Patent Application
20150010815
Korean Patent Application No. 10-2013-0079843, filed on Jul. 8, 2013, and Korean Patent Application No. 10-2013-0149459, filed on Dec. 3, 2013, in the Korean Intellectual Property Office, and entitled: “Binder Composition For Rechargeable Lithium Battery, Preparing Method Of Same, and Rechargeable Lithium Battery Including Binder Composition,” is incorporated by reference herein in its entirety.
1. Field
Embodiments are directed to a binder composition for a rechargeable lithium battery, a method of preparing the same, and a rechargeable lithium battery including the same are disclosed.
2. Description of the Related Art
A rechargeable lithium battery includes positive and negative electrodes including a material that can reversibly intercalate/deintercalate lithium ions as positive and negative active materials and an organic electrolyte solution or a polymer electrolyte solution filled between the positive and negative electrodes. The positive and negative electrodes intercalate and deintercalate lithium ions and produce electrical energy through oxidation and reduction reactions.
As for a positive active material for a lithium rechargeable battery, a lithium-transition metal oxide being capable of intercalating lithium such as LiCoO2, LiMn2O4, LiNi1-xCoxO2 (0<x<1), and the like has been used.
As for a negative active material for a lithium rechargeable battery, various carbon-based materials such as artificial graphite, natural graphite, and hard carbon capable of intercalating and deintercalating lithium ions have been used.
Embodiments are directed to a binder composition for a rechargeable lithium battery including a semi-interpenetrating polymer network (semi-IPN) including a copolymer having a repeating unit represented by the following Chemical Formula 1 and a repeating unit represented by the following Chemical Formula 2; and polyacrylamide,
The repeating unit represented by the above Chemical Formula 1 may be included in an amount of about 40 mol % to about 90 mol % based on a total amount of the copolymer.
The repeating unit represented by the above Chemical Formula 2 may be included in an amount of about 10 mol % to about 60 mol % based on a total amount of the copolymer.
A mole ratio of the copolymer to the polyacrylamide may range from about 1:9 to about 5:5.
The binder composition may further include a free alkali metal ion.
The free alkali metal ion may be included in an amount of about 1 part by mole to about 10 parts by mole based on 100 parts by mole of the semi interpenetrating polymer network.
The binder composition may further include an alkali metal ion and a phosphorus (P)-based compound.
The phosphorus-based compound may be phosphorus-containing anion.
The alkali metal ion and the phosphorus-based compound may be adsorbed on the semi interpenetrating polymer network.
The phosphorus-based compound may be included in an amount of about 1 part by mole to about 10 parts by mole based on 100 parts by mole of the semi interpenetrating polymer network.
The binder composition for a rechargeable lithium battery may further include polyalkylene glycol.
The polyalkylene glycol may be included in an amount of about 5 mol % to about 50 mol % based on total amount of the binder composition for a rechargeable lithium battery.
The polyalkylene glycol may have a weight-average molecular weight of about 400 g/mol to about 10,000 g/mol.
The binder composition may have a pH of about 6 to about 11.
A viscosity of the binder composition may range from about 10,000 cps to about 100,000 cps.
Embodiments are also directed to a rechargeable lithium battery including an electrode including the binder composition according to claim 1, and an active material; and an electrolyte.
The active material may include Si, SiOx, a Si—C composite, a Si-Q alloy, graphite, or a combination thereof, wherein x in SiOx is in the range of 0<x<2, and Q in Si-Q is an alkali metal, an alkaline-earth metal, a Group 13 to 16 element, a transition element, a rare earth element, or a combination thereof, but is not Si.
Embodiments are also directed to a method of manufacturing a binder composition for a rechargeable lithium battery including preparing a copolymer of at least one monomer selected from an olefin-based monomer, an aromatic vinyl monomer, and an alkyl vinyl ether monomer, and a cyclic unsaturated acid anhydride monomer, adding an alkali metal-containing compound to a solution including the copolymer, and adding an acrylamide monomer to the solution to perform polymerization such that a semi-interpenetrating network structure of the copolymer and polyacrylamide is formed.
The cyclic unsaturated acid anhydride monomer may be included in an amount of about 40 mol % to about 90 mol % based on a total amount of the copolymer.
The at least one monomer selected from the olefin-based monomer, the aromatic vinyl monomer, and the alkyl vinyl ether monomer may be included in an amount of about 10 mol % to about 60 mol % based on the total amount of the copolymer.
During adding the alkali metal-containing compound to the solution, the alkali metal-containing compound may be included in an amount of about 28 parts by weight to about 34 parts by weight based on 100 parts by weight of the copolymer.
A mole ratio of the copolymer to the polyacrylamide may range from about 1:9 to about 5:5.
The method may further include, during performing polymerization and forming the semi-interpenetrating network structure after adding the acrylamide monomer to the solution, adding a polymerization initiator to the solution.
The method may further include, after forming the semi-interpenetrating network structure, adding an alkali metal compound.
The alkali metal compound may be added such that a lithium ion content is about 1 part by mole to about 10 parts by mole based on 100 parts by mole of the semi interpenetrating network structure.
The manufacturing method may further include adding a compound including an alkali metal and phosphorus after forming the semi interpenetrating network structure.
The compound including an alkali metal and phosphorus may be a lithium phosphate-based compound.
The compound including an alkali metal and phosphorus may be added in an amount of about 1 part by mole to about 10 parts by mole based on 100 parts by mole of the semi interpenetrating network structure.
The method of manufacturing the binder composition for a rechargeable lithium battery may further include adding polyalkylene glycol to the solution including the copolymer after preparing the copolymer.
The polyalkylene glycol may be included in an amount of about 5 mol % to about 50 mol % based on total amount of the binder composition for a rechargeable lithium battery.
The polyalkylene glycol may have a weight-average molecular weight of about 400 g/mol to about 10,000 g/mol.
Features will become apparent to those of skill in the art by describing in detail exemplary embodiments with reference to the attached drawings in which:
Example embodiments will now be described more fully hereinafter with reference to the accompanying drawings; however, they may be embodied in different forms and should not be construed as limited to the embodiments set forth herein. Rather, these embodiments are provided so that this disclosure will be thorough and complete, and will fully convey exemplary implementations to those skilled in the art. In the drawing figures, the dimensions of layers and regions may be exaggerated for clarity of illustration.
As used herein, when a definition is not otherwise provided, the term “substituted” may refer to substitution with a halogen, a C1 to C30 alkyl group; a C2 to C30 alkenyl group, a C2 to C30 alkynyl group, a C1 to C10 alkylsilyl group; a C3 to C30 cycloalkyl group; C6 to C30 aryl group; a C1 to C30 heteroaryl group; or a C1 to C10 alkoxy group, instead of at least one hydrogen of a compound.
As used herein, when a definition is not otherwise provided, the term “hetero” may refer to one selected from N, O, S, and P.
As used herein, when a definition is not otherwise provided, the tem). “alkyl group” may refer to “a saturated alkyl group” without any alkenyl group or alkynyl group; or “an unsaturated alkyl group” including at least one alkenyl group or alkynyl group. The term “alkenyl group” may refer to a substituent having at least one carbon-carbon double bond of at least two carbons, and the term “alkyne group” may refer to a substituent having at least one carbon-carbon triple bond of at least two carbons. The alkyl group may be a branched, linear, or cyclic alkyl group.
The alkyl group may be a C1 to C20 alkyl group, for example, a C1 to C6 lower alkyl group, a C7 to C10 medium-sized alkyl group, or a C11 to C20 higher alkyl group.
For example, a C1 to C4 alkyl group may have 1 to 4 carbon atoms in an alkyl chain and may be selected from methyl, ethyl, propyl, iso-propyl, n-butyl, iso-butyl, sec-butyl, and t-butyl.
Examples of the alkyl group may be a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, an isobutyl group, a t-butyl group, a pentyl group, a hexyl group, an ethenyl group, a propenyl group, a butenyl group, a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, a cyclohexyl group, or the like.
The term “aryl group” may refer to a cyclic substituent including all elements having a p-orbital which form conjugation and may refer to a monocyclic or fused ring (i.e., a plurality of rings sharing adjacent pairs of carbon atoms).
The substituted or unsubstituted C6 to C30 aryl group may be, for example, a substituted or unsubstituted phenyl group, a substituted or unsubstituted naphthyl group, a substituted or unsubstituted anthracenyl group, a substituted or unsubstituted phenanthryl group, a substituted or unsubstituted naphthacenyl group, a substituted or unsubstituted pyrenyl group, a substituted or unsubstituted biphenylyl group, a substituted or unsubstituted p-terphenyl group, a substituted or unsubstituted m-terphenyl group, a substituted or unsubstituted chrysenyl group, a substituted or unsubstituted triphenylenyl group, a substituted or unsubstituted perylenyl group, a substituted or unsubstituted indenyl group, or a combination thereof, as examples.
As used herein, when a definition is not otherwise provided, the term “copolymerization” may refer to block copolymerization, random copolymerization, graft copolymerization, or alternating copolymerization, and the term “copolymer” may refer to a block copolymer, a random copolymer, a graft copolymer, or an alternating copolymer.
In an embodiment, a binder composition for a rechargeable lithium battery includes a semi-interpenetrating polymer network (semi-IPN) including a copolymer including a repeating unit represented by the following Chemical Formula 1 and a repeating unit represented by the following Chemical Formula 2; and polyacrylamide.
In the above Chemical Formula 1, R1 and R2 are the same or different and are independently selected from hydrogen, or a substituted or unsubstituted C1 to C10 alkyl group, and R3 and R4 are an alkali metal.
In the above Chemical Formula 2, R5 to R8 are the same or different, and are independently hydrogen, a substituted or unsubstituted C1 to C30 alkyl group, a substituted or unsubstituted C6 to C30 aryl group, or a substituted or unsubstituted C1 to C30 alkoxy group.
The semi interpenetrating polymer network has a net structure of a copolymer including a repeating unit represented by Chemical Formula 1 and a repeating unit represented by Chemical Formula 2 and cross-linked polyacrylamide.
The semi-interpenetrating polymer network may have strong and tough characteristics and may simultaneously exhibit excellent flexibility. The binder composition including the same may control expansion of an active material effectively, and may have improved adherence and stability with an electrolyte. In addition, the binder composition may be used with an aqueous solvent and thus may be environment-friendly. A rechargeable lithium battery including the binder composition may provide high capacity and excellent initial efficiency, charge and discharge characteristics, and cycle-life characteristics.
The repeating unit represented by the above Chemical Formula 1 may be derived from a cyclic unsaturated acid anhydride monomer such as maleic anhydride, or the like. The copolymer may be dissolved in an aqueous solvent due to the repeating unit represented by the above Chemical Formula 1.
In the above Chemical Formula 1, R3 and R4 may be an alkali metal, for example, lithium, sodium, potassium, rubidium, cesium, or the like. For example, R3 and R4 may be lithium. In this way, by using the copolymer having a structure where an alkali metal is the substituent at the R3 and R4 positions of the above Chemical Formula 1, the initial efficiency of a rechargeable lithium battery including the same may be improved.
The repeating unit represented by the above Chemical Formula 1 may be included in an amount of about 40 mol % to about 90 mol % based on the total amount of the copolymer. For example, the repeating unit may be included in an amount of about 50 mol % to about 90 mol %, or about 50 mol % to about 80 mol %. The copolymer and the binder composition including the same may be desirably dissolved in an aqueous solvent and flexibility and adherence may be ensured.
In the above Chemical Formula 2, as examples, the C1 to C30 alkyl group may be a C1 to C20 alkyl group, a C1 to C10 alkyl group, or a C1 to C5 alkyl group. For example, the C1 to C30 alkyl group may be a methyl group, an ethyl group, a propyl group, or the like.
As specific examples, the C6 to C30 aryl group may be a C6 to C20 aryl group, or a C6 to C10 aryl group, and the C1 to C30 alkoxy group may be, for example a C1 to C20 alkoxy group, a C1 to C10 alkoxy group, or the like.
The repeating unit represented by the above Chemical Formula 2 may be derived from the olefin-based monomer, an aromatic vinyl monomer, an alkyl vinyl ether monomer, or the like.
The olefin-based monomer may be, for example ethylene, propylene, butylene, isobutylene, 1-heptene, 1-decene, 1-octadecene, or the like, and the aromatic vinyl monomer may be styrene, o-ethyl styrene, m-ethyl styrene, p-ethyl styrene, α-methyl styrene, or the like. The alkyl vinyl ether monomer may be methylvinylether, ethylvinylether, propylvinylether, butylvinylether, or the like. These may be used singularly or as a mixture thereof.
The repeating unit represented by the above Chemical Formula 2 may be included in an amount of about 10 mol % to about 60 mol % based on the total amount of the copolymer. For example, the repeating unit may be included in an amount of about 10 mol % to about 50 mol %, or about 20 mol % to about 50 mol %. Within the above range, the copolymer and the binder composition including the same may have excellent flexibility, may be may be dissolved in an aqueous solvent, and may control expansion of an active material.
The copolymer forms a semi-interpenetrating network structure with polyacrylamide. The binder composition includes a semi-interpenetrating polymer network (semi-IPN), and the semi-interpenetrating polymer network includes the above-described copolymer and polyacrylamide.
The term “interpenetrating polymer network (IPN)” may refer to a network of heterogeneous polymers combined without a covalent bond. Among the interpenetrating polymer networks, a term “semi-interpenetrating network” (semi-IPN) refers to a material at which linear polymers and cross-linking polymers form a network structure.
Such a semi-interpenetrating polymer network may include two kinds of polymers in a chain shape to form a network structure, and may have strong and tough characteristics and excellent flexibility compared with a general copolymer. Accordingly, the binder composition including the semi-interpenetrating polymer network may effectively control the expansion of an active material.
In the semi-interpenetrating polymer network, a mole ratio of the copolymer to the polyacrylamide may range from about 1:9 to about 5:5. For example, the mole ratio may range from about 2:8 to about 5:5, or about 2:8 to about 4:6.
The polyacrylamide may be included in an amount of about 50 mol % to about 90 mol % based on the total amount of the semi-interpenetrating polymer network. For example, the polyacrylamide may be included in an amount of about 50 mol % to about 80 mol %, or about 60 mol % to about 80 mol %.
In this case, the semi-interpenetrating polymer network may ensure excellent adherence and flexibility, and thus the binder composition may be effectively capable of controlling expansion of an active material.
The binder composition may further include a free alkali metal ion. The free alkali metal ion may be, for example Li+, Na+, K+, Rb+, Cs+, and the like. In this case, a rechargeable lithium battery including the binder composition may have more improved charge and discharge characteristics.
The free alkali metal ion may be included in an amount of about 1 part by mole to about 10 parts by mole based on 100 parts by mole of the semi interpenetrating polymer network. For example, the free alkali metal ion may be included in an amount of about 1 part by mole to about 9 parts by mole, about 1 part by mole to about 8 parts by mole, or about 1 part by mole to about 7 parts by mole. In this case, charge and discharge characteristics of a battery may be effectively improved.
The binder composition may further include an alkali metal ion and a phosphorus (P)-based compound.
The phosphorus-based compound may be, for example a phosphorus-based anion, i.e, a phosphorus-containing anion. The phosphorus-based compound may be a phosphoric acid anion, for example, PO43−, HPO42−, H2PO4−, or a combination thereof.
The alkali metal ion and the phosphorus-based compound may have a structure so as to be adsorbed on the semi interpenetrating polymer network.
In this way, when the alkali metal ion and the phosphorus-based compound are further included in the binder composition, gas generation during preparation of the binder composition (slurry) and charge and discharge of a battery may be suppressed. Accordingly, a rechargeable lithium battery having excellent cycle-life and initial efficiency and stable charge and discharge characteristics may be provided.
The alkali metal ion may be included in an amount of about 1 part by mole to about 10 parts by mole based on 100 parts by mole of the semi interpenetrating polymer network. The alkali metal ion may be included in an amount of about 1 part by mole to about 9 parts by mole, about 1 part by mole to about 8 parts by mole, or about 1 part by mole to about 7 parts by mole. In addition, an amount of the phosphorus-based compound may be about 1 part by mole to about 10 parts by mole based on 100 parts of by mole the semi interpenetrating polymer network. For example, the amount may be about 1 part by mole to about 9 parts by mole, about 1 part by mole to about 8 parts by mole, or about 1 part by mole to about 7 parts by mole. In this case, gas generation may be suppressed effectively, and thus stable charge and discharge characteristics of a battery may be realized.
The binder composition for a rechargeable lithium battery may further include polyalkylene glycol.
Herein, the polyalkylene glycol may be blended with the semi interpenetrating polymer network.
When the binder composition for a rechargeable lithium battery further includes polyalkylene glycol, cracking of a binder layer is cracked and bending of an electrode when coated may be reduced, and also, a density of a coating layer for an active material layer before drying may be improved. Thus, a loading level of an electrode may be increased.
The polyalkylene glycol may be, for example polymethylene glycol, polyethylene glycol, polypropylene glycol, polybutylene glycol, polyisobutylene glycol, and the like.
The polyalkylene glycol may have a weight-average molecular weight of about 400 g/mol to about 10,000 g/mol. For example, the polyalkylene glycol may have a weight-average molecular weight of about 400 g/mol to about 9,000 g/mol, or about 400 g/mol to about 8,000 g/mol.
The binder composition for a rechargeable lithium battery may include polyalkylene glycol in an amount of about 0 to about 50 mol %, for example, about 5 mol % to about 50 mol %, about 5 mol % to about 40 mol %, or about 5 mol % to about 30 mol %. Herein, the binder composition for a rechargeable lithium battery may effectively control expansion of an active material and simultaneously reduce cracking or bending of a binder layer when the binder is dried. Also, a density of a wet film may be improved and thus, a loading level of an electrode may be increased.
The binder composition may include a solvent as well as the copolymer, or free alkali metal ion. The solvent may be an organic solvent or an aqueous solvent. The binder composition may be used with an aqueous solvent, and thus, may be environmentally friendly.
The binder composition may have a pH of about 6 to about 11.
For example, when the binder composition further includes the phosphorus-based compound, the binder composition may have a pH of about 6 to about 8, or, for example, about 7 to about 8.
A viscosity of the binder composition may range from about 10,000 cps to about 100,000 cps. For example, viscosity may range from about 10,000 cps to about 90,000 cps, about 10,000 cps to about 80,000 cps, or about 10,000 cps to about 70,000 cps.
In another embodiment, a method of preparing a binder composition for a rechargeable lithium battery includes preparing a copolymer of at least one monomer selected from the olefin-based monomer, aromatic vinyl monomer, and alkyl vinyl ether monomer and a cyclic unsaturated acid anhydride monomer, adding an alkali metal-containing compound to a solution including the copolymer, and adding an acrylamide monomer to the solution to perform polymerization, and forming a semi-interpenetrating network structure of the copolymer and polyacrylamide.
The binder composition prepared by the above method may effectively control expansion of an active material, and may have improved adherence and stability with an electrolyte. The binder composition may use an aqueous solvent and may be environment-friendly. In addition, a rechargeable lithium battery including the binder composition may have a high capacity and excellent initial efficiency, charge and discharge characteristics and cycle-life characteristics.
The cyclic unsaturated acid anhydride monomer may be represented by the following Chemical Formula 3.
In the above Chemical Formula 3, R′ and R2 may be the same or different and may be independently selected from hydrogen or a substituted or unsubstituted C1 to C10 alkyl group.
The cyclic unsaturated acid anhydride monomer may be, for example maleic anhydride.
The amount of the cyclic unsaturated acid anhydride monomer may range from about 40 mol % to about 90 mol % based on the total amount of the copolymer. For example, the amount may range from about 40 mol % to about 80 mol %, or about 50 mol % to about 80 mol %. In this case, the copolymer and the binder composition including the same may be desirably dissolved in an aqueous solvent and flexibility and adherence may be ensured.
The amount of the at least one monomer selected from the olefin-based monomer, aromatic vinyl monomer, and alkyl vinyl ether monomer may range from about 10 mol % to about 60 mol % based on the total amount of the copolymer. For example, the amount may range from about 20 mol % to about 50 mol %, or about 20 mol % to about 40 mol %. Within the above range, the copolymer and the binder composition including the same may have excellent flexibility, may be may be dissolved in an aqueous solvent, and may control expansion of an active material.
The olefin-based monomer, aromatic vinyl monomer, and alkyl vinyl ether monomer are the same as described above.
When adding the alkali metal-containing compound to the solution, the alkali metal-containing compound may be included in an amount of about 28 parts by weight to about 34 parts by weight based on 100 parts by weight of the copolymer.
In the alkali metal-containing compound, the alkali metal may be, for example, lithium, sodium, potassium, rubidium, cesium, or the like, and may be, for example lithium. The alkali metal-containing compound may be an alkali metal hydroxide, an alkali metal salt, or the like.
By adding the alkali metal-containing compound to the copolymer, the copolymer may include a dicarboxyl repeating unit substituted with an alkali metal as in Chemical Formula 1. Thereby, initial efficiency of a rechargeable lithium battery may be improved.
In the interpenetrating network structure, a mole ratio of the copolymer to the polyacrylamide may range from about 1:9 to about 5:5. For example, the mole ratio may range from about 2:8 to about 5:5 or about 2:8 to about 4:6. The polyacrylamide may be included in an amount of about 50 mol % to about 90 mol % based on the total amount of the semi-interpenetrating polymer network. For example, the polyacrylamide may be included in an amount of about 50 mol % to about 80 mol %, or about 60 mol % to about 80 mol %. In this case, the semi-interpenetrating polymer network may ensure excellent adherence and flexibility, and thereby the binder composition may effectively control expansion of an active material.
The semi-interpenetrating network structure may be formed by any suitable method. In one implementation, a first polymer may be primarily synthesized and swelled, then a monomer of a second polymer, a cross-linking agent, an initiator, or the like may be added, and the second polymer is synthesized in the presence of the first polymer. In another implementation, a first polymer and a second polymer may be synthesized according to a different mechanism from each other, a monomer or prepolymer of the first polymer, a monomer or prepolymer of the second polymer, a cross-linking agent, initiator, or the like may be mixed to perform cross-linking polymerization of the first polymer and the second polymer simultaneously and to form the semi-interpenetrating network structure.
In still another implementation, a monomer of acrylamide may be added and polymerized in a presence of the copolymer, to form the semi-interpenetrating network structure.
In the preparing method, a cross-linking agent, a polymerization initiator, and the like may be added with the acrylamide monomer.
The polymerization initiator may include ammonium persulfate, sodium persulfate, potassium persulfate, hydrogen peroxide, 2,2-azobis-(2-amidinopropane)dihydrochloride, 2,2-azobis-(N,N-dimethylene)isobutyramidine dihydrochloride, 2-(carbamoylazo)isobutyronitrile, 2,2-azobis[2-(2-imidazolin-2-yl)propane]dihydrochloride, 4,4-azobis-(4-cyanovaleric acid), ascorbic acid, benzoyl peroxide, dibenzoyl peroxide, lauryl peroxide, ditertiarybutyl peroxide, or the like.
The preparing method may further include adding an alkali metal compound after forming the semi-interpenetrating network structure. The binder composition may further include a free alkali metal ion. In this case, a rechargeable lithium battery including the binder composition may have improved charge and discharge characteristics.
The alkali metal may be, for example lithium, sodium, potassium, rubidium, cesium, and the like. The term “alkali metal compound” may refer to an alkali metal-containing compound, which may be, for example an alkali metal hydroxide, an alkali metal salt, or the like.
The alkali metal compound may be added in an amount of about 1 part by mole to about 10 parts by mole based on 100 parts by mole of the semi interpenetrating network structure. For example, the alkali metal compound may be added in an amount of about 1 part by mole to about 9 parts by mole, about 1 part by mole to about 8 parts by mole, or about 1 part by mole to about 7 parts by mole. In this case, charge and discharge characteristics of a battery may be effectively improved.
The alkali metal compound may be for example ‘a compound including an alkali metal and phosphorus. The manufacturing method may further include adding’ a compound including an alkali metal and phosphorus after forming the semi interpenetrating network structure.
The term “compound including an alkali metal and phosphorus” refers to a compound including an alkali metal and phosphorus simultaneously. Such a compound may be, for example, an alkali metal phosphate-based compound. The compound including an alkali metal and phosphorus may be a lithium phosphate-based compound, for example LiH2PO4, Li2HPO4, Li3PO4, or a combination thereof.
When the compound including an alkali metal and phosphorus is added to the binder composition, the binder composition may further include the alkali metal ion and also, the phosphorus-based compound. For example, the binder composition may have a semi interpenetrating network structure in which the alkali metal ion and the phosphorus-based compound are absorbed. In other implementations, the binder composition may have a semi interpenetrating network structure including phosphorus.
The phosphorus-based compound may be phosphorus or a phosphorus-containing compound. The phosphorus-based compound may be a phosphoric acid anion, for example PO43−, HPO42−, H2PO4−, or a combination thereof.
When the manufacturing method further includes an addition of a compound including an alkali metal and phosphorus to the binder composition, a problem of gas generation during preparation of the binder composition (slurry) and during charge and discharge of a battery may be suppressed. Accordingly, a rechargeable lithium battery having excellent cycle-life and initial efficiency and stable charge and discharge characteristics may be provided.
The compound including an alkali metal and phosphorus may be added in an amount of about 1 part by mole to about 10 parts by mole, or, for example, about 1 part by mole to about 9 parts by mole, about 1 part by mole to about 8 parts by mole, or about 1 part by mole to about 7 parts by mole based on 100 parts by mole of the semi interpenetrating network structure. In this case, gas generation may be effectively suppressed, and thus, stable charge and discharge characteristics of a battery may be realized.
The method of manufacturing the binder composition for a rechargeable lithium battery may further include adding polyalkylene glycol to the solution including the copolymer after preparing the copolymer. Herein, the binder composition may have a structure that the semi interpenetrating polymer network is blended with polyalkylene glycol.
Herein, cracking of a binder layer or bending of an electrode may be reduced when the binder composition is coated and dried, and in addition, a loading level of an electrode may be increased due to density improvement of a wet film.
The polyalkylene glycol may be included in an amount of about 5 mol % to about 50 mol % based on total amount of the binder composition for a rechargeable lithium battery. For example, the polyalkylene glycol may be included in an amount of about 5 mole % to about 40 mol %, or about 5 mol % to about 30 mol %. Cracking of a binder layer or bending of an electrode may be reduced when the binder composition is coated and dried. In addition, a loading level of an electrode may be increased due to density improvement of a wet film.
The polyalkylene glycol may be as described above.
In another embodiment, a rechargeable lithium battery including the above-described binder composition is provided. For example, the rechargeable lithium battery may include electrodes and an electrolyte, the electrode may include a current collector and an active material layer positioned on the current collector, and the active material layer may include an active material and the above-described binder composition.
The active material may include a silicon-based compound, graphite, or a combination thereof. For example, the active material may include Si, SiOx, where x is in the range of 0<x<2, a Si—C composite, a Si-Q alloy, where Q is an alkali metal, an alkaline-earth metal, a Group 13 to 16 element, a transition element, a rare earth element, or a combination thereof but not Si, graphite, or a combination thereof.
The silicon-based electrode active material has large capacity but undergoes volume expansion as a cycle goes, and a cycle-life of a battery may be deteriorated. When a general binder composition is used, a silicon-based negative active material may undergo volume expansion as a cycle proceeds, and a cycle-life of a battery may be deteriorated. When the silicon-based active material is used with the above-described binder composition, the binder composition may effectively control volume expansion of the silicon-based negative active material, and cycle-life characteristics of a battery may be improved.
Accordingly, a rechargeable lithium battery having high charge and discharge capacity and simultaneously, excellent cycle-life characteristics and stability may be provided.
The electrode may include a positive electrode and a negative electrode. The binder composition according to one embodiment may be used in either a positive electrode or a negative electrode.
According to an implementation, the binder composition may be applied to a negative electrode.
The rechargeable lithium battery is described referring to
Referring to
The negative electrode 112 includes a current collector and a negative active material layer formed on the current collector.
The current collector may include 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, or a combination thereof.
The negative active material layer includes a negative active material, the binder composition, and optionally, a conductive material.
The negative active material may include a material that reversibly intercalates/deintercalates lithium ions, a lithium metal, a lithium metal alloy, a material being capable of doping and dedoping lithium, or a transition metal oxide.
The material that reversibly intercalates/deintercalates lithium ions may be a carbon material, and may be any generally-used carbon-based negative active material in a rechargeable lithium ion battery. Examples thereof may include crystalline carbon, amorphous carbon, or a combination thereof. Examples of the crystalline carbon may be a graphite such as a shapeless, sheet-shaped, flake, spherical shaped or fiber-shaped natural graphite or artificial graphite, and examples of the amorphous carbon may be soft carbon or hard carbon, a mesophase pitch carbonized product, fired cokes, or the like.
The lithium metal alloy may include an alloy of lithium and a metal of Na, K, Rb, Cs, Fr, Be, Mg, Ca, Sr, Si, Sb, Pb, In, Zn, Ba, Ra, Ge, Al, or Sn.
The material being capable of doping and dedoping lithium may be Si, SiOx (0<x<2), a Si—C composite, a Si-Q alloy (wherein Q is an alkali metal, an alkaline-earth metal, a Group 13 to 16 element, a transition metal, a rare earth element, or a combination thereof, and not Si), Sn, SnO2, a Sn—C composite, Sn—R (wherein R is an alkali metal, an alkaline-earth metal, Group 13 to 16 elements, a transition metal, a rare earth element, or a combination thereof, and not Sn), and the like. Specific examples of the Q and R may be Mg, Ca, Sr, Ba, Ra, Sc, Y, Ti, Zr, Hf, V, Nb, Ta, Cr, Mo, W, Tc, Re, Fe, Pb, Ru, Os, Rh, Ir, Pd, Pt, Cu, Ag, Au, Zn, Cd, B, Al, Ga, Sn, In, Tl, Ge, P, As, Sb, Bi, S, Se, Te, Po, or a combination thereof.
The transition metal oxide may be vanadium oxide, lithium vanadium oxide, or the like.
The binder composition is the same as described above, and these descriptions thereof are not repeated.
The conductive material may improve the electrical conductivity of the electrode. Any suitable electrically conductive material that does not cause chemical change may be used as the conductive material. Examples thereof may include a carbon-based material such as natural graphite, artificial graphite, carbon black, acetylene black, ketjen black, a carbon fiber, or the like; a metal-based material such as a metal powder or a metal fiber or the like of copper, nickel, aluminum, silver, or the like; a conductive polymer such as a polyphenylene derivative or the like; or a mixture thereof.
The positive electrode 114 includes a current collector and a positive active material layer formed on the current collector.
The current collector may be Al, as an example.
The positive active material layer includes a positive active material, the binder composition, and optionally a conductive material.
The positive active material may include lithiated intercalation compounds that reversibly intercalate and deintercalate lithium ions. For example, at least one lithium metal composite oxide of lithium and a metal of cobalt, manganese, nickel, or a combination thereof may be used. Specific examples thereof may include a compound represented by one of the following chemical formulae. LiaA1-bRbD2 (0.90≦a≦1.8 and 0≦b≦0.5); LiaE1-bRbO2-cDc (0.90≦a≦1.8, 0≦b≦0.5 and 0≦c≦0.05); LiaE2-bRbO4-cDc (0.90≦a≦1.8, 0≦b≦0.5, 0≦c≦0.05); LiaNi1-b-cCobRcDa (0.90≦a≦1.8, 0≦b≦0.5, 0≦c≦0.05 and 0≦α≦2); LiaNi1-b-c CobRcO2-αZα (0.90≦a≦1.8, 0≦b≦0.5, 0≦c≦0.05 and 0≦α≦2); LiaNi1-b-cCobRcO2-αZ2 (0.90≦a≦1.8, 0≦b≦0.5, 0≦c≦0.05 and 0≦α≦2); LiaNi1-b-cMnbRcDα (0.90≦a≦1.8, 0≦b≦0.5, 0≦c≦0.05 and 0≦α≦2); LiaNi1-b-cMnbRcO2-αZα (0.90≦a≦1.8, 0≦b≦0.5, 0≦c≦0.05 and 0≦α≦2); LiaNi1-b-cMnbRcO2-αZ2 (0.90≦a≦1.8, 0≦b≦0.5, 0≦c≦0.05 and 0≦α≦2); LiaNibEcGdO2 (0.90≦a≦1.8, 0≦b≦0.9, 0≦c≦0.5 and 0.001≦d≦0.1); LiaNibCocMndGeO2 (0.90≦a≦1.8, 0≦b≦0.9, 0≦c≦0.5, 0≦d≦0.5 and 0.001≦e≦0.1); LiaNiGbO2 (0.90≦a≦1.8 and 0.001≦b≦0.1); LiaCoGbO2 (0.90≦a≦1.8 and 0.001≦b≦0.1); LiaMnGbO2 (0.90≦a≦1.8 and 0.001≦b≦0.1); LiaMn2GbO4 (0.90≦a≦1.8 and 0.001≦b≦0.1); QO2; QS2; LiQS2; V2O5; LiV2O5; LiTO2; LiNiVO4; Li(3-f)J2(PO4)3 (0≦f≦2); Li(3-f)Fe2(PO4)3 (0≦f≦2); and LiFePO4.
In the above chemical formulae, A is Ni, Co, Mn, or a combination thereof; R is Al, Ni, Co, Mn, Cr, Fe, Mg, Sr, V, a rare earth element, or a combination thereof; D is O, F, S, P, or a combination thereof; E is Co, Mn, or a combination thereof; Z is F, S, P, or a combination thereof; G is Al, Cr, Mn, Fe, Mg, La, Ce, Sr, V, or a combination thereof; Q is Ti, Mo, Mn, or a combination thereof; T is Cr, V, Fe, Sc, Y, or a combination thereof; and J is V, Cr, Mn, Co, Ni, Cu, or a combination thereof.
The positive active material may include the positive active material with a coating layer, or a compound of the active material and the active material coated with the coating layer. The coating layer may include a coating element compound of an oxide of a coating element, a hydroxide of a coating element, an oxyhydroxide of a coating element, an oxycarbonate of a coating element, or a hydroxycarbonate of a coating element. The compound for the coating layer may be either amorphous or crystalline. The coating element included in the coating layer may be Mg, Al, Co, K, Na, Ca, Si, Ti, V, Sn, Ge, Ga, B, As, Zr, or a mixture thereof. The coating process may include any suitable process (e.g., spray coating, dipping) that does not causes any side effects on the properties of the positive active material.
The binder composition may be the above-described binder composition, or a generally-used binder.
Examples of the generally-used binder may include 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, or the like.
The conductive material may improve the electrical conductivity of the electrode. Any suitable electrically conductive material that does not cause a chemical change may be used as the conductive material. Examples thereof may include natural graphite, artificial graphite, carbon black, acetylene black, ketjen black, carbon fiber, copper, nickel, aluminum, silver, or the like, a metal powder, a metal fiber, or the like. One or more kinds of a conductive material, such as a polyphenylene derivative or the like, may be mixed.
The negative electrode 112 and the positive electrode 114 may be manufactured by mixing each active material, a conductive material, and a binder in a solvent to prepare an active material composition, and coating the composition on a current collector.
The electrolyte may include a non-aqueous organic solvent and a lithium salt.
The non-aqueous organic solvent may serve as a medium for transmitting ions taking part in the electrochemical reaction of a 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), or the like. The ester-based solvent may include methyl acetate, ethyl acetate, n-propyl acetate, dimethylacetate, methylpropionate, ethylpropionate, γ-butyrolactone, decanolide, valerolactone, mevalonolactone, caprolactone, or the like. The ether-based solvent may include dibutyl ether, tetraglyme, diglyme, dimethoxyethane, 2-methyltetrahydrofuran, tetrahydrofuran or the like. The ketone-based solvent may include cyclohexanone, or the like. The alcohol-based solvent may include ethanol, isopropyl alcohol, or the like. The aprotic solvent may include nitriles such as R—CN (wherein R is a C2 to C20 linear, branched, or cyclic hydrocarbon group, and may include a double bond, an aromatic ring, or an ether bond), amides such as dimethylformamide, dioxolanes such as 1,3-dioxolane, sulfolanes, or the like.
The non-aqueous organic solvent may be used singularly or in a mixture. When the organic solvent is used in a mixture, its mixture ratio may be controlled in accordance with desirable performance of a battery.
The carbonate-based solvent may be prepared by mixing a cyclic carbonate and a linear carbonate. The cyclic carbonate and the linear carbonate may be mixed together in a volume ratio of about 1:1 to about 1:9, which may enhance the performance of the electrolyte.
The non-aqueous organic solvent may include an aromatic hydrocarbon-based organic solvent as well as the carbonate based solvent. The carbonate-based solvent and the aromatic hydrocarbon-based organic solvent may be mixed together in a volume ratio of about 1:1 to about 30:1.
The aromatic hydrocarbon-based organic solvent may be an aromatic hydrocarbon-based compound represented by the following Chemical Formula 4.
In the above Chemical Formula 4, R10 to R15 may be the same or different and may be selected from hydrogen, a halogen, a C1 to C10 alkyl group, a 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 non-aqueous electrolyte may further include vinylene carbonate or an ethylene carbonate-based compound represented by the following Chemical Formula 5 in order to improve cycle-life of a battery.
In the above Chemical Formula 5, R16 and R17 are the same or different and are 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 R16 and R17 are not simultaneously hydrogen.
Examples of the ethylene carbonate-based compound include difluoro ethylenecarbonate, chloroethylene carbonate, dichloroethylene carbonate, bromoethylene carbonate, dibromoethylene carbonate, nitroethylene carbonate, cyanoethylene carbonate, fluoroethylene carbonate, or the like. The use amounts of additives for improving the cycle life may be adjusted within an appropriate range.
The lithium salt is dissolved in the non-aqueous solvent, supplies lithium ions in a rechargeable lithium battery, basically operates the rechargeable lithium battery, and improves lithium ion transfer between positive and negative electrodes. The lithium salt may include at least one supporting salt selected from LiPF6, LiBF4, LiSbF6, LiAsF6, LiC4F9SO3, LiClO4, LiAlO2, LiAlCl4, LiN(CxF2x+1SO2)(CyF2y+1SO2) (wherein, x and y are natural numbers), LiCl, LiI, LiB(C2O4)2 (lithium bis(oxalato)borate, LiBOB), or a combination thereof. The lithium salt may be used in a concentration of about 0.1 M to about 2.0M. 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.
A separator may be present between the positive electrode and negative electrode depending on a kind of a rechargeable lithium battery. Such a separator may include polyethylene, polypropylene, polyvinylidene fluoride or a multilayer thereof, for example a mixed multilayer such as a polyethylene/polypropylene double-layered separator, polyethylene/polypropylene/polyethylene triple-layered separator, polypropylene/polyethylene/polypropylene triple-layered separator, and the like.
The following Examples and Comparative Examples are provided in order to highlight characteristics of one or more embodiments, but it is to be understood that the Examples and Comparative Examples are not to be construed as limiting the scope of the embodiments, nor are the Comparative Examples to be construed as being outside the scope of the embodiments. Further, it is to be understood that the embodiments are not limited to the particular details described in the Examples and Comparative Examples.
(1) 390 g of deionized water and 30 g of isobutylene-co-maleic anhydride were put in a 2L reaction container having a heater, a cooler, and an agitator. (2) Then, a solution prepared by dissolving 9.32 g of lithium hydroxide in 93.2 g of deionized water at room temperature was slowly added thereto, and the mixture was agitated for 10 minutes. The reaction container was heated up to 80° C. under a nitrogen atmosphere and maintained for 3 hours. (3) Subsequently, a solution prepared by dissolving 0.125 g of ammonium persulfate in 10 g of deionized water was added to the agitated resultant, the resulting mixture was maintained for 20 minutes, and an aqueous solution prepared by dissolving 70 g of acrylamide in deionized water was added thereto in a dropwise fashion. (4) The resulting mixture was maintained for a reaction for 1 hour and cooled down to less than and equal to 40° C. An aqueous solution prepared by dissolving 2.9 g of lithium hydroxide in 20 g of deionized water was added thereto in a dropwise fashion for 10 minutes and maintained for 30 minutes, and packed, obtaining a binder having 15.0 wt % of a solid content, pH 9.5, and viscosity of 25,700 cps. The binder included a semi-interpenetrating polymer including a copolymer having a repeating unit represented by the following Chemical Formula 1 and a repeating unit represented by the following Chemical Formula 2; and polyacrylamide.
The repeating unit represented by the above Chemical Formula 1 was included in an amount of 40 mol % based on the total amount of the copolymer, and the repeating unit represented by the above Chemical Formula 2 was included in an amount of 60 mol % based on the total amount of the copolymer. Furthermore, in the semi-interpenetrating polymer network, a mole ratio of the copolymer to polyacrylamide was 3:7. The weight-average molecular weight of polyalkylene glycol was 3000 g/mol, and the amount of free lithium ion was 6.6 mol %.
A binder composition was prepared according to the same method as Synthesis Example 1 except for adding 4.3 g of LiH2PO4 instead of lithium hydroxide in the step 4. The binder had a solid content of 15.5%, pH of 7.5, and viscosity of 4,500 cps.
Referring to the IR peak of the binder (LPIMAM) of Synthesis Example 1 in the top graph of
Thermogravimetric analysis of the mixture of LPIBA and PAM and the binder (LPIMAM) synthesized according to Synthesis Example 1 was performed, and the results are provided in
Referring to
Accordingly, a battery having stability, excellent cycle-life characteristics, and the like may be provided.
A negative active material slurry was prepared by mixing each component in the amounts provided in the following Table 1 in water. The negative active material slurry was coated onto a copper foil, dried at 110° C. to evaporate water therefrom, and compressed, manufacturing a negative electrode. The negative electrode was loaded with about 3.8 g/cm2. The negative electrode was formed to have a cylinder shape having a diameter of 16 mm.
A half-cell was fabricated by using the negative electrode and a 100 μm thick lithium metal having a 18 mm disk-shape as a counter electrode.
A positive electrode as a counter electrode was manufactured by mixing an active material (LiNi0.6CO0.2Mn0.2O2), a conductive material (Denka black), a binder (polyvinylidene fluoride) in a weight ratio of 94:3:3 in N-methyl pyrrolidone to prepare slurry composition, and forming the positive electrode into a 14 mm disk.
A polypropylene separator and an electrolyte solution were prepared by mixing ethylene carbonate (EC):diethyl carbonate (DEC):fluoro ethylene carbonate (FEC) in a volume ratio of 5:70:25 and adding LiPF6 in a concentration of 1.5 mol/L in the mixed solvent, manufacturing a rechargeable lithium battery cell.
Each component in Table 1 was used by a unit of wt %.
The components in Table 1 are illustrated as follows.
Active Material
As the alloy, a silicon-based active material (V6 made by 3M) was used, and as graphite, V6 made by 3M and TIMREX SFG6 made by Timcal Inc. were used.
Conductive Material
KB600JD ketjen black made by LION Company was used.
Binder
LPIBMA is a poly isobutylene-co-maleic anhydride lithium salt, and SBR is a styrene butadiene rubber. CMC indicates carboxylmethyl cellulose, and PAI indicates polyamideimide.
A negative active material slurry was prepared by mixing each component in the amounts as provided in the following Table 2 in water.
The negative active material slurry was coated on a copper foil, dried at 110° C. to evaporate water, and compressed, manufacturing a negative electrode.
The negative electrode had a loading level of about 5.5 g/cm2 and had a mass density of 1.5 g/cc.
A positive electrode as a counter electrode was manufactured by mixing an active material (LiNi0.6CO0.2Mn0.2O2), a conductive material (denka black), and a binder (PVdF) in a ratio of 94:3:3 in N-methyl pyrrolidone to prepare a slurry composition, followed by manufacturing an electrode and then, making the electrode into a 14 mm disk.
Herein, a polypropylene separator and an electrolyte solution prepared by dissolving LiPF6 in a concentration of 1.5 mol/L in a mixed solvent of ethylene carbonate (EC):diethyl carbonate (DEC):fluoro ethylene carbonate (FEC) in a volume ratio of 5:70:25 were used to manufacture a rechargeable lithium battery cell.
Each component in Table 2 was used by a unit of wt %.
Each component in Table 2 is illustrated as follows.
As an alloy, V6 made by 3M, was used. As graphite, MC20 made by Mitsubishi Chemical Co. and TIMREX SFG6 made by Timcal Inc., were used.
KB600JD ketjen black of LION Company was used.
SBR refers to a styrene butadiene rubber, CMC refers to carboxylmethyl cellulose, and PVdF refers to polyfluorinated vinylidene.
The rechargeable lithium battery cells according to Examples 1 to 6 and Comparative Examples 1 to 7 were charged and discharged at 0.1 C, charge capacity and discharge capacity of the rechargeable lithium battery cells were measured, a ratio of the discharge capacity relative to the charge capacity was calculated, and the results are provided in the following Table 2.
The rechargeable lithium battery cells according to Examples and Comparative Examples were measured regarding a capacity ratio of 100 cycles relative to 1 cycle under a condition of 1C, and the results are provided in the following Table 3.
As shown in Table 3, the rechargeable lithium battery cells of Examples showed sharply improved initial efficiency and cycle-life characteristics compared with the rechargeable lithium battery cells of Comparative Examples.
By way of summation and review, recently, demand for a battery having high energy density increasingly has made a negative active material having high theoretical capacity density desirable. Accordingly, Si, Sn, and Ge alloyed with lithium, an oxide thereof, an alloy thereof have drawn attention.
In particular, a Si-based negative active material has very high charge capacity and is widely applied to a high-capacity battery. However, a Si-based negative active material may expand by about 300% to about 400% during charging and discharging. Thus, charge and discharge characteristics and cycle-life characteristics of a battery may be reduced.
Accordingly, research on a binder capable of effectively controlling expansion of the Si-based negative active material has been actively conducted. Particularly, research for a binder composition capable of effectively controlling expansion of the active material has been actively performed.
Embodiments provide a binder composition for a rechargeable lithium battery capable of effectively controlling expansion of an active material, having improved adherence and stability with an electrolyte solution, capable of increasing a loading level of an electrode, and reducing cracks or bending during drying. Another embodiment provides a method of manufacturing the same. Still another embodiment provides a rechargeable lithium battery having improved initial efficiency, charge and discharge characteristics, and cycle-life characteristics due to the binder composition.
Example embodiments have been disclosed herein, and although specific terms are employed, they are used and are to be interpreted in a generic and descriptive sense only and not for purpose of limitation. In some instances, as would be apparent to one of ordinary skill in the art as of the filing of the present application, features, characteristics, and/or elements described in connection with a particular embodiment may be used singly or in combination with features, characteristics, and/or elements described in connection with other embodiments unless otherwise specifically indicated. Accordingly, it will be understood by those of skill in the art that various changes in form and details may be made without departing from the spirit and scope as set forth in the following claims.
| Number | Date | Country | Kind |
|---|---|---|---|
| 10-2013-0079843 | Jul 2013 | KR | national |
| 10-2013-0149459 | Dec 2013 | KR | national |
