Patent Application
20140178748
Any and all priority claims identified in the Application Data Sheet, or any correction thereto, are hereby incorporated by reference under 37 CFR 1.57.
This application claims priority to and the benefit of Korean Patent Application No. 10-2012-0151253 filed in the Korean Intellectual Property Office on Dec. 21, 2012, the entire contents of which are incorporated herein by reference.
1. Field
An electrolyte additive, an electrolyte including the electrolyte additive, and a rechargeable lithium battery including the electrolyte are disclosed.
2. Description of the Related Technology
Batteries transform chemical energy generated from the electrochemical redox reaction of a chemical material in the batteries into electrical energy. Such batteries are divided into a primary battery, which should be disposed after consuming all the energy, and a rechargeable battery, which can be recharged many times. The rechargeable battery may be charged/discharged many times based on the reversible transformation between chemical energy and electrical energy. Recent developments in high-tech electronics have allowed electronic devices to become small and light in weight, which leads to an increase in portable electronic devices. Such portable electronic devices increasingly demand batteries with high energy density as a power source. Accordingly, research on a lithium rechargeable battery is briskly under progress.
The rechargeable lithium battery is fabricated by injecting an electrolyte into an electrode assembly, which includes a positive electrode including a positive active material capable of intercalating/deintercalating lithium and a negative electrode including a negative active material capable of intercalating/deintercalating lithium.
An electrolyte includes an organic solvent in which a lithium salt is dissolved and plays a critical role of determining stability and performance of the rechargeable lithium battery. Particularly, in case of a large capacity rechargeable lithium battery, stability is more important.
One embodiment provides an electrolyte additive having improved performance while ensuring stability.
Another embodiment provides an electrolyte including the electrolyte additive.
Yet another embodiment provides a rechargeable lithium battery including the electrolyte.
According to one embodiment, an electrolyte additive represented by the following Chemical Formula 1 is provided.
In Chemical Formula 1,
R1 to R4 are independently hydrogen (H), a substituted or unsubstituted C1 to C30 alkyl group, a substituted or unsubstituted C3 to C30 cycloalkyl group, a substituted or unsubstituted C1 to C30 haloalkyl group, a substituted or unsubstituted C6 to C30 aryl group, a substituted or unsubstituted C6 to C30 halgenated aryl group, a substituted or unsubstituted C3 to C30 cycloalkenyl group, a substituted or unsubstituted C7 to C20 arylalkyl group, a substituted or unsubstituted C1 to C20 heteroalkyl group, a substituted or unsubstituted C2 to C30 heterocycloalkyl group, a substituted or unsubstituted C2 to C30 heteroaryl group, a substituted or unsubstituted C2 to C30 alkenyl group, a substituted or unsubstituted C2 to C30 alkynyl group, a substituted or unsubstituted C1 to C20 aldehyde group, or a combination thereof.
In Chemical Formula 1, le may be a substituted or unsubstituted C1 to C30 fluoroalkyl group, or a substituted or unsubstituted C1 to C30 perfluoroalkyl group.
In Chemical Formula 1, R2 to R4 are independently hydrogen (H), or a substituted or unsubstituted C1 to C30 alkyl group.
The electrolyte additive represented by above Chemical Formula 1 may include 4-methyl-2-[(2,2,3,3,4,4,5,5-octafluoropentyl)oxy]-1,3,2-dioxaphosphinane.
According to another embodiment, an electrolyte for a rechargeable lithium battery including a lithium salt, a non-aqueous organic solvent, and the electrolyte additive represented by above Chemical Formula 1 is provided.
In Chemical Formula 1,
R1 to R4 are independently hydrogen (H), or a substituted or unsubstituted C1 to C30 alkyl group, a substituted or unsubstituted C3 to C30 cycloalkyl group, a substituted or unsubstituted C1 to C30 haloalkyl group, a substituted or unsubstituted C6 to C30 aryl group, a substituted or unsubstituted C6 to C30 halgenated aryl group, a substituted or unsubstituted C3 to C30 cycloalkenyl group, a substituted or unsubstituted C7 to C20 arylalkyl group, a substituted or unsubstituted C1 to C20 heteroalkyl group, a substituted or unsubstituted C2 to C30 heterocycloalkyl group, a substituted or unsubstituted C2 to C30 heteroaryl group, a substituted or unsubstituted C2 to C30 alkenyl group, a substituted or unsubstituted C2 to C30 alkynyl group, a substituted or unsubstituted C1 to C20 aldehyde group, or a combination thereof.
In Chemical Formula 1, R1 may be a substituted or unsubstituted C1 to C30 fluoroalkyl group, or a substituted or unsubstituted C1 to C30 perfluoroalkyl group.
In Chemical Formula 1, R2 to R4 may be independently hydrogen (H) or a substituted or unsubstituted C1 to C30 alkyl group.
The electrolyte additive represented by above Chemical Formula 1 may include 4-methyl-2-[(2,2,3,3,4,4,5,5-octafluoropentyl)oxy]-1,3,2-dioxaphosphinane.
The electrolyte additive may be included in an amount of about 0.1 wt % to about 20 wt %, and specifically about 2 wt % to about 12 wt % based on the total amount of the electrolyte.
The electrolyte additive may be included in an amount of about 4 wt % to about 6 wt % based on the total amount of the electrolyte.
According to yet another embodiment, a rechargeable lithium battery including a positive electrode including a positive active material, a negative electrode including a negative active material, and the electrolyte is provided.
The positive active material may include over lithiated oxide (OLO).
The positive active material may be a compound represented by the following Chemical Formula 2.
Li1+xMyOz
In Chemical Formula 2, 0<x<1.5, 0<y<2, 1<z<4, and M is at least one metal selected from Ti, V, Cr, Mn, Fe, Co, Ni, Cu, Al, Mg, Zr, Mo, and B.
The positive active material may release oxygen during charge and discharge of the positive electrode, and the released oxygen may be bonded with an additive included in the electrolyte.
Accordingly, the present embodiments may decrease exothermic heat of the electrode and thus, secure stability of a battery and simultaneously, capture oxygen gas generated from the electrode and thus, improve battery performance.
This disclosure will be more fully described hereinafter, in which example embodiments are shown. As those skilled in the art would realize, the described embodiments may be modified in various different ways, all without departing from the spirit or scope of the present embodiments.
As used herein, when a definition is not otherwise provided, the term ‘substituted’ may refer to one substituted with a substitutent selected from a halogen (F, Br, Cl, or I), a hydroxyl group, an alkoxy group, a nitro group, a cyano group, an amino group, an azido group, an amidino group, a hydrazino group, a hydrazono group, a carbonyl group, a carbamyl group, a thiol group, an ester group, a carboxyl group or a salt thereof, a sulfonic acid group or a salt thereof, a phosphoric acid group or a salt thereof, a C1 to C20 alkyl group, a C2 to C20 alkenyl group, a C2 to C20 alkynyl group, a C6 to C30 aryl group, a C7 to C30 arylalkyl group, a C1 to C4 alkoxy group, a C1 to C20 heteroalkyl group, C3 to C20 heteroarylalkyl group, a C3 to C30 cycloalkyl group, a C3 to C15 cycloalkenyl group, a C6 to C15 cycloalkynyl group, a C2 to C20 heterocycloalkyl group, and a combination thereof, instead of hydrogen of a compound.
The electrolyte additive according to one embodiment is a compound represented by the following Chemical Formula 1.
In Chemical Formula 1,
R1 to R4 are independently hydrogen (H), or a substituted or unsubstituted C1 to C30 alkyl group, a substituted or unsubstituted C3 to C30 cycloalkyl group, a substituted or unsubstituted C1 to C30 haloalkyl group, a substituted or unsubstituted C6 to C30 aryl group, a substituted or unsubstituted C6 to C30 halgenated aryl group, a substituted or unsubstituted C3 to C30 cycloalkenyl group, a substituted or unsubstituted C7 to C20 arylalkyl group, a substituted or unsubstituted C1 to C20 heteroalkyl group, a substituted or unsubstituted C2 to C30 heterocycloalkyl group, a substituted or unsubstituted C2 to C30 heteroaryl group, a substituted or unsubstituted C2 to C30 alkenyl group, a substituted or unsubstituted C2 to C30 alkynyl group, a substituted or unsubstituted C1 to C20 aldehyde group, or a combination thereof.
In Chemical Formula 1, le may be a substituted or unsubstituted C1 to C30 fluoroalkyl group, or a substituted or unsubstituted C1 to C30 perfluoroalkyl group.
In Chemical Formula 1, R2 to R4 are independently hydrogen (H), or a substituted or unsubstituted C1 to C30 alkyl group.
The electrolyte additive represented by above Chemical Formula 1 may include 4-methyl-2-[(2,2,3,3,4,4,5,5-octafluoropentyl)oxy]-1,3,2-dioxaphosphinane.
The electrolyte additive represented by above Chemical Formula 1 is added to an electrolyte and thus improves electrochemical performance and thermal stability of a battery.
An electrolyte for a rechargeable lithium battery according to another embodiment includes the electrolyte additive represented by above Chemical Formula 1, a non-aqueous organic solvent, and a lithium salt.
In Chemical Formula 1,
R1 to R4 are independently hydrogen (H), or a substituted or unsubstituted C1 to C30 alkyl group, a substituted or unsubstituted C3 to C30 cycloalkyl group, a substituted or unsubstituted C1 to C30 haloalkyl group, a substituted or unsubstituted C6 to C30 aryl group, a substituted or unsubstituted C6 to C30 halgenated aryl group, a substituted or unsubstituted C3 to C30 cycloalkenyl group, a substituted or unsubstituted C7 to C20 arylalkyl group, a substituted or unsubstituted C1 to C20 heteroalkyl group, a substituted or unsubstituted C2 to C30 heterocycloalkyl group, a substituted or unsubstituted C2 to C30 heteroaryl group, a substituted or unsubstituted C2 to C30 alkenyl group, a substituted or unsubstituted C2 to C30 alkynyl group, a substituted or unsubstituted C1 to C20 aldehyde group, or a combination thereof.
In Chemical Formula 1, R1 may include a substituted or unsubstituted C1 to C30 fluoroalkyl group, or a substituted or unsubstituted C1 to C30 perfluoroalkyl group.
In Chemical Formula 1 R2 to R4 are independently hydrogen (H), or a substituted or unsubstituted C1 to C30 alkyl group.
The electrolyte additive represented by above Chemical Formula 1 may include 4-methyl-2-[(2,2,3,3,4,4,5,5-octafluoropentyl)oxy]-1,3,2-dioxaphosphinane.
The electrolyte additive opens its cycle to bind with oxygen, and then recyclization occurs to form a cyclic compound and a film on an electrode surface, and thus, oxygen generated in a battery may be captured. When 4-methyl-2-[(2,2,3,3,4,4,5,5-octafluoropentyl)oxy]-1,3,2-dioxaphosphinane is used as the additive, the compound is captured with, i.e. is bonded to oxygen gas generated during charge and discharge, and to convert a compound represented by Chemical Formula 1B.
The electrolyte additive may be included in an amount of about 0.1 wt % to 20 wt % based on the total amount of the electrolyte. Within the above ranges, electrochemical performance and thermal stability of an electrolyte may be improved while not deteriorating battery performance.
Within the ranges, the electrolyte additive may be included in an amount of about 2 wt % to about 12 wt %, and for example, about 4 wt % to about 6 wt % based on the total amount of the electrolyte.
The non-aqueous organic solvent plays a role of 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), ethylmethyl carbonate (EMC), ethylene carbonate (EC), propylene carbonate (PC), butylene carbonate (BC), and the like, and the ester-based solvent may include methyl acetate, ethyl acetate, n-propyl acetate, dimethylacetate, methylpropionate, ethylpropionate, gamma-butyrolactone, decanolide, gamma-valerolactone, mevalonolactone, caprolactone, and the like.
The ether-based solvent may include dibutyl ether, tetraglyme, diglyme, dimethoxyethane, 2-methyltetrahydrofuran, tetrahydrofuran and the like, and the ketone-based solvent may include cyclohexanone, and the like. The alcohol-based solvent may include ethanol, isopropyl alcohol, and the like. The aprotic solvent 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, dimethylacetamide, dioxolanes such as 1,3-dioxolane, sulfolanes, and 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 include a mixture of a cyclic carbonate and a linear carbonate. The cyclic carbonate and the linear carbonate are mixed together in a volume ratio of about 1:1 to about 1:9, which may enhance performance of an electrolyte.
In addition, the non-aqueous organic solvent may be prepared by further adding the aromatic hydrocarbon-based organic solvent to the carbonate-based solvent. The carbonate-based solvent and the aromatic hydrocarbon-based organic solvent are mixed together in a volume ratio of about 1:1 to about 30:1.
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 lithium salt is dissolved in the non-aqueous organic solvent and supplies lithium ions in a rechargeable lithium battery, and basically operates the rechargeable lithium battery and improves lithium ion transfer between positive and negative electrodes. Such a lithium salt includes one or more of LiPF6, LiBF4, LiSbF6, LiAsF6, LiN(SO2C2F5)2, Li(CF3SO2)2N, LiN(SO3C2F5)2, LiC4F9SO3, LiClO4, LiAlO2, LiAlCl4, LiN(CxF2x+1SO2)(CyF2y+1SO2) (wherein, x and y are natural numbers), LiC1, and LiI.
The lithium salt may be used at a concentration of about 0.1M to about 2.0M. When the lithium salt is included within the above concentration range, it may electrolyte performance and lithium ion mobility due to optimal electrolyte conductivity and viscosity.
The electrolyte may further include an additive selected from lithium bis(oxalato)borate (LiBOB), lithium bis(salicylato)borate (LiBSB), and a combination thereof. The bis(oxalato)borate (LiBOB), lithium bis(salicylato)borate (LiBSB) improves thermal stability of an electrolyte and cycle performance of a battery.
Hereinafter, a rechargeable lithium battery according to another embodiment is described referring to
Referring to
The rechargeable lithium battery 100 is fabricated by sequentially laminating a negative electrode 112, a positive electrode 114, and a separator 113, spirally winding them, and housing the spiral-wound product in a battery case 120.
The negative electrode 112 may a current collector and a negative active material layer disposed on at least one side of 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 binder 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 transition metal oxide.
The material that reversibly intercalates/deintercalates lithium ions includes a carbon material. The carbon material may be any generally-used carbon-based negative active material in a lithium ion rechargeable battery. Examples of the carbon material include crystalline carbon, amorphous carbon, and a mixture thereof. The crystalline carbon may be non-shaped or sheet, flake, spherical, or fiber shaped natural graphite or artificial graphite. The amorphous carbon may be a soft carbon, a hard carbon, mesophase pitch carbonization products, fired coke, and the like.
Examples of the lithium metal alloy include 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 include Si, SiOx(0<x<2), a Si—C composite, a Si-Q alloy (wherein Q is an alkali metal, an alkaline-earth metal, Group 13 to Group 16 elements, a transition element, a rare earth element, or a combination thereof, and is not Si), Sn, SnO2, a Sn—C composite, a Sn-R alloy (wherein R is an alkali metal, an alkaline-earth metal, Group 13 to Group 16 elements, a transition element, a rare earth element, or a combination thereof, and not Sn), and the like. The elements Q and R may include 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, Tl, Ge, P, As, Sb, Bi, S, Se, Te, Po, or a combination thereof.
The transition metal oxide may include vanadium oxide, lithium vanadium oxide, and the like.
The binder improves properties of binding active material particles with one another and a negative active material with a current collector. The binder includes a non-water-soluble binder, a water-soluble binder, or a combination thereof. The non-water-soluble binder includes 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 includes 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. The cellulose-based compound includes one or more of carboxylmethyl cellulose, hydroxypropylmethyl cellulose, methyl cellulose, or alkali metal salts thereof. The alkali metal may be Na, K, or Li. The cellulose-based compound may be included in an amount of about 0.1 to about 3 parts by weight based on 100 parts by weight of the negative active material.
The conductive material improves electrical conductivity of a negative electrode. Any electrically conductive material can be used as a conductive agent, 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, 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, and the like; or a mixture thereof.
The positive electrode 114 includes a current collector and a positive active material layer disposed on the current collector.
The current collector may be an Al, but is not limited thereto.
The positive active material layer includes a positive active material, a binder, and a conductive material.
The positive active material includes lithiated intercalation compounds that reversibly intercalate and deintercalate lithium ions. The positive active material may include a composite oxide including at least one selected from the group consisting of cobalt, manganese, and nickel, as well as lithium. Specific examples may be the compounds represented by the following chemical formulae:
LiaA1−bRbD2 (0.90≦a≦2.5 and 0≦b≦0.5); LiaE1−bRbO2−cDc (0.90≦a≦2.5, 0≦b≦0.5 and 0≦c≦0.05); LiE2−bRbO4−cDc (0≦b≦0.5, 0≦c≦0.05); LiaNi1−b−cCobRcDα (0.90≦α≦2.5, 0≦b≦0.5, 0≦c≦0.05 and 0<α≦2); LiaNi1−b−cCobRcO2−αZα (0.90≦a≦2.5, 0≦b≦0.5, 0≦c≦0.05 and 0<α<2); LiaNi1−b−cCobRcO2−αZ2 (0.90≦a≦2.5, 0≦b≦0.5, 0≦c≦0.05 and 0<α<2); LiaNi1−b−cMnbRcDα (0.90≦a≦2.5, 0≦b≦0.5, 0≦c≦0.05 and 0<α≦2); LiaNi1−b−cMnbRcO2−αZα (0.90≦a≦2.5, 0≦b≦0.5, 0≦c≦0.05 and 0<α<2); LiaNi1−b−cMnbRcO2−αZ2 (0.90≦a≦2.5, 0≦b≦0.5, 0≦c≦0.05 and 0<α<2); LiaNibEcGdO2 (0.90≦a≦2.5, 0≦b≦0.9, 0≦c≦0.5 and 0.001≦d≦0.1.); LiaNibCocMndGeO2 (0.90≦a≦2.5, 0≦b≦0.9, 0≦c≦0.5, 0≦d≦0.5 and 0.001≦e≦0.1.); LiaNiGbO2 (0.90≦a≦2.5 and 0.001≦b≦0.1.); LiaCoGbO2 (0.90≦a≦2.5 and 0.001≦b≦0.1.); LiaMnGbO2 (0.90≦a≦2.5 and 0.001≦b≦0.1.); LiaMn2GbO4 (0.90≦a≦2.5 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 be a compound with a coating layer on the surface or a mixture of the active material and a compound with the coating layer thereon. The coating layer may include at least one coating element compound selected from the group consisting of an oxide of the coating element, a hydroxide of the coating element, an oxyhydroxide of the coating element, an oxycarbonate of the coating element, and a hydroxycarbonate of the 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 conventional processes unless it causes any side effects on the properties of the positive active material (e.g., spray coating, immersing), which is well known to those who have ordinary skill in this art and will not be illustrated in detail.
The positive active material may release oxygen O2 during the charge and discharge.
The positive active material may include over lithiated oxide. The over lithiated oxide includes lithium in a mole ratio of greater than 1. This over lithiated oxide has a high operation voltage and high discharge capacity but is electrically unstable and thus, may release oxygen during the oxidation/reduction reaction.
The positive active material may include a compound represented by the following Chemical Formula 2.
Li1+xMyOz
In Chemical Formula 2, 0<x<1.5, 0<y<2, 1<z<4, and M is at least one metal selected from Ti, V, Cr, Mn, Fe, Co, Ni, Cu, Al, Mg, Zr, Mo, and B.
The compound represented by the above Chemical Formula 2 is over lithiated oxide, and may release oxygen during charge and discharge. For example, the x may be in the following range: 0.1<x<1.0.
For example, representative examples of the over lithiated oxide (OLO) have the following composition:
Li1.20Ni0.18Mn0.53CO0.09O2.
Oxygen in Li2MnO3 which is one of the examples of the positive active material, is partially oxidized during charge as follows.
Li2MnO3→2Li++2e−+MnO2+1/2O2
The OLO positive active material generates oxygen during the charge.
For example, a compound represented by the above Chemical Formula 2 or a compound including the compound represented by the above formula 2 as one component may be at least one compound selected from the group consisting of xLiMO2. (1−x)Li2M′O3 (0≦x<1, M is a metal selected from Ti, V, Cr, Mn, Fe, Co, Ni, Cu, Al, Mg, Zr, Mo, and B and having an average oxidation number of +3, M′ is a metal selected from Ti, V, Cr, Mn, Fe, Co, Ni, Cu, Al, Mg, Zr, Mo, and B and having an average oxidation number of +4) and Li2MO2 (M is at least one metal selected from Ni, Co, Fe, Cu, Ti, and V) but is not limited thereto and may include any lithium metal oxide releasing oxygen gas during the charge and discharge.
The released oxygen may be removed through a reaction with an additive represented by the above Chemical Formula 1.
Referring to
Referring to
The conductive material improves electrical conductivity of a negative electrode. Any electrically conductive material can be used as a conductive agent unless it causes a chemical change. Examples of the conductive material include natural graphite, artificial graphite, carbon black, acetylene black, ketjen black, a carbon fiber, a metal powder or a metal fiber including copper, nickel, aluminum, silver, and the like. A conductive material such as a polyphenylene derivative and the like may be mixed.
The negative and positive electrodes may be manufactured in a method of preparing an active material composition by mixing the active material and a binder, and optionally a conductive material, and coating the active material composition on a current collector. The solvent includes N-methylpyrrolidone, water and the like but is not limited thereto. The electrode manufacturing method is well known and thus, is not described in detail in the present specification.
The separator 113 separates the positive electrode 114 and negative electrode 112 and provides a path for transferring lithium ions. The separator 113 may be any separator that is generally used in a lithium ion battery. The separator may have low resistance against electrolyte ions and excellent moisturizing capability of an electrolyte. For example, the separator may be selected from a glass fiber, polyester, TEFLON (tetrafluoroethylne), polyethylene, polypropylene, polytetrafluoroethylene (PTFE), or a combination thereof and may have a non-woven fabric type or a fabric type. For example, a polyolefin-based polymer separator such as polyethylene, polypropylene, and the like is used for a lithium ion battery, a separator coated with a ceramic component or a polymer material may be used to secure heat resistance or mechanical strength. The separator may have a singular layer or multi-layers.
The rechargeable lithium battery may be classified as a lithium ion battery, a lithium ion polymer battery, and a lithium polymer battery according to the presence of a separator and the kind of an electrolyte used therein. The rechargeable lithium battery may have a variety of shapes and sizes and thus, may include a cylindrical, prismatic, coin, or pouch-type battery and a thin film type or a bulky type in size. The structure and manufacturing method for a lithium ion battery pertaining to the present embodiments are well known in the art.
The electrolyte is the same as described above.
The following examples illustrate the aspects of present embodiments described above, in more detail. These examples, however, should not in any sense be interpreted as limiting the scope of the present embodiments.
29.90 g (0.129 mol) of 2,2,3,3,4,4,5,5-octafluoro-1-propanol and 15.65 g (0.155 mol) of triethylamine were dissolved in 180 ml of hexane to prepare a solution, and another solution was prepared by dissolving 20.00 g (0.129 mol) of 2-chloro-4-methyl-1,3,2-dioxaphosphinane in 20 ml of hexane. The latter solution was dropped to the former solution while the former solution was fervently agitated at −10° C. for 3.5 hours. During the process, a formation of a white triethylammonium hydrochloride precipitate was to be found. The reaction mixture was further agitated for 3 hours at room temperature and allowed to stand for one night. The triethylammonium hydrochloride was separated from the resulting mixture and washed with hexane. Then, hexane was removed under the atmospheric pressure, and the residues were distilled under vacuum, obtaining 32.53 g of a compound represented by the following Chemical Formula 1A, 4-methyl-2-[(2,2,3,3,4,4,5,5-octafluoropentyl)oxy]-1,3,2-dioxaphosphinane. A yield was 72%.
The characteristics for the compound represented by Chemical Formula 1A were as follows:
1H NMR (CDCl3, d, ppm): 1.20 d (3H, CH3 for minor isomer, 3JHH6.3 Hz); 1.39 d (3H, CH3 for major isomer, 3JHH 6.3 Hz); 2.04 m (1H, CH2 for major isomer); 2.15 m (1H, CH2 for major isomer); 3.97 m (1H, CH for major isomer); 4.25 td (2H, CH2CF2 for major isomer, 3JHF 14.0 Hz, 3JHP 7.5 Hz); 4.35 m (2H, CH2O); 6.04 tt (1H, CHF2, 2JHF52.0 Hz, 3JHF 5.5 Hz); signals of protons of CH2, CH, CH2CF2, CH2O and CHF2 groups for minor are masked by more intensive signals.
13C NMR (d, ppm): 21.21 d (CH3 for minor isomer, 3JCP 4.9 Hz); 22.65 (CH3 for major isomer); 32.75 d (CH2 for major isomer, 3JCP 11.8 Hz); 35.43 d (CH2 for minor isomer, 3JCP4.8 Hz); 58.80 d (CH2O for major isomer, 2JCP 2.6 Hz); 59.70 td (CH2CF2 for major isomer, 2JCF26.5 Hz, 2JCP21.4 Hz); 60.28 d (CH2O for minor isomer, 2JCP 2.0 Hz); 66.56 (CH for minor isomer); 70.12 d (CH for major isomer, 2JCP 5.2 Hz); 107.67 tt (HCF2 for major isomer, 1JCF 254.3 Hz, 2JCF3 0.6 Hz); 110.00 tqn (HCF2CF2 for major isomer, 1JCF2 54.1 Hz, 2JCF 30.5 Hz); 111.00 tqn (CF2CF2CH2 for major isomer, 1JCF 265.0 Hz, 2JCF30.2 Hz); 115.16 ttd (CF2CH2 for major isomer, 1JCF2 56.9 Hz, 2JCF 30.6 Hz, 3JCP5.5 Hz); signals of 13C of HCF2CF2CF2CH2 fragment for minor isomer are masked by more intensive signals.
19F NMR (CDCl3, d, ppm) for major isomer: −137.48 dm (2F, HCF2, 2JHF52.0 Hz); −130.42 m (2F, CF2); −125.40 m (2F, CF2); −120.46 m (2F, CF2).
31P NMR (CDCl3, d, ppm): 130.71 t for minor isomer (4JPF 5.7 Hz) and 134.22 t for major isomer (4JPF 5.7 Hz).
IR (film, cm−1): 2981 s, 2938 m, 2904 w, 1475 w, 1459 m, 1444 m, 1429 w, 1402 w, 1388 m, 1377 w, 1361 w, 1334 w, 1289 m, 1252 m, 1226 m, 1173 s, 1158 sh, 1132 s, 1097 m, 1074 s, 1034 s, 982 m, 966 m, 925 s, 901 m, 887 m, 842 m, 809 m, sh 767 m, 752 s, 728 m, 704 sh, 629 w, 609 m, 573 w, 561 w, 546 m, 538 w, 520 w, 508 w, 487 w.
Found, %: C, 30.61; H, 3.16; F, 43.62; P, 9.12. C9H11F8O3P. Calcd, %: C, 30.87; H, 3.17; F, 43.41; P, 8.85.
An electrolyte solution for a rechargeable lithium battery was prepared by adding 1.3M LiPF6 as a lithium salt to a mixed solvent prepared by mixing ethylene carbonate (EC), ethylmethylcarbonate (EMC), and dimethylcarbonate (DMC) in a ratio of 3/4/3 (v/v/v) and 10 wt % of the additive according to Synthesis Example thereto based on 100 wt % of the electrolyte solution.
An electrolyte solution was prepared according to the same method as Preparation Example 1 except for adding 5 wt % of the additive according to Synthesis Example.
An electrolyte solution for a rechargeable lithium battery was prepared according to the same method as Example 1 except for using no additive.
Li1.20Ni0.18Mn0.53Co0.09O2 as a positive active material, polyvinylidene fluoride as a binder, and denka black as a conductive agent were mixed in a weight ratio of 90:4:6, and the mixture was dispersed into N-methyl-2-pyrrolidone to prepare a positive active material slurry. This positive active material slurry was coated on an aluminum foil and then, dried and compressed, fabricating a positive electrode.
A metal lithium was used as a counter electrode.
The positive electrode, the counter electrode, and the electrolyte solution according to Preparation Example 1 were used to fabricate a coin-type half-cell.
Positive slurry was prepared by using Li1.20Ni0.18Mn0.53C0.09O2 as a positive active material, polyvinylidene fluoride as a binder, and denka black as a conductive agent in a weight ratio of 90:4:6 and dispersing the mixture into N-methyl-2-pyrrolidone. The slurry was coated on an aluminum foil, dried, compressed, fabricating a positive electrode.
A negative active material slurry was prepared by mixing graphite as a negative active material, styrene-butadiene rubber (SBR) as a binder, and carboxylmethylcellulose as a thickener in a weight ratio of 97.5:1.5:1 and dispersing the mixture into water. The slurry was coated on a copper foil and then, dried and compressed, fabricating a negative electrode.
The positive electrode, the negative electrode, and the electrolyte solution according to Preparation Example 2 were used to fabricate a battery cell.
A coin-type half-cell was fabricated according to the same method as Example 1 except for using the electrolyte solution according to Comparative Preparation Example 1 instead of the electrolyte solution according to Preparation Example 1.
A full-cell was fabricated according to the same method as Example 2 except for using the electrolyte solution according to Comparative Preparation Example 1 instead of the electrolyte solution according to Preparation Example 2.
The half-cells according to Example 1 and Comparative Example 1 were examined regarding dQ/dV change depending on a change of Li/Li+.to Voltage/V
The result is provided in
Referring to
The half-cells according to Example 1 and Comparative Example 1 were charged and discharged 50 times (operation voltage: 2.0V to 4.7V) with 1C at 25° C. and measures regarding discharge capacity depending on each cycle.
Referring to
Referring to
Referring to
The rechargeable lithium battery cells according to Example 2 and Comparative Example 2 were charged and discharged 300 times (operation voltage: 2.0V to 4.6V) at 1C at 25° C. and measured regarding discharge capacity depending on each cycle.
The following Table 1 shows specific discharge capacity of the ‘graphite/OLO’ full cells according to Example 2 and Comparative Example 2.
Considering 230 mAh/g, a theoretical value of specific capacity of a over lithiated oxide positive electrode material, the full cell according to Example 2 might more likely reproduce the result than the one according to Comparative Example 2. Herein, the specific capacity difference is generated by an additive included in an electrolyte solution. Accordingly, the additive (Preparation Example 2) used in Example 2 had excellent effects compared with the additive used in Comparative Example 2.
Referring to
Each rechargeable lithium battery cell was fabricated according to the same method as Example 2 except for respectively using the electrolyte solutions according to Preparation Examples 1 and 2 and Comparative Preparation Example 1. The rechargeable lithium battery cells were full-charged at 4.6V and separated in a drying room, obtaining electrodes. The electrodes were washed and dried. Then, the electrodes were put in a stainless steel pan and sealed and then, measured regarding exothermic heat using differential scanning calorimetry (TA instruments auto Q20). The calorific value was measured by increasing 10° C. per a minute in a range of 50° C. to 400° C.
The results are provided in the following Table 2.
Referring to Table 2, the cells respectively including the electrotlyes according to Preparation Examples 1 and 2 had about 30% decreased exothermic heat than the one including no additive.
The cells were measured regarding exothermic heat according to the same method as used in Table 2 except for pouring the same electrolyte solution as used in each cell on the dried electrode.
The results are the same as shown in the following Table 3.
Referring to Table 3, the cells using the electrolyte solutions including an additive according to Preparation Examples 1 and 2 had decrease exothermic heat despite further pouring an electrolyte solution on a dry electrode. The cells using the electrolytes according to Preparation Examples 1 and 2 had about 55% decreased exothermic heat compared with the cell using an electrolyte including no additive.
Referring to Tables 2 and 3, the rechargeable lithium battery cells respectively including an additive according to Preparation Examples 1 and 2 had decreased exothermic heat. The reason is that the additive was combined with oxygen gas and formed a layer on the positive electrode and decreasing exothermic heat from the positive electrode.
While these embodiments have been described in connection with what is presently considered to be practical example embodiments, it is to be understood that the embodiments are not limited to the disclosed embodiments, but, on the contrary, is intended to cover various modifications and equivalent arrangements included within the spirit and scope of the appended claims.
| Number | Date | Country | Kind |
|---|---|---|---|
| 10-2012-0151253 | Dec 2012 | KR | national |
