Patent Application
20230170470
This application claims priority to and the benefit of Korean Patent Application No. 10-2021-0166116, filed on Nov. 26, 2021, in the Korean Intellectual Property Office, the content of which is incorporated by reference herein in its entirety.
One or more embodiments of the present disclosure relate to a composite cathode active material, a cathode and a lithium battery that include the composite cathode active material, and a method of preparing the composite cathode active material.
For miniaturization and high performance of one or more suitable devices, high energy density of lithium batteries is becoming more important and imperative in addition to small-size and light-weight characteristics. In other words, high-capacity lithium batteries are becoming important and critical.
To implement lithium batteries suitable for the utilization above, cathode active materials having high capacity are being considered.
However, cathode active materials of the related art have degraded lifespan characteristics and poor thermal stability due to side reactions.
Therefore, there is a need or desire for a method capable of preventing or reducing deterioration of battery performance while including a suitable cathode active material.
One or more aspects of embodiments of the present disclosure are directed toward a composite cathode active material capable of inhibiting a side reaction of the composite cathode active material and improving reversibility of an electrode reaction, so as to prevent or reduce deterioration of performance of a lithium battery.
One or more aspects of embodiments of the present disclosure are directed toward a cathode including the composite cathode active material.
One or more aspects of embodiments of the present disclosure are directed toward a method of providing a lithium battery including the cathode.
One or more aspects of embodiments of the present disclosure are directed toward a method of preparing the composite cathode active material.
Additional aspects will be set forth in part in the description which follows and, in part, will be apparent from the description, or may be learned by practice of the presented embodiments of the disclosure.
According to one or more embodiments of the present disclosure, provided is a composite cathode active material, including:
a core including a lithium transition metal oxide; and
a shell on (e.g., arranged on) and conformed to a surface of the core,
wherein the shell may include: at least one first metal oxide represented by MaOb (where 0<a≤3, 0<b<4, and when a is 1, 2, or 3, b is not an integer), a first carbon-based material, and a second carbon-based material,
the at least one first metal oxide is arranged in a matrix of the first carbon-based material, and M is at least one metal selected from among Groups 2 to 13, 15, and 16 of the Periodic Table of Elements, and
the second carbon-based material may include fibrous carbon having an aspect ratio of greater than or equal to 10.
According to one or more embodiments of the present disclosure, provided is a cathode including the cathode active material.
According to one or more embodiments of the present disclosure, provided is a lithium battery including the cathode.
According to one or more embodiments of the present disclosure, provided is a method of preparing the composite cathode active material, the method including:
providing a lithium transition metal oxide;
providing a composite;
providing a second carbon-based material; and
mechanically milling the lithium transition metal oxide, the composite, and the second carbon-based material,
wherein the composite may include: at least one first metal oxide represented by MaOb (where 0<a≤3, 0<b<4, and when a is 1, 2, or 3, b is not an integer) and a first carbon-based material,
the at least one first metal oxide is arranged in a matrix of the first carbon-based material, and M is at least one metal selected from among Groups 2 to 13, 15, and 16 of the Periodic Table of Elements, and
the second carbon-based material may include fibrous carbon having an aspect ratio of greater than or equal to 10.
The above and other aspects, features, and advantages of certain embodiments of the disclosure will be more apparent from the following description taken in conjunction with the accompanying drawings, in which:
Reference will now be made in more detail to embodiments, examples of which are illustrated in the accompanying drawings, wherein like reference numerals refer to like elements throughout, and duplicative descriptions thereof may not be provided. In this regard, the embodiments of the present disclosure may have different forms and should not be construed as being limited to the descriptions set forth herein. Accordingly, the embodiments are merely described, by referring to the drawings, to explain aspects of the present disclosure. As utilized herein, the terms “and/or” and “or” may include any and all combinations of one or more of the associated listed items. Expressions such as “at least one of,” when preceding a list of elements, modify the entire list of elements and do not modify the individual elements of the list.
As the present disclosure allows for one or more suitable changes and numerous embodiments, particular embodiments will be illustrated in the drawings and described in more detail in the written description. However, this is not intended to limit the present disclosure to particular modes of practice, and it is to be appreciated that all changes, equivalents, and substitutes that do not depart from the spirit and technical scope of the present disclosure are encompassed in the present disclosure.
The terms utilized in the present disclosure are merely utilized to describe particular embodiments, and are not intended to limit the present disclosure. An expression utilized in the singular encompasses the expression of the plural, unless it has a clearly different meaning in the context. In the present disclosure, it is to be understood that the terms such as “including”, “having,” and/or the like, are intended to indicate the existence of the features, numbers, steps, actions, components, parts, ingredients, materials, or combinations thereof disclosed in the disclosure, and are not intended to preclude the possibility that one or more other features, numbers, steps, actions, components, parts, ingredients, materials, or combinations thereof may exist or may be added. As utilized herein, “/” may be construed, depending on the context, as referring to “and” or “or”.
In the drawings, the thicknesses of layers and regions are exaggerated or reduced for clarity. Like reference numerals in the drawings and specification denote like elements. In the present disclosure, it will be understood that when an element, e.g., a layer, a film, a region, or a substrate, is referred to as being “on” or “above” another element, it can be directly on the other element or intervening layers may also be present. While such terms as “first”, “second”, and/or the like, may be utilized to describe one or more suitable components, such components must not be limited to the above terms. The above terms are utilized only to distinguish one component from another.
The term “particle diameter” as utilized herein may refer to an average diameter of particles when the particles are spherical (e.g., substantially spherical), and may refer to an average major axis length of particles when the particles are non-spherical. The particle diameter of the particles may be measured utilizing a particle size analyzer (PSA). The “particle diameter” of the particles may be an average particle diameter. The average particle diameter may be, for example, a median particle diameter (D50). The medium particle diameter D50 may refer to, in a cumulative distribution curve of particles sizes where particles accumulate in the order of particle size from the smallest to the largest, the size of particles corresponding to a cumulative value of 50% calculated from particles having the smallest particle size. The cumulative value may be, for example, a cumulative volume. The median particle diameter D50 may be, for example, measured by laser diffraction.
As utilized herein, the singular forms “a,” “an,” and “the” are intended to include the plural forms as well, unless the context clearly indicates otherwise. Further, the use of “may” when describing embodiments of the present disclosure refers to “one or more embodiments of the present disclosure”.
As utilized herein, the terms “substantially,” “about,” and similar terms are used as terms of approximation and not as terms of degree, and are intended to account for the inherent deviations in measured or calculated values that would be recognized by those of ordinary skill in the art.
Any numerical range recited herein is intended to include all sub-ranges of the same numerical precision subsumed within the recited range. For example, a range of “1.0 to 10.0” is intended to include all subranges between (and including) the recited minimum value of 1.0 and the recited maximum value of 10.0, that is, having a minimum value equal to or greater than 1.0 and a maximum value equal to or less than 10.0, such as, for example, 2.4 to 7.6. Any maximum numerical limitation recited herein is intended to include all lower numerical limitations subsumed therein and any minimum numerical limitation recited in this specification is intended to include all higher numerical limitations subsumed therein. Accordingly, Applicant reserves the right to amend this specification, including the claims, to expressly recite any sub-range subsumed within the ranges expressly recited herein.
Hereinafter, according to example embodiments, a composite cathode active material, a cathode and a lithium battery that include the composite cathode active material, and a method of preparing the composite cathode active material will be further described in more detail.
One or more embodiments of the present disclosure provide a composite cathode active material including: a core including a lithium transition metal oxide; and a shell on (e.g., arranged on) and conformed to a surface of the core, wherein the shell may include: at least one first metal oxide represented by MaOb (where 0<a≤3, 0<b<4, and when a is 1, 2, or 3, b is not an integer); a first carbon-based material; and a second carbon-based material, where the at least one first metal oxide is arranged in a matrix of the first carbon-based material, M is at least one metal selected from among Groups 2 to 13, 15, and 16 of the Periodic Table of Elements, and the second carbon-based material may include fibrous carbon having an aspect ratio of greater than or equal to 10.
Hereinafter, a theoretical basis for providing an excellent or suitable effect of a composite cathode active material according to one or more embodiments will be described, but the theoretical basis is to help understanding of the present disclosure and is not intended to limit the present disclosure in any way.
Referring to
In one or more embodiments, the shell 20 may include a second carbon-based material that is fibrous carbon having an aspect ratio of greater than or equal to 10. Therefore, a conducting path of the composite cathode active material may further be lengthened. The second carbon-based material forms a three-dimensional conductive network among a plurality of composite cathode active materials (e.g., a plurality of composite cathode active material particles) to reduce internal resistance of a cathode including the composite cathode active material. When the fibrous carbon is fixed on the composite cathode active material, a substantially uniform and stable three-dimensional conductive network may be formed among a plurality of composite cathode active material particles. Therefore, by including the second carbon-based material in the composite cathode active material, a lithium battery including the composite cathode active material may have improved high-rate characteristics. In contrast, a simple mixture of the core of the lithium transition metal oxide and fibrous carbon as the second carbon-based material may be, due to agglomeration of fibrous carbon, difficult to form a substantially uniform three-dimensional conductive network among a plurality of lithium transition metal oxide particles. As shown in
In one or more embodiments, the second carbon-based material may have an aspect ratio of greater than or equal to 10 or greater than or equal to 20. The aspect ratio of the second carbon-based material may be, for example, in a range of about 10 to about 100,000, about 10 to about 80,000, about 10 to about 50,000, about 10 to about 10,000, about 10 to about 5000, about 10 to about 1000, about 10 to about 500, about 10 to about 100, or about 10 to about 50. The aspect ratio of the second carbon-based material is, for example, a ratio of length of the major axis passing through the center of the second carbon-based material to length of the minor axis that is perpendicular to the major axis, wherein the major axis passes through the second carbon-based material and the center of the second carbon-based material, and the minor axis is perpendicular to the major axis and is a diameter of the second carbon-based material.
In one or more embodiments, the diameter of the second carbon-based material may be, for example, less than or equal to about 50 nanometers (nm), less than or equal to about 30 nm, less than or equal to about 20 nm, or less than or equal to 10 nm. In some embodiments, the diameter of the second carbon-based material may be, for example, in a range of about 1 nm to about 50 nm, about 1 nm to about 30 nm, or about 1 nm to about 10 nm. When the diameter of the second carbon-based material is excessively large, the absolute number of strands per volume may decrease, and thus the effect of reducing internal resistance may be insignificant. When the diameter of the second carbon-based material is too small, substantially uniform dispersion may be difficult.
In one or more embodiments, the length of the second carbon-based material may be, for example, less than or equal to about 1,000 micrometer (μm), less than or equal to about 100 μm, less than or equal to about 50 μm, less than or equal to about 10 μm, less than or equal to about 5 μm, less than or equal to about 2 μm, less than or equal to about 1 μm, less than or equal to about 500 nm, or less than or equal to about 300 nm. In some embodiments, the length of the second carbon-based material may be, for example, in a range of about 100 nm to about 1,000 μm, about 100 nm to about 500 μm, about 100 nm to about 100 μm, about 100 nm to about 50 μm, about 100 nm to about 10 μm, about 100 nm to about 5 μm, about 100 nm to 2 about μm, about 100 nm to about 1 μm, about 100 nm to about 500 nm, or about 100 nm to about 300 nm. In some embodiments, the length of the second carbon-based material may be, for example, in a range of about 500 nm to about 1,000 μm, about 500 nm to about 500 μm, about 500 nm to about 100 μm, about 500 nm to about 50 μm, about 500 nm to about 10 μm, about 500 nm to about 5 μm, or about 500 nm to about 2 μm. As the length of the second carbon-based material increases, the internal resistance of an electrode may decrease. When the length of the second carbon-based material is too short, an effective conductive path may not be provided.
In one or more embodiments, the second carbon-based material may include, for example, carbon nanofiber, carbon nanotube, or a combination thereof.
In some embodiments, the carbon nanotube may include, for example, a primary carbon nanotube structure, a secondary carbon nanotube structure formed by agglomeration of multiple particles of the primary carbon nanotube structure, or a combination thereof.
In some embodiments, the primary carbon nanotube structure may be one carbon nanotube unit. The carbon nanotube unit may include a graphite sheet in a cylindrical shape with a nano-sized diameter, and may have an sp2 bond structure. According to a bending angle and a structure of the graphite sheet, the characteristics of conductors or the characteristics of semiconductors may be exhibited. The carbon nanotube unit may be classified, depending on the number of bonds forming a wall, into a single-walled carbon nanotube (SWCNT), a double-walled carbon nanotube (DWCNT), multi-walled carbon nanotube (MWCNT), and/or the like. As the wall thickness of the carbon nanotube structure unit decreases, the resistance may be lowered.
In some embodiments, the primary carbon nanotube structure may include, for example, an SWCNT, a DWCNT, an MWCNT, or a combination thereof. In some embodiments, the diameter of the primary carbon nanotube structure may be, for example, greater than or equal to about 1 nm or greater than or equal to 2 nm. In some embodiments, the diameter of the primary carbon nanotube structure may be, for example, less than or equal to about 20 nm or less than or equal to about 10 nm. In some embodiments, the diameter of the primary carbon nanotube structure may be, for example, in a range of about 1 nm to about 20 nm, about 1 nm to about 15 nm, or about 1 nm to about 10 nm. In some embodiments, the length of the primary carbon nanotube structure may be, for example, greater than or equal to about 100 nm or greater than or equal to 200 nm. In some embodiments, the length of the primary carbon nanotube structure may be, for example, less than or equal to about 1 μm, less than or equal to about 500 nm, or less than or equal to about 300 nm. In some embodiments, the length of the primary carbon nanotube structure may be, for example, in a range of about 100 nm to about 2 μm, about 100 nm to about 1 μm, about 100 nm to about 500 nm, about 100 nm to about 400 nm, about 100 nm to about 300 nm, or about 200 nm to about 300 nm. The diameter and length of the primary carbon nanotube structure may be measured from a scanning electron microscope (SEM) image or a transmission electron microscope (TEM) image. In one or more embodiments, the diameter and/or length of the primary carbon nanotube structure may be measured by laser diffraction method.
In one or more embodiments, the secondary carbon nanotube structure may be a structure formed by assembling the primary carbon nanotube structure to form a bundle type or kind or a rope type or kind, in whole or in part. In some embodiments, the secondary carbon nanotube structure may include, for example, a bundle-type or kind carbon nanotube, a rope-type or kind carbon nanotube, or a combination thereof. In some embodiments, The diameter of the secondary carbon nanotube structure may be, for example, greater than or equal to 2 nm or greater than or equal to 3 nm. In some embodiments, the diameter of the secondary carbon nanotube structure may be, for example, less than or equal to about 50 nm, less than or equal to about 30 nm, less than or equal to about 20 nm, or less than or equal to about 10 nm. In some embodiments, the diameter of the secondary carbon nanotube structure may be, for example, in a range of about 2 nm to about 50 nm, about 2 nm to about 30 nm, or about 2 nm to about 20 nm. In some embodiments, the length of the secondary carbon nanotube structure may be, for example, greater than or equal to 500 nm, greater than or equal to 700 nm, greater than or equal to about 1 μm, or greater than or equal to about 10 μm. In some embodiments, the length of the secondary carbon nanotube structure may be, for example, less than or equal to about 1,000 μm, less than or equal to about 500 μm, or less than or equal to about 100 μm. In some embodiments, the length of the secondary carbon nanotube structure may be, for example, in a range of about 500 nm to about 1,000 μm, about 500 nm to about 500 μm, about 500 nm to about 200 μm, 500 nm to about 100 μm, or about 500 nm to about 50 μm. The diameter and length of the secondary carbon nanotube structure may be measured from an SEM image or an optical microscope image. In one or more embodiments, the diameter and/or length of the secondary carbon nanotube structure may be measured by a laser diffraction method.
In one or more embodiments, the secondary carbon nanotube structure may be utilized in the preparation of the composite cathode active material by, for example, dispersing in a solvent and/or the like to be converted into the primary carbon nanotube structure.
In one or more embodiments, the content (e.g., amount) of the second carbon-based material may be, for example, in a range of about 0.1 wt % to about 50 wt %, about 1 wt % to about 40 wt %, or about 5 wt % to about 30 wt %, based on the total weight of the first carbon-based material and the second carbon-based material. When the composite cathode active material includes the first carbon-based material and the second carbon-based material within the ranges above, a conduction path may be further effectively secured in the composite cathode active material, and thus the internal resistance of the composite cathode active material may be further reduced. Consequently, the cycle characteristics of a lithium battery including the composite cathode active material may be further improved. In some embodiments, the content (e.g., amount) of the second carbon-based material may be, for example, in a range of about 0.001 wt % to about 5 wt %, about 0.01 wt % to about 3 wt %, about 0.01 wt % to about 1 wt %, about 0.01 wt % to about 0.5 wt %, or about 0.01 wt % to about 0.1 wt % of the total weight of the composite cathode active material. When the composite cathode active material includes the second carbon-based material within the ranges above, a conduction path may be secured in the composite cathode active material, and thus the internal resistance of the composite cathode active material may be further reduced. Consequently, the cycle characteristics of a lithium battery including the composite cathode active material may be further improved.
In one or more embodiments, the shell may also include a first metal oxide and a first carbon-based material. Because the first carbon-based material is derived from, for example, a graphene matrix, the first carbon-based material may have a relatively low density and high porosity, compared to a carbon-based material derived from a graphite-based material. In some embodiments, a d 002 interplanar distance of the carbon-based material may be, for example, greater than or equal to about 3.38 angstrom (A), greater than or equal to about 3.40 Å, greater than or equal to about 3.45 Å, greater than or equal to about 3.50 Å, greater than or equal to about 3.60 Å, greater than or equal to about 3.80 Å, or greater than or equal to about 4.00 Å. In some embodiments, the d 002 interplanar distance of the first carbon-based material included in the shell may be, for example, in a range of about 3.38 to about 4.0 Å, about 3.38 to about 3.8 Å, about 3.38 to about 3.6 Å, about 3.38 to about 3.5 Å, or about 3.38 to about 3.45 Å. In contrast, the d 002 interplanar distance of a carbon-based material derived from a graphite-based material may be, for example, less than or equal to about 3.38 Å or in a range of about 3.35 Å to about 3.38 Å. Because the first metal oxide has voltage resistance, deterioration of the lithium transition metal oxide included in the core may be prevented or reduced during charging and discharging at a high voltage. For example, in some embodiments, the shell may include one type or kind of the first metal oxide or two or more different types (kinds) of the first metal oxide. Consequently, high-temperature cycle characteristics of a lithium battery including the above-described composite cathode active material may be improved. In some embodiments, the content (e.g., amount) of the shell may be, for example, in a range of about 0.1 wt % to about 5 wt %, about 0.1 wt % to about 4 wt %, about 0.1 wt % to about 3 wt %, about 0.1 wt % to about 2.5 wt %, about 0.1 wt % to about 2 wt %, or about 0.1 wt % to about 1.5 wt %, based on the total weight of the composite cathode active material. In some embodiments, the content (e.g., amount) of the first metal oxide may be, for example, in a range of about 0.06 wt % to about 3 wt %, about 0.06 wt % to about 2.4 wt %, about 0.06 wt % to about 1.8 wt %, about 0.06 wt % to about 1.5 wt %, about 0.06 wt % to about 1.2 wt %, or about 0.06 wt % to about 0.9 wt %. When the composite cathode active material includes the shell and the first metal oxide within the ranges above, respectively, cycle characteristics of a lithium battery may be further improved.
In one or more embodiments, the first metal oxide may include a first metal, and the first metal may be, for example, one or more selected from among aluminum (Al), niobium (Nb), magnesium (Mg), scandium (Sc), titanium (Ti), zirconium (Zr), vanadium (V), tungsten (W), manganese (Mn), iron (Fe), cobalt (Co), palladium (Pd), copper (Cu), silver (Ag), zinc (Zn), antimony (Sb), and selenium (Se). In some embodiments, the first metal oxide may be, for example, one or more selected from among Al2Oz (where 0<z<3), NbOx (where 0<x<2.5), MgOx (where 0<x<1), Sc2Oz (where 0<z<3), TiOy (where 0<y<2), ZrOy (where 0<y<2), V2Oz (where 0<z<3), WOy (where 0<y<2), MnOy (where 0<y<2), Fe2Oz (where 0<z<3), Co3Ow (where 0<w<4), PdOx (where 0<x<1), CuOx (where 0<x<1), AgOx (where 0<x<1), ZnOx (where 0<x<1), Sb2Oz (where 0<z<3), and SeOy (where 0<y<2). By disposing the first metal oxide in a matrix of the first carbon-based material, uniformity of the shell arranged on the core may be improved, and voltage resistance of the composite cathode active material may be further improved. For example, in some embodiments, the shell may include Al2Ox (wherein 0<x<3) as the first metal oxide.
In one or more embodiments, the shell may further include at least one second metal oxide represented by MaOc (where 0<a≤3, 0<c≤4, and when a is 1, 2, or 3, c is an integer). M may be at least one metal selected from among Groups 2 to 13, 15, and 16 of the Periodic Table of Elements. For example, in some embodiments, the second metal oxide may include a metal identical to a metal comprised in the first metal oxide, and a ratio of c to a, c/a, in the second metal oxide may be greater than a ratio of b to a, b/a, in the first metal oxide. For example, c/a>b/a. in some embodiments, the second metal oxide may be selected from among Al2O3, NbO, NbO2, Nb2O5, MgO, Sc2O3, TiO2, ZrO2, V2O3, WO2, MnO2, Fe2O3, Co3O4, PdO, CuO, AgO, ZnO, Sb2O3, and SeO2. In some embodiments, the first metal oxide may be, for example, a reduction product of the second metal oxide. The first metal oxide may be obtained by reducing some or all of the second metal oxide. Accordingly, the first metal oxide may have a lower oxygen content (e.g., amount) and a lower metal oxidation number than the second metal oxide. In some embodiments, the shell may include, for example, Al2Ox (where 0<x<3) as the first metal oxide and Al2O3 as the second metal oxide.
In one or more embodiments, the shell may include, for example, the first carbon-based material, and the core may include, for example, a lithium transition metal oxide. In some embodiments, the first carbon-based material and a transition metal of the lithium transition metal oxide may be, for example, chemically bound through a chemical bond. The carbon atom (C) of the first carbon-based material and the transition metal (Me) of the lithium transition metal oxide may be, for example, chemically bound through an oxygen atom-mediated C—O-Me bond (e.g., C—O—Ni bond or C—O—Co bond). The first carbon-based material arranged on the lithium transition metal oxide of the core may be chemically bound through a chemical bond so that the core and the shell may form a composite. Accordingly, the composite cathode active material may be distinguished from a simple physical mixture of the first carbon-based material and the lithium transition metal oxide. In some embodiments, the first metal oxide and the first carbon-based material may be also chemically bound through a chemical bond. Herein, the chemical bond may refer to, for example, a covalent bond or an ionic bond.
In one or more embodiments, the shell may include, for example, one or more selected from among the first metal oxide and the second metal oxide, and the one or more selected from among the first metal oxide and the second metal oxide may have a particle diameter (or particle size), for example, in a range of about 1 nm to about 100 nm, about 1 nm to about 50 nm, about 1 nm to about 30 nm, about 5 nm to about 30 nm, or about 10 nm to about 30 nm. When the first metal oxide and/or the second metal oxide has such a nano-scale particle diameter (or particle size), the first metal oxide and/or the second metal oxide may be further uniformly distributed in a matrix of the first carbon-based material. When the particle diameter of the one or more of the first metal oxide and the second metal oxide is excessively increased, the thickness of the shell may be increased, and the internal resistance of the composite cathode active material may increase. When the particle diameter of the one or more of the first metal oxide and the second metal oxide is excessively reduced, the first metal oxide and/or the second metal oxide may not be uniformly dispersed.
In one or more embodiments, the shell may include the first metal oxide and/or the second metal oxide, and may include the first carbon-based material. The first carbon-based material may be arranged in a direction protruding from the surface of the first metal oxide and/or the second metal oxide. The first carbon-based material may be arranged in a direction protruding from the surface of the first metal oxide and/or the second metal oxide by growing directly from the surface of the first metal oxide and/or the second metal oxide. The first carbon-based material arranged in a direction protruding from the surface of the first metal oxide and/or the second metal oxide may be, for example, a carbon-based two-dimensional nanostructure, a carbon-based flake, or graphene.
In some embodiments, the thickness of the shell may be, for example, in a range of about 1 nm to about 5 μm, about 1 nm to about 1 μm, about 1 nm to about 500 nm, about 1 nm to about 200 nm, about 1 nm to about 100 nm, about 1 nm to about 90 nm, about 1 nm to about 80 nm, about 1 nm to about 70 nm, about 1 nm to about 60 nm, about 1 nm to about 50 nm, about 1 nm to about 40 nm, about 1 nm to about 30 nm, or about 1 nm to about 20 nm. When the thickness of the shell is within the ranges above, a cathode including the composite cathode active material may have further improved electronic conductivity.
In one or more embodiments, the composite cathode active material may further include, for example, a third metal doped on the core and/or a third metal oxide coated on the core. In some embodiments, the shell may be on (e.g., arranged on) the third metal doped on the core and/or the third metal oxide coated on the core. For example, after the third metal is doped on the surface of the core of the lithium transition metal oxide or the third metal oxide is coated on the surface of the lithium transition metal oxide, the shell may be arranged on the third metal and/or the third metal oxide. For example, in some embodiments, the composite cathode active material may include: a core; an interlayer on (e.g., arranged on) the core; and a shell on (e.g., arranged on) the interlayer, wherein the interlayer may include a third metal or a third metal oxide. The third metal may be one or more metals selected from among Al, Zr, W, and Co, and the third metal oxide may be Al2O3, Li2O—ZrO2, WO2, CoO, Co2O3, Co3O4, or a combination thereof.
In one or more embodiments, the shell conformed to the surface of the core may include, for example, one or more selected from the composite including the first metal oxide and the first carbon-based material such as graphene, and the second carbon-based material and/or a milling product. The first metal oxide may be arranged in a matrix of the carbon-based material, for example, a graphene matrix. In some embodiments, the shell may be, for example, prepared utilizing the composite including the first metal oxide and the first carbon-based material such as graphene. In some embodiments, the composite may further include a second metal oxide, in addition to the first metal oxide. In some embodiments, a first composite may include, for example, two or more types (kinds) of the first metal oxide. In some embodiments, the first composite may include, for example, two or more types (kinds) of the first metal oxide and two or more types (kinds) of the second metal oxides.
In one or more embodiments, the content (e.g., amount) of one or more of the composites and the milling products may be, for example, less than or equal to about 5 wt %, less than or equal to about 3 wt %, less than or equal to about 2 wt %, less than or equal to about 2.5 wt % or less, or less than or equal to about 1.5 wt %, based on the total weight of the composite cathode active material. In some embodiments, the content (e.g., amount) of at least one selected from among the composite and the milling product may be in a range of about 0.01 wt % to about 5 wt %, about 0.01 wt % to about 4 wt %, about 0.01 wt % to about 3 wt %, about 0.01 wt % to about 2.5 wt %, about 0.01 wt % to about 2 wt %, about 0.01 wt % to about 1.5 wt %, based on the total weight of the composite cathode active material. When the composite cathode active material includes one or more of the composites and the milling product thereof in the content (e.g., amount) within the ranges above, cycle characteristics of a lithium battery including the composite cathode active material may be further improved.
In one or more embodiments, the composite may include at least one selected from among the first metal oxide and the second metal oxide. The particle diameter of the one or more selected from among the first metal oxide and the second metal oxide may be in a range of about 1 nm to about 100 nm, about 1 nm to about 50 nm, about 1 nm to about 30 nm, about 5 nm to about 30 nm, or about 10 nm to about 30 nm. Because the first metal oxide and/or the second metal oxide has a particle size in the nanometer range, it may be more uniformly distributed in a matrix of the first carbon-based material of the composite. Accordingly, such a composite may be uniformly coated on the core without agglomeration to form a shell. In some embodiments, when the first metal oxide and/or the second metal oxide may be further uniformly arranged on the core by having the particle diameter within the ranges above. Therefore, by uniformly arranging the first metal oxide and/or the second metal oxide on the core, high voltage resistance may be more effectively exhibited. The particle diameter of the first metal oxide and/or the second metal oxide may be measured by, for example, a measurement apparatus utilizing a laser diffraction method or a dynamic light scattering method. In some embodiments, the particle diameter may be measured utilizing, for example, a laser scattering particle size distribution meter (e.g., LA-920 of Horiba Ltd.), and is a value of the median particle diameter (D50) when the metal oxide particles are accumulated to 50% from small particles in volume conversion. The uniformity deviation of at least one selected from among the first metal oxide and the second metal oxide may be less than or equal to about 3%, less than or equal to about 2%, or less than or equal to about 1%. The uniformity may be obtained by, for example, XPS. Accordingly, at least one selected from among the first metal oxide and the second metal oxide may have a deviation of less than or equal to about 3%, less than or equal to about 2%, or less than or equal to about 1%, and may be uniformly distributed in the composite.
In one or more embodiments, the composite may include the first carbon-based material. The first carbon-based material may have, for example, a branched structure, and at least one selected from among the first metal oxide and the second metal oxide may be distributed in the branched structure of the first carbon-based material. The branched structure of the first carbon-based material may include, for example, a plurality of first carbon-based material particles contacting each other. Because the first carbon-based material has a branched structure, one or more suitable conducting paths may be provided. In some embodiments, the first carbon-based material may be, for example, graphene. Graphene may, for example, have a branched structure, and at least one metal oxide selected from among the first metal oxide and the second metal oxide may be distributed in the branched structure of graphene. The branched structure of graphene may include, for example, a plurality of graphene particles contacting each other. Because graphene has the branched structure, one or more suitable conducting paths may be provided.
In one or more embodiments, the first carbon-based material may have, for example, a spherical structure (e.g., a substantially spherical structure), and at least one metal oxide selected from among the first metal oxide and the second metal oxide may be distributed in the spherical structure. The spherical structure of the first carbon-based material may have a size in a range of about 50 nm to about 300 nm. A plurality of the first carbon-based materials having a spherical structure may be provided. Because the first carbon-based material has a spherical structure, the composite may have a rigid structure. In some embodiments, the first carbon-based material may be, for example, graphene. Graphene may have, for example, a spherical structure (e.g., a substantially spherical structure), and at least one metal oxide selected from among the first metal oxide and the second metal oxide may be distributed in the spherical structure. The spherical structure of graphene may have a size in a range of about 50 nm to about 300 nm. A plurality of graphenes having a spherical structure may be provided. Because graphene has a spherical structure, the composite may have a rigid structure.
In one or more embodiments, the first carbon-based material may have, for example, a spiral structure in which a plurality of spherical structures (e.g., substantially spherical structures) are connected to each other, and at least one metal oxide selected from among the first metal oxide and the second metal oxide may be distributed in the spherical structure of the spiral structure. The spiral structure of the first carbon-based material may have a size in a range of about 500 nm to about 100 μm. Because the first carbon-based material has a spiral structure, the composite may have a rigid structure. In some embodiments, the first carbon-based material may be, for example, graphene. Graphene may have, for example, a spiral structure in which a plurality of spherical structures are connected, and at least one metal oxide selected from among the first metal oxide and the second metal oxide may be distributed in the spherical structure of the spiral structure. The spiral structure of graphene may have a size in a range of about 500 nm to about 100 μm. Because graphene has a spiral structure, the composite may have a rigid structure.
In one or more embodiments, the first carbon-based material may have, for example, a cluster structure in which a plurality of spherical structures (e.g., substantially spherical structures) are aggregated with each other, and at least one metal oxide selected from among the first metal oxide and the second metal oxide may be distributed in the spherical structure off the cluster structure. The cluster structure of the first carbon-based material may have a size in a range of about 0.5 mm to about 10 mm. Because the first carbon-based material has a cluster structure, the composite may have a rigid structure. In some embodiments, the first carbon-based material may be, for example, graphene. Graphene may have, for example, a cluster structure in which a plurality of spherical structures (e.g., substantially spherical structures) are aggregated, and at least one metal oxide selected from among the first metal oxide and the second metal oxide may be distributed in the spherical structure of the cluster structure. The size of the cluster structure of the graphene may be in a range of about 0.5 mm to about 10 mm. The graphene may have a cluster structure, and thus, the first composite may have a robust structure.
In one or more embodiments, the first composite, for example, may be a crumpled faceted-ball structure, and at least one selected from among the first metal oxide and the second metal oxide may be distributed inside or on a surface of the crumpled faceted-ball structure. As the first composite is such a faceted-ball structure, the first composite may be easily coated on an irregular surface of the core.
In one or more embodiments, the first composite, for example, may be a planar structure, and at least one selected from among the first metal oxide and the second metal oxide may be distributed inside or on a surface of the planar structure. As the first composite is such a two-dimensional planar structure, the first composite may be easily coated on an irregular surface of the core.
In one or more embodiments, the first carbon-based material may extend from the first metal oxide by a distance of less than or equal to about 10 nm, and may include at least 1 to 20 carbon-based material layers. For example, when a plurality of first carbon-based material layers are laminated, a first carbon-based material having a total thickness of less than or equal to about 12 nm may be arranged on the first metal oxide. For example, in some embodiments, the total thickness of the first carbon-based material may be in a range of about 0.6 nm to about 12 nm. In some embodiments, the first carbon-based material may be, for example, graphene. Graphene may extend from the first metal oxide by a distance of less than or equal to about 10 nm, and may include at least 1 to 20 graphene layers. For example, when a plurality of graphene layers are laminated, graphene having a total thickness of less than or equal to about 12 nm may be arranged on the first metal oxide. For example, in some embodiments, the total thickness of graphene may be in a range of about 0.6 nm to about 12 nm.
In one or more embodiments, the composite cathode active material may include a core, and the core may include, for example, a lithium transition metal oxide represented by one of Formulae 1 to 8:
LiaNixCOyMzO2−bAb Formula 1
wherein, in Formula 1, 1.0≤a≤1.2, 0≤b≤0.2, 0.8≤x<1, 0<y<0.3, 0<z≤0.3, and x+y+z=1, and M may be manganese (Mn), niobium (Nb), vanadium (V), magnesium (Mg), gallium (Ga), silicon (Si), tungsten (W), molybdenum (Mo), iron (Fe), chromium (Cr)), copper (Cu), zinc (Zn), titanium (Ti), aluminum (Al), boron (B), or a combination thereof, and A may be F, S, CI, Br, or a combination thereof,
LiNixCoyMnzO2 Formula 2
LiNixCoyAlzO2 Formula 3
wherein, in Formulae 2 and 3, 0.8≤x≤0.95, 0≤y≤0.2, 0≤z≤0.2, and x+y+z=1,
LiNixCoyMnzAlwO2 Formula 4
wherein, in Formula 4, 0.8≤x≤0.95, 0≤y≤0.2, 0<z≤0.2, 0<w≤0.2, and x+y+z+w=1,
in some embodiments, the lithium transition metal oxides of Formulae 1 to 4 may include nickel in the content (e.g., amount) of greater than or equal to about 80 mol %, greater than or equal to about 85 mol %, greater than or equal to about 90 mol %, or greater than or equal to about 92 mol %, with respect to the total moles of transition metals in the lithium transition metal oxides of Formulae 1 to 4, and may provide excellent or suitable initial capacity and lifespan characteristics at room temperature and at high temperature. For example, in some embodiments, the nickel content (e.g., amount) in the lithium transition metal oxides of Formulae 1 to 4 may be in a range of about 80 mol % to about 99 mol %, about 85 mol % to about 99 mol %, or about 90 mol % to about 97 mol % with respect to the total moles of transition metals in the lithium transition metal oxides,
LiaCOxMyO2−bAb Formula 5
wherein, in Formula 5, 1.0≤a≤1.2, 0≤b≤0.1, and x+y=1, M may be Mn, Nb, V, Mg, Ga, Si, W, Mo, Fe, Cr, Cu, Zn, Ti, Al, B, or a combination thereof, and A is F, S, CI, Br, or a combination thereof,
LiaNixMnyM′zO2−bAb Formula 6
wherein, in Formula 6, 1.0≤a≤1.2, 0≤b≤0.2, 0<x≤0.3, 0.5≤y<1, 0<z≤0.3, and x+y+z=1, M′ may be Co, Nb, V Mg, Ga, Si, W, Mo, Fe, Cr, Cu, Zn, Ti, Al, B, or a combination thereof, and A is F, S, CI, Br, or a combination thereof,
LiaM1xM2yPO4−bXb Formula 7
wherein, in Formula 7, 0.90≤a≤1.1, 0≤x≤0.9, 0≤y≤0.5, 0.9<x+y<1.1, and 0≤b≤2, M1 may be chromium (Cr), manganese (Mn), iron (Fe), cobalt (Co), nickel (Ni), copper (Cu), zirconium (Zr), or a combination thereof, M2 may be Mg, Ca, Sr, Ba, Ti, Zn, B, Nb, Ga, In, Mo, W, Al, Si, Cr, V, Sc, Y, or a combination thereof, and X may be O, F, S, P, or a combination thereof,
LiaM3zPO4 Formula 8
wherein, in Formula 8, 0.90≤a≤1.1, 0.9≤z≤1.1, and M3 may be Cr, Mn, Fe, Co, Ni, Cu, Zr, or a combination thereof.
In one or more embodiments, a cathode may include the composite cathode active material. By including the composite cathode active material, the cathode may provide improved energy density, improved cycle characteristics, and increased conductivity.
When the shell of the composite cathode active material includes the second carbon-based material, the composite cathode active material may additionally act as a conductor. Accordingly, the content (e.g., amount) of the conductor utilized in the cathode may be reduced. The conductor is necessary to improve the conductivity of a battery. However, when the content (e.g., amount) of the conductor is increased, mixture density of the cathode may decrease, and consequently, energy density of a lithium battery may decrease. In contrast, because the cathode disclosed herein uses the above-described composite cathode active material, the content (e.g., amount) of the conductor may be reduced without an increase in the internal resistance. Therefore, the mixture density of the cathode may increase, and consequently, the energy density of a lithium battery may be improved. In some embodiments, by increasing the content (e.g., amount) of the composite cathode active material while decreasing the content (e.g., amount) of the conductor in a high-capacity lithium battery, the energy density of a lithium battery may significantly increase.
In one or more embodiments, the cathode may be, for example, prepared by a wet method. The cathode may be, for example, prepared according to the following method, but the preparation method thereof is not necessarily limited to the exemplified method and may be adjusted to required conditions.
First, a cathode active material composition is prepared by mixing the above-described composite cathode active material, a conductor, a binder, and a solvent. The prepared cathode active material composition may be directly coated and dried on an aluminum current collector to form a cathode plate provided with a cathode active material layer. In one or more embodiments, a film obtained by casting the cathode active material composition on a separate support, which then may be separated from the support and laminated on an aluminum current collector to prepare a cathode plate on which the cathode active material layer is formed.
Non-limiting examples of the conductor may be: carbon black, graphite particulates, natural graphite, artificial graphite, acetylene black, Ketjen black, carbon fibers; carbon nanotubes; metallic powder, metallic fiber, or metallic tube of copper, nickel, aluminum, silver, and/or the like; and/or a conductive polymer such as a polyphenylene derivative. However, embodiments of the present disclosure are not limited thereto, and any suitable conductor available in the art may be utilized. In one or more embodiments, the cathode may not include (e.g., may exclude), for example, a separate conductor.
Non-limiting examples of the binder may be a vinylidene fluoride/hexafluoropropylene copolymer, polyvinylidene fluoride, polyacrylonitrile, polymethyl methacrylate, polytetrafluoroethylene (PTFE), or a mixture thereof. A styrene butadiene-rubber polymer and/or the like may also be utilized. As a solvent, N-methyl pyrrolidone (NMP), acetone, water, and/or the like may be utilized. However, embodiments of the present disclosure are not limited thereto, and any suitable binder and solvent available in the art may be utilized.
In some embodiments, by further adding a plasticizer or a pore former to the cathode active material composition, pores may be formed inside an electrode plate.
The contents (e.g., amounts) of the composite cathode active material, conductor, binder, and solvent utilized in the cathode may be at levels suitable for utilization in lithium batteries. Depending on the utilization and configuration of the lithium battery, one or more of the conductor, the binder, and the solvent may not be provided.
In one or more embodiments, the content (e.g., amount) of the binder utilized in the cathode may be in a range of about 0.1 wt % to about 10 wt % or about 0.1 wt % to about 5 wt %, with respect to the total weight of the cathode active material layer. The content (e.g., amount) of the composite cathode active material utilized in the cathode may be in a range of about 80 wt % to about 99 wt %, about 90 wt % to about 99 wt %, or about 95 wt % to about 99 wt %, with respect to the total weight of the cathode active material layer. The content (e.g., amount) of the conductor utilized in the cathode may be in a range of about 0.01 wt % to about 10 wt %, about 0.01 wt % to about 5 wt %, about 0.01 wt % to about 3 wt %, about 0.01 wt % to about 1 wt %, about 0.01 wt % to about 0.5 wt %, or about 0.01 wt % to about 0.1 wt %, with respect to the total weight of the cathode active material layer. In some embodiments, the conductor may not be provided.
In some embodiments, the cathode may additionally include a general cathode active material other than the above-described composite cathode active material.
As the general cathode active material, any suitable lithium-containing metal oxide may be utilized without limitation. For example, at least one selected from composite oxides of lithium and a metal selected from among Co, Mn, Ni, and a combination thereof may be utilized, and a non-limiting example thereof may be a compound represented by one selected from among the following formulae: LiaA1−bBbD2 (where 0.90≤a≤1 and 0≤b≤0.5); LiaE1−bBbO2−cDc (where 0.90≤a≤1, 0≤b≤0.5, and 0≤c≤0.05); LiE2−bBbO4−cDc (where 0≤b≤0.5 and 0≤c≤0.05); LiaNi1−b−cCobBcDa (where 0.90≤a≤1, 0≤b≤0, 0≤c≤0.05, and 0<α≤2); LiaNi1−b−cCobBcO2−αFα (where 0.90≤a≤1, 0≤b≤0.5, 0≤c≤0.05, 0<a≤2); LiaNi1−b−cCobBcO2−aF2 (where 0.90≤a≤1, 0≤b≤0.5, 0≤c≤0.05, 0<α<2); LiaNi1−b−cMnbBcDα (where 0.90≤a≤1, 0≤b≤0.5, 0≤c≤0.05, 0<α≤2); LiaNi1−b−cMnbBcO2−αFα (where 0.90≤a≤1, 0≤b≤0.5, 0≤c≤0.05, 0<α<2); LiaNi1−b−cMnbBcO2−αF2 (where 0.90≤a≤1, 0≤b≤0.5, 0≤c≤0.05, 0<α<2); LiaNibEcGdO2 (where 0.90≤a≤1, 0≤c≤0.5, and 0.0010.1); LiaNibCocMndGeO2 (where 0.90≤a≤1, 0≤b≤ 0.9, 0≤c≤0.5, 0≤d≤0.5, and 0.001≤e≤0.1); LiaNiGbO2 (where 0.90≤a≤ 1 and 0.001≤b≤0.1); LiaCoGbO2 (where 0.90≤a≤1 and 0.001≤b≤0.1); LiaMnGbO2 (where 0.90≤a≤1 and 0.001≤b≤0.1); LiaMn2GbO4 (where 0.90≤a≤1 and 0.001≤b≤0.1); QO2; QS2; LiQS2; V2O5; LiV2O5; LiIO2; LiNiVO4; Li(3−f)J2(PO4)3 (were 0≤f≤2); Li(3−f)Fe2(PO4)3 (0≤f≤2); and LiFePO4.
In the formulae representing the above-described compounds, A may be Ni, Co, Mn, or a combination thereof; B may be Al, Ni, Co, Mn, Cr, Fe, Mg, Sr, V, a rare earth element, or a combination thereof; D may be oxygen (O), fluorine (F), sulfur (S), phosphorous (P), or a combination thereof; E may be Co, Mn, or a combination thereof; F may be fluorine (F), sulfur (S), phosphorous (P), or a combination thereof; G may be Al, Cr, Mn, Fe, Mg, La, Ce, Sr, V, or a combination thereof; Q may be Ti, Mo, Mn, or a combination thereof; I may be Cr, V, Fe, Sc, Y, or a combination thereof; and J may be V, Cr, Mn, Co, Ni, Cu, or a combination thereof. In some embodiments, a compound in which a coating layer is provided on the surface of the above-described compound may be utilized, and a mixture of the above-described compound and the compound provided with the coating layer may also be utilized. The coating layer provided on the surface of the above-described compound may include a coating element compound such as 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/or a hydroxycarbonate of a coating element. The compound constituting this coating layer may be 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 method of forming the coating layer may be selected within a range that does not adversely affect the physical properties of the cathode active material. The coating method may be, for example, spray coating, dipping method, and/or the like. A more detailed description of the coating method will not be provided because it may be well understood by those in the art.
In one or more embodiments, the cathode may be a dry cathode prepared in a dry manner.
A dry cathode may include a composite cathode active material, a dry conductor, and a dry binder, the dry composite cathode active material including: a core including a lithium transition metal oxide; and a shell on and conformed to a surface of the core, wherein the shell may include: at least one first metal oxide represented by MaOb (where 0<a≤3, 0<b<4, and when a is 1, 2, or 3, b is not an integer); a first carbon-based material; and a second carbon-based material, where the first metal oxide may be arranged in a matrix of the first carbon-based material, M may be at least one metal selected from among Groups 2 to 13, 15, and 16 of the Periodic Table of Elements, and the second carbon-based material may be fibrous carbon having an aspect ratio of greater than or equal to 10.
In one or more embodiments, a method of preparing a dry cathode may include: dry-mixing a dry composite cathode active material, a dry conductor, and a dry binder to prepare a dry mixture; providing a cathode current collector; arranging an interlayer on one surface of the cathode current collector; and arranging and rolling the dry mixture on the interlayer to prepare a cathode in which a cathode active material layer is arranged on the one surface of the cathode current collector.
First, a dry mixture may be prepared by dry-mixing a composite cathode active material, a dry conductor, and a dry binder. The dry-mixing may refer to mixing in a state that does not include a process solvent. The process solvent may refer to, for example, a solvent utilized in the preparation of an electrode slurry. The process solvent may be, for example, water, NMP, and/or the like, but embodiments of the present disclosure are not limited thereto. Any process solvent utilized in the preparation of an electrode slurry may not be utilized. In some embodiments, the dry-mixing may be performed, for example, at a temperature in a range of about 25° C. to about 65° C. utilizing a stirrer. In some embodiments, the dry-mixing may be performed, for example, at a rotation speed in a range of about 10 rpm to about 10,000 rpm or about 100 rpm to about 10,000 rpm. In some embodiments, the dry-mixing may be performed, for example, for about 1 minute to about 200 minutes or about 1 minute to about 150 minutes. The composite anode active material may be a dry composite anode active material.
In some embodiments, the dry-mixing may be performed, for example, at least once. First, a first mixture may be prepared by performing first dry-mixing on a composite cathode active material, a dry conductor, and a dry binder. The first dry-mixing may be performed, for example, at a temperature in a range of about 25° C. to about 65° C., at a rotation speed of less than or equal to about 2,000 rpm, and for 15 minutes or less. In some embodiments, the first dry-mixing may be performed, for example, at a temperature in a range of about 25° C. to about 65° C., at a rotation speed in a range of about 500 rpm to about 2,000 rpm, and for about 5 minutes to about 15 minutes. By the first dry-mixing, the composite cathode active material, the dry conductor, and the dry binder may be uniformly mixed. Subsequently, a second mixture may be prepared by performing second dry-mixing on a composite cathode active material, a dry conductor, and a dry binder. In some embodiments, the second dry-mixing may be performed, for example, at a temperature in a range of about 25° C. to about 65° C., at a rotation speed of greater than or equal to about 4,000 rpm, and for 10 minutes or more. In some embodiments, the second dry-mixing may be performed, for example, at a temperature in a range of about 25° C. to about 65° C., at a rotation speed in a range of about 4,000 rpm to about 9,000 rpm, and for about 10 minutes to about 60 minutes. By the second dry-mixing, a dry mixture including a fibrillated dry binder may be obtained.
In some embodiments, the stirrer may be, for example, a kneader. The stirrer may include: for example, a chamber; at least one rotation axis arranged inside the chamber to rotate; and a blade rotatably coupled to the rotation axis and arranged in a longitudinal direction of the rotation axis. The blade may be, for example, at least one selected from among a ribbon blade, a sigma blade, a jet (Z) blade, a dispersion blade, and a screw blade. Because the blade is included, the dry composite cathode active material, the dry conductor, and the dry binder may be effectively mixed without utilizing a solvent to prepare a mixture in a dough-like shape.
In some embodiments, The prepared dry mixture may be introduced into an extrusion device and extruded in a sheet form. In some embodiments, the pressure at the time of extrusion may be, for example, in a range of about 4 MPa to about 100 MPa or about 10 MPa to about 90 MPa. The extrudate obtained in a sheet form may be a sheet for the cathode active material layer.
Non-limiting examples of the dry conductor may be: carbon black, graphite particulates, natural graphite, artificial graphite, acetylene black, Ketjen black, carbon fibers; carbon nanotubes; metallic powder, metallic fiber, or metallic tube of copper, nickel, aluminum, silver, and/or the like; and/or a conductive polymer such as a polyphenylene derivative. However, embodiments of the present disclosure are not limited thereto, and any suitable binder available in the art may be utilized. The conductor may be, for example, a carbon-based conductor. The dry conductor may be a conductive material that has not been in contact with a process solvent.
Non-limiting examples of the dry binder may be a vinylidene fluoride/hexafluoropropylene copolymer, polyvinylidene fluoride, polyacrylonitrile, polymethyl methacrylate, polytetrafluoroethylene (PTFE), a mixture of the above-described polymers, a styrene butadiene-rubber polymer, and/or the like. However, embodiments of the present disclosure are not limited thereto, and any suitable binder available in the art may be utilized. In some embodiments, the dry binder may be, for example, PTFE. The dry binder may be a binder that has not been in contact with a process solvent.
In some embodiments, by further adding a plasticizer or a pore former to the dry mixture, pores may be formed inside the cathode active material layer.
In some embodiments, the contents (e.g., amounts) of the dry composite cathode active material, dry conductor, and dry binder utilized in the dry cathode may be at substantially the same levels as the contents (e.g., amounts) of the composite cathode active material, conductor, and binder utilized in the wet cathode, respectively.
Next, a cathode current collector may be provided. The cathode current collector may be, for example, an aluminum foil.
Then, an interlayer may be arranged on one surface of the cathode current collector. The interlayer may include a carbon-based conductor and a binder. In some embodiments, the interlayer may not be provided.
Next, the prepared sheet for the cathode active material layer may be arranged on the interlayer, and rolled to prepare a cathode in which the cathode active material layer is arranged on the one surface of the cathode current collector. The interlayer may be arranged between the cathode current collector and the cathode active material layer. The rolling may include, for example, a roll press, a flat press, and/or the like, but embodiments of the present disclosure are not necessarily limited thereto. In some embodiments, the pressure at the time of rolling may be, for example, in a range of about 0.1 ton/cm2 to about 10.0 ton/cm2, but embodiments of the present disclosure are not limited thereto. When the pressure at the rolling is excessively increased, cracks may occur in the cathode current collector. When the pressure at the rolling is excessively low, the binding force between the cathode current collector and the cathode active material layer may be reduced.
In one or more embodiments, a lithium battery is provided to include a cathode that includes the composite cathode active material.
When the lithium battery includes the cathode including the above-described composite cathode active material, improved energy density, improved cycle characteristics, and improved thermal stability may be provided.
In one or more embodiments, the lithium battery may be, for example, prepared according to the following method, but the preparation method thereof may not necessarily be limited to the exemplified method and may be adjusted to required conditions.
First, a cathode may be prepared according to the above-described method of preparing the cathode.
Next, an anode may be manufactured as follows. The anode may be, for example, prepared in substantially the same manner as in the cathode, except that an anode active material is utilized instead of the composite cathode active material. In some embodiments, in the anode active material composition, the substantially same conductor, binder, and solvent utilized in the cathode preparation may be utilized.
For example, in some embodiments, an anode active material, a conductor, a binder, and a solvent may be mixed to prepare an anode active material composition. The anode active material composition may be directly coated on a copper current collector to prepare an anode electrode plate. In one or more embodiments, the anode active material composition may be cast on a separate support to form an anode active material film, which may then be separated from the support and laminated on a copper current collector to prepare an anode electrode plate.
As the anode active material, any suitable anode active material available in the art for a lithium battery may be utilized. For example, in some embodiments, the anode active material may include at least one selected from among lithium metal, a metal alloyable with lithium, a transition metal oxide, a non-transition metal oxide, and a carbon-based material. Non-limiting examples of the metal alloyable with lithium may be silicon (Si), tin (Sn), aluminum (Al), germanium (Ge), lead (Pb), bismuth (Bi), antimony (Sb), a Si—Y alloy (where Y is an alkali metal, an alkaline earth metal, a Group 13 element, a Group 14 element, a transition metal, a rare earth element, or a combination thereof, and Y is not Si), and a Sn—Y alloy (wherein Y is an alkali metal, an alkaline earth-metal, a Group 13 element, a Group 14 element, a transition metal, a rare earth element, or a combination thereof, and Y is not Sn). For example, Y may be magnesium (Mg), calcium (Ca), strontium (Sr), barium (Ba), radium (Ra), scandium (Sc), yttrium (Y), titanium (Ti), zirconium (Zr), hafnium (Hf), rutherfordium (Rf), vanadium (V), niobium (Nb), tantalum (Ta), dubnium (db), chromium (Cr), molybdenum (Mo), tungsten (W), seaborgium (Sg), technetium (Tc), rhenium (Re), bohrium (Bh), iron (Fe), lead (Pb), ruthenium (Ru), osmium (Os), hassium (Hs), rhodium (Rh), iridium (Ir), palladium (Pd), platinum (Pt), copper (Cu), silver (Ag), gold (Au), zinc (Zn), cadmium (Cd), boron (B), aluminum (Al), gallium (Ga), tin (Sn), indium (In), titanium (Ti), germanium (Ge), phosphorus (P), arsenic (As), antimony (Sb), bismuth (Bi), sulfur (S), selenium (Se), tellurium (Te), polonium (Po), or a combination thereof. For example, the transition metal oxide may be a lithium titanium oxide, a vanadium oxide, and/or a lithium vanadium oxide. The non-transition metal oxide may be, for example, SnO2, SiOx (where 0<x<2), and/or the like. The carbon-based material may be, for example, crystalline carbon, amorphous carbon, or a mixture thereof. The crystalline carbon may be, for example, amorphous, plate-like, flake-like, spherical, or fibrous graphite, such as natural graphite or artificial graphite. The amorphous carbon may be, for example, soft carbon (carbon sintered at a low temperature) or hard carbon, mesophase pitch carbide, sintered coke, and/or the like.
The contents of the anode active material, conductor, binder, and solvent may be at levels suitable for utilize in lithium batteries. In some embodiments, at least one selected from among the conductive agent, the binder, and the solvent may not be provided according to the utilize and the structure of the lithium battery.
In some embodiments, the content (e.g., amount) of the binder utilized in the anode may be in a range of about 0.1 wt % to about 10 wt % or about 0.1 wt % to about 5 wt %, with respect to the total weight of the anode active material layer. The content (e.g., amount) of the conductor utilized in the anode may be in a range of about 0.1 wt % to about 10 wt % or about 0.1 wt % to about 5 wt %, with respect to the total weight of the anode active material layer. The content (e.g., amount) of the anode active material utilized in the anode may be in a range of about 80 wt % to about 99 wt %, about 90 wt % to about 99 wt %, or about 95 wt % to about 99 wt %, with respect to the total weight of the anode active material layer. In some embodiments, when the anode active material is lithium metal, the anode may not include (e.g., may exclude) a binder and a conductor.
Next, a separator to be disposed between the cathode and the anode may be prepared.
The separator may be any suitable separator that is utilized in lithium batteries. The separator may have, for example, low resistance to migration of ions in an electrolyte and have electrolyte solution-retaining ability. In some embodiments, the separator may be, for example, glass fiber, polyester, Teflon, polyethylene, polypropylene, PTFE, or a combination thereof, each of which may be in a non-woven fabric form or a woven fabric form. For a lithium-ion battery, a rollable separator including, for example, polyethylene or polypropylene may be utilized. A separator with a good or suitable organic electrolyte solution-retaining ability may be utilized for a lithium-ion polymer battery.
The separator may be, for example, prepared according to the following example method, but embodiments of the present disclosure are not limited thereto, and the method may be controlled or selected according to the required conditions.
First, a polymer resin, a filler, and a solvent may be mixed together to prepare a separator composition. Then, the separator composition may be directly coated on an electrode, and then dried to form a separator. In one or more embodiments, the separator composition may be cast on a support and then dried to form a separator film, which may then be separated from the support and laminated on an electrode to form a separator.
The polymer utilized in the preparation of the separator is not particularly limited, and any suitable polymer that is utilized as a binder for an electrode plate may be utilized. For example, a vinylidenefluoride/hexafluoropropylene copolymer, polyvinylidene fluoride (PVDF), polyacrylonitrile, polymethylmethacrylate, or a mixture thereof may be utilized.
Next, an electrolyte may be prepared.
The electrolyte may be, for example, an organic electrolyte solution. The organic electrolyte solution may be, for example, prepared by dissolving a lithium salt in an organic solvent.
The organic solvent may be any suitable organic solvent available in the art. In some embodiments, the organic solvent may be, for example, propylene carbonate, ethylene carbonate, fluoroethylene carbonate, butylene carbonate, dimethyl carbonate, diethyl carbonate, methyl ethyl carbonate, methyl propyl carbonate, ethyl propyl carbonate, methyl isopropyl carbonate, dipropyl carbonate, dibutyl carbonate, benzonitrile, acetonitrile, tetrahydrofuran, 2-methyl tetrahydrofuran, γ-butyrolactone, dioxolan, 4-methyl dioxolan, N, N-dimethyl formamide, dimethyl acetamide, dimethyl sulfoxide, dioxane, 1,2-dimethoxyethane, sulfolane, dichloroethane, chlorobenzene, nitrobenzene, diethylene glycol, dimethyl ether, or a mixture thereof.
The lithium salt may be any suitable lithium salt available in the art. In some embodiments, the lithium salt may be, for example, LiPF6, LiBF4, LiSbF6, LiAsF6, LiClO4, LiCF3SO3, Li(CF3SO2)2N, LiC4F9SO3, LiAlO2, LiAlCl4, LiN(CxF2x+1SO2)(CyF2y+1SO2) (where x and y may each be a natural number of 1 to 20), LiCl, LiI, or any mixture thereof.
In one or more embodiments, the electrolyte may be a solid electrolyte. The solid electrolyte may be, for example, boron oxide or lithium oxynitride, but embodiments of the present disclosure are not limited thereto. The solid electrolyte may be any suitable solid electrolyte available in the art. The solid electrolyte may be formed on the anode by a method, such as sputtering, or a separate solid electrolyte sheet may be laminated on the anode.
In some embodiments, the solid electrolyte may be, for example, an oxide-based solid electrolyte or a sulfide-based solid electrolyte.
In some embodiments, the solid electrolyte may be, for example, an oxide-based solid electrolyte. The oxide-based solid electrolyte may include at least one selected from among Li1+x+yAlxTi2−xSiyP3−yO12 (where 0<x<2 and 0≤y<3), BaTiO3, Pb(Zr,Ti)O3 (PZT), Pb1−xLaxZr1−y TiyO3 (PLZT) (where O≤x<1 and O≤y<1), PB(Mg3Nb2/3)O3—PbTiO3 (PMN-PT), HfO2, SrTiO3, SnO2, CeO2, Na2O, MgO, NiO, CaO, BaO, ZnO, ZrO2, Y2O3, Al2O3, TiO2, SiO2, Li3PO4, LixTiy(PO4)3 (where 0<x<2 and 0<y<3), LixAlyTiz(PO4)3 (where 0<x<2, 0<y<1, and 0<z<3), Li1+x+y(Al, Ga)x(Ti, Ge)2−xSiyP3−yO12 (where 0≤x≤1 and 0≤y≤1), LixLayTiO3 (where 0<x<2 and 0<y<3), Li2O, LiOH, Li2CO3, LiAlO2, Li2O—Al2O3—SiO2—P2O5—TiO2—GeO2, and Li3+xLa3M2O12 (where M may be Te, Nb, and/or Zr, and x may be an integer from 1 to 10). The solid electrolyte may be prepared by a sintering method and/or the like. For example, in some embodiments, the oxide-based solid electrolyte may include a garnet-type or kind solid electrolyte selected from Li7La3Zr2O12 (LLZO) and Li3+xLa3Zr2−aMaO12 (M-doped LLZO) (where M may be Ga, W, Nb, Ta, and/or Al, and x may be an integer from 1 to 10).
The sulfide-based solid electrolyte may be, for example, lithium sulfide, silicon sulfide, phosphorus sulfide, boron sulfide, or a combination thereof. In some embodiments, the sulfide-based solid electrolyte particles may include Li2S, P2S5, SiS2, GeS2, B2S3, or a combination thereof. In some embodiments, the sulfide-based solid electrolyte particles may be Li2S or P2S5. The sulfide-based solid electrolyte particles are suitable to have higher lithium ion conductivity than other inorganic compounds. For example, in some embodiments, the sulfide-based solid electrolyte may include Li2S and P2S5. When the sulfide solid electrolyte material constituting the sulfide-based solid electrolyte includes Li2S—P2S5, a mixing molar ratio of Li2S to P2S5 may be, for example, in a range of about 50:50 to about 90:10. In some embodiments, an inorganic solid electrolyte prepared by adding Li3PO4, halogen, a halogen compound, Li2+2xZn1−xGeO4 (“LISICON”) (where 0≤x<1), Li3+yPO4−xNx (“LIPON”) (where 0<x<4 and 0<y<3), Li3.25Ge0.25P0.75S4 (“Thio-LISICON”), Li2O—Al2O3—TiO2—P2O5 (“LATP”), and/or the like to an inorganic solid electrolyte, such as Li2S—P2S5, SiS2, GeS2, B2S3, or a combination thereof may be utilized as the sulfide solid electrolyte. Non-limiting examples of the sulfide solid electrolyte material may be: Li2S—P2S5; Li2S—P2S5—LiX (where X may be a halogen element); Li2S—P2S5—Li2O; Li2S—P2S5—Li2O—LiI; Li2S—SiS2; Li2S—SiS2—LiI; Li2S—SiS2—LiBr; Li2S—SiS2—LiCl; Li2S—SiS2—B2S3—LiI; Li2S—SiS2—P2S5—LiI; Li2S—B2S3; Li2S —P2S5—ZmSn (where 0<m<10, 0<n<10, and Z may be Ge, Zn, and/or Ga); Li2S—GeS2; Li2S—SiS2—Li3PO4; and/or Li2S—SiS2-LipMOq (where 0<p<10, 0<q<10, and M may be P, Si, Ge, B, Al, Ga, and/or In). In this regard, the sulfide-based solid electrolyte material may be prepared by treating raw starting materials of the sulfide-based solid electrolyte material (e.g., Li2S, P2S5, etc.) by a melt quenching method, a mechanical milling method, and/or the like. Also, a calcinations process may be performed after the treatment. The sulfide-based solid electrolyte may be amorphous or crystalline, or may be in a mixed state.
Referring to
Referring to
Referring to
A pouch-type or kind lithium battery each corresponds to utilization of a pouch as a battery case for lithium batteries of
Because the lithium battery may have excellent or suitable lifespan characteristics and excellent or suitable high-rate characteristics, the lithium battery may be utilized in, for example, an electric vehicle (EV). For example, the lithium battery may be utilized in a hybrid vehicle, such as a plug-in hybrid electric vehicle (PHEV). In some embodiments, the lithium battery may be applicable to the high-power storage field. For example, the lithium battery may be utilized in an electric bicycle, a power tool, and/or the like.
In one or more embodiments, a plurality of the lithium batteries may be stacked to form a battery module, and a plurality of the battery modules may form a battery pack. The battery pack may be utilized in a device that requires large capacity and high power. For example, the battery pack may be utilized in a laptop computer, a smart phone, or an electric vehicle. The battery module may include, for example, multiple batteries and a frame that holds the multiple batteries. The battery pack may include, for example, a plurality of battery modules and a bus bar connecting the battery modules. The battery module and/or the battery pack may further include a cooling device. A plurality of battery packs may be controlled or selected by a battery management system. The battery management system may include a battery pack and an electronic control apparatus connected to the battery pack.
In one or more embodiments, a method of preparing a composite cathode active material is provided include: providing a lithium metal oxide; providing a composite; providing a second carbon-based material; and mechanically milling the lithium metal oxide, the composite, and the second carbon-based material, wherein the composite may include: at least one metal oxide represented by MaOb (where 0<a≤3, 0<b<4, when a is 1, 2, or 3, and b is not be an integer), a first carbon-based material, and the second carbon-based material, wherein the at least one first metal oxide may be arranged in a matrix of the first carbon-based material, M may be at least one metal selected from among Groups 2 to 13, 15, and 16 of the Periodic Table of Elements, and the second carbon-based material may include fibrous carbon having an aspect ratio of greater than or equal to 10.
Then, a lithium transition metal oxide may be provided. The lithium transition metal oxide may be, for example, the compound represented by Formula 1 to 6.
In one or more embodiments, the composite may be provided. The providing of the composite may include, for example, providing a reaction gas including a carbon source gas to a structure including the second metal oxide, and performing heat treatment to provide the composite. In some embodiments, the providing of the composite may include, for example, supplying reaction gas formed of a carbon source gas to at least one of second metal oxide represented by MaOc (where 0<a≤3, 0<c≤4, and when a is 1, 2, or 3, c is an integer) and performing heat treatment to prepare the composite, wherein M may be at least one metal selected from among Groups 2 to 13, 15, and 16 of the period table.
The carbon source gas may be gas including (e.g., consisting of) a compound represented by Formula 9, or may be mixed gas including at least one selected from among a compound represented by Formula 9, a compound represented by Formula 10, and oxygen-containing gas represented by Formula 11.
CnH(2n+2−a)[OH]a Formula 9
wherein, in Formula 9, n may be 1 to 20, and a may be 0 or 1;
CnH2n Formula 10
wherein, in Formula 10, n may be 2 to 6;
CxHyOz Formula 11
wherein, in Formula 11, x may be 0 or an integer of 1 to 20, y may be 0 or an integer of 1 to 20, and z may be 1 or 2.
The compound represented by Formula 9 and the compound represented by Formula 10 may be at least one selected from the group consisting of methane, ethylene, propylene, methanol, ethanol, and propanol. The oxygen-containing gas represented by Formula 11 may include, for example, carbon dioxide (CO2), carbon monoxide (CO), water vapor (H2O), or a mixture thereof.
After the providing of the reaction gas including (e.g., consisting of) the carbon raw source gas to the second metal oxide represented by MaOc (where 0<a≤3, 0<c≤4, and when a is 1, 2, or 3, c is an integer) and the performing of the heat treatment, at least one inert gas selected from among nitrogen, helium, and argon may be utilized to further proceed a cooling process. The cooling process may refer to adjusting the reaction temperature to room temperature (20° C. to 25° C.). In some embodiments, the carbon source gas may include at least one inert gas selected from nitrogen, helium, and argon.
In the preparation method of the composite, a process of growing a carbon-based material, e.g., graphene, may be performed under one or more suitable conditions depending on a gas reaction.
In one or more embodiments, in a first condition, for example, methane may be provided first to a reactor, in which the second metal oxide represented by MaOc (where 0<a≤3 and 0<c≤4, and when a is 1, 2, or 3, c is an integer) is arranged and provided, and the reaction temperature may be raised to the heat treatment temperature T. The time for raising the temperature to the heat treatment temperature T may be 10 minutes to about 4 hours, and the heat treatment temperature T may be in a range of about 700° C. to about 1,100° C. The heat treatment may be performed during a reaction time at the heat treatment temperature T. The reaction time may be, for example, 4 hours to 8 hours. The heat-treated product may be cooled down to room temperature to prepare a composite. The time required for the process of cooling from the heat treatment temperature T to room temperature may be, for example, about 1 hour to about 5 hours.
In one or more embodiments, in a second condition, for example, hydrogen may be provided first to a reactor, in which the second metal oxide represented by MaOc (where 0<a≤3 and 0<c≤4, and when a is 1, 2, or 3, c is an integer) is arranged and provided, and the reaction temperature may be raised to the heat treatment temperature T. The time for raising the temperature to the heat treatment temperature T may be 10 minutes to about 4 hours, and the heat treatment temperature T may be in a range of about 700° C. to about 1,100° C. After the heat-treatment is performed at the heat-treatment temperature T for a set or predetermined reaction time, methane gas may be supplied thereto, and the heat-treatment may be performed for residual reaction time. The reaction time may be, for example, 4 hours to 8 hours. The heat-treated product may be cooled down to room temperature to prepare a composite. In the cooling process, nitrogen may be provided thereto. The time required for the process of cooling from the heat treatment temperature T to room temperature may be, for example, about 1 hour to about 5 hours.
In one or more embodiments, in a third condition, for example, hydrogen may be provided first to a reactor, in which the second metal oxide represented by MaOc (where 0<a≤3 and 0<c≤4, and when a is 1, 2, or 3, c is an integer) is arranged and provided, and the reaction temperature may be raised to the heat treatment temperature T. The time for raising the temperature to the heat treatment temperature T may be 10 minutes to about 4 hours, and the heat treatment temperature T may be in a range of about 700° C. to about 1,100° C. After the heat-treatment is performed at the heat-treatment temperature (T) for a set or predetermined reaction time, a mixed gas of methane and hydrogen is supplied thereto, and heat-treatment is performed for residual reaction time. The reaction time may be, for example, 4 hours to 8 hours. The heat-treated product may be cooled down to room temperature to prepare a composite. In the cooling process, nitrogen may be provided thereto. The time required for the process of cooling from the heat treatment temperature T to room temperature may be, for example, about 1 hour to about 5 hours.
In the preparation of the composite, when the carbon source gas includes water vapor, the composite having excellent or suitable conductivity may be obtained. The content (e.g., amount) of water vapor in the mixed gas is not limited, and may be, for example, in some embodiments, in a range of about 0.01 vol % to about 10 vol % based on 100 vol % of the total carbon source gas. The carbon source gas may be: for example, methane; a mixed gas including methane and an inert gas; or a mixed gas including methane and an oxygen-containing gas.
In some embodiments, the carbon source gas may be: for example, methane; a mixed gas including methane and carbon dioxide; or a mixed gas including methane, carbon dioxide, and water vapor. The molar ratio of methane and carbon dioxide in the mixed gas of methane and carbon dioxide may be in a range of about 1:0.20 to about 1:0.50, about 1:0.25 to about 1:0.45, or about 1:0.30 to about 1:0.40. The molar ratio of methane and carbon dioxide and water vapor in the mixed gas of methane and carbon dioxide and water vapor may be in a range of about 1:0.20 to about 0.50:0.01 to 1.45, about 1:0.25 to about 0.45:0.10 to 1.35, or about 1:0.30 to about 0.40:0.50 to 1.0.
In some embodiments, the carbon source gas may be, for example, carbon monoxide or carbon dioxide. In some embodiments, the carbon source gas may be, for example, a mixed gas of methane and nitrogen. The molar ratio of methane and nitrogen in the mixed gas of methane and nitrogen may be in a range of about 1:0.20 to about 1:0.50, about 1:0.25 to about 1:0.45, or about 1:0.30 to about 1:0.40. In some embodiments, the carbon source gas may not include (e.g., may exclude) an inert gas such as nitrogen.
In one or more embodiments, the heat-treatment pressure may be selected in consideration of the heat-treatment temperature, the composition of the gas mixture, and the desired or suitable coating amount of carbon. The heat-treatment pressure may be controlled or selected by adjusting the amount of the inflowing mixed gas and the amount of the outflowing gas mixture. In some embodiments, the heat-treatment pressure may be, for example, greater than or equal to about 0.5 atm, greater than or equal to about 1 atm, greater than or equal to about 2 atm, greater than or equal to about 3 atm, greater than or equal to about 4 atm, or greater than or equal to about 5 atm. In some embodiments, the heat-treatment pressure may be, for example, in a range of about 0.5 atm to about 10 atm, about 1 atm to about 10 atm, about 2 atm to about 10 atm, about 3 atm to about 10 atm, about 4 atm to about 10 atm, or about 5 atm to about 10 atm.
In one or more embodiments, the heat-treatment time is not particularly limited, and may be selected in consideration of the heat-treatment temperature, the heat-treatment pressure, the composition of the gas mixture, and the desired or suitable coating amount of carbon. For example, in some embodiments, the reaction time at the heat-treatment temperature may be, for example, about 10 minutes to about 100 hours, about 30 minutes to about 90 hours, or about 50 minutes to about 40 hours. For example, as the heat-treatment time increases, the amount of graphene (e.g., carbon) deposited increases, and thus, the electrical properties of the composite may be improved. However, this trend may not necessarily be directly proportional to time. For example, after a set or predetermined period of time, the deposition of carbon, e.g., graphene, may no longer occur, or the deposition rate of graphene may be lowered.
Through a gas phase reaction of the carbon source gas described above, even at a relatively low temperature, a composite may be obtained by providing substantially uniform coating of the first carbon-based material, e.g., coating of graphene, to at least one selected from among the second metal oxide represented by MaOc (where 0<a≤3, 0<c≤4, and when a is 1, 2, or 3, c is an integer) and a reduction product thereof that is the first metal oxide represented by MaOb (where 0<a≤3, 0<b<4, and when a is 1, 2, or 3, b is not an integer).
In one or more embodiments, the composite may include: for example, a first carbon-based material matrix, for example, a graphene matrix, having at least one structure selected from among a spherical structure (e.g., a substantially spherical structure), a spiral structure in which a plurality of spherical structures (e.g., substantially spherical structures) are connected, a cluster structure in which a plurality of spherical structures (e.g., substantially spherical structures) are aggregated, and a sponge structure; and at least one selected from among a second metal oxide represented by MaOc (wherein 0<a≤3, 0<c≤4, and when a is 1, 2, or 3, c is an integer) and a reduction product thereof that is the first metal oxide represented by MaOb (wherein 0<a≤3, 0<b<4, and when a is 1, 2, or 3, b is not an integer) in the first carbon-based material matrix.
Next, the lithium transition metal oxide, the composite, and the second carbon-based material may be mechanically milled.
In the mechanically milling process, the milling method is not particularly limited, and any method capable of directly contacting the lithium transition metal oxide, the composite, and the second carbon-based material utilizing a machine available in the art may be utilized.
For the milling, for example, in some embodiments, a Nobilta mixer and/or the like may be utilized. The number of rotations of the mixer at the time of milling may be, for example, in a range of about 1,000 rpm to about 5,000 rpm or about 2,000 rpm to about 4,000 rpm. When the milling rate is too low, the shear force applied to the lithium transition metal oxide, the composite, and the second carbon-based material may be weak, and thus the lithium transition metal oxide and the composite may not form a chemical bond. When the milling rate is too high, the composite and the second carbon-based material may be uniformly coated on the lithium transition metal oxide by the complexation being performed in an excessively short time, and thus a substantially uniform and substantially continuous shell may not be formed. In some embodiments, the milling time may be, for example, about 5 minutes to about 100 minutes, about 5 minutes to about 60 minutes, or about 5 minutes to about 30 minutes. When the milling time is too short, a substantially uniform shell may not be formed because the composite and the second carbon-based material may be uniformly coated on the lithium transition metal oxide. When the milling time is excessively long, the production efficiency may decrease. In some embodiments, the content (e.g., amount) of the composite may be less than or equal to about 5 wt %, less than or equal to about 4 wt %, less than or equal to about 3 wt %, less than or equal to about 2 wt %, or less than or equal to about 1 wt %, with respect to the total weight of the lithium transition metal oxide and the composite. In some embodiments, the content (e.g., amount) of the composite may be, for example, in a range of about 0.01 wt % to about 5 wt %, about 0.01 wt % to about 4 wt %, about 0.01 wt % to about 3 wt %, about 0.1 wt % to about 2 wt %, or about 0.1 wt % to about 1 wt %, with respect to the total weight of the lithium transition metal oxide and the composite. For example, in some embodiments, the content (e.g., amount) of the composite may be, based on 100 parts by weight of the lithium transition metal oxide and the composite, in a range of about 0.01 parts by weight to about 5 parts by weight, about 0.01 parts by weight to about 4 parts by weight, about 0.01 parts by weight to 3 parts by weight, about 0.1 parts by weight to about 3 parts by weight, about 0.1 parts by weight to about 2 parts by weight, or about 0.1 parts by weight to 1 part by weight. The average particle diameter (D50) of the composite utilized for the mechanical milling of the lithium transition metal oxide and the composite may be, for example, in a range of about 50 nm to about 200 nm, about 100 nm to about 300 nm, or about 200 nm to about 500 nm.
Hereinafter example embodiments will be described in more detail with reference to Examples and Comparative Examples. These examples are provided for illustrative purposes only and are not intended to limit the scope of the present disclosure.
Preparation Example 1: Al2O3@Gr Composite
Al2O3 particles (average particle diameter: about 20 nanometers (nm)) were placed in a reactor, and then the temperature inside the reactor was raised to 1,000° C. under the condition that CH4 was supplied into the reactor at about 300 standard cubic centimeters per minute (sccm) and about 1 atmosphere (atm) for about 30 minutes.
Subsequently, heat treatment was performed while maintaining the temperature at 1,000° C. for 7 hours. Then, the temperature inside the reactor was adjusted to room temperature (20° C. to 25° C.) to obtain a composite in which Al2O3 particles and Al2Oz (where 0<z<3) particles as a reduction product thereof were embedded in graphene.
The amount of alumina included in the composite was 60 wt %.
Preparation Example 2: Al2O3@Gr Composite
A composite was prepared in substantially the same manner as in Preparation Example 1, except that Al2O3 particles (average particle diameter: about 200 nm) were utilized instead of the Al2O3 particles (average particle diameter: about 20 nm).
SiO2 particles (average particle diameter: about 15 nm) were placed in a reactor, and then the temperature inside the reactor was raised to 1,000° C. under the condition that CH4 was supplied into the reactor at about 300 sccm and about 1 atm for about 30 minutes.
Subsequently, heat treatment was performed while maintaining the temperature at 1,000° C. for 7 hours. Then, the temperature inside the reactor was adjusted to room temperature (20° C. to 25° C.) to obtain a composite in which SiO2 particles and SiOy (where 0<y<2) particles as a reduction product thereof were embedded in graphene.
LiNi0.91Co0.05Al0.04O2 (hereinafter referred to as NCA91) having an average particle diameter of 10 μm, the composite prepared in Preparation Example 1, and carbon nanotube structure (hereinafter referred to as CNT) were milled at a rotation speed of about 1,000 revolutions per minutes (rpm) to about 2,000 rpm for about 5 minutes to about 30 minutes utilizing a Nobilta mixer (Hosokawa, Japan) to obtain a composite cathode active material. The NCA91, the composite, and the CNT were mixed at a ratio of 99.75:0.2:0.05 to prepare a composite cathode active material.
As shown in
The primary CNT includes (e.g., consists of) one CNT unit. The CNT unit had a length in a range of about 200 nm to about 300 nm, and the CNT had a diameter of about 10 nm.
The secondary CNT includes (e.g., consists of) a plurality of the CNT units. The secondary CNT structure had a length of greater than or equal to about 500 nm and a diameter of greater than or equal to about 40 nm.
A composite cathode active material was prepared in substantially the same manner as in Example 1, except that the mixing ratio of the composite and the CNT was changed from 0.2:0.05 to 0.15:0.05.
A composite cathode active material was prepared in substantially the same manner as in Example 1, except that the mixing ratio of the composite and the CNT was changed from 0.2:0.05 to 0.18:0.02.
A composite cathode active material was prepared in substantially the same manner as in Example 1, except that the mixing ratio of the composite and the CNT was changed from 0.2:0.05 to 0.10:0.10.
A composite cathode active material was prepared in substantially the same manner as in Example 1, except that the composite of Preparation Example 2 was utilized instead of the composite of Preparation Example 1.
NCA91 having an average particle diameter of 10 μm was utilized as it is as a composite cathode active material.
A composite cathode active material was prepared in substantially the same manner as in Example 1, except that the composite of Preparation Example 1 was not utilized and 0.25 wt % of the CNT was utilized.
A composite cathode active material was prepared in substantially the same manner as in Example 1, except that the composite obtained in Comparative Preparation Example 2 was utilized instead of the composite prepared in Preparation Example 1.
A simple mixture of NCA91 having an average particle diameter of 10 μm, the composite of Preparation Example 1, and CNT mixed at a weight ratio of 97.5:0.2:0.05 was utilized as it is as a composite cathode active material.
Manufacture of Cathode
A mixture of the composite cathode active material of Example 1, a carbon conductor (e.g., Denka Black), and PVDF mixed at a weight ratio of 98.85:0.5:0.65 was mixed with N-methyl pyrrolidone (NMP) in an agate mortar to prepare a slurry.
The slurry was bar-coated on an aluminum current collector having a thickness of 15 μm, dried at room temperature, further dried in vacuum at 120° C., and rolled and punched to prepare a cathode having a thickness of 60 μm.
Manufacture of Coin Cell
Each coin cell was manufactured utilizing the prepared cathode. Lithium metal was utilized as a counter electrode, PTFE was utilized as a separator, and a solution in which 1.5 M LiPF6 was dissolved in ethylene carbonate (EC)+ethylmethyl carbonate (EMC)+dimethyl carbonate (DMC) (at a volume ratio of 2:1:7) was utilized as an electrolyte.
Each coin cell was manufactured in substantially the same manner as in Example 6, except that the composite cathode active material of each of Examples 2 to 5 was utilized instead of the composite cathode active material of Example 1.
Each coin cell was manufactured in substantially the same manner as in Example 6, except that the composite cathode active material of each of Comparative Examples 1 to 4 was utilized instead of the composite cathode active material of Example 1.
The composite cathode active material of Example 1 as a dry composite cathode active material, a carbon conductor (e.g., Denka Black) as a dry conductor, and polytetrafluoroethylene(PTFE) as a dry binder were added at a weight ratio of 92:4:4 to a blade mixer. Then, a first dry-mixing process was performed at 25° C. and a speed of 1,000 rpm for 10 minutes to prepare a first mixture in which a dry composite cathode active material, a dry conductive material, and a dry binder were uniformly mixed.
Subsequently, to allow fiberization of the dry-type or kind binder to proceed, a second drying process was additionally performed on the first mixture at 25° C. and a speed of 5,000 rpm for 20 minutes to prepare a second mixture. In the preparation of the first mixture and the second mixture, a separate solvent was not utilized.
The prepared second mixture was added to an extruder to extrude a sheet-type or kind self-standing film with the cathode active material layer. The pressure at the time of extrusion was 50 MPa.
A carbon layer as an interlayer was arranged on one surface of an aluminum thin film having a thickness of 12 μm to prepare a first laminate on which the interlayer was arranged on one surface of a second cathode current collector.
The interlayer was prepared by coating an aluminum thin film with a composition including a carbon conductor (e.g., danka black) and PVDF and drying the aluminum thin film. The thickness of the interlayer arranged on one surface of the aluminum thin film was about 1 μm.
A self-standing film with the cathode active material layer was arranged on the interlayer of the prepared first laminate, and then rolled to prepare a cathode.
Each coin cell was manufactured utilizing the prepared cathode. Lithium metal was utilized as a counter electrode, PTFE was utilized as a separator, and a solution in which 1.5 M LiPF6 was dissolved in EC+EMC+DMC (at a volume ratio of 2:1:7) was utilized as an electrolyte.
A coin cell was manufactured in substantially the same manner as in Example 11, except that the composite cathode active material of Comparative Example 1 was utilized instead of the composite cathode active material of Example 1.
In the process of preparing the composite prepared in Preparation Example 1, XPS spectra were measured utilizing Quantum 2000 (Physical Electronics) over time. Before heating, XPS spectra of C 1s orbitals and Al 2p orbitals of samples were measured after 1 minute, after 5 minutes, after 30 minutes, after 1 hour, and after 4 hours, respectively. At the initial heating, the peak for the Al 2p orbital appeared, and the peak for the C 1s orbital did not appear. After 30 minutes, the peak for the C 1s orbital appeared clearly, and the size of the peak for the Al 2p orbital significantly reduced.
After 30 minutes, near 284.5 electron volt (eV), peaks for C 1s orbitals appeared clearly due to C—C bonds and C═C bonds due to graphene growth.
As reaction time elapsed, the oxidation number of aluminum decreased, and thus the peak position of the Al 2p orbital was shifted toward a lower binding energy (eV).
Accordingly, it was confirmed that, as the reaction proceeded, graphene was grown on Al2O3 particles, and Al2Ox (where 0<x<3), which is a reduction product of Al2O3, was produced.
The average contents (e.g., amounts) of carbon and aluminum were measured through XPS analysis results in 10 regions of the composite sample prepared in Preparation Example 1. With respect to the measurement results, a deviation of the aluminum content (e.g., amount) for each region was calculated. The deviation of the aluminum content (e.g., amount) was expressed as a percentage of the average value, and this percentage was referred to as uniformity. The percentage of the average value of the deviation of the aluminum content (e.g., amount), that is, the uniformity of the aluminum content (e.g., amount) was 1%. Therefore, it was confirmed that alumina was uniformly distributed in the composite prepared in Preparation Example 1.
The composite prepared in Preparation Example 1, the composite cathode active material prepared in Example 1, and the composite cathode active material prepared in Comparative Example 1 were subjected to scanning electron microscope (SEM) analysis, high-resolution transmission electron microscope (HR-TEM) analysis, and energy-dispersive X-ray spectroscope (EDX) analysis.
For SEM-EDX analysis, FEI Titan 80-300 available from Philips Company was utilized.
The composite prepared in Preparation Example 1 showed a structure in which Al2O3 particles and Al2Oz (where 0<z<3) particles, which are reduction products thereof, were embedded in graphene. It was confirmed that the graphene layer was disposed on the outer surface of one or more particles selected from Al2O3 particles and Al2Oz (where 0<z<3) particles. The one or more particles selected from Al2O3 particles and Al2Oz (where 0<z<3) particles were uniformly distributed in the graphene matrix. The one or more particles selected from Al2O3 particles and Al2Oz (where 0<z<3) particles had a particle diameter of about 20 nm. The composite prepared in Preparation Example 1 had a particle diameter in a range of about 50 nm to about 200 nm. It was confirmed that, in the composite cathode active material prepared in Example 1, a shell formed by a composite including graphene was arranged on the NCA91 core.
According to SEM-EDS mapping analysis of the composite cathode active materials prepared in Comparative Example 1 and Example 1, it was confirmed that the concentration of aluminum (Al) distributed on the surface of the composite cathode active material of Example 1 was increased compared to the surface of the cathode active material of Comparative Example 1.
It was also found that, in the cathode active material of Example 1, the composite prepared in Preparation Example 1 was uniformly coated on the NCA91 core to form a shell.
For the composite prepared in Preparation Example 1, the NCA91 of Comparative Example 1, and the composite cathode active material prepared in Example 1, XPS spectra of O 1s orbitals were measured utilizing Quantum 2000 (Physical Electronics), and the results thereof are shown
As shown in
The Raman spectra for the composite prepared in Preparation Example 1 and the composite cathode active material prepared in Example 1 were measured, and the results thereof are shown in
As shown in
In contrast, in the composite cathode active material of Example 1, the D band peak was shifted to 1351.3 cm−1 by about 12 cm−1, and the G band peak was shifted to 1593.6 cm−1 by about 18 cm−1, due to the shell including graphene.
The shift of the D band peak was determined to be due to the strain of graphene, which is bound to the core by milling to form a shell.
The shift of the G band peak was determined to be due to the charge transfer between the core and the graphene in the composite formed by the C—O—Ni bond between the core and the graphene.
Therefore, it was confirmed that graphene included in the shell formed on the core formed a covalent bond with Ni, which is a transition metal included in the core.
Each of the lithium batteries prepared in Examples 6 to 10 and Comparative Examples 5 to 8 was charged with a constant current of 0.1 C rate at 25° C. until a voltage reached 4.3 volts (V) (vs. Li), and was then cut-off at a current of 0.05 C rate while maintaining the voltage at 4.3 V in a constant voltage mode. Subsequently, each of the lithium batteries was discharged at a constant current of 0.1 C rate until the voltage reached 2.8 V (vs. Li) (formation cycle).
Each of the lithium batteries having undergone the formation cycle was charged with a constant current of 0.2 C rate at 45° C. until a voltage reached 4.3 V (vs. Li), and was then cut-off at a current of 0.05 C rate while maintaining the voltage at 4.3 V in a constant voltage mode. Subsequently, each of the lithium batteries was discharged at a constant current of 0.2 C rate until the voltage reached 2.8 V (vs. Li) (1st cycle). This cycle was repeated until the 50th cycle under the same conditions.
In all charge/discharge cycles, a 10-minute stop time was provided after every one charge/discharge cycle. Some of the results of the charging and discharging experiments at room temperature are shown in Tables 1 and 2. The initial efficiency is defined by Equation 1, and the capacity retention rate is defined by Equation 2:
Initial efficiency [%]=[discharge capacity in 1st cycle/charge capacity in 1st cycle]×100 Equation 1
Capacity retention (%)=(discharge capacity in 50th cycle/discharge capacity in 1st cycle)×100% Equation 2
With respect to the lithium batteries prepared in Examples 6 to 10 and Comparative Examples 5 to 8, before the evaluation of charging and discharging at high temperature and after the evaluation of charging and discharging at high temperature, DC-IR was measured by the following method, respectively:
after charging to a voltage of 50% of the state of charge with a current density of 0.5 C in the 1st cycle, a 10-minute resting time was provided after cut-off at 0.02 C;
after discharging at a constant current of 0.5 C for 30 seconds, a 10-minute resting time was provided after charging with a constant current of 0.5 C for 30 seconds;
after discharging at a constant current of 1.0 C for 30 seconds, a 10-minute resting time was provided after charging with a constant current of 0.5 C for 1 minute;
after discharging at a constant current of 2.0 C for 30 seconds, a 10-minute resting time was provided after charging with a constant current of 0.5 C for 2 minutes; and
after discharging at a constant current of 3.0 C for 30 seconds, a 10-minute resting time was provided after charging with a constant current of 0.5 C for 3 minutes.
From a ratio of average voltage change (ΔV) and average current change (ΔI) during discharging at a constant current at each C-rate, DC-IR (where R=ΔV/ΔI) was calculated, and an average value thereof was utilized as a measured value.
Some of the measured DC-IR before the evaluation of charging and discharging at high temperature and the DC-IR measurement results after the evaluation of charging and discharging at room temperature are shown in Table 2.
As shown in Table 1, the lithium batteries of Examples 7 to 10 had improved high-temperature lifespan characteristics compared to the lithium batteries of Comparative Examples 5 to 8.
The lithium battery of Comparative Example 6 had poor high-temperature lifespan characteristics compared to the lithium battery of Example 6. That is because, in the lithium battery of Comparative Example 6, a side effect between the NCA91 core and the electrolyte could not be effectively blocked because only CNT was arranged on the NCA91 core.
The lithium battery of Comparative Example 7 had poor high-temperature lifespan characteristics compared to the lithium battery of Example 6. That is because, in the lithium battery of Comparative Example 6, the high-voltage stability of the SiO2@Gr composite arranged on the NCA91 core was poor.
The lithium battery of Comparative Example 8 had poor high-temperature lifespan characteristics compared to the lithium battery of Example 6. That is because, in the lithium battery of Comparative Example 8, a side effect between the NCA91 core and the electrolyte could not be effectively blocked because the NCA91, the composite, and the CNT were simply mixed, and a shell could not be formed on the NCA91 core.
Although not shown in Table 1, the lithium battery of Example 11 had improved lifespan characteristics compared to the lithium battery of Comparative Example 9.
As shown in Tables 1 and 2, the lithium batteries of Examples 6 and 7 had improved initial efficiency and high-temperature lifespan characteristics, and suppressed or reduced an increase in DC-IR, compared to the lithium battery of Comparative Example 5.
Although not shown in Table 2, the lithium batteries of Examples 8 to 10 had improved initial efficiency and suppressed or reduced an increase in DC-IR, compared to the lithium battery of Comparative Example 5.
Each of the lithium batteries prepared in Examples 6 to 10 and Comparative Examples 5 to 8 was charged with a constant current of 0.1 C rate at 25° C. until a voltage reached 4.3 volts (V) (vs. Li), and was then cut-off at a current of 0.05 C rate while maintaining the voltage at 4.3 V in a constant voltage mode. Subsequently, each of the lithium batteries was discharged at a constant current of 0.1 C rate until the voltage reached 2.8 V (vs. Li) (formation cycle).
Each of the lithium batteries having undergone the formation cycle was charged with a constant current of 0.2 C rate at 25° C. until a voltage reached 4.3 V (vs. Li), and was then cut-off at a current of 0.05 C rate while maintaining the voltage at 4.3 V in a constant voltage mode. Subsequently, each of the lithium batteries was discharged at a constant current of 0.2 C rate until the voltage reached 2.8 V (vs. Li) (1st cycle).
Each of the lithium batteries having undergone the 1st cycle was charged with a constant current of 0.2 C rate at 25° C. until a voltage reached 4.3 V (vs. Li), and was then cut-off at a current of 0.05 C rate while maintaining the voltage at 4.3 V in a constant voltage mode. Subsequently, each of the lithium batteries was discharged at a constant current of 0.5 C rate until the voltage reached 2.8 V (vs. Li) (2nd cycle).
Each of the lithium batteries having undergone the 2nd cycle was charged with a constant current of 0.2 C rate at 25° C. until a voltage reached 4.3 V (vs. Li), and was then cut-off at a current of 0.05 C rate while maintaining the voltage at 4.3 V in a constant voltage mode. Subsequently, each of the lithium batteries was discharged at a constant current of 1.0 C rate until the voltage reached 2.8 V (vs. Li) (3rd cycle).
In all charge/discharge cycles, a 10-minute stop time was provided after every one charge/discharge cycle. Some of the results of the room-temperature charge/discharge test are shown in Table 3. The high rate characteristics were defined by Equation 3.
The reversibility of the electrode reaction was represented by Equation 4. The reversibility of the electrode reaction is a ratio of capacity charged in a constant current mode to the total charge capacity:
High rate characteristics [%]=[discharge capacity at 1.0 C rate (3rd cycle discharge capacity)/discharge capacity at 0.2 C rate (1st cycle discharge capacity)]×100 Equation 3
Reversibility of electrode reaction [%]=[charge capacity in constant current mode at 0.2 C rate (1st cycle CC charge capacity)/charge capacity in constant current mode at 0.2 C rate and constant voltage mode (1st cycle CC+CV charge capacity)]×100 Equation 4
As shown in Table 3, the lithium batteries of Examples 6 to 10 had improved high-rate characteristics and improved reversibility of the electrode reaction, compared to the lithium battery of Comparative Example 5.
According to one or more embodiments of the present disclosure, because the composite cathode active material includes a shell including a first metal oxide, a first carbon-based material, and a second carbon-based material, a lithium battery including the composite cathode active material may have improved high-temperature cycle characteristics, suppress or reduce an increase in internal resistance, and improve high-rate characteristics.
The electronic device, the battery management device/system and/or any other relevant devices or components according to embodiments of the present invention described herein may be implemented utilizing any suitable hardware, firmware (e.g., an application-specific integrated circuit), software, or a combination of software, firmware, and hardware. For example, the various components of the apparatus may be formed on one integrated circuit (IC) chip or on separate IC chips. Further, the various components of the apparatus may be implemented on a flexible printed circuit film, a tape carrier package (TCP), a printed circuit board (PCB), or formed on one substrate. Further, the various components of the apparatus may be a process or thread, running on one or more processors, in one or more computing devices, executing computer program instructions and interacting with other system components for performing the various functionalities described herein. The computer program instructions are stored in a memory which may be implemented in a computing device using a standard memory device, such as, for example, a random access memory (RAM). The computer program instructions may also be stored in other non-transitory computer readable media such as, for example, a CD-ROM, flash drive, or the like. Also, a person of skill in the art should recognize that the functionality of various computing devices may be combined or integrated into a single computing device, or the functionality of a particular computing device may be distributed across one or more other computing devices without departing from the scope of the embodiments of the present disclosure.
It should be understood that embodiments described herein should be considered in a descriptive sense only and not for purposes of limitation. Descriptions of features or aspects within each embodiment should typically be considered as available for other similar features or aspects in other embodiments. While one or more embodiments have been described with reference to the drawings, it will be understood by those of ordinary skill in the art that one or more suitable changes in form and details may be made therein without departing from the spirit and scope of the disclosure as defined by the following claims and equivalents thereof.
| Number | Date | Country | Kind |
|---|---|---|---|
| 10-2021-0166116 | Nov 2021 | KR | national |
