Patent Application
20230411617
This application claims priority to and the benefit of Korean Patent Application No. 10-2022-0074829 filed in the Korean Intellectual Property Office on Jun. 20, 2022, the entire contents of which are incorporated herein by reference.
This disclosure relates to a lithium halide-based nanocomposite, a preparing method thereof, and a positive electrode active material, a solid electrolyte, and an all-solid-state battery.
Recently, lithium ion batteries are expanding from power sources for small mobile devices to power sources for electric vehicles and energy storage devices (ESS) such as medium and large-sized pure electric vehicles (EVs) and hybrid electric vehicles (HEVs). In particular, interest in electric vehicles, which are eco-friendly vehicles, is very high, and major automakers around the world are accelerating technology development by recognizing electric vehicles as a next-generation growth technology under the motto of eco-friendliness. In the case of medium-sized and large-sized lithium-ion batteries, unlike small-sized lithium-ion batteries, it is essential to secure safety because they include many batteries as well as harsh operating environments such as temperature or shock. Accordingly, as industrial fields requiring lithium ion batteries expand their application range to large batteries, interest in safety issues of lithium ion batteries is also greatly increasing.
Existing lithium-ion batteries have problems such as low thermal stability, ignitability, and leakage because organic liquid electrolytes are used. In fact, as explosion accidents of products applied with this technology are continuously reported, it is urgently required to solve these problems. Accordingly, an all-solid-state battery using a solid electrolyte is emerging as an alternative.
In order to exhibit the performance of such an all-solid-state battery, it is necessary to have excellent contact characteristics between particles of a solid electrolyte and an active material. Accordingly, sulfide-based solid electrolytes are electrochemically excellent and have better ductile properties than oxide-based solid electrolytes with hard mechanical properties, so that close contact between solid electrolyte and active material particles may be achieved only by cold pressing due to particle characteristics. This has the advantage of obtaining an all-solid-state battery with improved lithium ionic conductivity.
The sulfide-based solid electrolytes may be prepared only by simple cold pressing due to their high ionic conductivity and brittle mechanical properties, but have low electrochemical stability and inferior atmospheric stability compared to oxide-based solid electrolytes, which may cause difficulties in the manufacturing process of all-solid-state batteries. In addition, there are inherent risk factors due to the generation of H2S gas in the manufacturing process. In order to solve the above problems, various studies have been conducted on halide-based solid electrolytes.
For example, studies using Li3YCl6 and Li3YBr6 have been conducted to improve atmospheric stability, which is a problem of sulfide-based solid electrolytes. As a central element material is a rare earth material, there is still a problem in the manufacturing process of the all-solid-state battery in terms of toxicity or price. In addition, there is also a problem that side reactions between sulfide and halide-based solid electrolytes occur at high voltage when applied to an all-solid-state battery at the same time as a sulfide solid electrolyte.
In addition, for the competitiveness of halide-based solid electrolytes, methods such as central metal or anion substitution are being studied to improve ionic conductivity to the level of sulfide-based materials, but there is still a limit to improving ionic conductivity.
An embodiment provides a lithium halide-based nanocomposite that can provide a solid electrolyte for a rechargeable lithium battery with improved ionic conductivity and electrochemical oxidation stability.
Another embodiment provides a method of preparing the lithium halide-based nanocomposite.
Another embodiment provides a positive electrode active material for a rechargeable lithium battery including the lithium halide-based nanocomposite.
Another embodiment provides a solid electrolyte for a rechargeable lithium battery including the lithium halide-based nanocomposite and a sulfide based solid electrolyte.
Another embodiment provides a double-layer solid electrolyte for a rechargeable lithium battery including the lithium halide-based nanocomposite.
Another embodiment provides an all-solid-state battery including the solid electrolyte.
Another embodiment provides an all-solid-state battery including the double-layer solid electrolyte.
An embodiment provides a lithium halide-based nanocomposite represented by any one of Chemical Formulas 1A to 1C, in which a nanosized compound selected from M1Oc, LiX, and a combination thereof is dispersed in a halide compound of LiaM2Xb.
M1Oc—LiaM2Xb [Chemical Formula 1A]
In Chemical Formula 1A, M1 and M2 are different from each other and are each independently one or more selected from Mg, Ca, Zn, Cd, Cu, Sc, Y, B, Al, Ga, In, Ln (La, Ce, Pr, Nd, Pm, Sm, Eu, Gd, Tb, Dy, Ho, Er, Yb, or Lu), Ti, Zr, Hf, Nb, Ta, Mo, W, Sb, Si, Ge, Sn, V, Cr, Mn, Fe, Co, and Ni, X is Cl, Br, F, or I, and a, b, and c are each independently in the range of 0.01 to 10.
LiX—LiaM2Xb [Chemical Formula 1B]
In Chemical Formula 1B, M2 is one or more selected from Mg, Ca, Zn, Cd, Cu, Sc, Y, B, Al, Ga, In, Ln (La, Ce, Pr, Nd, Pm, Sm, Eu, Gd, Tb, Dy, Ho, Er, Yb, or Lu), Ti, Zr, Hf, Nb, Ta, Mo, W, Sb, Si, Ge, Sn, V, Cr, Mn, Fe, Co, and Ni, X is Cl, Br, F, or I, and a and b are each independently in the range of 0.01 to 10.
M1Oc—LiX—LiaM2Xb [Chemical Formula 1C]
In Chemical Formula 1C, M1 and M2 are different from each other and are each independently one or more selected from Mg, Ca, Zn, Cd, Cu, Sc, Y, B, Al, Ga, In, Ln (La, Ce, Pr, Nd, Pm, Sm, Eu, Gd, Tb, Dy, Ho, Er, Yb, or Lu), Ti, Zr, Hf, Nb, Ta, Mo, W, Sb, Si, Ge, Sn, V, Cr, Mn, Fe, Co, and Ni, X is Cl, Br, F, or I, and a, b, and c are each independently in the range of 0.01 to 10.
In LiaM2Xb of Chemical Formulas 1A to 1C, Xb may be X1b-dX2d wherein X1 and X2 may be different from each other and may each independently be Cl, Br, F, or I, b may be in the range of 0.01 to 10, and d may be in the range of 0.01 to 4.
In LiaM2Xb of Chemical Formulas 1A to 1C, Xb may be Clb-dFd or Clb-dId, b may be in the range of 0.01 to 10, and d may be the range of 0.01 to 4.
The lithium halide-based nanocomposite represented by Chemical Formula 1A may include about 1 to about 20 vol % of M1Oc and about 80 to about 99 vol % of LiaM2Xb; the lithium halide-based nanocomposite represented by Chemical Formula 1B may include about 6 to about 34 vol % of LiX and about 66 to about 94 vol % of LiaM2Xb; and the lithium halide-based nanocomposite represented by Chemical Formula 1C may include about 1 to about 13 vol % of M1Oc, about 1 to about 29 vol % of LiX, and about to about 94 vol % of LiaM2Xb.
The nanosized compound selected from M1Oc, LiX, and the combination thereof may be an in-situ grown compound and may have a crystal size of less than or equal to about 100 nm.
The nanosized compound selected from M1Oc, LiX, and the combination thereof may be formed in a network shape inside a halide compound (LiaM2Xb).
The lithium halide-based nanocomposite may have an ionic conductivity of about to about 5 mS/cm at 30° C.
The lithium halide-based nanocomposite may have a glass-ceramic crystal structure.
The lithium halide-based nanocomposite may exhibit a first effective peak and a second effective peak in the ranges of about 0.4 to about 0.6 ppm and about −0.2 to about ppm, respectively, in a 6Li MAS NMR analysis result, and an intensity ratio of the first effective peak to the second effective peak may be about 0.7 to about 0.8. Another embodiment provides a lithium halide-based nanocomposite represented by any one of Chemical Formulas 2A to 2C, in which a nanosized compound selected from M1Oc, LiX, and a combination thereof is dispersed in a halide compound of LiaM2X1b-dX2d.
M1Oc—LiaM2X1b-dX2d [Chemical Formula 2A]
In Chemical Formula 2A, M1 and M2 are the same or different, and are each independently one or more selected from Mg, Ca, Zn, Cd, Cu, Sc, Y, B, Al, Ga, In, Ln (La, Ce, Pr, Nd, Pm, Sm, Eu, Gd, Tb, Dy, Ho, Er, Yb, or Lu), Ti, Zr, Hf, Nb, Ta, Mo, W, Sb, Si, Ge, Sn, V, Cr, Mn, Fe, Co, and Ni, X1 and X2 are different from each other and are each independently Cl, Br, F, or I, a, b, and c are each independently in the range of 0.01 to 10, and d is in the range of 0.01 to 4.
LiX—LiaM2X1b-dX2d [Chemical Formula 2B]
In Chemical Formula 2B, M2 is one or more selected from Mg, Ca, Zn, Cd, Cu, Sc, Y, B, Al, Ga, In, Ln (La, Ce, Pr, Nd, Pm, Sm, Eu, Gd, Tb, Dy, Ho, Er, Yb, or Lu), Ti, Zr, Hf, Nb, Ta, Mo, W, Sb, Si, Ge, Sn, V, Cr, Mn, Fe, Co, and Ni, X is Cl, Br, F, or I, X l and X2 are different from each other and are each independently Cl, Br, F, or I, a and b are each independently in the range of 0.01 to 10, and d is in the range of 0.01 to 4.
M1Oc—LiX—LiaM2X1b-dX2d [Chemical Formula 2C]
In Chemical Formula 2C, M1 and M2 are each independently one or more selected from Mg, Ca, Zn, Cd, Cu, Sc, Y, B, Al, Ga, In, Ln (La, Ce, Pr, Nd, Pm, Sm, Eu, Gd, Tb, Dy, Ho, Er, Yb, or Lu), Ti, Zr, Hf, Nb, Ta, Mo, W, Sb, Si, Ge, Sn, V, Cr, Mn, Fe, Co, and Ni, X is Cl, Br, F, or I, X1 and X2 are different from each other and are each independently Cl, Br, F, or I, a, b, and c are each independently in the range of 0.01 to 10, and d is in the range of 0.01 to 4.
LiaM2X1b-dX2d in Chemical Formulas 2A to 2C may be LiaM2Clb-dFd or LiaM2Clb-dId, wherein a and b may be in the range of 0.01 to 10, and d may be in the range of 0.01 to 4.
In LiaM2X1b-dX2d of Chemical Formulas 2A to 2C, a portion of M2 may be substituted with M3 to be a compound represented by LiaM21-eM3eX1b-dX2d, wherein M2, X1, X2, a, b, and d are the same as in Chemical Formulas 2A to 2C, and M 3 may be the same as or different from M l, and may be one or more selected from Mg, Ca, Zn, Cd, Cu, Sc, Y, B, Al, Ga, In, Ln (La, Ce, Pr, Nd, Pm, Sm, Eu, Gd, Tb, Dy, Ho, Er, Yb, or Lu), Ti, Zr, Hf, Nb, Ta, Mo, W, Sb, Si, Ge, Sn, V, Cr, Mn, Fe, Co, and Ni, and e may be in the range of 0.01 to 0.9.
The lithium halide-based nanocomposite represented by Chemical Formula 2A may include about 1 to about 20 vol % of M1Oc and about 80 to about 99 vol % of LiaM2X1b-dX2d; the lithium halide-based nanocomposite represented by Chemical Formula 2B may include about 6 to about 34 vol % of LiX and about 66 to about 94 vol % of LiaM2X1b-dX2d; and the lithium halide-based nanocomposite represented by Chemical Formula 2C may include about 1 to about 13 vol % of M1Oc, about 1 to about 29 vol % of LiX, and about 65 to about 94 vol % of LiaM2X1b-dX2d.
The nanosized compound selected from M1Oc, LiX, and the combination thereof may be an in-situ grown compound and may have a crystal size of less than or equal to about 100 nm.
The nanosized compound selected from M1Oc, LiX, and the combination thereof may be formed in a network shape inside a halide compound (LiaM2X1b-dX2d).
The lithium halide-based nanocomposite may have an ionic conductivity of about to about 5 mS/cm at 30° C.
The lithium halide-based nanocomposite may have a glass-ceramic crystal structure.
The lithium halide-based nanocomposite may exhibit a first effective peak and a second effective peak in the ranges of about 0.4 to about 0.6 ppm and about −0.2 to about ppm, respectively, in a 6Li MAS NMR analysis result, and an intensity ratio of the first effective peak to the second effective peak may be about 0.7 to about 0.8.
Another embodiment provides a lithium halide-based nanocomposite represented by any one of Chemical Formulas 3A to 3C, in which a nanosized compound selected from M1Oc, LiX, and a combination thereof is dispersed in a halide compound of LiaM21-eM3eXb.
M1Oc—LiaM21-eM3eXb [Chemical Formula 3A]
In Chemical Formula 3A, M1, M2, and M3 are each independently one or more selected from Mg, Ca, Zn, Cd, Cu, Sc, Y, B, Al, Ga, In, Ln (La, Ce, Pr, Nd, Pm, Sm, Eu, Gd, Tb, Dy, Ho, Er, Yb, or Lu), Ti, Zr, Hf, Nb, Ta, Mo, W, Sb, Si, Ge, Sn, V, Cr, Mn, Fe, Co, and Ni, X is Cl, Br, F, or I, M2 and M3 are different from each other, a, b, and c are each independently in the range of 0.01 to 10, and e is in the range of 0.01 to 0.9.
LiX—LiaM21-eM3eXb [Chemical Formula 3B]
In Chemical Formula 3B, M2 and M3 are different from each other and are each independently one or more selected from Mg, Ca, Zn, Cd, Cu, Sc, Y, B, Al, Ga, In, Ln (La, Ce, Pr, Nd, Pm, Sm, Eu, Gd, Tb, Dy, Ho, Er, Yb, or Lu), Ti, Zr, Hf, Nb, Ta, Mo, W, Sb, Si, Ge, Sn, V, Cr, Mn, Fe, Co, and Ni, X is Cl, Br, F, or I, a and b are each independently in the range of 0.01 to 10, and e is in the range of 0.01 to 0.9.
M1Oc—LiX—LiaM21-eM3eXb [Chemical Formula 3C]
In Chemical Formula 3C, M1, M2, and M3 are each independently one or more selected from Mg, Ca, Zn, Cd, Cu, Sc, Y, B, Al, Ga, In, Ln (La, Ce, Pr, Nd, Pm, Sm, Eu, Gd, Tb, Dy, Ho, Er, Yb, or Lu), Ti, Zr, Hf, Nb, Ta, Mo, W, Sb, Si, Ge, Sn, V, Cr, Mn, Fe, Co, and Ni, X is Cl, Br, F, or I, a, b, and c are each independently in the range of 0.01 to 10, and e is in the range of 0.01 to 0.9.
In LiaM21-eM3eXb of Chemical Formula 3A to 3C, Xb may be X1b-dX2d wherein X1 and X2 may be different from each other and may each independently be Cl, Br, F, or I, b may be in the range of 0.01 to 10, and d may be in the range of 0.01 to 4.
In LiaM21-eM3eXb of Chemical Formulas 3A to 3C, Xb may be Clb-dFd or Clb-dId, b may be in the range of 0.01 to 10, and d may be in the range of 0.01 to 4.
The lithium halide-based nanocomposite represented by Chemical Formula 3A may include about 1 to about 20 vol % of M1Oc and about 80 to about 99 vol % of LiaM21-eM3eXb; the lithium halide-based nanocomposite represented by Chemical Formula 3B may include about 6 to about 34 vol % of LiX, and about 66 to about 94 vol % of LiaM21-eM3eXb; and the lithium halide-based nanocomposite represented by Chemical Formula 3C may include about 1 to about 13 vol % of M1Oc, about 1 to about 29 vol % of LiX, and about 65 to about 94 vol % of LiaM21-eM3eXb.
The nanosized compound selected from M1Oc, LiX, and the combination thereof may be an in-situ grown compound and may have a crystal size of less than or equal to about 100 nm.
The nanosized compound selected from M1Oc, LiX, and the combination thereof may be formed in a network shape inside a halide compound (LiaM21-eM3eXb).
The lithium halide-based nanocomposite may have an ionic conductivity of about 0.1 to about 5 mS/cm at 30° C.
The lithium halide-based nanocomposite may have a glass-ceramic crystal structure.
The lithium halide-based nanocomposite may exhibit a first effective peak and a second effective peak in the ranges of about 0.4 to about 0.6 ppm and about −0.2 to about 0.2 ppm, respectively, in a 6Li MAS NMR analysis result, and an intensity ratio of the first effective peak to the second effective peak may be about 0.7 to about 0.8.
Another embodiment provides a method of preparing the lithium halide-based nanocomposite represented by any one of Chemical Formulas 1A to 1C which includes performing a solid-phase reaction of a lithium-containing oxidizing agent and a first metal (M1)-containing halide under an inert gas atmosphere to obtain first metal (M1) oxide and a lithium halide, and performing a solid-phase reaction of the first metal (M1) oxide, lithium halide, and second metal (M2)-containing halide.
Another embodiment provides a method for preparing a lithium halide-based nanocomposite represented by any one of Chemical Formulas 2A to 2C which includes
Another embodiment provides a method for preparing a lithium halide-based nanocomposite represented by any one of Chemical Formulas 3A to 3C which includes
The lithium-containing oxidizing agent is the same as described above.
Another embodiment includes a positive electrode active material for a rechargeable lithium battery including a core including a composite metal oxide capable of reversible intercalation/deintercalation of lithium; and a shell disposed on the core and including the lithium halide-based nanocomposite.
Another embodiment provides a solid electrolyte for a rechargeable lithium battery including the lithium halide-based nanocomposite and a sulfide-based solid electrolyte.
Another embodiment provides a double-layer solid electrolyte for a rechargeable lithium battery which includes a solid electrolyte for a positive electrode including the lithium halide-based nanocomposite; and a solid electrolyte for a negative electrode disposed on the solid electrolyte for the positive electrode and including a sulfide-based solid electrolyte.
Another embodiment provides an all-solid-state battery including a positive electrode; a negative electrode; and the solid electrolyte between the positive electrode and the negative electrode.
Another embodiment provides an all-solid-state battery that includes a positive electrode; a negative electrode; and the double-layer solid electrolyte between the positive electrode and negative electrode; wherein the positive electrode is disposed on the solid electrolyte for the positive electrode of the double-layer solid electrolyte, and the negative electrode is disposed on the solid electrolyte for the negative electrode of the double-layer solid electrolyte.
Another embodiment provides a device including the all-solid-state battery, and the device may be a communication device, a transportation device, or an energy storage device.
Another embodiment provides an electric device including the all-solid-state battery, and the electric device may be an electric vehicle, a hybrid electric vehicle, a plug-in hybrid electric vehicle, or an electric power storage device.
The lithium halide-based nanocomposite may provide an electrolyte that has excellent atmospheric stability as a nanosized compound selected from M1Oc, LiX, and a combination thereof is dispersed in the halide compound, has improved ionic conductivity by activating an interface conduction phenomenon, and can significantly improve an interfacial stability and high-potential cycle stability with a sulfide-based solid electrolyte.
Hereinafter, embodiments will be described in detail so that those skilled in the art can easily implement them. However, a structure actually applied may be implemented in many different forms and is not limited to the implementation described herein.
In the drawings, the thickness of layers, films, panels, regions, etc., are exaggerated for clarity. It will be understood that when an element such as a layer, film, region, or substrate is referred to as being “on” another element, it may be directly on the other element or intervening elements may also be present. In contrast, when an element is referred to as being “directly on” another element, there are no intervening elements present.
In the drawings, parts having no relationship with the description are omitted for clarity of the embodiments, and the same or similar constituent elements are indicated by the same reference numerals throughout the specification.
Hereinafter, the terms “lower” and “upper” are used for better understanding and ease of description, but do not limit the position relationship.
As used herein, “size” means an average particle diameter in the case of a sphere and the length of the longest portion in the case of a non-spherical shape. In addition, the size may be measured by a method well known to those skilled in the art, for example, may be measured by a particle size analyzer, or may be measured by a transmission electron micrograph or a scanning electron micrograph.
In the present inventive concepts, the term “or” is not to be construed as an exclusive meaning, and for example, “A or B” is construed to include A, B, A+B, and/or the like.
As used herein, “at least one of A, B, or C,” “one of A, B, C, or any combination thereof” and “one of A, B, C, and any combination thereof” refer to each constituent element, and any combination thereof (e.g., A; B; C; A and B; A and C; B and C; or A, B, and C).
It will be understood that elements and/or properties thereof may be recited herein as being “the same” or “equal” as other elements, and it will be further understood that elements and/or properties thereof recited herein as being “identical” to, “the same” as, or “equal” to other elements may be “identical” to, “the same” as, or “equal” to or “substantially identical” to, “substantially the same” as or “substantially equal” to the other elements and/or properties thereof. While the term “same,” “equal” or “identical” may be used in description of some example embodiments, it should be understood that some imprecisions may exist. Thus, when one element is referred to as being the same as another element, it should be understood that an element or a value is the same as another element within a desired manufacturing or operational tolerance range (e.g., ±10%).
When the term “about” is used in this specification in connection with a numerical value, it is intended that the associated numerical value includes a manufacturing or operational tolerance (e.g., ±10%) around the stated numerical value. Further, regardless of whether numerical values or shapes are modified as “about” or “substantially,” it will be understood that these values and shapes should be construed as including a manufacturing or operational tolerance (e.g., ±10%) around the stated numerical values or shapes. When ranges are specified, the range includes all values therebetween such as increments of 0.1%.
Hereinafter, unless otherwise defined, “metal” includes a metal and a semimetal.
Hereinafter, a lithium halide-based nanocomposite according to an embodiment is described.
As described above, the existing lithium ion battery has a stability problem due to frequent fire events due to a use of an ignitable organic liquid electrolyte. Accordingly, research is being conducted to solve stability problem by replacing the organic liquid electrolyte with a halide-based solid electrolyte, which is an inorganic solid electrolyte that is not ignitable, and to increase ionic conductivity at the same time.
Therefore, the present invention has been completed by confirming that in order to improve low ionic conductivity and high interfacial resistance of existing halide-based solid electrolytes, a nanosized compound selected from M1Oc, LiX, and a combination thereof is dispersed in a halide compound to form a nanocomposite, thereby improving atmospheric stability and significantly improving interfacial stability and high-potential cycle stability with a sulfide-based solid electrolyte while improving ionic conductivity due to activation of an interfacial conduction phenomenon.
A lithium halide-based nanocomposite according to an embodiment is represented by any one of Chemical Formulas 1A to 1C, in which a nanosized compound selected from M1Oc, LiX, and a combination thereof is dispersed in a halide compound of LiaMzXb.
M1Oc—LiaM2Xb [Chemical Formula 1A]
In Chemical Formula 1A, M1 and M2 are different from each other and are each independently one or more selected from Mg, Ca, Zn, Cd, Cu, Sc, Y, B, Al, Ga, In, Ln (La, Ce, Pr, Nd, Pm, Sm, Eu, Gd, Tb, Dy, Ho, Er, Yb, or Lu), Ti, Zr, Hf, Nb, Ta, Mo, W, Sb, Si, Ge, Sn, V, Cr, Mn, Fe, Co, and Ni, X is Cl, Br, F, or I, and a, b, and c are each independently in the range of 0.01 to 10.
LiX—LiaM2Xb [Chemical Formula 1B]
In Chemical Formula 1B, M2 is one or more selected from Mg, Ca, Zn, Cd, Cu, Sc, Y, B, Al, Ga, In, Ln (La, Ce, Pr, Nd, Pm, Sm, Eu, Gd, Tb, Dy, Ho, Er, Yb, or Lu), Ti, Zr, Hf, Nb, Ta, Mo, W, Sb, Si, Ge, Sn, V, Cr, Mn, Fe, Co, and Ni, X is Cl, Br, F, or I, and a and b are each independently in the range of 0.01 to 10.
M1Oc—LiX—LiaM2Xb [Chemical Formula 1C]
In Chemical Formula 1C, M1 and M2 are different from each other and are each independently one or more selected from Mg, Ca, Zn, Cd, Cu, Sc, Y, B, Al, Ga, In, Ln (La, Ce, Pr, Nd, Pm, Sm, Eu, Gd, Tb, Dy, Ho, Er, Yb, or Lu), Ti, Zr, Hf, Nb, Ta, Mo, W, Sb, Si, Ge, Sn, V, Cr, Mn, Fe, Co, and Ni, X is Cl, Br, F, or I, and a, b, and c are each independently in the range of 0.01 to 10.
In LiaM2Xb of Chemical Formulas 1A to 1C, Xb may be X1b-dX2d wherein X1 and X2 may be different from each other and may each independently be Cl, Br, F, or I, b may be in the range of 0.01 to 10, and d may be in the range of 0.01 to 4.
In LiaM2Xb of Chemical Formulas 1A to 1C, Xb may be Clb-dFd or Clb-dId, b may be in the range of 0.01 to 10, and d may be the range of 0.01 to 4.
In Chemical Formulas 1A to 1C, M1 may be Mg, Zr, Si, Sn, Al, or Y, M2 may be Zr, Y or Mg, X may be Cl, and a, b, and c may each independently be an integer of 1 to 10. For example, specific examples of the lithium halide-based nanocomposite represented by Chemical Formula 1A may be one or more selected from Al2O3-Li2ZrCl6, Y2O3-Li2ZrCl6, ZrO2-Li3YCl6, SiO2-Li2ZrCl6, and SnO2-Li2ZrCl6, and for example, specific examples of the lithium halide-based nanocomposite represented by Chemical Formula 1B may be LiF—Li2ZrCl6 or LiCl—Li2ZrCl6, and specific examples of the lithium halide-based nanocomposite represented by Chemical Formula 1C include LiCl—Al2O3—Li2ZrCl6, LiCl—SiO2-Li2ZrCl6, and LiCl—SnO2-Li2ZrCl6.
The lithium halide-based nanocomposite represented by Chemical Formula 1A may include about 1 to about 20 vol % of M1Oc and about 80 to about 99 vol % of LiaM2Xb, for example about 6 to about 9 vol % of M1Oc and about 91 to about 94 vol % of LiaM2Xb, or for example about 7 to about 8 vol % of M1Oc and about 92 to about 93 vol % of LiaM2Xb. For example, the M1Oc may be included in an amount of greater than or equal to about 1 vol %, greater than or equal to about 2 vol %, greater than or equal to about 3 vol %, greater than or equal to about 4 vol %, greater than or equal to about 5 vol %, greater than or equal to about 6 vol %, or greater than or equal to about 7 vol % and less than or equal to about 20 vol %, less than or equal to about 19 vol %, less than or equal to about 18 vol %, less than or equal to about 17 vol %, less than or equal to about 16 vol %, less than or equal to about 15 vol %, less than or equal to about 14 vol %, less than or equal to about 13 vol %, less than or equal to about 12 vol %, less than or equal to about 11 vol %, less than or equal to about 10 vol %, less than or equal to about 9 vol %, less than or equal to about 8 vol %, or less than or equal to about 7 vol %, and the LiaM2Xb may be included in an amount of greater than or equal to about 80 vol %, greater than or equal to about 81 vol %, greater than or equal to about 82 vol %, greater than or equal to about 83 vol %, greater than or equal to about 84 vol %, greater than or equal to about 85 vol %, greater than or equal to about 86 vol %, greater than or equal to about 87 vol %, greater than or equal to about 88 vol %, greater than or equal to about 89 vol %, greater than or equal to about 90 vol %, or greater than or equal to about 91 vol % and less than or equal to about 99 vol %, less than or equal to about 98 vol %, less than or equal to about 97 vol %, less than or equal to about 96 vol %, less than or equal to about 95 vol %, less than or equal to about 94 vol %, or less than or equal to about 93 vol %, or a combination thereof. Within these ranges, a sufficient interfacial ion conductive phase may be provided and improved ionic conductivity may be secured.
The lithium halide-based nanocomposite represented by Chemical Formula 1B may include about 6 to about 34 vol % of LiX and about 66 to about 94 vol % of LiaM2Xb, for example, about 7 to about 9 vol % of LiX and about 91 to about 93 vol % of LiaM2Xb. For example, the LiX may be included in an amount of greater than or equal to about 6 vol %, greater than or equal to about 7 vol %, or greater than or equal to about 8 vol % and less than or equal to about 34 vol %, less than or equal to about 33 vol %, less than or equal to about 32 vol %, less than or equal to about 31 vol %, less than or equal to about 30 vol %, less than or equal to about 29 vol %, less than or equal to about 28 vol %, less than or equal to about 27 vol %, less than or equal to about 26 vol %, less than or equal to about 25 vol %, less than or equal to about 24 vol %, less than or equal to about 23 vol %, less than or equal to about 22 vol %, less than or equal to about 21 vol %, less than or equal to about 20 vol %, less than or equal to about 19 vol %, less than or equal to about 18 vol %, less than or equal to about 17 vol %, less than or equal to about 16 vol % or less than or equal to about 15 vol % and the LiaM2Xb may be included in an amount of greater than or equal to about 66 vol %, greater than or equal to about 67 vol %, greater than or equal to about 68 vol %, greater than or equal to about 69 vol %, greater than or equal to about 70 vol %, greater than or equal to about 71 vol %, greater than or equal to about 72 vol %, greater than or equal to about 73 vol %, greater than or equal to about 74 vol %, greater than or equal to about 75 vol %, greater than or equal to about 76 vol %, greater than or equal to about 77 vol %, greater than or equal to about 78 vol %, greater than or equal to about 79 vol %, greater than or equal to about 80 vol %, greater than or equal to about 85 vol %, or greater than or equal to about 90 vol % and less than or equal to about 94 vol %, less than or equal to about 93 vol %, or less than or equal to about 92 vol %, or a combination thereof.
Within these ranges, a sufficient interfacial ion conductive phase may be provided and improved ionic conductivity may be secured.
The lithium halide-based nanocomposite represented by Chemical Formula 1C may include about 1 to about 13 vol % of M1Oc, about 1 to about 29 vol % of LiX, and about 65 to about 94 vol % of LiaM2Xb, for example about 2 to about 12 vol % of M1Oc, about 2 to about 25 vol % of LiX, and about 66 to about 93 vol % of LiaM2Xb, for example about 5 to about 12 vol % of M1Oc, about 2 to about 25 vol % of LiX, and about 66 to about 93 vol % of LiaM2Xb, or for example about 8 to about 12 vol % of M1Oc, about 21 to about 25 vol % of LiX, and about 66 to about 68 vol % of LiaM2Xb. For example, the M1Oc may be included in an amount of greater than or equal to about 1 vol %, greater than or equal to about 2 vol %, greater than or equal to about 3 vol %, greater than or equal to about 4 vol %, greater than or equal to about 5 vol %, greater than or equal to about 6 vol %, greater than or equal to about 7 vol %, or greater than or equal to about 8 vol % and less than or equal to about 13 vol %, less than or equal to about 12 vol %, less than or equal to about 11 vol %, or less than or equal to about 10 vol %, the LiX may be included in an amount of greater than or equal to about 1 vol %, greater than or equal to about 2 vol %, greater than or equal to about 3 vol %, greater than or equal to about 4 vol %, greater than or equal to about 5 vol %, greater than or equal to about 6 vol %, greater than or equal to about 7 vol %, greater than or equal to about 8 vol %, greater than or equal to about 9 vol %, greater than or equal to about 10 vol %, greater than or equal to about 15 vol %, or greater than or equal to about 20 vol % and less than or equal to about 29 vol %, less than or equal to about 28 vol %, less than or equal to about 27 vol %, less than or equal to about 26 vol %, or less than or equal to about 25 vol %, and the LiaM2Xb may be included in an amount of greater than or equal to about 65 vol % or greater than or equal to about 66 vol % and less than or equal to about 94 vol %, less than or equal to about 93 vol %, less than or equal to about 92 vol %, less than or equal to about 91 vol %, less than or equal to about 90 vol %, less than or equal to about 85 vol %, less than or equal to about 80 vol %, less than or equal to about 75 vol %, or less than or equal to about 70 vol %, or a combination thereof. Within these ranges, a sufficient interfacial ion conductive phase may be provided and improved ionic conductivity may be secured.
A lithium halide-based nanocomposite according to another embodiment is represented by any one of Chemical Formulas 2A to 2C, in which a nanosized compound selected from M1Oc, LiX, and a combination thereof is dispersed in a halide compound of LiaM2X1b-dX2d.
M1Oc—LiaM2X1b-dX2d [Chemical Formula 2A]
In Chemical Formula 2A, M1 and M2 are the same or different, and are each independently one or more selected from Mg, Ca, Zn, Cd, Cu, Sc, Y, B, Al, Ga, In, Ln (La, Ce, Pr, Nd, Pm, Sm, Eu, Gd, Tb, Dy, Ho, Er, Yb, or Lu), Ti, Zr, Hf, Nb, Ta, Mo, W, Sb, Si, Ge, Sn, V, Cr, Mn, Fe, Co, and Ni, X1 and X2 are different from each other and are each independently Cl, Br, F, or I, a, b, and c are each independently in the range of 0.01 to 10, and d is in the range of 0.01 to 4.
LiX—LiaM2X1b-dX2d [Chemical Formula 2B]
In Chemical Formula 2B, M2 is one or more selected from Mg, Ca, Zn, Cd, Cu, Sc, Y, B, Al, Ga, In, Ln (La, Ce, Pr, Nd, Pm, Sm, Eu, Gd, Tb, Dy, Ho, Er, Yb, or Lu), Ti, Zr, Hf, Nb, Ta, Mo, W, Sb, Si, Ge, Sn, V, Cr, Mn, Fe, Co, and Ni, X is Cl, Br, F, or I, X1 and X2 are different from each other and are each independently Cl, Br, F, or I, a and b are each independently in the range of 0.01 to 10, and d is in the range of 0.01 to 4.
M1Oc—LiX—LiaM2X1b-dX2d [Chemical Formula 2C]
In Chemical Formula 2C, M1 and M2 are each independently one or more selected from Mg, Ca, Zn, Cd, Cu, Sc, Y, B, Al, Ga, In, Ln (La, Ce, Pr, Nd, Pm, Sm, Eu, Gd, Tb, Dy, Ho, Er, Yb, or Lu), Ti, Zr, Hf, Nb, Ta, Mo, W, Sb, Si, Ge, Sn, V, Cr, Mn, Fe, Co, and Ni, X is Cl, Br, F, or I, X1 and X2 are different from each other and are each independently Cl, Br, F, or I, a, b, and c are each independently in the range of 0.01 to 10, and d is in the range of 0.01 to 4.
LiaM2X1b-dX2d in Chemical Formulas 2A to 2C may be LiaM2Clb-dFd or LiaM2Clb-dId wherein a and b may be in the range of 0.01 to 10, and d may be in the range of 0.01 to 4.
In LiaM2X1b-dX2d of Chemical Formulas 2A to 2C, a portion of M2 may be substituted with M3 to be a compound represented by LiaM21-eM3eX1b-dX2d, wherein M2, X1, X2, a, b, and d are the same as in Chemical Formulas 2A to 2C, and M3 may be the same as or different from M1 and may be one or more selected from Mg, Ca, Zn, Cd, Cu, Sc, Y, B, Al, Ga, In, Ln (La, Ce, Pr, Nd, Pm, Sm, Eu, Gd, Tb, Dy, Ho, Er, Yb, or Lu), Ti, Zr, Hf, Nb, Ta, Mo, W, Sb, Si, Ge, Sn, V, Cr, Mn, Fe, Co, and Ni, and e may be in the range of 0.01 to 0.9.
In Chemical Formulas 2A to 2C, M1 may be Zr, Mg, Al, or Y, M2 may be Zr, Mg, Y, or In, and a, b, and c may each independently be in the range of 0.01 to 10. For example, specific examples of the lithium halide-based nanocomposite represented by Chemical Formulas 2A to 2C may include ZrO2-Li2ZrCl5F, ZrO2—Li2ZrCl4.5F15, ZrO2-Li2ZrCl4F2, ZrO2—LiF—Li2ZrCl5F, Al2O3-Li2ZrCl5F.
The lithium halide-based nanocomposite represented by Chemical Formula 2A may include about 1 to about 20 vol % of M1Oc and about 80 to about 99 vol % of LiaM2X1b-dX2d, for example, about 6 to about 9 vol % of M1Oc and about 91 to about 94 vol % of LiaM2X1b-dX2d, or for example, about 7 to about 8 vol % of M1Oc and about 92 to about 93 vol % of LiaM2X1b-dX2d. For example, the M1Oc may be included in an amount of greater than or equal to about 1 vol %, greater than or equal to about 2 vol %, greater than or equal to about 3 vol %, greater than or equal to about 4 vol %, greater than or equal to about 5 vol %, greater than or equal to about 6 vol %, or greater than or equal to about 7 vol % and less than or equal to about 20 vol %, less than or equal to about 19 vol %, less than or equal to about 18 vol %, less than or equal to about 17 vol %, less than or equal to about 16 vol %, less than or equal to about 15 vol %, less than or equal to about 14 vol %, less than or equal to about 13 vol %, less than or equal to about 12 vol %, less than or equal to about 11 vol %, less than or equal to about 10 vol %, less than or equal to about 9 vol %, less than or equal to about 8 vol %, or less than or equal to about 7 vol %, and the LiaM2X1b-dX2d may be included in an amount of greater than or equal to about 80 vol %, greater than or equal to about 81 vol %, greater than or equal to about 82 vol %, greater than or equal to about 83 vol %, greater than or equal to about 84 vol %, greater than or equal to about 85 vol %, greater than or equal to about 86 vol %, greater than or equal to about 87 vol %, greater than or equal to about 88 vol %, greater than or equal to about 89 vol %, greater than or equal to about 90 vol %, or greater than or equal to about 91 vol % and less than or equal to about 99 vol %, less than or equal to about 98 vol %, less than or equal to about 97 vol %, less than or equal to about 96 vol %, less than or equal to about 95 vol %, less than or equal to about 94 vol % or less than or equal to about 93 vol %, or a combination thereof. Within these ranges, a sufficient interfacial ion conductive phase may be provided and improved ionic conductivity may be secured.
The lithium halide-based nanocomposite represented by Chemical Formula 2B may include about 6 to about 34 vol % of LiX and about 66 to about 94 vol % of LiaM2X1b-dX2d, or for example, about 7 to about 9 vol % of LiX and about 91 to about 93 vol % of LiaM2X1b-dX2d. For example, the LiX may be included in an amount of greater than or equal to about 6 vol %, greater than or equal to about 7 vol %, or greater than or equal to about 8 vol % and less than or equal to about 34 vol %, less than or equal to about 33 vol %, less than or equal to about 32 vol %, less than or equal to about 31 vol %, less than or equal to about 30 vol %, less than or equal to about 29 vol %, less than or equal to about 28 vol %, less than or equal to about 27 vol %, less than or equal to about 26 vol %, less than or equal to about 25 vol %, less than or equal to about 24 vol %, less than or equal to about 23 vol %, less than or equal to about 22 vol %, less than or equal to about 21 vol %, less than or equal to about 20 vol %, less than or equal to about 19 vol %, less than or equal to about 18 vol %, less than or equal to about 17 vol %, less than or equal to about 16 vol %, or less than or equal to about 15 vol %, and the LiaM2X1b-dX2d may be included in an amount of greater than or equal to about 66 vol %, greater than or equal to about 67 vol %, greater than or equal to about 68 vol %, greater than or equal to about 69 vol %, greater than or equal to about 70 vol %, greater than or equal to about 71 vol %, greater than or equal to about 72 vol %, greater than or equal to about 73 vol %, greater than or equal to about 74 vol %, greater than or equal to about 75 vol %, greater than or equal to about 76 vol %, greater than or equal to about 77 vol %, greater than or equal to about 78 vol %, greater than or equal to about 79 vol %, greater than or equal to about 80 vol %, greater than or equal to about 85 vol %, or greater than or equal to about 90 vol % and less than or equal to about 94 vol %, less than or equal to about 93 vol %, or less than or equal to about 92 vol %, or a combination thereof. Within these ranges, a sufficient interfacial ion conductive phase may be provided and improved ionic conductivity may be secured.
The lithium halide-based nanocomposite represented by Chemical Formula 2C may include about 1 to about 13 vol % of M1Oc, about 1 to about 29 vol % of LiX, and about 65 to about 94 vol % of LiaM2X1b-dX2d, for example, about 2 to about 12 vol % of M1Oc, about 2 to about 25 vol % of LiX, and about 66 to about 93 vol % of LiaM2X1b-dX2d, for example about 5 to about 12 vol % of M1Oc, about 2 to about 25 vol % of LiX, and about 66 to about 93 vol % of LiaM2X1b-dX2d, or for example, about 8 to about 12 vol % of M1Oc, about 21 to about 25 vol % of LiX, and about 66 to about 68 vol % of LiaM2X11-dX2d. For example, the M1Oc may be included in an amount of greater than or equal to about 1 vol %, greater than or equal to about 2 vol %, greater than or equal to about 3 vol %, greater than or equal to about 4 vol %, greater than or equal to about 5 vol %, greater than or equal to about 6 vol %, greater than or equal to about 7 vol %, or greater than or equal to about 8 vol % and less than or equal to about 13 vol %, less than or equal to about 12 vol %, less than or equal to about 11 vol %, or less than or equal to about 10 vol %, the LiX may be included in an amount of greater than or equal to about 1 vol %, greater than or equal to about 2 vol %, greater than or equal to about 3 vol %, greater than or equal to about 4 vol %, greater than or equal to about 5 vol %, greater than or equal to about 6 vol %, greater than or equal to about 7 vol %, greater than or equal to about 8 vol %, greater than or equal to about 9 vol %, greater than or equal to about 10 vol %, greater than or equal to about 15 vol %, or greater than or equal to about 20 vol % and less than or equal to about 29 vol %, less than or equal to about 28 vol %, less than or equal to about 27 vol %, less than or equal to about 26 vol %, or less than or equal to about 25 vol %, and the LiaM2X1b-dX2d may be included in an amount of greater than or equal to about 65 vol % or greater than or equal to about 66 vol % and less than or equal to about 94 vol %, less than or equal to about 93 vol %, less than or equal to about 92 vol %, less than or equal to about 91 vol %, less than or equal to about 90 vol %, less than or equal to about 85 vol %, less than or equal to about 80 vol %, less than or equal to about 75 vol %, or less than or equal to about 70 vol % or a combination thereof. Within these ranges, a sufficient interfacial ion conductive phase may be provided and improved ionic conductivity may be secured.
Another embodiment provides a lithium halide-based nanocomposite represented by any one of Chemical Formulas 3A to 3C, in which a nanosized compound selected from M1Oc, LiX, and a combination thereof is dispersed in a halide compound of LiaM21-eM3eXb.
M1Oc—LiaM21-eM3eXb [Chemical Formula 3A]
In Chemical Formula 3A, M1, M2, and M3 are each independently one or more selected from Mg, Ca, Zn, Cd, Cu, Sc, Y, B, Al, Ga, In, Ln (La, Ce, Pr, Nd, Pm, Sm, Eu, Gd, Tb, Dy, Ho, Er, Yb, or Lu), Ti, Zr, Hf, Nb, Ta, Mo, W, Sb, Si, Ge, Sn, V, Cr, Mn, Fe, Co, and Ni, X is Cl, Br, F, or I, M2 and M3 are different from each other, a, b, and c are each independently in the range of 0.01 to 10, and e is in the range of 0.01 to 0.9.
LiX—LiaM21-eM3eXb [Chemical Formula 3B]
In Chemical Formula 3B, M2 and M3 are different from each other and are each independently one or more selected from Mg, Ca, Zn, Cd, Cu, Sc, Y, B, Al, Ga, In, Ln (La, Ce, Pr, Nd, Pm, Sm, Eu, Gd, Tb, Dy, Ho, Er, Yb, or Lu), Ti, Zr, Hf, Nb, Ta, Mo, W, Sb, Si, Ge, Sn, V, Cr, Mn, Fe, Co, and Ni, X is Cl, Br, F, or I, a and b are each independently in the range of 0.01 to 10, and e is in the range of 0.01 to 0.9.
M1Oc—LiX—LiaM21-eM3eXb [Chemical Formula 3C]
In Chemical Formula 3C, M1, M2, and M3 are each independently one or more selected from Mg, Ca, Zn, Cd, Cu, Sc, Y, B, Al, Ga, In, Ln (La, Ce, Pr, Nd, Pm, Sm, Eu, Gd, Tb, Dy, Ho, Er, Yb, or Lu), Ti, Zr, Hf, Nb, Ta, Mo, W, Sb, Si, Ge, Sn, V, Cr, Mn, Fe, Co, and Ni, X is Cl, Br, F, or I, a, b, and c are each independently in the range of 0.01 to 10, and e is in the range of 0.01 to 0.9.
In LiaM21_eM3eXb of Chemical Formulas 3A to 3C, Xb may be X1b-dX2d wherein X1 and X2 may be different from each other and may each independently be Cl, Br, F, or I, b may be in the range of 0.01 to 10, and d may be in the range of 0.01 to 4.
In LiaM21-eM3eXb of Chemical Formulas 3A to 3C, Xb may be Clb-dFd or Clb-dId, wherein b may be in the range of 0.01 to 10, and d may be in the range of 0.01 to 4.
In Chemical Formulas 3A to 3C, M1 may be Zr, Mg, Al, or Y, M2 may be Zr or Mg, M3 may be Fe or Y, X may be Cl, and a, b, and c may each independently be in the range of 0.01 to 10. For example, specific examples of the lithium halide-based nanocomposite represented by Chemical Formulas 3A to 3C may be ZrO2—Li2Zr0.9Fe0.1Cl6 or ZrO2-Li2Zr0.75Y0.25Cl6.
The lithium halide-based nanocomposite represented by Chemical Formula 3A may include about 1 to about 20 vol % of M1Oc and about 80 to about 99 vol % of LiaM21-eM3eXb, for example, about 6 to about 9 vol % of M1Oc and about 91 to about 94 vol % of LiaM21_eM3eXb, or for example, about 7 to about 8 vol % of M1Oc and about 92 to about 93 vol % of LiaM21-eM3eXb. For example, the M1Oc may be included in an amount of greater than or equal to about 1 vol %, greater than or equal to about 2 vol %, greater than or equal to about 3 vol %, greater than or equal to about 4 vol %, greater than or equal to about 5 vol %, greater than or equal to about 6 vol %, or greater than or equal to about 7 vol % and less than or equal to about 20 vol %, less than or equal to about 19 vol %, less than or equal to about 18 vol %, less than or equal to about 17 vol %, less than or equal to about 16 vol %, less than or equal to about 15 vol %, less than or equal to about 14 vol %, less than or equal to about 13 vol %, less than or equal to about 12 vol %, less than or equal to about 11 vol %, less than or equal to about 10 vol %, less than or equal to about 9 vol %, less than or equal to about 8 vol %, or less than or equal to about 7 vol %, and the LiaM21-eM3eXb may be included in an amount of greater than or equal to about 80 vol %, greater than or equal to about 81 vol %, greater than or equal to about 82 vol %, greater than or equal to about 83 vol %, greater than or equal to about 84 vol %, greater than or equal to about 85 vol %, greater than or equal to about 86 vol %, greater than or equal to about 87 vol %, greater than or equal to about 88 vol %, greater than or equal to about 89 vol %, greater than or equal to about 90 vol %, or greater than or equal to about 91 vol % and less than or equal to about 99 vol %, less than or equal to about 98 vol %, less than or equal to about 97 vol %, less than or equal to about 96 vol %, less than or equal to about 95 vol %, less than or equal to about 94 vol %, or less than or equal to about 93 vol %, or a combination thereof. Within these ranges, a sufficient interfacial ion conductive phase may be provided and improved ionic conductivity may be secured.
The lithium halide-based nanocomposite represented by Chemical Formula 3B may include about 6 to about 34 vol % of LiX and about 66 to about 94 vol % of LiaM21-eM3eXb, or for example, about 7 to about 9 vol % of LiX and about 91 to about 93 vol % of LiaM21-eM3eXb. For example, the LiX may be included in an amount of greater than or equal to about 6 vol %, greater than or equal to about 7 vol %, or greater than or equal to about 8 vol % and less than or equal to about 34 vol %, less than or equal to about 33 vol %, less than or equal to about 32 vol %, less than or equal to about 31 vol %, less than or equal to about 30 vol %, less than or equal to about 29 vol %, less than or equal to about 28 vol %, less than or equal to about 27 vol %, less than or equal to about 26 vol %, less than or equal to about 25 vol %, less than or equal to about 24 vol %, less than or equal to about 23 vol %, less than or equal to about 22 vol %, less than or equal to about 21 vol %, less than or equal to about 20 vol %, less than or equal to about 19 vol %, less than or equal to about 18 vol %, less than or equal to about 17 vol %, less than or equal to about 16 vol %, or less than or equal to about 15 vol % and the LiaM21-eM3Xb may be included in an amount of greater than or equal to about 66 vol %, greater than or equal to about 67 vol %, greater than or equal to about 68 vol %, greater than or equal to about 69 vol %, greater than or equal to about 70 vol %, greater than or equal to about 71 vol %, greater than or equal to about 72 vol %, greater than or equal to about 73 vol %, greater than or equal to about 74 vol %, greater than or equal to about 75 vol %, greater than or equal to about 76 vol %, greater than or equal to about 77 vol %, greater than or equal to about 78 vol %, greater than or equal to about 79 vol %, greater than or equal to about 80 vol %, greater than or equal to about 85 vol %, or greater than or equal to about 90 vol % and less than or equal to about 94 vol %, less than or equal to about 93 vol %, or less than or equal to about 92 vol %, or a combination thereof. Within these ranges, a sufficient interfacial ion conductive phase may be provided and improved ionic conductivity may be secured.
The lithium halide-based nanocomposite represented by Chemical Formula 3C may include about 1 to about 13 vol % of M1Oc, about 1 to about 29 vol % of LiX, and about 65 to about 94 vol % of LiaM21-eM3eXb, for example, about 2 to about 12 vol % of M1Oc, about 2 to about 25 vol % of LiX, and about 66 to about 93 vol % of LiaM21-eM3eXb, for example about 5 to about 12 vol % of M1Oc, about 2 to about 25 vol % of LiX, and about 66 to about 93 vol % of LiaM21-eM3eXb, or for example about 8 to about 12 vol % of M1Oc, about 21 to about 25 vol % of LiX, and about 66 to about 68 vol % of LiaM21-eM3eXb. For example, the M1Oc may be included in an amount of greater than or equal to about 1 vol %, greater than or equal to about 2 vol %, greater than or equal to about 3 vol %, greater than or equal to about 4 vol %, greater than or equal to about 5 vol %, greater than or equal to about 6 vol %, greater than or equal to about 7 vol %, or greater than or equal to about 8 vol % and less than or equal to about 13 vol %, less than or equal to about 12 vol %, less than or equal to about 11 vol %, or less than or equal to about 10 vol %, the LiX may be included in an amount of greater than or equal to about 1 vol %, greater than or equal to about 2 vol %, greater than or equal to about 3 vol %, greater than or equal to about 4 vol %, greater than or equal to about 5 vol %, greater than or equal to about 6 vol %, greater than or equal to about 7 vol %, greater than or equal to about 8 vol %, greater than or equal to about 9 vol %, greater than or equal to about 10 vol %, greater than or equal to about 15 vol %, or greater than or equal to about 20 vol % and less than or equal to about 29 vol %, less than or equal to about 28 vol %, less than or equal to about 27 vol %, less than or equal to about 26 vol %, or less than or equal to about 25 vol %, and the LiaM21-eM3eXb may be included in an amount of greater than or equal to about 65 vol % or greater than or equal to about 66 vol % and less than or equal to about 94 vol %, less than or equal to about 93 vol %, less than or equal to about 92 vol %, less than or equal to about 91 vol %, less than or equal to about 90 vol %, less than or equal to about 85 vol %, less than or equal to about 80 vol %, less than or equal to about 75 vol %, or less than or equal to about 70 vol % or a combination thereof. Within these ranges, a sufficient interfacial ion conductive phase may be provided and improved ionic conductivity may be secured.
The lithium halide-based nanocomposite is a composite including a nanosized compound selected from M1Oc, LiX, and a combination thereof and a halide compound (LiaM2Xb, LiaM2X1b-dX2d, or LiaM21_eM3eXb). The “nanosized” means a size of several nanometers to hundreds of nanometers, and specifically means having a size of greater than or equal to about 0.1 nm and less than or equal to about 100 nm, for example, less than or equal to about 50 nm, less than or equal to about 40 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 the above, the size means a diameter in the case of a particle shape and the longest length in the case of an irregular shape. The particle size of the nanosized compound selected from M1Oc, LiX, and the combination thereof may be obtained as a result of transmission electron microscopy (TEM) analysis.
The nanosized compound selected from M1Oc, LiX, and the combination thereof may be located at a grain boundary of a halide compound.
The nanosized compound selected from M1Oc, LiX, and the combination thereof may be in-situ grown into crystalline particles when forming a nanocomposite. These nanosized compounds may be formed in a network (reticular) shape inside a halide compound (LiaM2Xb, LiaM2X1b-dX2d, or LiaM21-eM3eXb).
By growing the nanosized compound into particles of a certain size or less, aggregation of particles may not occur and improved dispersibility in the halide compound may be maintained. In an embodiment, the nanosized compound may be ZrO2, and may have an average crystal size of about 5 to about 10 nm.
The nanosized compound (e.g., ZrO2) may be grown in-situ by mechanical milling of raw materials of the nanocomposite, and may improve ionic conductivity of the nanocomposite by increasing the active interfacial ion conduction, and provide excellent dispersibility and uniformity because agglomeration does not occur. Accordingly, interfacial stability and cycle stability between the sulfide-based solid electrolyte and the halide-based solid electrolyte may be increased.
The nanosized compound and the halide compound of the lithium halide-based nanocomposite may provide high ionic conductivity by generating a space charge layer phenomenon at a solid electrolyte interface. In addition, the lithium halide-based nanocomposite may prevent direct contact between the halide-based solid electrolyte and the sulfide-based solid electrolyte, thereby suppressing a side reaction occurring at the interface in a high-temperature and high-voltage environment, and further improving cycle stability at a high potential.
The lithium halide-based nanocomposite may have an ionic conductivity of about 0.1 to about 5 mS/cm, for example about 0.7 to about 3 mS/cm, about 1.17 to about 2 mS/cm, or about 1.28 to about 1.33 mS/cm at 30° C.
The lithium halide-based nanocomposite shows a crystal phase through X-ray diffraction analysis (XRD) and may have a glass-ceramic crystal structure. The glass-ceramic crystal structure has an X-ray diffraction pattern consistent with the X-ray diffraction result of the hexagonal close-packed (hcp) trigonal Li2ZrCl6 (space group: P-3 ml), and there is a possibility of low crystallinity and structural distortion due to the broad peak. In particular, when the volume ratio of lithium halide and metal oxide increases, the X-ray diffraction pattern of the hexagonal close-packed (hcp) trigonal Li2ZrCl6 (space group: P-3 ml) decreases and a lithium halide-based X-ray diffraction pattern may be exhibited.
In addition, the lithium halide-based nanocomposite may exhibit a first effective peak and a second effective peak in the ranges of about 0.4 to about 0.6 ppm and about −0.2 to about 0.2 ppm, respectively, in a 6Li MAS NMR analysis result, and an intensity ratio of the first effective peak to the second effective peak may be about 0.7 to about 0.8. In particular, the first effective peak means that interfacial lithium ion conduction has occurred.
Hereinafter, a method for preparing a lithium halide-based nanocomposite is described.
The lithium halide-based nanocomposite represented by any one of Chemical Formulas 1A to 1C may be prepared by the following method using compounds in which M1 and M2 are different from each other.
First, a solid-phase reaction of a lithium-containing oxidizing agent and a first metal (M1)-containing halide is performed under an inert gas atmosphere to obtain first metal (M1) oxide and a lithium halide, and
The lithium-containing oxidizing agent may be a lithium-containing salt and may be selected from Li2O, Li2CO3, Li2SO4, and LiNO3.
The lithium-containing oxidizing agent may function as an oxidizing agent because it contains oxygen. That is, the lithium-containing oxidizing agent reacts with the metal halide to generate metal oxide and lithium halide, and these products form a space charge layer at the interface of the solid electrolyte to improve the ionic conductivity of the lithium halide-based nanocomposite. Furthermore, the metal oxide and the lithium halide prevent direct contact between the halide-based solid electrolyte and the sulfide-based solid electrolyte, thereby suppressing a side reaction at the interface between the halide-based solid electrolyte and the sulfide-based solid electrolyte at high temperature and high voltage.
The first metal (M1)-containing halide is abundant in the earth's crust and contains an inexpensive element, thereby preparing a low-cost solid electrolyte. The first metal (M1)-containing halide may be appropriately selected according to the type of the first metal (M1), and specific examples thereof may be one or more selected from TiCl4, TiBr4, ZrCl4, ZrBr4, HfCl4, and HfBr4.
The lithium halide may be one or more selected from LiCl, LiBr, LiF, and LiI.
When the lithium-containing oxidizing agent is Li2O, the first metal (M1)-containing halide is AlCl3 and the second metal (M2)-containing halide is ZrCl4, the preparation method may be represented by Reaction Schemes 1A and 1B:
3Li2O+2AlCl3→6LiCl+Al2O3 [Reaction Scheme 1A]
6aLiC1+aAl2O3+bZrCl4→aAl2O3+(6a−2b)LiCl+bLi2ZrCl6 [Reaction Scheme 1B]
In Reaction Scheme 1B, a is in the range of 0≤a≤6 and b is in the range of 0≤b≤6.
In Reaction Scheme 1A, Li2O oxidizes AlCl3 to form LiCl and in-situ grown Al2O3, and Al2O3, LiCl, and ZrCl4 react to form Li2ZrCl6. The resulting LiCl, in-situ grown Al2O3 and Li2ZrCl6 are combined to form a lithium halide-based nanocomposite having an Al2O3—LiCl—Li2ZrCl6 structure.
When the metal oxides (e.g., Al2O3, SiO2, SnO2, and ZrO2) grown in-situ in the lithium halide-based nanocomposite react with the halide-based solid electrolyte, an ionic conductivity may increase at the interface of the solid electrolyte when reacting with a halide-based solid electrolyte and a reactivity is reduced at high voltage when reacting with a sulfide-based solid electrolyte to manufacture an all-solid-state battery having a high energy density. The inert gas may be at least one selected from argon, helium, neon, and nitrogen.
The solid-phase mixing may be performed by any one of mechanical milling selected from ball mill, vibration mill, turbo mill, mechanofusion, and disk mill, and in an embodiment, the solid-phase mixing may be desirably performed by ball mill or vibration mill. The lithium halide-based nanocomposites obtained through such mechanical milling may improve ionic conductivity by about 2 to about 10 times compared to conventional halide-based solid electrolyte materials.
The mechanical milling may be performed for about 10 to about 50 hours at a rotational speed of about 300 to about 800 rpm, for example for about 7 to about 18 hours at a rotational speed of about 500 to about 700 rpm, or for example for about 9 to about 11 hours at a rotational speed of about 580 to about 620 rpm.
A method for preparing the lithium halide-based nanocomposite represented by any one of Chemical Formulas 2A to 2C is as follows.
In the case of the lithium halide-based nanocomposite in which M1 and M2 are the same in Chemical Formulas 2A to 2C, a lithium-containing oxidizing agent; a first halide of the first metal (M1) or the second metal (M2) and a second halide of the first metal (M1) or the second metal (M2); and a lithium-containing first halide and a lithium-containing second halide are subjected to a solid-phase reaction under an inert gas atmosphere.
The lithium halide-based nanocomposite in Chemical Formulas 2A to 2C where M1 and M2 are different from each other may be prepared as follows: a lithium-containing oxidizing agent, a first metal (M1)-containing first halide, and a first metal (M1)-containing second halide may be subjected to a solid-phase reaction under an inert gas atmosphere to obtain a first metal (M1) oxide, a lithium-containing first halide, and a lithium-containing second halide; and the first metal (M1) oxide, lithium-containing first halide, lithium-containing second halide, a second metal (M2)-containing first halide, and a second metal (M2)-containing second halide may be subjected to a solid-phase reaction.
The lithium-containing oxidizing agent, solid-phase mixing, and mechanical milling are as described above.
The first halide of the first metal (M1) or the second metal (M2) and the second halide of the first metal (M1) or the second metal (M2) may be the first halide including the first metal (M1) or the second metal (M2) or the second halide including the first metal (M1) or the second metal (M2) and may be appropriately selected according to the type of the first metal (M1) or the second metal (M2).
A method for preparing the lithium halide-based nanocomposite represented by any one of Chemical Formulas 3A to 3C is as follows.
In the case of the lithium halide-based nanocomposite in Chemical Formulas 3A to 3C where M1 and M2 are the same, a lithium-containing oxidizing agent, a first metal (M1)-containing halide, and a lithium halide are subjected to a solid-phase reaction under an inert gas atmosphere to obtain the lithium halide-based nanocomposite in which M1 and M2 are same in Chemical Formulas 1A to 1C, and
In the case of the lithium halide-based nanocomposite in Chemical Formulas 3A to 3C where M1 and M2 are different from each other, a lithium-containing oxidizing agent and a first metal (M1)-containing halide and optionally a lithium halide are subjected to a solid-phase reaction under an inert gas atmosphere to obtain a first metal (M1) oxide and a lithium halide, and the first metal (M1) oxide, lithium halide, and second metal (M2)-containing halide are subjected to a solid-phase reaction to obtain a lithium halide-based nanocomposites in which M1 and M2 are different from each other in Chemical Formulas 1A to 1C, and
The lithium-containing oxidizing agent, solid-phase mixing, and mechanical milling are as described above.
The first metal (M1)-containing halide, second metal (M2)-containing halide, and third metal (M3)-containing halide contain abundant and inexpensive elements in the earth's crust to prepare a low-cost solid electrolyte. The first metal (M1)-containing halide, the second metal (M2)-containing halide and the third metal (M3)-containing halide may be appropriately selected according to the first metal (M1), the second metal (M2), and the third metal (M3).
The lithium halide may be at least one selected from LiCl, LiBr, LiF, and LiI.
Hereinafter, a positive electrode active material including the nanocomposite is described.
A positive electrode active material according to an embodiment includes a core including a composite metal oxide capable of reversibly intercalating/deintercalating lithium; and a shell on the core and including the lithium halide-based nanocomposite.
A sulfide-based solid electrolyte has attracted much attention as materials suitable for all-solid-state batteries due to their high ionic conductivity and brittle mechanical properties, but are electrochemically unstable. The sulfide-based solid electrolyte may cause serious side reactions when in direct contact with the 4V-class positive electrode active material. Recently, in order to prevent direct contact between the sulfide-based solid electrolyte and the 4V-class positive electrode active material, research on making an oxide-based solid electrolyte in a shell form for the positive electrode active material is being developed.
However, although the oxide-based solid electrolyte shell can suppress side reactions of the sulfide-based solid electrolyte, it acts as a resistance layer inside the all-solid-state battery due to its low ionic conductivity, causing deterioration in the performance of the all-solid-state battery. In the above embodiment, by replacing the oxide-based solid electrolyte shell with the lithium halide-based nanocomposite shell according to an embodiment to form a positive electrode active material, side reactions between the positive electrode active material and the sulfide-based solid electrolyte may be suppressed and at the same time an internal resistance of the all-solid-state battery may be minimized due to improved ionic conductivity to manufacture an all-solid-state battery with excellent performance.
Provided is a solid electrolyte for a rechargeable lithium battery including the lithium halide-based nanocomposite according to an embodiment and a sulfide-based solid electrolyte.
The sulfide-based solid electrolyte may be Li7+x-yMx4+M1-x5+S6-yXy (M4+: Si, Ge, S or Sn; M5+: P, Sb; X: Cl, Br, or I, 0≤x≤1, and 0≤y≤2), Li10+a[GebM4+1-b]1+aP2aS12-cXc (M4+: Si or Sn; X: Cl, Br, or I, 0≤a≤2, 0≤b≤1, and 0≤c≤4), or a mixture thereof, but is not limited thereto.
A specific example of Li7+x-yMx4+M1-x5+S6-yXy may be Li6PS5Cl, and a specific example of Li10+a[GebM4+1-b]1+aP2aS12-cXc may be Li9.54Si1.74P1.44S11.7Cl0.3.
In addition, provided is a double-layer solid electrolyte for a rechargeable lithium battery including a solid electrolyte for a positive electrode including a lithium halide-based nanocomposite according to an embodiment; and a solid electrolyte for a negative electrode disposed on the solid electrolyte for the positive electrode and including a sulfide-based solid electrolyte.
The above-described solid electrolyte includes the halide-based nanocomposites, and thus it has no problem of generating hydrogen sulfide, and has excellent oxidation stability like oxides and may be usefully applied to all-solid-state batteries. In particular, since the double-layer solid electrolyte includes the lithium halide-based nanocomposite, interfacial side reactions between the solid electrolyte for the positive electrode and the solid electrolyte for the negative electrode can be solved in an all-solid-state battery, and excellent cycle stability can be exhibited.
In addition, provided is an all-solid-state battery including a positive electrode; a negative electrode; and the aforementioned solid electrolyte between the positive electrode and negative electrode.
Hereinafter, an all-solid-state battery is described with reference to
The solid electrolyte layer 300 may include the lithium halide-based nanocomposite and the sulfide-based solid electrolyte.
An all-solid-state battery according to an embodiment includes a positive electrode; a negative electrode; and the aforementioned double-layer solid electrolyte between the positive electrode and negative electrode, wherein the positive electrode is disposed on the solid electrolyte for the positive electrode of the double-layer solid electrolyte, and the negative electrode is disposed on the solid electrolyte for the negative electrode
The double-layer solid electrolyte may include a solid electrolyte for a positive electrode including the lithium halide-based nanocomposite; and a solid electrolyte for a negative electrode disposed on the solid electrolyte for a positive electrode and including a sulfide-based solid electrolyte of the double-layer solid electrolyte.
Also, as a device including an all-solid-state battery according to an embodiment, the device may be any one selected from a communication device, a transportation device, and an energy storage device.
Also, as an electric device including an all-solid-state battery according to an embodiment, the electric device may be one selected from electric vehicles, hybrid electric vehicles, plug-in hybrid electric vehicles, and power storage devices.
The metal oxide (e.g., Al2O3) grown in-situ in the lithium halide-based nanocomposite increases ionic conductivity at the interface of the solid electrolyte when reacting with a halide-based solid electrolyte, and decreases reactivity at high voltage when reacting with a sulfide-based solid electrolyte, resulting in providing an all-solid-state battery having a high energy density.
The inert gas may be at least one selected from argon, helium, neon, and nitrogen, and in an embodiment, argon or helium may be desirable, or argon may be more desirable.
The solid-phase mixing may be performed by any one mechanical milling selected from ball mill, vibration mill, turbo mill, mechanofusion and disc mill, desirably a ball mill or a vibration mill, and more desirably a ball mill. The halide-based nanocomposite obtained through such mechanical milling can improve ionic conductivity by about 2 to 10 times compared to conventional halide-based solid electrolyte materials.
The mechanical milling may be performed for about 10 to about 50 hours at a rotational speed of about 300 to about 800 rpm, desirably for about 7 to about 18 hours at a rotational speed of about 500 to about 700 rpm, and more desirably for about 9 to about 11 hours at a rotational speed of about 580 to about 620 rpm.
Hereinafter, various examples and experimental examples of the present invention will be described in detail. However, the following examples are merely some examples of the present invention, and the present invention should not be construed as being limited to the following examples.
A lithium-containing oxidizing agent (A) and first metal halide precursor (B) were put in a mole ratio (A:B) shown in Table 1 and then, mechanically milled by using Pulverisette 7 PL (Fritsch GmbH) under an Ar atmosphere in a 50 ml ZrO2 vial with 15 ZrO2 balls (Φ=10 mm) at 600 rpm for 20 hours, preparing a first metal oxide (C1) and a lithium halide (C2) (first step).
The first metal oxide (C1), the lithium halide (C2), and a second metal halide precursor (D) were put in a mole ratio ((C1+C2):D) shown in Table 1 and then, mechanically milled by using Pulverisette 7 PL (Fritsch GmbH) under the Ar atmosphere in a 50 ml ZrO2 vial with 15 ZrO2 balls (Φ=10 mm) at 600 rpm for 20 hours, preparing a lithium halide-based nanocomposite represented by one of Chemical Formulae 1A to 1C (second step). The prepared lithium halide-based nanocomposites are shown in Table 1.
The lithium halide-based nanocomposites according to Synthesis Examples 1-1 to 1-9 were measured with respect to ionic conductivity in the following method. In a glove box under an argon atmosphere, each sample was weighed and placed in a polyetheretherketone tube (a PEEK tube with an interior diameter of 13 mm, an exterior diameter of 32 mm, and a height of 10 mm) and the PEEK tube was inserted so that upper and lower portions of the PEEK tube contact a powder-molding jig containing Ti. Subsequently, the samples were pressed into pellets with a diameter of 13 mm and any thickness at a molding pressure of about 370 MPa by using a single screw press. Then, the obtained pellets were placed in a sealed electrochemical cell capable of maintaining the argon atmosphere.
The ionic conductivity was measured by using an impedance/gain phase analyzer (SP-300, BioLogic) as a frequency response analyzer (FRA) and a small environmental tester as a constant temperature device. The measurement was started from a high frequency region at an AC voltage of 10 mV to 100 mV within a frequency range of 10 Hz to 7 MHz at a temperature of 30° C.
Herein, the results of Synthesis Examples 1-2 to 1-9 are shown in Table 2.
Referring to Table 2, the lithium halide-based nanocomposites according to Synthesis Examples 1-2 to 1-9 exhibited improved ionic conductivity.
A metal halide precursor was added to a lithium-containing oxidizing agent in a mole ratio shown in Table 3 and mechanically milled by using Pulverisette 7 PL (Fritsch GmbH) under an Ar atmosphere in a 50 ml ZrO2 vial with 15 ZrO2 balls (ϕ=10 mm) at 600 rpm for 20 hours, preparing each lithium halide-based nanocomposite represented by Chemical Formulas 2A to 2C. The prepared lithium halide-based nanocomposites are shown in Table 3. For comparison, lithium halide-based composites having each composition of Comparative Synthesis Examples 1 and 2-1 to 2-4 are described.
The lithium halide-based composites or the lithium halide-based nanocomposites were measured with respect to ionic conductivity in the following method. In a glove box under an argon atmosphere, samples were weighed and placed in a polyetheretherketone tube (a PEEK tube with an interior diameter of 13 mm, an exterior diameter of 32 mm, and a height of 10 mm) and then, the PEEK tube was inserted so that upper and lower portions of the PEEK tube contact a powder-molding jig containing Ti. Subsequently, the samples were pressed into pellets with a diameter of 13 mm and any thickness by using a single screw press at a molding pressure of about 370 MPa. The obtained pellets were placed in the sealed electrochemical cell capable of maintaining the argon atmosphere.
The ionic conductivity was measured by using an impedance/gain phase analyzer (SP-300, BioLogic) as a frequency response analyzer (FRA) and a small environmental tester as a constant temperature device. The measurement was started from a high frequency region at an AC voltage of 10 mV to 100 mV within a frequency range of 10 Hz to 7 MHz at a temperature of 30° C.
Herein, the results of Synthesis Examples 2-1 to 2-3 are shown in Table 4. For comparison, the results of Comparative Synthesis Examples 1 and 2-1 to 2-4 are also described.
Referring to Table 4, the lithium halide-based nanocomposites according to Synthesis Examples 2-1 to 2-3 exhibited improved ionic conductivity, compared with the lithium halide-based composites according to Comparative Synthesis Examples 1 and 2-1 to 2-4.
represented by any one of Chemical Formulas 3A to 3C and measurement of ionic conductivity A lithium-containing oxidizing agent (A), first metal halide (B), and lithium halide (C1) were put in a mole ratio (A:B:C1) shown in Table 5 and then, mechanically milled by using Pulverisette 7 PL (Fritsch GmbH) under an Ar atmosphere in a 50 ml ZrO2 vial with 15 ZrO2 balls (Φ=10 mm) at 600 rpm for 20 hours, preparing lithium halide-based nanocomposite (D) represented by one of Chemical Formulas 1A to 1C (first step).
The halide-based nanocomposite powder (D) represented by one of Chemical Formulas 1A to 1C, third metal halide (E1), and lithium halide (C2) were put in a mole ratio shown in Table 5 and then, mechanically milled by using Pulverisette 7 PL (Fritsch GmbH) under an Ar atmosphere in a 50 ml ZrO2 vial with 15 ZrO2 balls (Φ=10 mm) at 600 rpm for 20 hours, preparing lithium a halide-based nanocomposite represented by one of Chemical Formulae 3A to 3C (second step).
The lithium halide-based nanocomposites according to Synthesis Examples 3-1 to 3-7 were measured with respect to ionic conductivity in the following method. In a glove box under an argon atmosphere, each sample was weighed and placed in a polyetheretherketone tube (a PEEK tube with an interior diameter of 13 mm, an exterior diameter of 32 mm, and a height of 10 mm), and the PEEK tube was inserted so that upper and lower portions of the PEEK tube contact a powder-molding jig containing Ti. Subsequently, the samples were pressed into pellets with a diameter of 13 mm and any thickness by using a single screw press at a molding pressure of about 370 MPa. Then, the obtained pellets were placed in a sealed electrochemical cell capable of maintaining the argon atmosphere.
The ionic conductivity was measured by using an impedance/gain phase analyzer (SP-300, BioLogic) as a frequency response analyzer (FRA) and a small environmental tester as a constant temperature device. The measurement was started from a high frequency region at an AC voltage of 10 mV to 100 mV within a frequency range of 10 Hz to 7 MHz at a temperature of 30° C.
The measurement results are shown in Table 6.
Referring to Table 6, the lithium halide-based nanocomposites according to Synthesis Examples 3-1 to 3-7 exhibited improved ionic conductivity.
The impedance was measured in the following method. In a glove box under an argon atmosphere, samples were weighed and placed in a polyetheretherketone tube (a PEEK tube with an interior diameter of 13 mm, an exterior diameter of 32 mm, and a height of 10 mm), and the PEEK tube was inserted so that upper and lower portions of the PEEK tube contact a powder-molding jig containing Ti. Subsequently, the samples were pressed into pellets with a diameter of 13 mm and any thickness by using a single screw press at a molding pressure of about 370 MPa. Then, the obtained pellets were placed in a sealed electrochemical cell capable of maintaining the argon atmosphere.
The impedance was measured by using an impedance/gain phase analyzer (SP-300, BioLogic) as a frequency response analyzer (FRA) and a small environmental tester as a constant temperature device. The measurement was started from a high frequency region at an AC voltage of 10 mV to 100 mV within a frequency range of 10 Hz to 7 MHz at a temperature of 30° C.
The lithium halide-based composites of Comparative Synthesis Example 1 and the lithium halide-based nanocomposites of Synthesis Examples 2-3, 3-1, and 3-2 were measured with respect to impedance, and the results are shown in
The Composites were Evaluated with Respect to Electrochemical Stability Through cyclic voltammetry performed within a voltage range of 3 V to 5 V.
The lithium halide-based nanocomposites of Synthesis Examples 1-1 to 3-7 and the lithium halide-based composites of Comparative Synthesis Examples 1 to 2-4 were respectively used as a solid electrolyte to manufacture all-solid-state battery cells in the following method. LiCoO2 as a positive electrode active material, a solid electrolyte, and Super-C as a conductive material were used in a weight ratio of 70:30:3 to prepare slurry and coating the slurry on an Al foil and drying and pressing it to prepare a positive electrode active material layer. The positive electrode active material layer (40 μm), a solid electrolyte layer (150 μm) including the lithium halide-based composites or the lithium halide-based nanocomposite, and Li—In as a negative electrode (130 μm) were stacked and pressed to manufacture all-solid-state battery cells. Hereinafter, the all-solid-state battery cells manufactured in “Manufacture of all-solid-state battery cell I” are marked as Examples 1-1A to 3-7A and Comparative Examples 1A to 2-4A.
All-solid-state battery cells were manufactured in the same manner as in “Manufacture of all-solid-state battery cell I” except that LiNi0.88Co0.11Al0.01O2 was used instead of the LiCoO2 as the positive electrode active material. Hereinafter, the all-solid-state battery cells manufactured in “Manufacture of all-solid-state battery cell II” were marked as Examples 1-1B to 3-7B and Comparative Examples 1B to 2-4B.
The manufactured all-solid-state battery cells were charged with a constant current up to 4.3 V, paused at 4.3 V until the current reached 0.1 C, and cut off and then, discharged with the constant current to 3.0 V in environments of 30° C. and 60° C. to evaluate charge and discharge characteristics. Subsequently, the all-solid-state battery cells were charged with a constant current to 4.3 V, paused at 4.3 V until the current reached 0.5 C, and cut off and then, discharged to 3.0 V with the constant current in the environments of 30° C. and 60° C., wherein this charge and discharge was 100 times repeated.
Herein, the charge and discharge characteristics at 30° C. and 60° C. of the all-solid-state battery cell of Example 2-3A are shown in Table 7, and the cycle-life characteristics at 30° C. are shown in
The all-solid-state battery cell of Example 2-3B was charged with a constant current up to 4.3 V, paused at 4.3 V until the current reached 0.5 C, and cut off and then, discharged with the constant current to 3.0 V in the environments of 30° C. and 60° C. to evaluate charge and discharge characteristics. Subsequently, the all-solid-state battery cell was charged with a constant current up to 4.3 V, paused at 4.3 V until the current reached 2 C, and cut off and then, discharged with a constant current to 3.0 V in the environments of 30° C. and 60° C., wherein this charge and discharge were 2000 times repeated.
The charge and discharge characteristics at 30° C. of the all-solid-state battery cell of Example 2-3B are shown in Table 7, and the cycle-life characteristics at 60° C. are shown in
Referring to Table 7 and
While this invention has been described in connection with what is presently considered to be practical example embodiments, it is to be understood that the invention is not limited to the disclosed embodiments. On the contrary, it is intended to cover various modifications and equivalent arrangements included within the spirit and scope of the appended claims.
| Number | Date | Country | Kind |
|---|---|---|---|
| 10-2022-0074829 | Jun 2022 | KR | national |
