Patent Application
20240405276
The present application claims priority to and the benefit of Korean Patent Application No. 10-2023-0072443, filed on Jun. 5, 2023, in the Korean Intellectual Property Office, the entire disclosure of which is incorporated by reference herein.
Embodiments of this disclosure relate to a rechargeable lithium battery.
A rechargeable lithium battery may be recharged and has three or more times higher energy density per unit weight than an existing lead storage battery, nickel-cadmium battery, nickel hydrogen battery, nickel zinc battery and the like, and may be highly charged and thus, is commercially manufactured for a laptop, a cell phone, an electric tool, an electric bike, and the like, and research on improvement of additional energy density have been actively made.
The rechargeable lithium battery may be manufactured by injecting electrolyte into a battery cell, which includes a positive electrode including a positive electrode active material capable of intercalating/deintercalating lithium and a negative electrode including a negative electrode active material capable of intercalating/deintercalating lithium.
One of the recent development directions for a rechargeable lithium battery is to improve high-temperature characteristics. In general, a rechargeable lithium battery may have problems such as metal being eluted at high temperatures, electrical resistance increasing, and/or cycle-life being reduced.
However, if the battery case housing the electrode assembly is a cylindrical can, the above problems may become worse depending on a volume of the cylindrical can.
Some example embodiments of the present disclosure reduce elution of metals at high temperatures, resistance increases, and/or cycle-life decreases in a rechargeable lithium battery using a cylindrical can.
Some example embodiments provide a rechargeable lithium battery including a cylindrical can; an electrode assembly accommodated in the cylindrical can; and an electrolyte impregnated in the electrode assembly, wherein a volume of the cylindrical can is controlled and a type (or kind) and a content of the electrolyte additive are limited. The volume of the cylindrical can and the type (or kind) and content of the electrolyte additive will be described in more detail herein below.
The rechargeable lithium battery of some example embodiments can suppress or reduce metal elution and suppress or reduce an increase in resistance at high temperatures, and/or secure or improve the cycle-life of the rechargeable lithium battery by controlling the volume of the cylindrical can and limiting the type (or kind) and content of the electrolyte additive.
The accompanying drawings, together with the specification, illustrate embodiments of the subject matter of the present disclosure, and, together with the description, serve to explain principles of embodiments of the subject matter of the present disclosure.
The accompanying drawing is a schematic view showing a rechargeable lithium battery according to some example embodiments of the present disclosure.
Hereinafter, a rechargeable lithium battery according to some example embodiments of the present disclosure will be described in more detail with reference to the attached drawings. However, these embodiments are examples, the present disclosure is not limited thereto and the disclosure is defined by the scope of the appended claims, and equivalents thereof.
Some example embodiments provide a rechargeable lithium battery including a cylindrical can; an electrode assembly accommodated in the cylindrical can; and an electrolyte impregnated in the electrode assembly.
The rechargeable lithium battery of some example embodiments can suppress or reduce metal elution and suppress or reduce an increase in resistance at high temperatures, and/or secure or improve cycle-life of the rechargeable lithium battery by controlling the volume of the cylindrical can and limiting the type (or kind) and content of the electrolyte additive. Herein, the term “content” is used synonymously with the term “amount.”
First, a description of the volume of the cylindrical can is as follows.
The cylindrical can may have a volume of greater than about 15 cm3, a diameter of greater than about 1.2 cm, and a height of greater than about 0.5 cm. If the volume of the cylindrical can is significantly smaller than about 15 cm3, there is no significant change in an amount of metal elution at high temperature even if the type (or kind) and content of the electrolyte additive are changed. If the volume of the cylindrical can exceeds about 15 cm3, an amount of metal elution changes as the type (or kind) and content of the electrolyte additive changes. For example, in some embodiments, the cylindrical can may have a volume of greater than or equal to about 16 cm3, a diameter of greater than or equal to about 1.8 cm, and a height of greater than or equal to about 6.5 cm.
In some embodiments, the volume of the cylindrical can may be less than or equal to about 296 cm3, the diameter may be less than or equal to about 5.6 cm, and the height may be less than or equal to about 12.0 cm. If the volume of the cylindrical can exceeds about 296 cm3, the amount of metal elution at high temperature may excessively increase, and resistance may increase and cycle-life of the rechargeable lithium battery may be reduced, regardless of the type (or kind) and content of the electrolyte additive. In some embodiments, if the volume of the cylindrical can is less than or equal to about 296 cm3, the amount of metal elution changes as the type (or kind) and content of the electrolyte additive changes. For example, in some embodiments, the cylindrical can may have a volume of less than or equal to about 133 cm3, a diameter of less than or equal to about 4.6 cm, and a height of less than or equal to about 8.0 cm.
A description of the electrolyte including the above two types (or kinds) of additives is as follows.
The electrolyte includes a non-aqueous organic solvent, a lithium salt, a first additive, and a second additive; wherein the first additive includes a compound represented by Chemical Formula 1; the second additive includes a compound represented by Chemical Formula 2, a derivative thereof, and/or an adduct thereof; and a content of the second additive is less than about 5 wt % based on 100 wt % of the electrolyte:
The first additive (compound represented by Chemical Formula 1) may stabilize the lithium salt to suppress or reduce side reactions of the electrolyte, and the second additive (compound represented by Chemical Formula 2) may be absorbed on the surface of the positive electrode through coordination of a lone pair of nitrogen atoms in the additive structure with a transition metal to stabilize the positive electrode and in some embodiments, suppress or reduce side reactions due to precipitation of the transition metal to improve cycle-life and high-temperature characteristics of the rechargeable battery.
However, when using the two types (or kinds) of additives concurrently (e.g., simultaneously), the content of the second additive in the electrolyte needs to be controlled to less than about 5 wt %. If the content of the second additive in the electrolyte is greater than or equal to about 5 wt %, resistance may increase, which may cause a problem in which the cycle-life of the rechargeable lithium battery is reduced at high temperatures. However, if the content of the second additive in the electrolyte is less than about 5 wt %, the cycle-life may be secured or improved while suppressing or reducing an increase in resistance of the rechargeable lithium battery at high temperatures.
Accordingly, compared to where only one of the additives or two types (or kinds) of additives are used concurrently (e.g., simultaneously) and the content of the second additive in the electrolyte is controlled to greater than or equal to about 5 wt %, when the two types (or kinds) of additives are used concurrently (e.g., simultaneously) and the content of the second additive in the electrolyte is controlled to less than about 5 wt %, high-temperature characteristics are improved in a rechargeable lithium battery.
In some embodiments, the first additive includes a compound represented by Chemical Formula 1:
The description of Chemical Formula 1 is as follows:
X1 may be a halogen atom, and, for example, a fluorine atom.
Y1 and Y2 may each independently be O or S, and, for example, both may be O.
Overall, Chemical Formula 1 may be represented by Chemical Formula 1-1:
In Chemical Formula 1-1, Z1 and Z2 may each independently be a substituted or unsubstituted C1 to C5 alkylene group. For example, Z1 may be *—CH2—*, and Z2 may be *—CHCH3—*.
A representative example of the first additive may be a compound represented by Chemical Formula 1-1-1:
A content of the first additive may be greater than or equal to about 0.05 wt %, greater than or equal to about 0.1 wt %, or greater than or equal to about 0.5 wt %; and may be less than or equal to about 3 wt % or less than or equal to about 2 wt % based on 100 wt % of the electrolyte. Within this range, an effect of improving high-temperature characteristics by the first additive can be significantly exhibited.
The second additive includes a compound represented by Chemical Formula 2, a derivative thereof, and/or an adduct thereof.
In Chemical Formula 2, Z is N or CH.
In Chemical Formula 2, when Z is N, the second additive may be a compound represented by Chemical Formula 2-1-1. In some embodiments, when Z in Chemical Formula 2 is CH, the second additive may be a compound represented by Chemical Formula 2-1-1.
The adduct of Chemical Formula 2 may include an adduct obtained by adding trimethyl aluminum, sulfur dioxide, borate, and/or hydrosilane to the compound represented by Chemical Formula 2. In some embodiments, the adduct of Chemical Formula 2 may be a compound represented by Chemical Formula 2-2 or Chemical Formula 2-2.
In the above formulas 2-2 and 2-3, respectively, the “arrow (→)” is an arrow drawn from the atom that donates electrons to the side that receives electrons, and means a coordination bond.
R3 and R4 may each independently be trimethylaluminum or sulfur dioxide. Y3 to Y5 may each independently be O or S, and, for example, all of Y3 to Y5 may be O. Z1 may be B or SiH.
Representative examples of the second additive are as follows:
The content of the second additive in 100 wt % of the electrolyte may be greater than or equal to about 0.05 wt %, greater than or equal to about 0.1 wt %, or greater than or equal to about 0.5 wt %; and may be less than or equal to about 3 wt % or less than or equal to about 2 wt %. Within this range, an effect of improving high-temperature characteristics by the second additive can be significantly exhibited.
In some embodiments, a weight ratio of the first additive and the second additive may be about 1:0.1 to about 1:3. In this way, when the second additive is used in an amount of about 0.1 to about 1.3 parts by weight based on 1 part by weight of the first additive, the synergistic effect of the two types (or kinds) of additives can be further increased.
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 include a carbonate-based, ester-based, ether-based, ketone-based, alcohol-based, and/or aprotic solvent.
The carbonate-based solvent may include ethylmethyl carbonate (EMC), dimethyl carbonate (DMC), diethyl carbonate (DEC), dipropyl carbonate (DPC), methylpropyl carbonate (MPC), ethylpropyl carbonate (EPC), methylethyl carbonate (MEC), ethylene carbonate (EC), propylene carbonate (PC), butylene carbonate (BC), and/or the like. The ester-based solvent may include methyl acetate, ethyl acetate, n-propyl acetate, t-butyl acetate, methylpropionate, ethylpropionate, propylpropionate, decanolide, mevalonolactone, caprolactone, and/or the like. The ether-based solvent may include dibutyl ether, tetraglyme, diglyme, dimethoxyethane, 2-methyltetrahydrofuran, tetrahydrofuran, and/or the like. The ketone-based solvent may include cyclohexanone and/or the like. The alcohol-based solvent may include ethyl alcohol, isopropyl alcohol, and/or the like, and examples of the aprotic solvent include nitriles such as R—CN (wherein R is a C2 to C20 linear, branched, or cyclic hydrocarbon group, a double bond, an aromatic ring, or an ether bond), amides such as dimethylformamide, dioxolanes such as 1,3-dioxolane, sulfolanes, and/or the like.
The non-aqueous organic solvent may be used alone or in combination with one or more of them, and when used in combination with one or more, a mixing ratio may be suitably or appropriately adjusted according to suitable or desired battery performance, which should be well understood by those skilled in the art upon reviewing this disclosure.
The carbonate-based solvent is prepared by mixing together a cyclic carbonate and a chain carbonate. The cyclic carbonate and chain carbonate are mixed together in a volume ratio of about 5:95 to about 50:50. When the mixture is used as an electrolyte, it may have enhanced performance.
In some embodiments, ethylene carbonate (EC) may be used as the cyclic carbonate, and ethylmethyl carbonate (EMC) and dimethyl carbonate (DMC) may be used as the chain carbonate.
In some embodiments, the non-aqueous organic solvent may include a carbonate-based solvent in which ethylene carbonate (EC), ethylmethyl carbonate (EMC), and dimethyl carbonate (DMC) are mixed together. For example, the carbonate-based solvent may include ethylene carbonate (EC), ethylmethyl carbonate (EMC), and dimethyl carbonate (DMC) mixed together in a volume ratio of EC:EMC:DMC=about 1:0.5:5 to about 5:3:10, which may improve performance of the electrolyte.
The non-aqueous organic solvent may further include an aromatic hydrocarbon-based solvent as well as the carbonate-based solvent. The carbonate-based solvent and aromatic hydrocarbon-based solvent may be mixed together in a volume ratio of about 1:1 to about 30:1.
In order to improve battery cycle-life, the electrolyte may further include vinylene carbonate, vinyl ethylene carbonate, and/or an ethylene carbonate-based compound of Chemical Formula 3 as a cycle-life improving additive.
In Chemical Formula 3, R207 and R208 are the same or different and are selected from hydrogen, a halogen, a cyano group (CN), a nitro group (NO2), and a C1 to C5 fluoroalkyl group, provided that at least one selected from R207 and R208 is a halogen, a cyano group (CN), a nitro group (NO2), or a C1 to C5 fluoroalkyl group, and R207 and R208 are not concurrently (e.g., simultaneously) hydrogen.
Examples of the ethylene carbonate-based compound include difluoro ethylenecarbonate, chloroethylene carbonate, dichloroethylene carbonate, bromoethylene carbonate, dibromoethylene carbonate, nitroethylene carbonate, cyanoethylene carbonate or fluoroethylene carbonate. The amount of the additive for improving cycle-life may be used within a suitable or appropriate range.
The lithium salt dissolved in the non-aqueous 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 include at least one selected from LiPF6, LiBF4, LiDFOP, LiDFOB, LiPO2F2, LiSbF6, LiAsF6, LiN(SO2C2F5)2, Li(CF3SO2)2N, LiN(SO3C2F5)2, Li(FSO2)2N (lithium bis(fluorosulfonyl)imide: LiFSI), LiC4F9SO3, LiClO4, LiAlO2, LiAlCl4, LiN(CxF2x+1SO2)(CyF2y+1SO2), wherein, x and y are natural numbers, for example an integer of 1 to 20, LiCl, Lil, and LiB(C2O4)2 (lithium bis(oxalato) borate: LiBOB). The lithium salt may be used in a concentration in a range from about 0.1 M to about 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 suitable or 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.
For example, at least one composite oxide of lithium and a metal of cobalt, manganese, nickel, or a combination thereof may be used.
The composite oxide having a coating layer on the surface thereof may be used, or a mixture of the composite oxide and the composite oxide having a coating layer may be used. The coating layer may include a coating element compound selected from an oxide of the coating element, a hydroxide of the coating element, an oxyhydroxide of the coating element, an oxycarbonate of the coating element, or 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 suitable processes generally used in the art as long as it does not (or substantially does not) cause any side effects (e.g., any undesirable side effects) on the properties of the positive electrode active material (e.g., spray coating, dipping), which should be readily apparent to persons having ordinary skill in this art upon review of this disclosure, and thus a detailed description thereof is not necessary here.
In some embodiments, the positive electrode active material may include a lithium nickel-based composite oxide represented by Chemical Formula A1:
Lia1 Nix1 M1y1 M2z1O2−b1Xb1. Chemical Formula A1
In Chemical Formula A1, 0.9≤a1≤1.2, 0.7≤x1≤1, 0≤y1≤0.2, 0≤z1≤0.2, 0.9≤x1+y1+z1≤1.1, and 0≤b1≤0.1; M1 and M2 are each independently one or more element selected from Al, B, Ba, Ca, Ce, Co, Cr, Cu, Fe, Mg, Mn, Mo, Nb, Si, Sr, Ti, V, W, and Zr; and X is one or more element selected from F, P, and S.
In Chemical Formula A1, 0.75≤x1≤1, 0≤y1≤0.18, and 0≤z1≤0.18; 0.85≤x1≤1, 0≤y1≤0.15, and 0≤z1≤0.15; or 0.9≤x1≤1, 0≤y1≤0.1, and 0≤z1≤0.1.
For example, the positive electrode active material may include a lithium nickel-based composite oxide represented by Chemical Formula A2. The compound represented by Chemical Formula A2 may be referred to as a lithium nickel cobalt-based complex oxide:
Lia2Nix2Coy2M3z2O2−b2Xb2. Chemical Formula A2
In Chemical Formula A2, 0.9≤2≤1.8, 0.7≤x2<1, 0<y2≤0.2, 0≤z2≤0.2, 0.9≤x2+y2+z2≤1.1, and 0≤b2≤0.1, M3 is one or more element selected from Al, B, Ba, Ca, Ce, Cr, Fe, Mg, Mn, Mo, Nb, Si, Sr, Ti, V, W, and Zr, and X is one or more element selected from F, P, and S.
In Chemical Formula A2, 0.75≤x2≤0.99, 0≤y2≤0.15, and 0≤z2≤0.15; 0.85≤x2≤0.99, 0.01≤y2≤0.15, and 0.01≤z2≤0.15; or 0.9≤x2≤0.99, 0.01≤y2≤0.1, and 0.01≤z2≤0.1.
As an example, the positive electrode active material may include a lithium nickel-based composite oxide represented by Chemical Formula A3. The compound of Chemical Formula A3 may be referred to as a lithium nickel-cobalt-aluminum oxide or a lithium nickel-cobalt-manganese oxide.
Lia3Nix3COy3M4z3M5w3O2−b3Xb3 Chemical Formula A3
In Chemical Formula A3, 0.9≤a3≤1.8, 0.7≤x3≤0.98, 0.01≤y3≤0.19, 0.01≤z3≤0.19, 0≤w3≤0.19, 0.9≤x3+y3+z3+w3≤1.1, and 0≤b3≤0.1, M4 is one or more element selected from Al, and Mn, M5 is one or more element selected from B, Ba, Ca, Ce, Cr, Fe, Mg, Mo, Nb, Si, Sr, Ti, V, W, and Zr, and X is one or more element selected from F, P, and S.
In Chemical Formula A3, 0.75≤x3≤0.98, 0≤y3≤0.16, and 0≤z3≤0.16; 0.85≤x3≤0.98, 0.01≤y3≤0.14, 0.01≤z3≤0.14, and 0≤w3≤0.14; or 0.9≤x3≤0.98, 0.01≤y3≤0.09, 0.01≤z3≤0.09, and 0≤w3≤0.09.
As an example, the positive electrode active material may include a lithium nickel-based composite oxide represented by Chemical Formula A4. The compound of Chemical Formula A4 may be referred to as a cobalt-free lithium nickel-manganese oxide.
Lia4Nix4Mny4M6z4O2−b4Xb4 Chemical Formula A4
In Chemical Formula A4, 0.9≤a2≤1.8, 0.7≤x4<1, 0<y4≤0.2, 0≤z4≤0.2, 0.9≤x4+y4+z4≤1.1, and 0≤b4≤0.1, M6 is one or more element selected from Al, B, Ba, Ca, Ce, Cr, Fe, Mg, Mo, Nb, Si, Sr, Ti, V, W, and Zr, and X is one or more element selected from F, P, and S.
In the positive electrode of some example embodiments, a content of the positive electrode active material may be about 90 wt % to about 98 wt %, about 50 wt % to about 99 wt %, about 60 wt % to about 99 wt %, about 70 wt % to 99 wt %, about 80 wt % to about 99 wt %, or about 90 wt % to about 99 wt % based on a total weight of the positive electrode active material layer.
In some embodiments of the present disclosure, the positive electrode active material layer may optionally include a conductive material (e.g., an electrically conductive material) and a binder. In some embodiments, each content of the conductive material and the binder may be about 1.0 wt % to about 5.0 wt %, based on a total weight of the positive electrode active material layer.
The conductive material is used to impart conductivity (e.g., electrical conductivity) to the negative electrode, and any suitable electrically conductive material may be used as a conductive material (e.g., an electrically conductive material) unless it causes a chemical change in a battery (e.g., an undesirable change in the rechargeable lithium battery). Examples of the conductive material may include a carbon-based material such as natural graphite, artificial graphite, carbon black, acetylene black, Ketjen black, carbon fiber, and the like; a metal-based material of a metal powder or a metal fiber including copper, nickel, aluminum, silver, and the like; a conductive polymer such as a polyphenylene derivative; or a mixture thereof.
The binder improves binding properties of positive electrode active material particles with one another and with a current collector and examples thereof may be polyvinyl alcohol, carboxylmethyl cellulose, hydroxypropyl cellulose, diacetyl cellulose, polyvinylchloride, carboxylated polyvinylchloride, polyvinylfluoride, an ethylene oxide-containing polymer, polyvinylpyrrolidone, polyurethane, polytetrafluoroethylene, polyvinylidene fluoride, polyethylene, polypropylene, a styrene-butadiene rubber, an acrylated styrene-butadiene rubber, an epoxy resin, nylon, and the like, but are not limited thereto.
The positive electrode current collector may include A1, 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 be a material that reversibly intercalates/deintercalates lithium ions, a lithium metal, a lithium metal alloy, a material capable of doping and dedoping lithium, and/or a transition metal oxide.
The material that reversibly intercalates/deintercalates lithium ions includes carbon materials. The carbon material may be any suitable generally-used carbon-based negative electrode active material in a rechargeable lithium battery. Examples of the carbon material include crystalline carbon, amorphous carbon, and a combination thereof. The crystalline carbon may be non-shaped, and/or sheet, flake, spherical, and/or fiber shaped natural graphite and/or artificial graphite. The amorphous carbon may be a soft carbon, a hard carbon, a mesophase pitch carbonized product, fired coke, and/or 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 and dedoping lithium may include Si, SiOx (0<x<2), a Si-Q alloy (wherein Q is selected from an alkali metal, an alkaline-earth metal, a Group 13 element, a Group 14 element, a Group 15 element, a Group 16 element, a transition metal, a rare earth element, and a combination thereof, and not Si), Sn, SnO2, a Sn—R alloy (wherein R is 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 element, a rare earth element, or a combination thereof, and not Sn), and/or the like. At least one of them may be mixed together with SiO2.
The elements Q and R may be selected from Mg, Ca, Sr, Ba, Ra, Sc, Y, Ti, Zr, Hf, Rf, V, Nb, Ta, Db, Cr, Mo, W, Sg, Tc, Re, Bh, Fe, Pb, Ru, Os, Hs, Rh, Ir, Pd, Pt, Cu, Ag, Au, Zn, Cd, B, Al, Ga, Sn, In, 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/or the like.
In some example embodiments, the negative electrode active material may include at least one selected from graphite and a Si composite.
The Si composite may include a core including Si particles and amorphous carbon, and for example, the Si particles may include at least one selected from Si composite, SiOk (0<k≤2), and an Si alloy.
For example, the Si—C composite may include a core including Si particles and amorphous carbon.
The central portion of the core may include pores, and the radius of the central portion may correspond to about 30% to about 50% of the radius of the Si—C composite.
The Si particles may have an average particle diameter of about 10 nm to about 200 nm.
As used herein, the average particle diameter may be a particle size (D50) at a volume ratio of 50% in a cumulative size-distribution curve.
When the average particle diameter of the Si particle is within the above range, volume expansion occurring during charging and discharging may be suppressed or reduced, and a disconnection of a conductive path due to particle crushing during charging and discharging may be prevented or reduced.
The Si particle may be included in an amount of about 1 wt % to about 60 wt %, for example, about 3 wt % to about 60 wt %, based on a total weight of the Si—C composite.
The central portion may not include amorphous carbon, but the amorphous carbon may be present only on the surface portion of the negative electrode active material.
Herein, the surface portion indicates a region from the central portion (e.g., a region just outside the central portion) of the negative electrode active material to the outermost surface of the negative electrode active material.
In some embodiments, the Si particles are substantially uniformly included over the negative electrode active material, for example, present at a substantially uniform concentration in the central portion and the surface portion thereof.
The amorphous carbon may be soft carbon, hard carbon, mesophase pitch carbonized product, calcined coke, or a combination thereof.
The negative electrode active material may further include crystalline carbon.
When the negative electrode active material includes a Si—C composite and crystalline carbon together, the Si—C composite and crystalline carbon may be included in the form of a mixture, and in some embodiments, the Si—C composite and crystalline carbon may be included in a weight ratio of about 1:99 to about 50:50. In some embodiments, the Si—C composite and crystalline carbon may be included in a weight ratio of about 3:97 to about 20:80 or about 5:95 to about 20:80.
The crystalline carbon may be for example graphite, and, for example, natural graphite, artificial graphite, or a mixture thereof.
The crystalline carbon may have an average particle diameter of about 5 μm to about 30 μm.
The amorphous carbon precursor may include a coal-based pitch, mesophase pitch, petroleum-based pitch, coal-based oil, petroleum-based heavy oil, and/or a polymer resin such as a phenol resin, a furan resin, and/or a polyimide resin.
In the negative electrode active material layer, the negative electrode active material may be included in an amount of about 95 wt % to about 99 wt % based on a total weight of the negative electrode active material layer.
In some example embodiments, the negative electrode active material layer may include a binder, and optionally a conductive material (e.g., an electrically conductive material). In the negative electrode active material layer, the amount of the binder may be about 1 wt % to about 5 wt % based on a total weight of the negative electrode active material layer. When it further includes the conductive material, it may include about 90 wt % to about 98 wt % of the negative electrode active material, about 1 wt % to about 5 wt % of the binder, and about 1 wt % to about 5 wt % of the conductive material.
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 and/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, ethylenepropylene copolymer, polyethyleneoxide, polyvinylpyrrolidone, polyepichlorohydrin, polyphosphazene, polyacrylonitrile, polystyrene, an ethylene propylenediene copolymer, polyvinylpyridine, chlorosulfonatedpolyethylene, latex, a polyester resin, an acrylic resin, a phenolic resin, an epoxy resin, polyvinylalcohol, and a combination thereof.
When the water-soluble binder is used as the 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 carboxylmethyl cellulose, hydroxypropylmethyl cellulose, methyl cellulose, and/or alkali metal salts thereof. The alkali metal may be Na, K, and/or Li. Such a thickener may be included in an amount of about 0.1 to about 3 wt % based on 100 wt % of the negative electrode active material.
The conductive material is included to provide electrode conductivity (e.g., electrical conductivity) and any suitable electrically conductive material may be used as a conductive material (e.g., an electrically conductive material) unless it causes a chemical change (e.g., unless it causes an undesirable change in the rechargeable lithium battery). Examples thereof may be a carbon-based material such as natural graphite, artificial graphite, carbon black, acetylene black, Ketjen black, carbon fiber and the like; a metal-based material such as a metal powder or a metal fiber of copper, nickel, aluminum, silver, and the like; a conductive polymer such as a polyphenylene derivative and the like, 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 (e.g., an electrically conductive material), 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 (or kind) of the rechargeable lithium battery. This separator may be a porous substrate; or may be 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, at least one selected from 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 some embodiments, the adhesive layer may include an adhesive resin and optionally a filler.
The filler may be an organic filler and/or an inorganic filler.
Referring to the accompanying drawing, a rechargeable lithium battery 100 according to some example embodiments includes an electrode assembly including a negative electrode 112, a positive electrode 114 facing the negative electrode 112, a separator 113 between the negative electrode 112 and the positive electrode 114, and an electrolyte impregnating the negative electrode 112, positive electrode 114, and separator 113, a battery case 120 housing the electrode assembly, and a sealing member 140 sealing the battery case 120. Herein, the battery case is a cylindrical can.
Hereinafter, examples and comparative examples of the present disclosure will be described. The following examples are only examples of embodiments of the present disclosure, and the present disclosure is not limited to the following examples.
As for a non-aqueous organic solvent, a carbonate-based solvent was prepared by mixing together ethylene carbonate (EC): ethylmethyl carbonate (EMC): dimethyl carbonate (DMC)=20:10:70 in a volume ratio.
To the non-aqueous organic solvent, 1.5 M lithium salt (LiPF6) was added, and 1 wt % of the first additive represented by Chemical Formula 1-1-1 (CAS No. 16415-09-1) and 0.5 wt % of the second additive represented by Chemical Formula 2-1-1 (CAS No. 280-57-9) were added thereto to finally prepare an electrolyte.
Herein, a content (wt %) of each of the additives means the content (wt %) of each of the additives based on 100 wt % of the electrolyte. The same was applied hereinafter.
An electrolyte for a rechargeable lithium battery was manufactured in substantially the same manner as in Preparation Example 1 except that 1 wt % of the first additive represented by Chemical Formula 1-1-1 (CAS No. 16415-09-1) and 1 wt % of the second additive represented by Chemical Formula 2-1-1 (CAS No. 280-57-9) were used as the additives.
An electrolyte for a rechargeable lithium battery was manufactured in substantially the same manner as in Preparation Example 1 except that 1 wt % of the first additive represented by Chemical Formula 1-1-1 (CAS No. 16415-09-1) and 3 wt % of the second additive represented by Chemical Formula 2-1-1 (CAS No. 280-57-9) were used as the additives.
An electrolyte for a rechargeable lithium battery was manufactured in substantially the same manner as in Preparation Example 1 except that 1 wt % of the first additive represented by Chemical Formula 1-1-1 (CAS No. 16415-09-1) and 5 wt % of the second additive represented by Chemical Formula 2-1-1 (CAS No. 280-57-9) were used as the additives.
An electrolyte for a rechargeable lithium battery was manufactured in substantially the same manner as in Preparation Example 1 except that the additives were not used at all.
An electrolyte for a rechargeable lithium battery was manufactured in substantially the same manner as in Preparation Example 1 except that 1 wt % of the first additive represented by Chemical Formula 1-1-1 (CAS No. 16415-09-1) was used as the additive but the second additive represented by Chemical Formula 2-1-1 (CAS No. 280-57-9) was not used.
An electrolyte for a rechargeable lithium battery was manufactured in substantially the same manner as in Preparation Example 1 except that the first additive represented by Chemical Formula 1-1-1 (CAS No. 16415-09-1) was not used but 0.5 wt % of the second additive represented by Chemical Formula 2-1-1 (CAS No. 280-57-9) was used as the additive.
LiNi0.94Co(0.04)Al(0.02)O2 as a positive electrode active material, polyvinylidene fluoride as a binder, and Ketjen black as a conductive material were mixed together respectively in a weight ratio of 97:2:1, and then, dispersed in N-methyl pyrrolidone to prepare a 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 to manufacture a positive electrode.
A mixture of artificial graphite and silicon particles in a weight ratio of 93.5:6.5 was used as the negative electrode active material, and the negative electrode active material, a styrene-butadiene rubber binder, and carboxylmethyl cellulose in a weight ratio of 97:1:2 were dispersed in distilled water to prepare a negative electrode active material slurry.
The negative electrode active material slurry was coated on a 10 μm-thick Cu foil, dried at 100° C., and pressed to manufacture a negative electrode.
An electrode assembly was manufactured by assembling the manufactured positive electrode and negative electrode and a 25 μm-thick polyethylene separator, the electrode assembly was housed in a cylindrical can having a volume of 17 cm3, a diameter of 1.8 cm, and a height of 6.5 cm as a battery case, and each rechargeable lithium battery cell was manufactured by injecting the electrolyte for a rechargeable lithium battery of Preparation Example 1.
A rechargeable lithium battery cell was manufactured in substantially the same manner as Example 1, except that a cylindrical can having a volume of 24 cm3, a diameter of 2.1 cm, and a height of 7.0 cm was used as the battery case.
A rechargeable lithium battery cell was manufactured in substantially the same manner as Example 1, except that a cylindrical can having a volume of 133 cm3 a diameter of 4.6 cm, and a height of 8.0 cm was used as the battery case.
A rechargeable lithium battery cell was manufactured in substantially the same manner as Example 1, except that a cylindrical can having a volume of 296 cm3 a diameter of 5.6 cm, and a height of 12.0 cm was used as the battery case.
A rechargeable lithium battery cell was manufactured in substantially the same manner as Example 1, except that the electrolyte of Preparation Example 2 was used as the electrolyte.
A rechargeable lithium battery cell was manufactured in substantially the same manner as Example 5, except that a cylindrical can having a volume of 24 cm3, a diameter of 2.1 cm, and a height of 7.0 cm was used as the battery case.
A rechargeable lithium battery cell was manufactured in substantially the same manner as Example 5, except that a cylindrical can having a volume of 133 cm3 a diameter of 4.6 cm, and a height of 8.0 cm was used as the battery case.
A rechargeable lithium battery cell was manufactured in substantially the same manner as Example 5, except that a cylindrical can having a volume of 296 cm3 a diameter of 5.6 cm, and a height of 12.0 cm was used as the battery case.
A rechargeable lithium battery cell was manufactured in substantially the same manner as Example 1, except that the electrolyte of Preparation Example 3 was used as the electrolyte.
A rechargeable lithium battery cell was manufactured in substantially the same manner as Example 9, except that a cylindrical can having a volume of 24 cm3, a diameter of 2.1 cm, and a height of 7.0 cm was used as the battery case.
A rechargeable lithium battery cell was manufactured in substantially the same manner as Example 9, except that a cylindrical can having a volume of 133 cm3 a diameter of 4.6 cm, and a height of 8.0 cm was used as the battery case.
A rechargeable lithium battery cell was manufactured in substantially the same manner as Example 9, except that a cylindrical can having a volume of 296 cm3 a diameter of 5.6 cm, and a height of 12.0 cm was used as the battery case.
A rechargeable lithium battery cell was manufactured in substantially the same manner as Example 1, except that the electrolyte of Preparation Example 4 was used as the electrolyte.
A rechargeable lithium battery cell was manufactured in substantially the same manner as Example 13, except that a cylindrical can having a volume of 24 cm3 a diameter of 2.1 cm, and a height of 7.0 cm was used as the battery case.
A rechargeable lithium battery cell was manufactured in substantially the same manner as Example 13, except that a cylindrical can having a volume of 133 cm3, a diameter of 4.6 cm, and a height of 8.0 cm was used as the battery case.
A rechargeable lithium battery cell was manufactured in substantially the same manner as Example 13, except that a cylindrical can having a volume of 296 cm3, a diameter of 5.6 cm, and a height of 12.0 cm was used as the battery case.
A rechargeable lithium battery cell was manufactured in substantially the same manner as Example 1, except that a cylindrical can having a volume of 1 cm3, a diameter of 1.2 cm, and a height of 0.5 cm was used as a battery case, and the electrolyte for a rechargeable lithium battery of Comparative Preparation Example 1 was used as an electrolyte.
A rechargeable lithium battery cell was manufactured in substantially the same manner as Comparative Example 1, except that a cylindrical can having a volume of 17 cm3, a diameter of 1.8 cm, and a height of 6.5 cm was used as the battery case.
A rechargeable lithium battery cell was manufactured in substantially the same manner as Comparative Example 1, except that a cylindrical can having a volume of 24 cm3, a diameter of 2.1 cm, and a height of 7.0 cm was used as the battery case.
A rechargeable lithium battery cell was manufactured in substantially the same manner as Comparative Example 1, except that a cylindrical can having a volume of 133 cm3, a diameter of 4.6 cm, and a height of 8.0 cm was used as the battery case.
A rechargeable lithium battery cell was manufactured in substantially the same manner as Comparative Example 1, except that a cylindrical can having a volume of 296 cm3, a diameter of 5.6 cm, and a height of 12.0 cm was used as the battery case.
A rechargeable lithium battery cell was manufactured in substantially the same manner as Comparative Example 1, except that the electrolyte for a rechargeable lithium battery of Comparative Preparation Example 2 was used as the electrolyte.
A rechargeable lithium battery cell was manufactured in substantially the same manner as Comparative Example 6, except that a cylindrical can having a volume of 17 cm3, a diameter of 1.8 cm, and a height of 6.5 cm was used as the battery case.
A rechargeable lithium battery cell was manufactured in substantially the same manner as Comparative Example 6, except that a cylindrical can having a volume of 24 cm3, a diameter of 2.1 cm, and a height of 7.0 cm was used as the battery case.
A rechargeable lithium battery cell was manufactured in substantially the same manner as Comparative Example 6, except that a cylindrical can having a volume of 133 cm3, a diameter of 4.6 cm, and a height of 8.0 cm was used as the battery case.
A rechargeable lithium battery cell was manufactured in substantially the same manner as Comparative Example 6, except that a cylindrical can having a volume of 296 cm3, a diameter of 5.6 cm, and a height of 12.0 cm was used as the battery case.
A rechargeable lithium battery cell was manufactured in substantially the same manner as Comparative Example 1, except that the electrolyte for a rechargeable lithium battery of Comparative Preparation Example 3 was used as the electrolyte.
A rechargeable lithium battery cell was manufactured in substantially the same manner as Comparative Example 11, except that a cylindrical can having a volume of 17 cm3, a diameter of 1.8 cm, and a height of 6.5 cm was used as the battery case.
A rechargeable lithium battery cell was manufactured in substantially the same manner as Comparative Example 11, except that a cylindrical can having a volume of 24 cm3, a diameter of 2.1 cm, and a height of 7.0 cm was used as the battery case.
A rechargeable lithium battery cell was manufactured in substantially the same manner as Comparative Example 11, except that a cylindrical can having a volume of 133 cm3, a diameter of 4.6 cm, and a height of 8.0 cm was used as the battery case.
A rechargeable lithium battery cell was manufactured in substantially the same manner as Comparative Example 11, except that a cylindrical can having a volume of 296 cm3, a diameter of 5.6 cm, and a height of 12.0 cm was used as the battery case.
A rechargeable lithium battery cell was manufactured in substantially the same manner as Example 1, except that a cylindrical can having a volume of 1 cm3, a diameter of 1.2 cm, and a height of 0.5 cm was used as the battery case.
A rechargeable lithium battery cell was manufactured in substantially the same manner as Example 5, except that a cylindrical can having a volume of 1 cm3, a diameter of 1.2 cm, and a height of 0.5 cm was used as the battery case.
A rechargeable lithium battery cell was manufactured in substantially the same manner as Example 9, except that a cylindrical can having a volume of 1 cm3, a diameter of 1.2 cm, and a height of 0.5 cm was used as the battery case.
A rechargeable lithium battery cell was manufactured in substantially the same manner as Example 13, except that a cylindrical can having a volume of 1 cm3, a diameter of 1.2 cm, and a height of 0.5 cm was used as the battery case.
Each of the rechargeable lithium battery cells was subjected to initial formation in the following process. The cells were CC-CV charged to 4.2 V with a current of 0.2 C (0.05 C cut-off) and then discharged to 2.5 V twice.
After the formation step, the rechargeable lithium battery cells were charged at 60° C. at 1 C under the conditions of 4.2 V cut-off constant current and 0.05 C cut-off constant voltage to SOC 100% (SOC, state of charge=100%) and stored for 60 days.
As described above, the rechargeable lithium battery cells were stored at a high temperature of 60° C., and then an amount of Ni eluted per volume of the cylindrical can, capacity retention rate, and resistance increase rate were evaluated. The capacity maintenance rate was obtained by Equation 1, and the resistance increase rate was obtained by Equation 2.
Herein, DC resistance (DC-IR) was calculated from a current difference and a voltage difference, when different currents were applied, and specifically, calculated from data at 18 seconds and 23 seconds obtained according to ΔR=ΔV/ΔI after constant current-discharging at 10 A for 10 seconds, at 1 A for 10 seconds, and at 10 A for 4 seconds in the initial full charge state.
Referring to Table 1, a change in the amount of metal elution occurs when the volume of the cylindrical can exceeds 15 cm3, for example, is greater than or equal to 16 cm3.
In some embodiments, compared to embodiments where only one of the additives or both additives are used concurrently (e.g., simultaneously) and the content of the second additive in the electrolyte is controlled to greater than or equal to 5 wt %, when the two types (or kinds) of additives are used concurrently (e.g., simultaneously) and the content of the second additive in the electrolyte is controlled to less than 5 wt %, high-temperature characteristics of the rechargeable lithium battery cells are more improved.
Overall, the rechargeable lithium battery cells according to some example embodiments represented by Examples 1 to 16 control the volumes of the cylindrical cans and limit the type (or kind) and content of the electrolyte additive, thereby suppressing or reducing metal elution and increasing resistance at high temperatures and/or improving cycle-life.
While the subject matter of this disclosure has been described in connection with what is presently considered to be practical example embodiments, it is to be understood that the disclosure 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, and equivalents thereof.
| Number | Date | Country | Kind |
|---|---|---|---|
| 10-2023-0072443 | Jun 2023 | KR | national |
