Patent Application
20240128508
This disclosure relates to an electrolyte for a rechargeable lithium battery and a rechargeable lithium battery including the same.
A rechargeable lithium battery may be recharged and has three or more times as high energy density per unit weight as a conventional lead storage battery, nickel-cadmium battery, nickel hydrogen battery, nickel zinc battery and the like. It may be also charged at a high rate and thus, is commercially manufactured for a laptop, a cell phone, an electric tool, an electric bike, and the like, and researches on improvement of additional energy density have been actively made.
Such a rechargeable lithium battery is manufactured by injecting an electrolyte into a battery cell, which includes a positive electrode including a positive electrode active material capable of intercalating/deintercalating lithium ions and a negative electrode including a negative electrode active material capable of intercalating/deintercalating lithium ions.
Particularly, the electrolyte uses an organic solvent in which a lithium salt is dissolved, and such an electrolyte is important in determining stability and performance of a rechargeable lithium battery.
LiPF6, which is most commonly used as a lithium salt of the electrolyte, has a problem of accelerating the depletion of the solvent and generating a large amount of gas by reacting with the organic solvent of the electrolyte. When LiPF6 decomposes, LiF and PF5 are produced, which causes electrolyte depletion in the battery, resulting in high-temperature performance degradation and poor safety.
Accordingly, there is a demand for an electrolyte with improved safety without performance deteriorate even at high-temperature condition.
An embodiment provides an electrolyte for a rechargeable lithium battery having improved high-temperature performance, thermal stability, and penetration stability.
Another embodiment provides a rechargeable lithium battery having improved high-temperature safety and high-temperature reliability by applying the electrolyte, and in particular, improved high-temperature storage characteristics by reducing gas generation during high-temperature storage.
An embodiment of the present invention provides an electrolyte for a rechargeable lithium battery including a non-aqueous organic solvent, a lithium salt, and an additive, wherein the additive is a composition including a first compound and a second compound, the first compound is a cesium salt compound, and the second compound is represented by Chemical Formula 1A or Chemical Formula 1B.
In Chemical Formula 1A and Chemical Formula 1B,
An anion of the cesium salt compound may be an imide-based anion or a phosphate-based anion.
The cesium salt compound may be represented by Chemical Formula 2 or 3.
In Chemical Formula 2 and Chemical Formula 3,
Chemical Formula 2 may be represented by Chemical Formula 2-1 or 2-2.
Chemical Formula 3 may be represented by Chemical Formula 3-1.
The first compound may be included in an amount of 0.05 to 3 parts by weight based on 100 parts by weight of the electrolyte for the rechargeable lithium battery.
Chemical Formula 1A may be represented by Chemical Formula 1A-I or Chemical Formula 1A-II.
In Chemical Formula 1A-I,
Chemical Formula 1A-II may be represented by Chemical Formula 1A-II-1 or Chemical Formula 1A-II-2.
In Chemical Formula 1A-II-1 and Chemical Formula 1A-II-2,
Chemical Formula 1B may be represented by Chemical Formula 1B-I or Chemical Formula 1B-II.
In Chemical Formula 1B-I,
Chemical Formula 1B-II may be represented by Chemical Formula 1 B-II-1 or Chemical Formula 1 B-II -2.
In Chemical Formula 1B-II-1 and Chemical Formula 1B-II-2,
The second compound may be represented by Chemical Formula 1A-II-3 or Chemical Formula 1B-II-3.
In Chemical Formula 1A-II-3 and Chemical Formula 1B-II-3,
The second compound may be included in an amount of 0.05 to 5 parts by weight based on 100 parts by weight of the electrolyte for the rechargeable lithium battery.
The composition may be included in an amount of 0.5 to 8.0 parts by weight based on 100 parts by weight of the electrolyte for the rechargeable lithium battery.
Another embodiment of the present invention provides a rechargeable lithium battery including a positive electrode including a positive electrode active material, a negative electrode including a negative electrode active material, and the aforementioned electrolyte for a rechargeable lithium battery.
The positive electrode active material may be represented by Chemical Formula 6 below.
LixM1yM2zM31−y−zO2-aXa [Chemical Formula 6]
In Chemical Formula 6,
In Chemical Formula 6, 0.8≤y≤1, 0≤z≤0.2, and M1 may be Ni.
The negative electrode active material may be graphite or may include a Si composite and graphite together.
The Si composite may include a core including Si-based particles and an amorphous carbon coating layer.
The Si-based particle may include one or more of a Si—C composite, SiOx (0<x≤2), and a Si alloy.
The Si—C composite may include a core including Si particles and crystalline carbon and an amorphous carbon coating layer on the surface of the core, and
Due to the additive with improved thermal safety, it is possible to implement a rechargeable lithium battery having improved high-temperature characteristics by suppressing an increase in internal resistance and generation of gas after being left at a high temperature, and by suppressing a voltage drop.
100: rechargeable lithium battery
112: negative electrode
113: separator
114: positive electrode
120: battery case
140: sealing member
Hereinafter, a rechargeable lithium battery according to an embodiment of the present invention will be described in detail with reference to the accompanying drawings. However, these embodiments are exemplary, the present invention is not limited thereto and the present invention is defined by the scope of claims.
In the present specification, unless otherwise defined, “substituted” means that at least one hydrogen in a substituent or compound is deuterium, a halogen group, a hydroxyl group, an amino group, a substituted or unsubstituted C1 to C30 amine group, a nitro group, a substituted or unsubstituted C1 to C40 silyl group, a C1 to C30 alkyl group, a C1 to C10 alkylsilyl group, a C6 to C30 arylsilyl group, a C3 to C30 cycloalkyl group, a C3 to C30 heterocycloalkyl group, a C6 to C30 aryl group, a C2 to C30 heteroaryl group, a C1 to C20 alkoxy group, a C1 to C10 fluoroalkyl group, a cyano group, or a combination thereof.
In one example of the present invention, “substituted” refers to replacement of at least one hydrogen of a substituent or a compound by deuterium, a halogen, a C1 to C30 alkyl group, a C1 to C10 alkylsilyl group, a C6 to C30 arylsilyl group, a C3 to C30 cycloalkyl group, a C3 to C30 heterocycloalkyl group, a C6 to C30 aryl group, a C2 to C30 heteroaryl group, a C1 to C10 fluoroalkyl group, or a cyano group. In addition, in specific examples of the present invention, “substituted” refers to replacement of at least on hydrogen of a substituent or a compound by deuterium, a halogen, a C1 to C20 alkyl group, a C6 to C30 aryl group, a C1 to C10 fluoroalkyl group, or a cyano group. In addition, in specific examples of the present invention, “substituted” refers to replacement of at least one hydrogen of a substituent or a compound by deuterium, a halogen, a C1 to C5 alkyl group, a C6 to C18 aryl group, a C1 to C5 fluoroalkyl group, or a cyano group. In addition, in specific examples of the present invention, “substituted” refers to replacement of at least one hydrogen of a substituent or a compound by deuterium, a cyano group, a halogen, a methyl group, an ethyl group, a propyl group, a butyl group, a phenyl group, a biphenyl group, a terphenyl group, a trifluoromethyl group, or a naphthyl group.
A rechargeable lithium battery may be classified into a lithium ion battery, a lithium ion polymer battery, and a lithium polymer battery depending on kinds of a separator and an electrolyte. It also may be classified to be cylindrical, prismatic, coin-type, pouch-type, and the like depending on shape. In addition, it may be bulk type and thin film type depending on sizes. Structures and manufacturing methods for lithium ion batteries pertaining to this disclosure are well known in the art.
Herein, as an example of a rechargeable lithium battery, a cylindrical rechargeable lithium battery is for example described.
Hereinafter, a more detailed configuration of the rechargeable lithium battery 100 according to an embodiment of the present invention will be described.
A rechargeable lithium battery according to one embodiment of the present invention includes an electrolyte, a positive electrode, and a negative electrode.
The electrolyte includes a non-aqueous organic solvent, a lithium salt, and an additive, wherein the additive is a composition including a first compound and a second compound, the first compound is a cesium salt compound, and the second compound is represented by Chemical Formula 1A or Chemical Formula 1B.
In Chemical Formula 1A and Chemical Formula 1B,
The first compound is a cesium salt compound, wherein the first compound is decomposed in the electrolyte to form a film on the positive and the negative electrode surfaces and thus effectively control elution of lithium ions generated from the positive electrode and resultantly, prevent decomposition of the positive electrode. Specifically, the first compound is earlier reduced and decomposed than a carbonate-based solvent included in the non-aqueous organic solvent to form an SEI (Solid Electrolyte Interface) film on the negative electrode and thus prevent decomposition of the electrolyte and the resulting decomposition of the electrode and resultantly, suppress an increase in internal resistance due to gas generation. A portion of the SEI film on the negative electrode is decomposed through the reduction reaction during the charge and discharge, moves toward the positive electrode surface, and also forms a film on the positive electrode surface through an oxidation reaction to prevent the decomposition of the positive electrode surface and oxidation reaction of the electrolyte, contributing to improving high-temperature and low-temperature cycle-life characteristics.
In other words, the composition includes the first compound represented by Chemical Formula 1, improving cycle-life characteristics and safety of the battery.
In addition, the composition includes a bisphosphate-based or bisphosphite-based compound as the second compound and forms each film on the positive and negative electrode surfaces during the high-temperature storage to suppress the resistance increase in the film and improve stability of the film, resulting in having an effect of improving high-temperature cycle-life and thermal safety characteristics.
The second compound is represented by Chemical Formula 1A or Chemical Formula 1B and has a structure that two phosphate moieties or two phosphite moieties are linked by a disulfide linker.
As this compound is decomposed into two phosphate-based compounds or two phosphite-based compounds centering on the disulfide linker, each film is formed on the positive and negative electrode surfaces.
In summary, when the first compound and the second compound are used in combination, compared with when each compound alone is used, the film is more firmly formed on the positive and negative electrode surfaces, further improving high-temperature storage characteristics.
For example, the anion of the cesium salt compound may be an imide-based anion or a phosphate-based anion.
As a specific example, the cesium salt compound may be represented by Chemical Formula 2 or 3.
In Chemical Formula 2 and Chemical Formula 3, R62 to R69 are each independently a fluoro group or a C1 to C4 fluoroalkyl group substituted with at least one fluoro group.
For example, R62 to R69 in Chemical Formulas 2 and 3 may each independently be a fluoro group or a C1 to C4 fluoroalkyl group substituted with at least two fluoro groups.
For example, R62 to R69 in Chemical Formulas 2 and 3 may each independently be a fluoro group or a C1 to C4 fluoroalkyl group substituted with at least three fluoro groups.
As a specific example, R62 to R69 in Chemical Formulas 2 and 3 may each independently be a fluoro group or a C1 to C3 fluoroalkyl group substituted with at least three fluoro groups.
As a more specific example, R62 to R69 in Chemical Formulas 2 and 3 may each independently be a fluoro group or a C1 to C2 fluoroalkyl group substituted with at least three fluoro groups.
For example, Chemical Formula 2 may be represented by Chemical Formula 2-1 or 2-2.
For example, Chemical Formula 3 may be represented by Chemical Formula 3-1.
For example, the first compound may be included in an amount of 0.05 to 3 parts by weight, for example, 0.05 to 2 parts by weight, 0.1 to 2 parts by weight, or 0.1 to 1 part by weight, based on 100 parts by weight of the electrolyte for the rechargeable lithium battery.
For example, Chemical Formula 1A may be represented by Chemical Formula 1A-I or Chemical Formula 1A-II.
In Chemical Formula 1A-I,
In an embodiment, R9 to R28 may each independently be hydrogen, a halogen group, or a substituted or unsubstituted C1 to C5 alkyl group, n1 to n4 may each independently be one of integers ranging from 0 to 3, and L1 and L2 may each independently be a substituted or unsubstituted C2 to C20 alkylene group.
In a specific example embodiment, R9 to R28 may each independently be hydrogen, a halogen group, or a substituted or unsubstituted C1 to C3 alkyl group, n1 to n4 may each independently be one of integers ranging from 0 to 2, and L1 and L2 may each independently be a substituted or unsubstituted C2 to C10 alkylene group.
In an embodiment, R29 and R39 may each independently be a substituted or unsubstituted C2 to C5 alkylene group, and L1 and L2 may each independently a substituted or unsubstituted C2 to C20 alkylene group.
In a specific embodiment, R29 and R39 may each independently a substituted or unsubstituted C2 to C4 alkylene group, and L1 and L2 may each independently be a substituted or unsubstituted C2 to C10 alkylene group.
For example, Chemical Formula 1A-II may be represented by Chemical Formula 1A-II-1 or Chemical Formula 1A-II-2.
In Chemical Formula 1A-II-1 and Chemical Formula 1A-II-2,
In an embodiment, R101 to R120 may each independently be hydrogen, a halogen group, or a substituted or unsubstituted C1 to C5 alkyl group.
In a specific embodiment, each of R101 to R120 may be hydrogen.
In another specific example, Chemical Formula 1B may be represented by Chemical Formula 1B-I or Chemical Formula 1B-II.
In Chemical Formula 1B-I,
In an embodiment, R31 to R50 may each independently be hydrogen, a halogen group, or a substituted or unsubstituted C1 to C5 alkyl group, n5 to n8 may each independently be one of integers ranging from 0 to 3, and L3 and L4 may each independently be a substituted or unsubstituted C2 to C20 alkylene group.
In a specific embodiment, R31 to R50 may each independently be hydrogen, a halogen group, or a substituted or unsubstituted C1 to C3 alkyl group, n5 to n8 may each independently be one of integers ranging from 0 to 2, and L3 and L4 may each independently be a substituted or unsubstituted C2 to C10 alkylene group.
In an embodiment, R51 and R52 may each independently be a substituted or unsubstituted C2 to C5 alkylene group, and L3 and L4 may each independently be a substituted or unsubstituted C2 to C20 alkylene group.
In a specific embodiment, R51 and R52 may each independently be a substituted or unsubstituted C2 to C4 alkylene group, and L3 and L4 may each independently be a substituted or unsubstituted C2 to C10 alkylene group.
For example, Chemical Formula 1B-II may be represented by Chemical Formula 1B-II-1 or Chemical Formula 1B-II-2.
In Chemical Formula 1B-II-1 and Chemical Formula 1B-II-2,
In an embodiment, R121 to R140 may each independently be hydrogen, a halogen group, or a substituted or unsubstituted C1 to C5 alkyl group.
In a specific embodiment, each of R121 to R140 may be hydrogen.
The second compound according to a specific example of the present invention may be represented by Chemical Formula 1A-II-3 or Chemical Formula 1B-II-3.
In Chemical Formula 1A-II-3 and Chemical Formula 1B-II-3,
In an embodiment, R101 to R108, R121 to R128, and R141 to R156 may each independently be hydrogen, a halogen group, or a substituted or unsubstituted C1 to C5 alkyl group.
In a specific embodiment, each of R101 to R108, R121 to R128, and R141 to R156 may be hydrogen.
For example, the second compound may be included in an amount of 0.05 to 5 parts by weight, for example, 0.1 to 5 parts by weight, 0.1 to 3 parts by weight, or 0.5 to 3 parts by weight, based on 100 parts by weight of the electrolyte for the rechargeable lithium battery.
The composition may be included in an amount of 0.5 to 8.0 parts by weight, specifically, 0.5 to 7.0 parts by weight, 0.5 to 6.0 parts by weight, 0.5 to 5.0 parts by weight, or 0.5 to 3.0 parts by weight, based on 100 parts by weight of the electrolyte for the rechargeable lithium battery.
When the content range of the additives including the composition is as described above, it is possible to implement a rechargeable lithium battery with improved cycle-life characteristics by preventing an increase in resistance at high temperatures.
The non-aqueous organic solvent serves as a medium for transmitting ions taking part in the electrochemical reaction of a battery.
The non-aqueous organic solvent may be a carbonate-based, ester-based, ether-based, ketone-based, alcohol-based, or aprotic solvent.
The carbonate-based solvent may be 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. The ester-based solvent may be methyl acetate, ethyl acetate, n-propyl acetate, t-butyl acetate, methyl propionate, ethyl propionate, propyl propionate, decanolide, mevalonolactone, caprolactone, and the like. The ether-based solvent may be dibutyl ether, tetraglyme, diglyme, dimethoxyethane, 2-methyltetrahydrofuran, tetrahydrofuran, and the like. In addition, the ketone-based solvent may be cyclohexanone, and the like. The alcohol-based solvent may include ethanol, isopropyl alcohol, and the like, and the aprotic solvent may include nitriles such as R18 —CN (wherein R18 is a hydrocarbon group having a C2 to C20 linear, branched, or cyclic structure and may include a double bond, an aromatic ring, or an ether bond), and the like, amides such as dimethyl formamide, and the like, dioxolanes such as 1,3-dioxolane, and the like, sulfolanes, and the like.
The non-aqueous organic solvent may be used alone or in a mixture, and when used in a mixture, the mixing ratio may be appropriately adjusted in accordance with a desired battery performance, which is widely understood by those skilled in the art.
The carbonate-based solvent is prepared by mixing a cyclic carbonate and a chain carbonate. When the cyclic carbonate and chain carbonate are mixed together in a volume ratio of 1:9 to 9:1, a performance of the electrolyte may be improved.
In particular, in an embodiment, the non-aqueous organic solvent may include the cyclic carbonate and the chain carbonate in a volume ratio of 2:8 to 5:5, and as a specific example, the cyclic carbonate and the chain carbonate may be included in a volume ratio of 2:8 to 4:6.
More specifically, the cyclic carbonate and the chain carbonate may be included in a volume ratio of 2:8 to 3:7.
The non-aqueous organic solvent may further include an aromatic hydrocarbon-based organic solvent in addition to the carbonate-based solvent. Herein, the carbonate-based solvent and the aromatic hydrocarbon-based organic solvent may be mixed in a volume ratio of 1:1 to 30:1.
The aromatic hydrocarbon-based organic solvent may be an aromatic hydrocarbon-based compound of Chemical Formula 2.
In Chemical Formula 4, R53 to R58 are the same or different and are hydrogen, a halogen, a C1 to C10 alkyl group, a haloalkyl group, or a combination thereof.
Specific examples of the aromatic hydrocarbon-based organic solvent 15 may be 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, 20 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, or a combination thereof.
The electrolyte may further include vinylene carbonate, vinyl ethylene carbonate, or an ethylene-based carbonate-based compound represented by Chemical Formula 5 as an additive to improve cycle-life of a battery.
In Chemical Formula 5, R59 and R60 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 R59 and R60 is selected from a halogen, a cyano group (CN), a nitro group (NO2), and a fluorinated C1 to C5 alkyl group, and both R59 and R60 are not hydrogen.
Examples of the ethylene-based carbonate-based compound may include difluoro ethylene carbonate, chloroethylene carbonate, dichloroethylene carbonate, bromoethylene carbonate, dibromoethylene carbonate, nitroethylene carbonate, cyanoethylene carbonate, or fluoroethylene carbonate. When such an additive for improving cycle-life is further used, its amount may be appropriately adjusted.
The lithium salt dissolved in the non-organic solvent supplies lithium ions in a battery, enables a basic operation of a rechargeable lithium battery, and improves transportation of the lithium ions between positive and negative electrodes. Examples of the lithium salt may include at least one selected from LiPF6, LiBF4, LiSbF6, LiAsF6, LiN(SO2C2F5)2, Li(CF3SO2)2N, LiN(SO3C2F5)2, Li(FSO2)2N (lithium bis(fluorosulfonyl)imide: LiFSI), LiC4F9SO3, LiClO4, LiAlO2, LiAlCl4, LiPO2F2, LiN(CxF2x+1SO2)(CyF2y+1SO2) (wherein x and y are natural numbers, for example an integer of 1 to 20), LiCl, LiI, LiB(C2O4)2 (lithium bis(oxalato) borate: LiBOB), LiDFOB (lithium difluoro(oxalato)borate), and Li[PF2(C2O4)2] (lithium difluoro (bis oxalato) phosphate). The lithium salt may be used in a concentration ranging from 0.1 M to 2.0 M. When the lithium salt is included at the above concentration range, an electrolyte may have excellent performance and lithium ion mobility due to optimal electrolyte conductivity and viscosity.
The positive electrode includes a positive electrode current collector and a positive electrode active material layer on the positive electrode current collector, and the positive electrode active material layer includes a positive electrode active material.
The positive electrode active material may include lithiated intercalation compounds that reversibly intercalate and deintercalate lithium ions.
Specifically, one or more of a composite oxide of a metal selected from cobalt, manganese, nickel, and a combinationsthereof and lithium may be used.
Of course, one having a coating layer on the surface of the lithium composite oxide may be used, or a mixture of the composite oxide and a compound having a coating layer may be used. The coating layer may include one or more coating element compound selected from an oxide of a coating element, a hydroxide of a coating element, an oxyhydroxide of a coating element, an oxycarbonate of a coating element, and a hydroxy carbonate of a coating element. The compound for the coating layer may be amorphous or crystalline. The coating element included in the coating layer may include Mg, Al, Co, K, Na, Ca, Si, Ti, V, Sn, Ge, Ga, B, As, Zr, or a mixture thereof. The coating process may include any conventional processes as long as it does not cause any side effects on the properties of the positive electrode active material (e.g., inkjet coating, dipping), which is well known to persons having ordinary skill in this art, so a detailed description thereof is omitted.
The positive electrode active material may be, for example, one or more of lithium composite oxides represented by Chemical Formula 6.
LixM11−y−z,M2yM3zO2−aXa [Chemical Formula 6]
In Chemical Formula 6,
In an embodiment, the positive electrode active material may be one or more selected from LiCoO2, LiNiO2, LiMnO2, LiMn2O4, LiNiaMnbCocO2(a+b+c=1), LiNiaMnbCocAldO2 (a+b+c+d=1), and LiNieCofAlgO2 (e+f+g=1).
In Chemical Formula 6, 0.8<y<1, 0<z<0.2, and M 1 may be Ni.
For example, in the case of LiNiaMnbCocO2 (a+b+c=1) and LiNiaMnbCocAldO2 (a+b+c+d=1), the nickel content may be greater than or equal to 60% (a≥0.6), and more specifically, greater than or equal to 80% (a≥0.8).
For example, in the case of LiNieCofAlgO2 (e+f+g=1), the nickel content may be greater than or equal to 60% (e≥0.6), and more specifically, greater than or equal to 80% (e≥0.8).
In a more specific embodiment, the positive electrode active material may be a lithium composite oxide represented by any one of Chemical Formulas 6-1 to 6-3.
Lix1Niy1Coz1Al1−y1−z1O2 [Chemical Formula 6-1]
In Chemical Formula 6-1, 1≤x1≤1.2, 0<y<1<1, and 0<z1<1.
Lix2Niy2Coz2Mn−y2−z2O2 [Chemical Formula 6-2]
In Chemical Formula 6-2,
1≤x2≤1.2, 0<y2<1, and 0<z2<1.
Lix3CoO2 [Chemical Formula 6-3]
In Chemical Formula 6-3,
0.5<x3≤1.
For example, in Chemical Formula 6-1, 1≤x1≤1.2, 0.5≤y1<1, and 0<z1≤0.5.
As a specific example, in Chemical Formula 6-1, 1≤x1≤1.2, 0.6≤y1<1, and 0<z1≤0.5.
As a more specific example, in Chemical Formula 6-1, 1≤x1≤1.2, 0.7≤y1<1, and 0<z1≤0.5.
For example, in Chemical Formula 6-1, 1≤x1≤1.2, 0.8≤y1<1, and 0<z1≤0.5.
For example, in Chemical Formula 6-2, 1≤x1≤1.2, 0.8≤y1<1, and 0<z1≤0.5.
As a specific example, in Chemical Formula 6-2, 1≤x2≤1.2, 0.6≤y2<1, and 0.3≤z2<1.
As a more specific example, in Chemical Formula 6-2, 1≤x2≤1.2, 0.7≤y2<1, and 0.3≤z2<1.
For example, in Chemical Formula 6-2, 1≤x2≤1.2, 0.8≤y2<1, and 0.3≤z2<1.
A content of the positive electrode active material may be 90 wt % to 98 wt % based on the total weight of the positive electrode active material layer.
In an embodiment of the present invention, the positive electrode active material layer may optionally include a conductive material and a binder. In this case, a content of the conductive material and the binder may be 1 wt % to 5 wt %, respectively, based on the total weight of the positive electrode active material layer.
The conductive material is included to impart conductivity to the positive electrode and any electrically conductive material may be used as a conductive material unless it causes a chemical change in the configured battery.
Examples of the conductive material may 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; or a mixture thereof.
The binder improves binding properties of positive electrode active material particles with one another and with a current collector. Examples thereof may be polyvinyl alcohol, carboxylmethyl cellulose, hydroxypropyl cellulose, diacetyl cellulose, polyvinylchloride, carboxylated polyvinylchloride, polyvinylfluoride, an ethylene oxide-containing polymer, polyvinylpyrrolidone, polyurethane, polytetrafluoroethylene, polyvinylidene fluoride, polyethylene, polypropylene, a styrene-butadiene rubber, an acrylated styrene-butadiene rubber, an epoxy resin, nylon, and the like, but is not limited thereto.
The positive electrode current collector may include Al, but is not limited thereto.
The negative electrode includes a negative electrode current collector and a negative electrode active material layer including a negative electrode active material formed on the negative electrode current collector.
The negative electrode active material may include a material that reversibly intercalates/deintercalates lithium ions, a lithium metal, a lithium metal alloy, a material capable of doping/dedoping lithium, or transition metal oxide.
The material that reversibly intercalates/deintercalates lithium ions includes carbon materials. The carbon material may be any generally-used carbon-based negative electrode active material in a rechargeable lithium battery and examples of the carbon material include crystalline carbon, amorphous carbon, and a combination thereof. The crystalline carbon may be non-shaped, or sheet, flake, spherical, or fiber shaped natural graphite or artificial graphite and the amorphous carbon may be a soft carbon, a hard carbon, a mesophase pitch carbonization product, calcined coke, and the like.
The lithium metal alloy may include lithium and a metal selected from Na, K, Rb, Cs, Fr, Be, Mg, Ca, Sr, Si, Sb, Pb, In, Zn, Ba, Ra, Ge, Al, and Sn.
The material capable of doping/dedoping lithium may be Si, Si—C composite, SiOx(0<x<2), a Si-Q alloy wherein Q is an element selected from an alkali metal, an alkaline-earth metal, a Group 13 element, a Group 14 element, a Group 15 element, a Group 16 element, a transition metal, a rare earth element, and a combination thereof, but not Si), Sn, SnO2, a Sn—R61 alloy (wherein R61 is an element selected from an alkali metal, an alkaline-earth metal, a Group 13 element, a Group 14 element, a Group 15 element, a Group 16 element, a transition metal, a rare earth element, and a combination thereof, but not Sn), and the like. One or more of these materials may be mixed with SiO2.
The elements Q and R61 may be selected from Mg, Ca, Sr, Ba, Ra, Sc, Y, Ti, Zr, Hf, Rf, V, Nb, Ta, Db, Cr, Mo, W, Sg, Tc, Re, Bh, Fe, Pb, Ru, Os, Hs, Rh, Ir, Pd, Pt, Cu, Ag, Au, Zn, Cd, B, Al, Ga, Sn, In, TI, Ge, P, As, Sb, Bi, S, Se, Te, Po, and a combination thereof.
The transition metal oxide may be a vanadium oxide, a lithium vanadium oxide, and the like.
In a specific embodiment, the negative electrode active material may be graphite or may include a Si composite and graphite together.
When the negative electrode active material includes the Si composite and graphite together, the Si composite and graphite may be included in the form of a mixture, and the Si composite and graphite may be included in a weight ratio of 1:99 to 50:50. More specifically, the Si composite and graphite may be included in a weight ratio of 3:97 to 20:80 or 5:95 to 20:80.
The Si composite may include a core including Si-based particles and an amorphous carbon coating layer. For example, the Si-based particles may include a Si—C composite, SiOx(0<x≤2), a Si alloy or mixture thereof. For example, the Si—C composite may include a core including Si particles and crystalline carbon, and an amorphous carbon coating layer on the surface of the core.
The crystalline carbon may include, for example, graphite, and more specifically, natural graphite, artificial graphite, or a mixture thereof.
An average particle diameter of the crystalline carbon may be 5 μm to 30 μm.
In the present specification, an average particle diameter may be a particle size (D50) at a volume ratio of 50% in a cumulative size-distribution curve.
In the Si—C composite, an average particle diameter of the Si particles may be 50 nm to 200 nm.
When the average particle diameter of the Si particles is within the above ranges, volume expansion occurring during charging and discharging may be suppressed, and interruption of a conductive path due to particle crushing during charging and discharging may be prevented.
The Si particles may be included in an amount of 1 wt % to 60 wt %, for example, 3 wt % to 60 wt %, based on the total weight of the Si—C composite.
The amorphous carbon may include soft carbon, hard carbon, a mesophase pitch carbonized product, calcined coke, or a mixture thereof.
The amorphous carbon may be included in an amount of 1 to 50 parts by weight, for example, 5 to 50 parts by weight, or 10 to 50 parts by weight based on 100 parts by weight of the crystalline carbon.
In the negative electrode active material layer, the negative electrode active material may be included in an amount of 95 wt % to 99 wt % based on the total weight of the negative electrode active material layer.
In an embodiment, the negative electrode active material layer may include a binder, and optionally a conductive material. The content of the binder in the negative electrode active material layer may be 1 wt % to 5 wt % based on the total weight of the negative electrode active material layer. In addition, when the conductive material is further included, 90 wt % to 98 wt % of the negative electrode active material, 1 wt % to 5 wt % of the binder, and 1 wt % to 5 wt % of the conductive material may be used.
The binder improves binding properties of negative electrode active material particles with one another and with a current collector. The binder may be a non-water-soluble binder, a water-soluble binder, or a combination thereof.
The non-water-soluble binder may be polyvinylchloride, carboxylated polyvinylchloride, polyvinylfluoride, polyurethane, polytetrafluoroethylene, polyvinylidene fluoride, polyethylene, polypropylene, polyamideimide, polyimide, or a combination thereof.
The water-soluble binder may be a rubber-based binder or a polymer resin binder. The rubber-based binder may be selected from a styrene-butadiene rubber, an acrylated styrene-butadiene rubber (SBR), an acrylonitrile-butadiene rubber, an acrylic rubber, a butyl rubber, a fluorine rubber, and a combination thereof. The polymer resin binder may be selected from polytetrafluoroethylene, ethylenepropyleneco polymer, polyethylene oxide, polyvinylpyrrolidone, polyepichlorohydrine, polyphosphazene, polyacrylonitrile, polystyrene, an ethylene propylene diene copolymer, polyvinylpyridine, chlorosulfonated polyethylene, latex, a polyester resin, an acrylic resin, a phenolic resin, an epoxy resin, polyvinyl alcohol, or a combination thereof.
When the water-soluble binder is used as a negative electrode binder, a cellulose-based compound may be further used to provide viscosity as a thickener. The cellulose-based compound includes one or more of carboxymethyl cellulose, hydroxypropylmethyl cellulose, methyl cellulose, or alkali metal salts thereof. The alkali metals may be Na, K, or Li. Such a thickener may be included in an amount of 0.1 to 3 parts by weight based on 100 parts by weight of the negative electrode active material.
The conductive material is included to improve electrode conductivity and any electrically conductive material may be used as a conductive material unless it causes a chemical change. Examples of the conductive material include a carbon-based material such as natural graphite, artificial graphite, carbon black, acetylene black, ketjen black, a carbon fiber, and the like; a metal-based material of a metal powder or a metal fiber including copper, nickel, aluminum, silver, and the like; a conductive polymer such as a polyphenylene derivative; or a mixture thereof.
The negative electrode current collector may be selected from a copper foil, a nickel foil, a stainless-steel foil, a titanium foil, a nickel foam, a copper foam, a polymer substrate coated with a conductive metal, and a combination thereof.
The rechargeable lithium battery may further include a separator between the negative electrode and the positive electrode, depending on a type of the battery. Such a separator may be a porous substrate or a composite porous substrate.
The porous substrate may be a substrate including pores, and lithium ions may move through the pores. The porous substrate may for example include polyethylene, polypropylene, polyvinylidene fluoride, and multi-layers thereof such as a polyethylene/polypropylene double-layered separator, a polyethylene/polypropylene/polyethylene triple-layered separator, and a polypropylene/polyethylene/polypropylene triple-layered separator.
The composite porous substrate may have a form including a porous substrate and a functional layer on the porous substrate. The functional layer may be, for example, one or more of a heat-resistant layer and an adhesive layer from the viewpoint of enabling additional function. For example, the heat-resistant layer may include a heat-resistant resin and optionally a filler.
In addition, the adhesive layer may include an adhesive resin and optionally a filler.
The filler may be an organic filler or an inorganic filler.
Hereinafter, examples of the present invention and comparative examples are described. These examples, however, are not in any sense to be interpreted as limiting the scope of the invention.
After setting a temperature at −5° C. under a nitrogen atmosphere, bis(2-hydroxyethyl)disulfide (6.8 g, 0.04 mol) and triethylamine (8.9 g, 0.09 mol) were added to 50 mL of dried dichloromethane. This mixed solution was slowly added in a dropwise fashion to 100 mL of a dried dichloromethane solution in which 2-chloro-2-oxo-1,3,2-dioxaphospholane (COP: 2-chloro-2-oxo-1,3,2-dioxaphospholane) (12.54 g, 0.088 mol) was dissolved. After stirring the mixture for 8 hours, salt produced therein was filtered and removed, and a filtrate therefrom was dried. Subsequently, 50 mL of toluene was added to the dried mixture, obtaining a white solid produced therein (12.9 g, 88%); 1H NMR (400 MHz, CDC3): δ4.40 (m, 12H), 3.01 (m, 4H); 31P NMR: δ17.98
After setting a temperature at −5° C. under a nitrogen atmosphere, bis(2-hydroxyethyl) disulfide (6.8 g, 0.04 mol) and triethylamine (8.9 g, 0.09 mol) were added to 50 mL of dried dichloromethane. This mixed solution was slowly added in a dropwise fashion to 100 mL of a dichloromethane solution in which 2-chloro-1,3,2-dioxaphospholane (11.1 g, 0.09 mol) was dissolved. After stirring the mixture for 8 hours, salt produced therein was filtered and removed, and a filtrate therefrom was dried. 50 mL of diehtly ether was added to the dried mixture, and after removing salt produced therein, a filtrate therefrom was dried, obtaining transparent oil. (10.7 g, 80%); 1H NMR (400 MHz, CDCl3): δ4.24 (m, 4H), 3.98 (m, 8H), 2.81 (m, 4H); 31P NMR: δ137.11
LiNi0.88Co0.07Al0.05O2 as a positive electrode active material, polyvinylidene fluoride as a binder, and ketjen black as a conductive material were mixed in a weight ratio of 97:2:1 and then, dispersed in N-methyl pyrrolidone, preparing positive electrode active material slurry.
The positive electrode active material slurry was coated on a 14 μm-thick Al foil, dried at 110° C., and pressed, manufacturing a positive electrode.
A negative electrode active material prepared by mixing artificial graphite and an Si—C composite in a weight ratio of 93:7, a styrene-butadiene rubber binder as a binder, and carboxylmethyl cellulose as a thickener were mixed in a weight ratio of 97:1:2 and then, dispersed in distilled water, preparing negative electrode active material slurry.
The Si—C composite included a core including artificial graphite and silicon particles and coal-based pitch coated on the surface of the core.
The negative electrode active material slurry was coated on a 10 μm-thick Cu and then, dried at 100° C. and pressed, manufacturing a negative electrode.
The positive electrode and the negative electrode were assembled with a 25 μm-thick polyethylene separator to manufacture an electrode assembly, and an electrolyte was injected thereinto, manufacturing a rechargeable lithium battery cell.
The electrolyte has a composition as follows.
(Composition of the electrolyte)
Rechargeable lithium battery cells were manufactured in the same method as in Example 1 except that the composition was changed into each composition shown in Table 1.
A rechargeable lithium battery cell was manufactured in the same manner as in Example 1 except that an electrolyte not including the additive was used.
A rechargeable lithium battery cell was manufactured in the same manner as in Example 2 except that an additive not using the compound represented by Chemical Formula a-1 was used to prepare an electrolyte.
A rechargeable lithium battery cell was manufactured in the same manner as in Example 1 except that an additive not using the compound represented by Chemical Formula a-1 was used to prepare an electrolyte.
A rechargeable lithium battery cell was manufactured in the same manner as in Example 1 except that an additive not using the compound represented by Chemical Formula 2-2 was used to prepare an electrolyte.
A rechargeable lithium battery cell was manufactured in the same manner as in Example 1 except that Li(CF3SO2)2N was used instead of the cesium bis(trifluoromethanesulfonyl)imide represented by Chemical Formula 2-2.
A rechargeable lithium battery cell was manufactured in the same manner as in Example 3 except that an additive not using the compound represented by Chemical Formula 2-2 was used to prepare an electrolyte.
A rechargeable lithium battery cell was manufactured in the same manner as in Example 3 except that Li(CF3SO2)2N was used instead of the cesium bis(trifluoromethanesulfonyl)imide represented by Chemical Formula 2-2 to prepare an electrolyte.
Initial DC-IR was measured in the following method.
The cells according to Examples 1 to 8 and Comparative Examples 1 to 7 were charged at 4.2 V and 4 A at room temperature (25° C.), cut off at 100 mA, and paused for 30 minutes. Subsequently, the cells were respectively discharged at 10 A for 10 seconds, 1 A and 10 seconds, and 10 A and 4 seconds and then, measured with respect to a current and a voltage respectively at 18 seconds and 23 seconds to calculate initial resistance (a difference between resistance at 18 seconds and resistance at 23 seconds) according to ΔR=ΔV/ ΔI.
The rechargeable lithium battery cells according to Examples 1 to 8 and Comparative Examples 1 to 7 were 100 cycles charged and discharged within 2.75 V to 4.2 V at a C-rate of 0.5 C at room temperature (25° C.) and then, measured with respect to a change in discharge capacity to calculate a capacity ratio of the discharge capacity at the 100th cycle to the discharge capacity at the 1st cycle (capacity retention), and the results are shown in Table 2.
The rechargeable lithium battery cells according to Examples 1 to 8 and Comparative Examples 1 to 7 were measured with respect to time when CID was OPEN, after being left in a state of charge (SOC=100%) at 90° C., and the results are shown in Table 2.
Each rechargeable lithium battery cell according to Examples 1 to 8 and Comparative Examples 1 to 7 was left in a state of charge (SOC=100%) at 142° C., ignition was recorded, and the results are shown in Table 2.
Each rechargeable lithium battery cell according to Examples 1 to 8 and Comparative Examples 1 to 7 was evaluated with respect to penetration characteristics by twice penetrating the cells in SOC 50 with a 3 1 pin at 150 mm/s and recording whether the cells ignited or not, and the results are shown in Table 2.
The rechargeable lithium battery cells using the composition of the specific mixed combination as an additive according to the present example embodiment turned out to realize excellent high-temperature characteristics and safety without deteriorating cycle-life characteristics and gas generation suppression performance during the high-temperature storage.
Referring to Table 2, the rechargeable lithium battery cells according to Examples 1 to 8 exhibited improved thermal safety and penetration stability and maintained equivalent DC resistance increase rate, room temperature capacity retention characteristics, and high-temperature leaving characteristics to the cells according to Comparative Examples 1 to 7.
In summary, the rechargeable lithium battery cells according to Examples 1 to 8 particularly exhibited excellent thermal safety and penetration stability, compared with the rechargeable lithium battery cells according to Comparative Examples 1 to 7.
While this invention has been described in connection with what is presently considered to be practical example embodiments, it is to be understood that the invention is not limited to the disclosed embodiments, 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 |
|---|---|---|---|
| 10-2021-0096467 | Jul 2021 | KR | national |
| Filing Document | Filing Date | Country | Kind |
|---|---|---|---|
| PCT/KR2022/095070 | 3/30/2022 | WO |
