used to manufacture a lithium secondary battery cell.
(1) Positive Electrode and Negative Electrode
A positive electrode and a negative electrode were manufactured according to the same method as Example 6.
(2) Preparation of Electrolyte
1.15 M LiPF6 was added to a mixed solution of ethylene carbonate (EC):ethyl methyl carbonate (EMC):dimethyl carbonate (DMC) mixed in a volume ratio of 20:40:40 to prepare a non-aqueous mixed solution.
1 wt % of vinylene carbonate and 0.1 wt % of a compound represented by Chemical Formula 1-1 based on 100 wt % of the non-aqueous mixed solution were added thereto to manufacture an electrolyte for a lithium secondary battery.
(3) Manufacture of Lithium Secondary Battery Cell
The positive and negative electrodes manufactured according to the (1), the electrolyte prepared according to the (2), and a polypropylene separator were used to manufacture a lithium secondary battery cell.
(1) Positive Electrode and Negative Electrode
A positive electrode and a negative electrode were manufactured according to the same method as Example 6.
(2) Preparation of Electrolyte
1.15 M LiPF6 was added to a mixed solution of ethylene carbonate (EC):ethyl methyl carbonate (EMC):dimethyl carbonate (DMC) mixed in a volume ratio of 20:40:40 to prepare a non-aqueous mixed solution.
1 wt % of vinylene carbonate and 3 wt % of a compound represented by Chemical Formula 1-1 based on 100 wt % of the non-aqueous mixed solution were added thereto to manufacture an electrolyte for a lithium secondary battery.
(3) Manufacture of Lithium Secondary Battery Cell
The positive and negative electrodes manufactured according to the (1), the electrolyte prepared according to the (2), and a polypropylene separator were used to manufacture a lithium secondary battery cell.
A lithium secondary battery cell was manufactured according to the same method as Example 6, except that 1 wt % of multi-wall carbon nanotube having a length (e.g., an average length) of 5 μm was added to prepare a positive electrode.
A lithium secondary battery cell was manufactured according to the same method as Example 6, except that 1 wt % of multi-wall carbon nanotube having a length (e.g., an average length) of 100 μm was added to prepare a positive electrode.
A lithium secondary battery cell was manufactured according to the same method as Example 6, except that 1 wt % of multi-wall carbon nanotube having a length (e.g., an average length) of 1 μm was added to prepare a positive electrode.
A lithium secondary battery cell was manufactured according to the same method as Example 6, except that 1 wt % of multi-wall carbon nanotube having a length (e.g., an average length) of 200 μm was added to prepare a positive electrode.
The positive electrodes according to Examples 6 to 13, Comparative Example 3, and Reference Examples 1 to 6 were each cut into 3×6 cm to prepare samples. The samples were immersed into the electrolyte according to Examples 6 to 13, Comparative Example 3, and Reference Examples 1 to 6 for 300 seconds, respectively, the samples were then taken out from the electrolyte, and the samples were each weighed. The amount of impregnated electrolyte is the difference between the weight of each sample after immersing into the electrolyte and before immersing into the electrolyte. The results are shown in Table 2.
The lithium secondary battery cells according to Examples 6 to 13, Comparative Example 3, and Reference Examples 1 to 6 were each charged at 0.5 C and discharged at 0.5 C within the range of 2.8 V to 4.25 V at a high temperature (60° C.) for 300 times. The capacity ratio of the 300th discharge capacity relative to the 1st discharge capacity was measured for each of the lithium secondary battery cells and the results are shown as the capacity retention, in Table 2.
For each of the lithium secondary battery cells according to Examples 6 to 13, Comparative Example 3, and Reference Examples 1 to 6, DC internal resistance (DC-IR) was evaluated by measuring a voltage drop (V), while a current flowed at 1 C for 1 second under a SOC50 condition (charged to be 50% of charge capacity based on 100% of the entire (e.g., full) battery charge capacity). The measured battery cells (e.g., the battery cells after the measurement) were each stored at 60° C. for 30 days, and DC-IR was evaluated again by the above method for each of the battery cells. The ratio of the increased DC-IR after storing for 30 days to DC-IR before storing at 60° C. were calculated. The results are shown in Table 2.
As shown in Table 2, the lithium secondary battery including a positive electrode with carbon nanotubes having a length (e.g., an average length) of 50 μm and the electrolyte including the compound of Chemical Formula 1-1 according to Example 6 exhibited better impregnation of the electrolyte and improved high-temperature capacity retention, and a remarkably reduced resistance increase rate, compared to the lithium secondary battery including a positive electrode with carbon nanotubes but the electrolyte including no compound of Chemical Formula 1-1 according to Comparative Example 3. These results indicate that even if carbon nanotubes are used in the positive electrode, the improved battery performances may only be obtained from the lithium secondary battery in which the electrolyte including the compound of Chemical Formula 1-1 is used. That is, the desired effects (e.g., the improved battery performances), may be obtained from the lithium secondary battery with both the positive electrode with carbon nanotubes and the electrolyte including the compound of Chemical Formula 1-1.
In case of using the electrolyte including the compound of Chemical Formula 1-1, the lithium secondary battery including 0.5 wt % to 3 wt % of carbon nanotubes in the positive electrode according to each of Examples 7 to 9 exhibited excellent impregnation of the electrolyte and improved high-temperature capacity retention, and a remarkably reduced resistance increase rate, compared to the lithium secondary batteries including carbon nanotubes at a smaller amount in the positive electrode according to Reference Example 1, or at a larger amount according to Reference Example 2.
In case of using carbon nanotubes in the positive electrode, the lithium secondary battery including 0.5 wt % to 2 wt % of the compound of Chemical Formula 1-1 in the electrolyte according to each of Examples 10 and 11 exhibited excellent impregnation of the electrolyte and improved high-temperature capacity retention, and a remarkably reduced resistance increase rate, compared to the lithium secondary batteries including electrolyte including the compound of Chemical Formula 1-1 at a smaller amount according to Reference Example 3, or at a larger amount according to Reference Example 4.
In case of using carbon nanotubes in the positive electrode and the compound of Chemical Formula 1-1 in the electrolyte, the lithium secondary battery including carbon nanotubes having a length (e.g., an average length) of 5 μm to 100 μm in the positive electrode according to each of Examples 12 and 13 exhibited excellent impregnation of the electrolyte and improved high temperature capacity retention, and a remarkably reduced resistance increase rate, compared to the lithium secondary batteries including carbon nanotubes having a shorter length (e.g., an average length) of 1 μm according to Reference 5 and a longer length (e.g., an average length) of 200 μm according to Reference 6.
While this invention has been described in connection with what is presently considered to be practical example embodiments, it is to be understood that the invention is not limited to the disclosed embodiments, and on the contrary, it is intended to cover various modifications and equivalent arrangements included within the spirit and scope of the appended claims, and equivalents thereof.
| Number | Date | Country | Kind |
|---|---|---|---|
| 10-2016-0126806 | Sep 2016 | KR | national |
This application is a continuation-in-part of U.S. patent application Ser. No. 16/335,240, filed on Mar. 20, 2019, which is a National Phase patent application of International Patent Application Number PCT/KR2017/009934, filed on Sep. 11, 2017, which claims priority of Korean Patent Application No. 10-2016-0126806, filed on Sep. 30, 2016. The entire contents of all of which are incorporated herein by reference.
| Number | Date | Country | |
|---|---|---|---|
| Parent | 16335240 | Mar 2019 | US |
| Child | 16655126 | US |
