Patent Application
20160301105
The present invention relates to a non-aqueous electrolytic solution and an electrochemical energy storage device comprising the same. More particularly, this invention pertains to non-aqueous electrolytic solutions that comprise (a) one or more solvents; (b) one or more ionic salts; and (c) one or more additives. Non-aqueous electrolytic solutions capable of protecting either negative electrode materials, such as lithium metal and carbonaceous materials, or positive electrode materials, such as metal composite oxide containing lithium, or both, in energy storage electrochemical cells (e.g., lithium metal batteries, lithium ion batteries and supercapacitors) include a cyclic carbonate, a linear carbonate, a sultone, and a phosphazene compound. Such electrolyte solutions enhance the battery performance; notable are significant reduction in cell swelling and capacity degradation during cycling and high temperature storage.
State-of-the-art lithium ion batteries commonly use electrolytes containing lithium hexafluorophosphate (LiPF6) as solute and mixtures of cyclic carbonates and linear carbonates as solvents. Ethylene carbonate (EC) is the indispensable cyclic carbonate for the formation of stable solid electrolyte interface (SEI) at the surface of the negative electrode so that good battery performance can be achieved or enhanced, especially long cycle life.
However, in many cases the SEI protection from conventional electrolytes with simple formulations such as LiPF6 in mixtures of EC and linear carbonates is insufficient in lithium ion batteries where the negative electrode materials are carbonaceous materials including graphite carbons and non-graphite carbons, for example inexpensive natural graphite (a kind of graphite carbon) and hard carbon (a kind of amorphous non-graphite carbon), which exhibits a higher initial discharge capacity but quickly loses capacity in subsequent cycles.
On the other hand, lithium ion batteries employing high capacity cathode materials, especially those with a large amount of nickel content, are desirable for longer run time in various applications.
Swelling of lithium ion batteries is a commonly encountered problem, especially with above-mentioned nickel-rich cathode materials. Swelling means volume increase of the cells, caused by generation of gaseous products from either degradation of the electrolyte and SEI film, or reactions between the electrolyte and the electrode materials. The swelling, as demonstrated by an increase in thickness as in prismatic cells, may cause rupture of the case or increase of required space for battery packs. Besides, swelling is usually accomplished by resistance increase, open-cell voltage decrease and/or capacity loss of the cell. The problem is especially significant when the cells are stored in a charged state at elevated temperatures.
Various approaches have been disclosed in the attempt to reduce or eliminate swelling for the lithium ion batteries. In U.S. 2008/0233485, a cyclic ether, such as furan, in combination with vinylene carbonate, was shown to reduce the swelling of the battery. In U.S. 2005/0233207, a mixed additive of 2-sulfobenzoic acid cyclic anhydride and divinyl sulfone were reported to reduce swelling. U.S. Pat. No. 7,510,807 disclosed that the addition of 1-alkyl-2-pyrrolidone based compound in combination with fluoroethylene carbonate reduced swelling for a pouch-type battery cell. Each approach has its problems. For example, capacity retention of the cells may deteriorate. Therefore, in order to prevent swelling of lithium ion batteries caused by gas generation from the reaction among SEI layer, negative electrode, positive electrode and electrolytes, further innovation is needed such that other characteristics of the cells may also improve.
The present invention provides a non-aqueous electrolytic solution having a suppressed swelling, a long cycle life and high capacity retention for lithium metal and lithium ion battery using the same. In particular, the present invention provides a non-aqueous electrolytic solution having at least one cyclic carbonate, at least one linear asymmetric carbonate, a third carbonate different from the others, a sultone, and a phosphazene compound.
More precisely, the invention relates to a secondary battery comprising: (a) an anode, (b) a cathode, and, (c) an electrolytic solution, comprising (i) a lithium salt, (ii) ethylene carbonate, (iii) ethyl methyl carbonate, (iv) a third carbonate different from the others, (v) propane sultone, and (vi) a phosphazene compound.
Such electrolytic solutions help to prevent or reduce swelling in a lithium secondary battery. Beneficial side effects may include the formation of a good solid-electrolyte interface (SEI) on the negative electrode surface of the batteries, better stability of the electrolyte and better interaction between the electrolyte and electrodes. Batteries using the electrolytic solutions with such additives have long life, high capacity retention and less swelling problems.
The electrolytic solution in the present invention comprises (a) one or more solvents, (b) one or more lithium salts, and (c) one or more additives. Typical lithium salts include LiPF6, LiBF4, LiAsF6, LiClO4, LiCF3SO3, LiN(SO2CF3)2, LiN(SO2F)2, LiB(C2O4)2 (i.e. LiBOB), LiBF2C2O4 (i.e. LiDFOB), LiF4(C2O4) (LiFOP), Li2B12FxH(12−x) where x=0-12, and others, while typical solvents include ethylene carbonate (EC), propylene carbonate (PC), dimethyl carbonate (DMC), diethyl carbonate (DEC), ethylmethyl carbonate (EMC), gamma-butyrolactone (GBL), methyl butyrate (MB), propyl acetate (PA), butyl acetate (BA) and others.
An embodiment of the invention is a secondary battery comprising an anode, a cathode, and an electrolytic solution, the electrolytic solution comprising a lithium salt, a cyclic carbonate, a linear asymmetric carbonate, a third carbonate different from the others, a sultone, and a phosphazene compound.
In a preferred embodiment, a secondary battery comprises an anode, a cathode, and an electrolytic solution, the electrolytic solution comprising a lithium salt, a cyclic carbonate, a linear asymmetric carbonate, a third carbonate different from the others, propane sultone, and a phosphazene compound.
These and other features and advantages of the present invention will become more readily apparent to those skilled in the art upon consideration of the following detailed description that described both the preferred and alternative embodiments of the present invention.
The following embodiments describe the preferred mode presently contemplated for carrying out the invention and are not intended to describe all possible modifications and variations consistent with the spirit and purpose of the invention. These and other features and advantages of the present invention will become more readily apparent to those skilled in the art upon consideration of the following detailed description that describes both the preferred and alternative embodiments of the present invention.
An embodiment of the invention is a secondary battery comprising an anode, a cathode, and an electrolytic solution, the electrolytic solution comprising a lithium salt, a cyclic carbonate, a linear asymmetric carbonate, a third carbonate different from the others, a sultone, and a phosphazene compound.
In a preferred embodiment, a secondary battery comprises an anode, a cathode, and an electrolytic solution, the electrolytic solution comprising a lithium salt, a cyclic carbonate, a linear asymmetric carbonate, a third carbonate different from the others, propane sultone, and a phosphazene compound.
Another embodiment of the invention is a method of making a lithium battery or lithium ion battery comprising: (a) providing an electrolytic solution comprising (i) a non-aqueous electrolytic solution comprising (1) a lithium salt, (2) ethylene carbonate, (3) ethyl methyl carbonate, (4) a third carbonate, (5) propane sultone, and (6) a phosphazene compound, (b) stacking atop one another (1) a first porous separator, (2) a cathode, (3) a second porous separator, and (4) an anode, (c) wrapping the electrodes and separators of (b) tightly together using adhesive to form an assembly, (d) inserting the assembly into an open-ended prismatic aluminum can, (e) attaching respective current leads to respective anode and cathode, (f) adding the electrolytic solution of (a) to the can, and (g) sealing the can.
In one embodiment, the non-aqueous electrolytic solution comprises: (a) 5-25 percent LiPF6, (b) 15-50 percent ethylene carbonate, (c) 35-70 percent ethyl methyl carbonate, (d) 0.01-5 percent vinylene carbonate, (e) 0.01-5 percent ethoxypentafluorocyclotriphosphazene, and (f) 0.01-5 percent propane sultone.
Another embodiment of the invention is a method of reducing swelling in a lithium battery or lithium ion battery (as defined by increase in cell thickness measured after storage at 60 degrees centigrade for 7 days) comprising: fabricating a lithium secondary battery including a non-aqueous electrolytic solution, wherein the non-aqueous electrolytic solution includes (i) LiPF6, (ii) ethylene carbonate (EC), (iii) ethyl methyl carbonate (EMC), (iv) vinylene carbonate (VC), (v) propane sultone (PS), and (vi) a phosphazene compound.
Various embodiments of the invention are set forth in Table 1.
20-45
40-65
Broadly, the invention provides a secondary battery comprising an anode, a cathode, and an electrolytic solution. The electrolytic solution comprises a non-aqueous electrolytic solvent, a salt, and additives. The major components, solvent, salt, anode and cathode are each described in turn herein below.
Solvents. The solvents to be used in the secondary batteries of the invention can be any of a variety of are a mixture of non-aqueous, aprotic, and polar organic compounds. Generally, solvents may be carbonates, carboxylates, ethers, lactones, sulfones, phosphates, and nitriles. Useful additional carbonate solvents herein include but are not limited to cyclic carbonates such as propylene carbonate, butylene carbonate, and linear carbonates such as dimethyl carbonate, diethyl carbonate, di(2,2,2-trifluoroethyl) carbonate, dipropyl carbonate, dibutyl carbonate, ethyl methyl carbonate, 2,2,2-trifluorethyl methyl carbonate, methyl propyl carbonate, ethyl propyl carbonate, and 2,2,2-trifluorethyl propyl carbonate. Useful carbon/late solvents include but are not limited to methyl formate, ethyl formate, propyl formate, butyl formate, methyl acetate, ethyl acetate, propyl acetate, butyl acetate, methyl propionate, ethyl propionate, propyl propionate, butyl propionate, methyl butyrate, ethyl butyrate, propyl butyrate, butyl butyrate. Useful ethers include but are not limited to tetrahydrofuran, 2-methyl tetrahydrofuran, 1,3-dioxolane, 1,4-dioxane, 1,2-dimethoxyethane, 1,2-diethoxyethane, 1,2-dibutoxyethane, methyl nonafluorobutyl ether, ethyl nonafluorobutyl ether. Useful lactones include but are not limited to gamma-butyrolactone, 2-methyl-gamma-butyrolactone, 3-methyl-gamma-butyrolactone, 4-methyl-gamma-butyrolactone, beta-propiolactone, and delta-valerolactone. Useful phosphates include but are not limited to trimethyl phosphate, triethyl phosphate, tris(2-chloroethyl)phosphate, tris(2,2,2-trifluoroethyl)phosphate, tripropyl phosphate, triisopropyl phosphate, tributyl phosphate, trihexyl phosphate, triphenyl phosphate, tritolyl phosphate, methyl ethylene phosphate and ethyl ethylene phosphate. Useful sulfones include but are not limited to non-fluorinated sulfones such as dimethyl sulfone, ethyl methyl sulfone, partially fluorinated sulfones such as methyl trifluoromethyl sulfone, ethyl trifluoromethyl sulfone, methyl pentafluoroethyl sulfone, ethyl pentafluoroethyl sulfone, and fully fluorinated sulfones such as di(trifluoromethyl)sulfone, di(pentafluoroethyl)sulfone, trifluoromethyl pentafluoroethyl sulfone, trifluoromethyl nonafluorobutyl sulfone, pentafluoroethyl nonafluorobutyl sulfone. Useful nitriles include but are not limited to acetonitrile, propionitrile, and butyronitrile. Two or more of these solvents may be used in mixtures. Other solvents may be used as long as they are non-aqueous and aprotic, and are capable of dissolving the salts, such as N,N-dimethyl formamide, N,N-dimethyl acetamide, N,N-diethyl acetamide, and N,N-dimethyl trifluoroacetamide. Most preferred are ethylene carbonate and ethylmethyl carbonate.
The electrolytic solution in the present invention may further comprise one or more additives, such as a sultone (e.g., 1,3-propane sultone, and 1,4-butane sultone), an acidic anhydride (e.g. succinic anhydride), nitriles (e.g. succinonitrile) and/or phosphazenes. Phosphazenes are a class of chemical compounds wherein a phosphorus atom is covalently linked to a nitrogen atom by a double bond and to three other atoms or radicals by single bonds. Suitable phosphazenes include (singly or in combination) ethoxy-pentafluorocyclotriphosphazene, phenoxy-pentafluorocyclotriphosphazene, diethyl-tetrafluorocyclotriphosphazene, N-methyl-trifluorophophazene, N-ethyl-trifluorophophazene, phosphazene E, and phosphazene O.
The additives serve to prevent or to reduce gas generation of the electrolytic solution as the battery is charged and discharged at temperatures higher than ambient temperature.
Further additives to the electrolytic solution may include one or more of vinylene carbonate, vinyl ethylene carbonate, 4-methylene-1,3-dioxolan-2-one and 4,5-dimethylene-1,3-dioxolan-2-one. The total concentration of 4-methylene-1,3-dioxolan-2-one and 4,5-dimethylene-1,3-dioxolan-2-one in the solution preferably does not exceed about 10 wt percent.
The electrolytic solution includes a cyclic carbonate, a linear carbonate and/or other non-aqueous, aprotic, and polar organic compounds as noted hereinabove. Overall, the non-aqueous electrolytic solution comprises about 10 percent to about 99 percent by weight, preferably about 40 percent to about 97 percent by weight, and more preferably about 60 percent to about 95 percent by weight of one or more solvents. The solvents include a cyclic carbonate, a linear asymmetric carbonate, a third carbonate different from the others that structurally resembles one of the commonly used solvent but may comprise one or more double bonds which will assist the formation of a stable SEI layer.
Salts. The solute of the electrolytic solution of the invention is an ionic salt containing at least one metal ion. Typically this metal ion is lithium (Li+). The salts herein function to transfer charge between the negative electrode and the positive electrode of a battery. The lithium salts are preferably halogenated, for example, LiPF6, LiBF4, LiSbF6, LiAsF6, LiTaF6, LiAlCl4, Li2B10Cl10, Li2B10F10, LiClO4, LiCF3SO3, Li2B12FxH(12−x) wherein x=0-12; LiPFx(RF)6−x and LiBFy(RF)4−y wherein RF represents perfluorinated C1-C20 alkyl groups or perfluorinated aromatic groups, x=0-5 and y=0-3, LiBF2[O2C(CX2)nCO2], LiPF2[O2C(CX2)nCO2]2, LiPF4[O2C(CX2)nCO2], wherein X is selected from the group consisting of H, F, Cl, C1-C4 alkyl groups and fluorinated alkyl groups, and n=0-4; LiN(SO2CmF2m+1)(SO2CnF2n+1), and LiC(SO2CkF2k+1)(SO2CmF2m+1)(SO2CnF2n+1), wherein k=1-10, m=1-10, and n=1-10, respectively; LiN(SO2CpF2pSO2), and LiC(SO2CpF2pSO2)(SO2CqF2q+1) wherein p=1-10 and q=1-10; lithium salts of chelated orthoborates and chelated orthophosphates such as lithium bis(oxalato)borate [LiB(C2O4)2], lithium bis(malonato) borate [LiB(O2CCH2CO2)2], lithium bis(difluoromalonato) borate [LiB(O2CCF2CO2)2], lithium (malonato oxalato) borate [LiB(C2O4)(O2CCH2CO2)], lithium (difluoromalonato oxalato) borate [LiB(C2O4)(O2CCF2CO2)], lithium tris(oxalato) phosphate [LiP(C2O4)3], and lithium tris(difluoromalonato) phosphate [LiP(O2CCF2CO2)3]; and any combination of two or more of the aforementioned salts. Most preferably the electrolytic solution comprises LiPF6.
The concentration of the solute in the electrolytic solution may be any concentration, but normally from 0.1 to 3.0 M (mol/liter), preferably 0.2 to 2.8 M, more preferably 0.3 to 2.5M, more preferably 0.4 to 2 M and more preferably 0.5 to 1.5M.
Cathode. The cathode comprises at least one lithium mixed metal oxide (Li-MMO). Lithium mixed metal oxides contain at least one other metal selected from the group consisting of Mn, Co, Cr, Fe, Ni, V, and combinations thereof. For example the following Li-MMOs may be used in the cathode: LiCoO2, LiMnO2, LiMn2O4, Li2Cr2O7, Li2CrO4, LiNiO2, LiFeO2, LiNixCo1−xO2 (0<x<1), LiFePO4, LiVPO4, (0<z<1) (which includes LiMn0.5Ni0.5O2), LiMn1/3Co1/3Ni1/3O2, LiMc0.5Mn1.5O4, wherein Mc is a divalent metal; and LiNixCoyMezO2 wherein Me may be one or more of Al, Mg, Ti, B, Ga, or Si and 0<x,y,z<1. Furthermore, transition metal oxides such as MnO2 and V2O5; transition metal sulfides such as FeS2, MoS2 and TiS2; and conducting polymers such as polyaniline and polypyrrole may be present. The preferred positive electrode material is the lithium transition metal oxide, including, especially, LiCoO2, LiMn2O4, LiNi0.80Co0.15Al0.05O2, LiFePO4, and LiNi1/3Mn1/3CO1/3O2. Mixtures of such oxides may also be used.
Anode. The anode material is selected from lithium metal, lithium alloys, carbonaceous materials and lithium metal oxides capable of being intercalated and de-intercalated with lithium ions. Carbonaceous materials useful herein include graphite, amorphous carbon and other carbon materials such as activated carbon, carbon fiber, carbon black, and mesocarbon microbeads. Lithium metal anodes may be used. Lithium MMOs such as LiMnO2 and Li4Ti5O12 are also envisioned. Alloys of lithium with transition or other metals (including metalloids) may be used, including LiAl, LiZn, Li3Bi, Li3Cd, Li3Sb, Li4Si, Li4.4Pb, Li4.4Sn, LiC6, Li3FeN2, Li2.6Co0.4N, Li2.6Cu0.4N, and combinations thereof. The anode may further comprise an additional material such as a metal oxide including SnO, SnO2, GeO, GeO2, In2O, In2O3, PbO, PbO2, Pb2O3, Pb3O4, Ag2O, AgO, Ag2O3, Sb2O3, Sb2O4, Sb2O5, SiO, ZnO, CoO, NiO, FeO, and combinations thereof.
Either the anode or the cathode, or both, may further comprise a polymeric binder. In a preferred embodiment, the binder may be polyvinylidene fluoride, styrene-butadiene rubber, polyamide or melamine resin, and combinations thereof.
It is envisioned that the salt additives, electrolytic solutions and batteries discussed herein have a wide range of applications, including, at least, calculators, wrist watches, hearing aids, electronics such as computers, cell phones, and games, and transportation applications such as battery powered and/or hybrid vehicles.
The following compositions and batteries represent exemplary embodiments of the invention. They are presented to explain the invention in more detail, and do not limit the invention.
(1) Preparation of a Cathode. A positive electrode slurry was prepared by dispersing LiCoO2 (as positive electrode active material, 90 wt percent), poly(vinylidenfluoride) (PVdF, as bonder, 5 wt percent), and acetylene black (as electro-conductive agent, 5 wt percent) into 1-methyl-2-pyrrolidone (NMP). The slurry was coated on aluminum foil, dried, and compressed to give a positive electrode.
(2) Preparation of an Anode. Artificial graphite (as negative electrode active material, 95 wt percent) and PVdF (as binder, 5 wt percent) were mixed into NMP to give a negative active material slurry which was coated on copper foil, dried, and pressed to give a negative electrode
(3) Preparation of Electrolytic Solutions. The Baseline Electrolyte is formed by blending 61.0 g LiPF6 into 161.1 g EC and 277.9 g EMC to give 500 g baseline electrolyte. To the baseline electrolyte, 0 to 2 wt percent of different additive combination were added to create the electrolyte samples 1 to 6 as well as comparative electrolyte samples 1-4, according to table 2.
(4) Assembly of a Lithium Ion Secondary Battery. In a dry box under an inert atmosphere, a lithium ion secondary battery was assembled using a prismatic cell. That is, a microporous polypropylene separator, a cathode, another microporous polypropylene separator and an anode were laid on top of each other and then wrapped tightly together. The assembly was then inserted into a one-end-opened prismatic aluminum can. Current leads were attached to both the cathode and anode with proper insulation against each other and connection to the outside terminals. The open end was then covered leaving just a small hole. Then through the hole the electrolytic solution of the electrolyte samples 1 to 6 and the Comparative electrolyte samples 1 to 4 was added to each of the batteries and allowed to absorb to create battery examples 1 to 6 and comparative battery example 1 to 4. Finally, a small steel ball was used to seal the orifice and thus the cell, completing the assembly of the prismatic type lithium ion secondary batteries.
(5) Testing of the Batteries. Evaluation of the aforementioned assembled battery was carried out by initial charging and discharging process (formation and capacity confirmation), followed by life cycle testing and high temperature storage testing.
Initial charging and discharging of the aforementioned assembled battery was performed to form the solid electrolyte interface (SEI) on graphite electrode according to the constant current/voltage charging and the constant current discharging method in a room temperature atmosphere. That is, the battery was first charged up to 3.4 V at a constant current rate of 15 mA, followed by charging at a constant current rate of 110 mA up to 3.95V. The battery was then discharged and charged with normal constant-current constant voltage profile. During charge, after reaching 4.2 V, the battery was continually charged at a constant voltage of 4.2 V until the charging current was less than or equal to 25 mA. Then the battery was discharged at a constant current rate of 275 mA/cm2 until the cut-off voltage 3.0 V reached. Standard capacity of a non-aqueous electrolyte secondary battery was 550 mAh.
High temperature storage test was conducted by first charging the aforementioned initially charged/discharged battery under room temperature at a constant current rate of C (550 mA) to 4.2 V and then charged at a constant voltage of 4.2 V until the current was less than or equal to 25 mA. The battery was then discharged at a constant current rate of C (550 mA) until the cut-off voltage 3.0 V was reached. This discharge capacity was noted as the starting discharge capacity. The battery was then charged again under room temperature at a constant current rate of C (550 mA) to 4.2 V and then charged at a constant voltage of 4.2 V until the current was less than or equal to 25 mA. The fully charged battery was stored at oven set at constant temperature of 60 degrees centigrade for one week. Thickness of the battery was measured before and after the storage when the battery was at both the storage temperature and room temperature. The retained discharge capacity was obtained by constant current discharge at C rate (550 mA) under room temperature after the storage. The recoverable discharge capacity was obtained by continuing cycling the battery the same way as before the storage test.
The thickness increase rate was calculated as (Thickness before the storage−thickness after the storage)+thickness after the storage×100 percent.
The capacity retention ratio was calculated as retained capacity after the storage÷starting capacity×100 percent.
The recoverable capacity ratio was calculated as Recoverable capacity after the storage÷starting discharge capacity×100 percent
As shown in Table 3, the thickness increase rate of Examples 1-6 according to the present invention were much smaller than those of the comparative examples 1-4, indicating an improvement (reduction) in swelling after storage at high temperature storage.
At the same time, the capacity retention ratios of Examples 1-6 according to the present invention under high temperature storage was also improved (or remained substantially the same as the Comparative Examples), as shown in Table 4.
Cycle life test was conducted at room temperature by charging the aforementioned initially charged/discharged battery at a constant current rate of C (550 mA) to 4.2 V and then charged at a constant voltage of 4.2 V until the current was less than or equal to 25 mA. The battery was then discharged at a constant current rate of C (550 mA) until the cut-off voltage 3.0 V was reached.
The 1st C-rate cycle efficiency and discharge capacity retention of each example cell are shown in Table 4. Discharge capacity retention rate of cycle life (percent)=(nth cycle discharge capacity/1st cycle discharge capacity)×100 percent. NM means not measured.
As shown in Table 5, 1st C-rate cycle discharge capacity and capacity retention of Examples 1-6 were improved over Comparative Examples. Overall, only Examples 1-6 according to current invention show the simultaneous improvement both on the thickness aspect and capacity retention aspects.
Certain embodiments of the invention are envisioned where at least some percentages, temperatures, times, and ranges of other values are preceded by the modifier “about.” “Comprising” is intended to provide support for “consisting of” and “consisting essentially of.” Where ranges in the claims of this provisional application do not find explicit support in the specification, it is intended that such claims provide their own disclosure as support for claims or teachings in a later filed non-provisional application. Numerical ranges of ingredients that are bounded by zero on the lower end (for example, 0-10 wt percent VC) are intended to provide support for the concept “up to [the upper limit],” for example “up to 10 wt percent VC,” vice versa, as well as a positive recitation that the ingredient in question is present in an amount that does not exceed the upper limit. An example of the latter is “comprises VC, provided the amount does not exceed 10 wt percent.” A recitation such as “8-25 wt percent (EC+MEC+VC)” means that any or all of EC, MEC and/or VC may be present in an amount of 8-25 wt percent of the composition.
While the invention herein disclosed has been described by means of specific embodiments and applications thereof, numerous modifications and variations could be made thereto by those skilled in the art without departing from the scope of the invention set forth in the claims. Furthermore, various aspects of the invention may be used in other applications than those for which they were specifically described herein.
This application is a CON of Ser. No. 13/012,832 filed Jan. 25, 2011. The entire disclosure of the aforesaid application is incorporated herein in its entirety by reference
| Number | Date | Country | |
|---|---|---|---|
| Parent | 13012832 | Jan 2011 | US |
| Child | 15190225 | US |
