Patent Application
20240039041
This application claims priority to and the benefit of Korean Patent Application No. 10-2022-0094981 filed in the Korean Intellectual Property Office on Jul. 29, 2022, the entire contents of which are incorporated herein by reference.
A solid electrolyte and a preparing method of the same are disclosed.
Recently, as a risk of explosion of a battery using a liquid electrolyte has been reported, development of an all-solid-state battery has been actively conducted. However, a solid electrolyte, compared with the liquid electrolyte, may exhibit low ion conductivity, resistance on the interface with solid particles of a positive electrode active material and the like in a battery, deterioration of ion conduction performance by formation of a depletion layer by solid-to-solid bonding, and the like.
An example embodiment provides a solid electrolyte, including sulfide-based solid electrolyte particles and lithium-metal-oxide on the surface of the sulfide-based solid electrolyte particles, wherein in an X-ray diffraction (XRD) analysis of the solid electrolyte, a full width at half maximum (FWHM) of a main peak is less than or equal to about 0.160.
Another example embodiment provides a method for preparing a solid electrolyte, including mixing sulfide-based solid electrolyte particles and lithium-metal-oxide and performing heat treatment at about 250° C. to about 350° C.
Features will become apparent to those of skill in the art by describing in detail exemplary embodiments with reference to the attached drawings, in which:
Example embodiments will now be described more fully hereinafter with reference to the accompanying drawings; however, they may be embodied in different forms and should not be construed as limited to the embodiments set forth herein. Rather, these embodiments are provided so that this disclosure will be thorough and complete, and will fully convey exemplary implementations to those skilled in the art.
The singular expression includes the plural expression unless the context clearly dictates otherwise. As used herein, “combination thereof” means a mixture, laminate, composite, copolymer, alloy, blend, reaction product, and the like of the constituents.
Herein, it should be understood that terms such as “comprises,” “includes,” or “have” are intended to designate the presence of an embodied feature, number, step, element, or a combination thereof, but it does not preclude the possibility of the presence or addition of one or more other features, number, step, element, or a combination thereof
In addition, “layer” herein includes not only a shape formed on the whole surface when viewed from a plan view, but also a shape formed on a partial surface.
In addition, the average particle diameter may be measured by a method well known to those skilled in the art, e.g., may be measured by a particle size analyzer, or may be measured by a transmission electron microscopic photograph or a scanning electron microscopic photograph. Alternatively, it is possible to obtain an average particle diameter value by measuring a size using a dynamic light scattering method, performing data analysis, counting the number of particles for each particle size range, and calculating from this. The average particle diameter may be measured with a microscope image or a particle size analyzer, and may mean a diameter (D50) of particles having a cumulative volume of 50 volume % in a particle size distribution.
Herein, “or” is not to be construed as an exclusive meaning, e.g., “A or B” is construed to include A, B, A+B, and the like.
An embodiment provides a method for preparing a solid electrolyte including mixing sulfide-based solid electrolyte particles and lithium-metal-oxide and performing heat treatment at about 250° C. to about 350° C.
In general, a solid electrolyte should have an appropriate particle size distribution to exhibit excellent ion conduction performance in a battery and implement high energy density, and should implement excellent particle fluidity, i.e., a high-density electrode plate and electrolyte film. At the same time, the solid electrolyte should be able to exhibit improved ion conductivity by maintaining high crystallinity.
A general sulfide-based solid electrolyte is a material capable of realizing high ion conductivity among various solid electrolytes. Immediately after synthesis at a high temperature, since the particles are severely agglomerated or have a large particle size, it is necessary to pulverize them. However, the ion conductivity decreases due to the pulverizing operation, and if heat treatment is performed to increase the ion conductivity, the particles may re-aggregate and grow.
In contrast, according to example embodiments, heat treatment is performed in a temperature range of about 250° C. to about 350° C., while coating lithium-metal-oxide on pulverized sulfide-based solid electrolyte particles. According to this method, the crystallinity of the solid electrolyte is increased, the ion conductivity is improved, and at the same time, particle aggregation and growth are suppressed, so that a high-density electrode plate and electrolyte film may be implemented with an appropriate particle size distribution. Such a solid electrolyte also has high moisture stability, and can improve capacity characteristics, initial charge/discharge efficiency, and cycle-life characteristics of a battery.
In the heat treatment, if the heat treatment is performed at a temperature of less than about 250° C., crystallinity may not be sufficiently increased, and thus high ion conductivity may not be realized. In addition, when heat treatment is performed at a temperature greater than about 350° C., aggregation and growth of particles occur, so that an appropriate particle size distribution is not obtained, and thus, crystallinity is lowered. The higher the heat treatment at a higher temperature, the more coating agents are required, which may cause a problem in that the ion conductivity is rather deteriorated.
The heat treatment may be performed in a nitrogen atmosphere or an inert gas atmosphere, e.g., He, Ar, or N2. In addition, the heat treatment may be performed for about 0.5 hours to about 10 hours, e.g., for about 1 hour to about 8 hours. In the case of heat treatment under these conditions, the prepared solid electrolyte can realize an appropriate particle size distribution while exhibiting excellent ion conductivity.
The lithium-metal-oxide may be mixed in an amount of about 0.01 parts by weight to about 3 parts by weight, e.g., about 0.01 parts by weight to about 2 parts by weight, about 0.01 parts by weight to about 1 part by weight, about 0.01 parts by weight to about 0.8 parts by weight, or about 0.1 parts by weight to about 0.75 parts by weight, based on 100 parts by weight of the sulfide-based solid electrolyte particles. When mixed in this content range, the prepared solid electrolyte may have an appropriate particle size distribution without particle size aggregation while exhibiting high ion conductivity. For example, if about 0.01 parts by weight to about 0.8 parts by weight of lithium-metal-oxide is mixed based on 100 parts by weight of sulfide-based solid electrolyte particles, the surface of the sulfide-based solid electrolyte is evenly coated with an appropriate amount of lithium-metal-oxide to further improve the ion conductivity of the solid electrolyte.
For example, a method for preparing a solid electrolyte according to an embodiment includes mixing and heat-treating sulfur-containing raw materials to synthesize a sulfide-based solid electrolyte, pulverizing the synthesized sulfide-based solid electrolyte, and, e.g., simultaneously, mixing the pulverized sulfide-based solid electrolyte particles with lithium-metal-oxide and performing heat treatment at about 250° C. to about 350° C. to obtain a solid electrolyte in which lithium-metal-oxide is disposed on the surface of the sulfide-based solid electrolyte particles.
In an embodiment, mixing and heat-treating sulfide-based solid electrolyte particles and lithium-metal-oxide may be referred to as a type of dry coating method. That is, the method of preparing the solid electrolyte according to an embodiment is a method of coating sulfide-based solid electrolyte particles, e.g., a method of dry-coating lithium-metal-oxide on the surface of sulfide-based solid electrolyte particles. Unlike other oxide-based inorganic solid electrolytes or positive electrode active materials, sulfide-based solid electrolytes have characteristics that make wet coating difficult and vulnerable to high-temperature heat treatment, and thus, the sulfide-based solid electrolytes require a design for difficult coating conditions. In addition, in general, wet coating methods use alcohol-based solvents or alkoxide-based raw materials, and accordingly, carbon components remain locally after coating, which may adversely affect conductivity and the like. Therefore, the method of preparing a solid electrolyte according to example embodiments has different conditions from coating other types of solid electrolyte particles, and is also distinguished from general wet coating.
For example, the sulfide-based solid electrolyte particles may be Li2S-P2S5, Li2S-P2S5-LiX (X is a halogen element, e.g., I or Cl), 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 (m and n is each an integer and Z is Ge, Zn or Ga), Li2S-GeS2, Li2S-SiS2-Li3PO4, Li2S-SiS2-LipMOq (p and q are integers and M is P, Si, Ge, B, Al, Ga, or In), or a combination thereof
For example, such sulfide-based solid electrolyte particles may be obtained by mixing Li2S and P2S5 at a mole ratio of about 50:50 to about 90:10, e.g., about 50:50 to about 80:20, and optionally performing heat treatment. Within the above mixing ratio range, a sulfide-based solid electrolyte having excellent ion conductivity may be prepared. The ion conductivity may be further improved by further including, e.g., SiS2, GeS2, B2S3, and the like, as additional components.
A method of mixing sulfur-containing raw materials for preparing a sulfide-based solid electrolyte may be mechanical milling or a solution method. The mechanical milling is a method of mixing the starting materials into microparticles by putting the starting materials and a ball mill in a reactor and vigorously stirring them. In the case of using the solution method, a solid electrolyte can be obtained as a precipitate by mixing the starting materials in a solvent. In addition, in the case of performing heat treatment for the mixture, crystals of the solid electrolyte may be more robust and ion conductivity may be improved. For example, the sulfide-based solid electrolyte may be prepared by mixing sulfur-containing raw materials and heat-treating the same two or more times. In this case, a sulfide-based solid electrolyte having high ion conductivity and robustness may be prepared.
For example, the sulfide-based solid electrolyte particles according to an embodiment may be prepared through a first heat treatment of mixing sulfur-containing raw materials and firing at about 120° C. to about 350° C. and a second heat treatment of mixing the resultant of the first heat treatment and firing the same at about 350° C. to about 800° C. The first heat treatment and the second heat treatment may be performed in an inert gas or nitrogen atmosphere, respectively. The first heat treatment may be performed for about 1 hour to about 10 hours, and the second heat treatment may be performed for about 5 hours to about 20 hours. Small raw materials may be milled through the first heat treatment, and a final solid electrolyte can be synthesized through the second heat treatment. Through such two or more heat treatments, a sulfide-based solid electrolyte having high ion conductivity and high performance can be obtained, and such a solid electrolyte may be suitable for mass production. For example, the temperature of the first heat treatment may be about 150° C. to about 330° C., e.g., about 200° C. to about 300° C., and the temperature of the second heat treatment may be about 380° C. to about 700° C., e.g., about 400° C. to about 600° C.
For example, the sulfide-based solid electrolyte particles may include argyrodite-type sulfide. For example, the argyrodite-type sulfide may be represented by the chemical formula LiaMbPcSdAe (wherein a, b, c, d, and e are all 0 or more and 12 or less, M is Ge, Sn, Si, or a combination thereof, and A is F, Cl, Br, or I), and as a specific example, it may be represented by the chemical formula of Li7-xPS6-xAx(wherein x is 0.2 or more and 1.8 or less, and A is F, Cl, Br, or I). For example, the argyrodite-type sulfide may be Li3PS4, Li7P3S11, Li7PS6, Li6PS5Cl, Li6PS5Br, Li5.8PS4.8Cl1.2, Li6.2PS5.2BrO8, and the like.
The sulfide-based solid electrolyte particles including such argyrodite-type sulfide may have high ion conductivity close to the range of about 10−4 to about 10−2 S/cm, which is the ion conductivity of general liquid electrolytes at room temperature, and may form an intimate (e.g., close) bond between the positive electrode active material and the solid electrolyte without causing a decrease in ion conductivity, and furthermore, an intimate interface between the electrode layer and the solid electrolyte layer. An all-solid-state battery including the same may have improved battery performance, e.g., rate capability, coulombic efficiency, and cycle-life characteristics.
For example, the argyrodite-type sulfide-based solid electrolyte may be prepared by mixing lithium sulfide and phosphorus sulfide, and optionally lithium halide. Heat treatment may be performed after mixing. The heat treatment may include, e.g., two or more heat treatment steps.
A method of preparing a solid electrolyte according to an embodiment includes preparing argyrodite-type sulfide-based solid electrolyte particles by mixing lithium sulfide, phosphorus sulfide, and optionally lithium halide, mixing the prepared argyrodite-type sulfide-based solid electrolyte particles and lithium metal-oxide, and performing heat treatment at about 250° C. to about 350° C.
For example, the method for preparing the solid electrolyte includes preparing argyrodite-type sulfide-based solid electrolyte particles by mixing lithium sulfide, phosphorus sulfide, and optionally lithium halide and heat-treating, pulverizing the prepared argyrodite-type sulfide-based solid electrolyte particles, mixing the pulverized argyrodite-type sulfide-based solid electrolyte particles and lithium-metal-oxide, and heat-treating at about 250° C. to about 350° C.
For example, during preparation of the argyrodite-type sulfide-based solid electrolyte, the heat treatment may include a first heat treatment in which raw materials are mixed and fired at about 120° C. to about 350° C., and a second heat treatment in which the resultant of the first heat treatment is mixed again and fired at about 350° C. to about 800° C.
An average particle diameter (D50) of the sulfide-based solid electrolyte particles according to an embodiment may be less than or equal to about 5.0 μm, e.g., about 0.1 μm to about 5.0 μm, about 0.1 μm to about 4.0 μm, about 0.1 μm to about 3.0 μm, about 0.5 μm to about 2.0 μm, or about 0.1 μm to about 1.5 μm. The sulfide-based solid electrolyte particles having this particle size range can effectively penetrate between positive electrode active materials, and have excellent contact with the positive electrode active material and connectivity between solid electrolyte particles. The average particle diameter of the sulfide-based solid electrolyte particles may be measured using a microscope image, and for example, a particle size distribution may be obtained by measuring the size of about 20 particles in a scanning electron microscope image, and D50 may be calculated therefrom.
The lithium-metal-oxide according to an embodiment may refer to an oxide including lithium and a metal other than lithium. Herein, the metal is a concept including general metals, transition metals, and semi-metals. In the lithium-metal-oxide, the metal may be one or more of, e.g., Al, B, Ca, Ce, Cr, Fe, Mg, Mo, Nb, Si, Sn, Sr, Ta, V, W, and Zr.
The lithium-metal-oxide may be amorphous. According to an embodiment, when amorphous lithium-metal-oxide is coated on the sulfide-based solid electrolyte particles, the prepared solid electrolyte may realize higher ion conductivity and interfacial resistance with other solid particles, e.g., with a positive electrode active material in a battery, prevent aggregation of solid electrolyte particles, improve ion conductivity, and improve capacity characteristics, cycle-life characteristics, and the like.
The lithium-metal-oxide mixed in the method for preparing a solid electrolyte may be in the form of particles, and its average particle diameter (D50) may be, e.g., about 0.01 μm to about 1.0 μm, about 0.01 μm to about 0.9 μm, about 0.01 μm to about 0.8 μm, or about 0.01 μm and about 0.5 μm. An average particle diameter of the lithium-metal-oxide may be smaller than that of the sulfide-based solid electrolyte particles. When using the lithium-metal-oxide having such a particle size range, it can be evenly coated on the surface of the sulfide-based solid electrolyte particles, sufficiently increase ion conductivity of the solid electrolyte, and improve moisture stability.
In an embodiment, the solid electrolyte includes sulfide-based solid electrolyte particles and lithium-metal-oxide on the surface of the sulfide-based solid electrolyte particles, wherein in an X-ray diffraction (XRD) analysis of the solid electrolyte, a full width at half maximum (FWHM) of a main peak is less than or equal to about 0.160.
The lithium-metal-oxide may be present in the form of a film or an island on the surface of the sulfide-based solid electrolyte particle. For example, the solid electrolyte according to an embodiment may include a sulfide-based solid electrolyte particle and a coating layer on the surface of the particle, and the coating layer may include the lithium-metal-oxide.
The solid electrolyte according to an embodiment is a form in which lithium-metal-oxide is coated on the surface of sulfide-based solid electrolyte particles, but the crystallinity of the solid electrolyte is sufficiently high to realize excellent ion conductivity and at the same time to obtain an appropriate particle size distribution without particle aggregation. As the crystallinity of the solid electrolyte increases or the size of the crystal increases, full width at half maximum (FWHM) of the main peak may decrease in X-ray diffraction analysis and the solid electrolyte according to an embodiment has the full width at half maximum of the main peak of less than or equal to about 0.160. Herein, the main peak refers to a peak having the highest diffraction intensity in X-ray diffraction analysis. In the X-ray diffraction analysis of the solid electrolyte according to an embodiment, the full width at half maximum of the main peak may be, e.g., less than or equal to about 0.159, or less than or equal to about 0.155. It is known that the ion conductivity is improved if the full width at half maximum is decreased, i.e., if the crystallinity is increased, and for example it is understood that as the size of the crystal increases, the grain boundary decreases and the ion conductivity improves.
In general, as described above, the sulfide-based solid electrolyte has particles aggregated or has a large particle size immediately after synthesis, and when it is subjected to a process, e.g., pulverization, to adjust the particle size for use in a battery, crystallinity thereof may be lowered and ion conductivity may be lowered. In contrast, in the solid electrolyte according to an embodiment, by heating sulfide-based solid electrolyte particles in a specific temperature range while coating lithium-metal-oxide, the crystallinity may be increased and the full width at half maximum of the main peak may be adjusted to less than or equal to about 0.160, and at the same time, to have an even particle size distribution without particle aggregation or growth, improving ion conductivity.
In the solid electrolyte according to an embodiment, the lithium-metal-oxide may be included in an amount of about 0.01 wt % to about 3 wt %, e.g., about 0.01 wt % to about 2 wt %, about 0.01 wt % to about 1 wt %, about 0.01 wt % to about 0.8 wt %, or about 0.1 wt % to about 1.0 wt %, based on 100 wt % of the solid electrolyte. When the content of lithium-metal-oxide is the above range, the solid electrolyte may exhibit an appropriate particle size distribution without particle aggregation while realizing high ion conductivity. In particular, if the content of lithium-metal-oxide satisfies the range of 0.01 wt % to 0.8 wt %, based on 100 wt % of the solid electrolyte, the surface of the sulfide-based solid electrolyte particles may be evenly coated with lithium-metal-oxide. Accordingly, the ion conductivity and moisture stability of the solid electrolyte may be further improved, and the efficiency and cycle-life characteristics of the battery may be further improved.
In the solid electrolyte, the lithium-metal-oxide positioned or coated on the surface of the sulfide-based solid electrolyte particles may be in an amorphous form. When the amorphous lithium-metal-oxide is coated, the solid electrolyte exhibits superior ion conductivity and lowers interfacial resistance, thereby improving battery performance.
An average particle diameter (D50) of the solid electrolyte may be about 0.1 μm to about 5.0 μm, e.g., about 0.1 μm to about 4.0 μm, about 0.1 μm to about 3.0 μm, about 0.5 μm to about 2.0 μm, or about 0.1 μm to about 1.5 μm. Such a solid electrolyte can effectively penetrate between positive electrode active materials, and has excellent contact with the positive electrode active material and connectivity between solid electrolyte particles. The average particle diameter of the solid electrolyte may be measured using a microscope image, e.g., a particle size distribution may be obtained by measuring the size of about 20 particles in a scanning electron microscope image, and D50 may be calculated therefrom.
The solid electrolyte according to an embodiment is characterized by having a uniform particle size distribution without particle aggregation. For example, a value of (D90-D10)/D50 in the particle size distribution for the solid electrolyte may be greater than about 1 and less than or equal to about 5, e.g., about 1.1 to about 4.0, about 1.1 to about 3.0, or about 1.1 to about 2.0. The (D90-D10)/D50 value may indicate a degree of broadness of the peak in the particle size distribution graph for the solid electrolyte, specifically, the horizontal axis represents the particle size (μm) and the vertical axis represents the cumulative volume % of the particles. The smaller the corresponding number, the narrower the peak width of the graph, which may be interpreted as having a uniform particle size. Herein, D10 means a diameter of particles whose cumulative volume is 10 volume % in the particle size distribution, D50 means a diameter of particles whose cumulative volume is 50 volume % in the particle size distribution, and D90 means a diameter of particles whose cumulative volume is 90 volume % in the particle size distribution.
For example, the D10 of the solid electrolyte may be about 0.05 μm to about 0.7 μm, e.g., about 0.05 μm to about 0.6 μm, about 0.1 μm to about 0.5 μm, or about 0.2 μm to about 0.4 μm. In addition, the D90 of the solid electrolyte may be, e.g., about 0.9 μm to about 5.0 μm, about 1.0 μm to about 4.0 μm, about 1.0 μm to about 3.0 μm, or about 1.2 μm to about 2.0 μm. When the solid electrolyte has such a particle size distribution, battery performance may be improved by realizing high energy density while implementing excellent ion conductivity.
The solid electrolyte may have an ion conductivity of greater than or equal to about 2.9 mS/cm at 25° C., e.g., about 2.9 mS/cm to about 5.0 mS/cm, about 3.0 mS/cm to about 4.5 mS/cm, or about 3.0 mS/cm to about 4.0 mS/cm. The ion conductivity may be measured through electrochemical impedance spectroscopy (EIS).
The following Examples and Comparative Examples are provided in order to highlight characteristics of one or more embodiments, but it will be understood that the Examples and Comparative Examples are not to be construed as limiting the scope of the embodiments. Further, it will be understood that the embodiments are not limited to the particular details described in the Examples and Comparative Examples.
An argyrodite-type sulfide-based solid electrolyte was synthesized through a method described later. All processes of mixing raw materials and pre- and post-heat treatments were performed in a glove box under an argon atmosphere. Specifically, the raw materials of lithium sulfide (Li2S), phosphorus pentasulfide (P2S5), and lithium chloride (LiCl) were mixed in a mole ratio of 2.5:0.5:1, preparing mixed powder. The mixed powder was uniformly mixed with a Henschel mixer and then, primarily fired at 250° C. for 5 hours in a tube furnace through which argon gas was flowing at a constant speed of 8 SLM.
The primarily fired powder was uniformly mixed again with the Henschel mixer, sifted, and then, secondarily fired at 500° C. for 10 hours in the tube furnace through which argon gas was flowing at the constant speed of 8 SLM. The secondarily fired powder was pulverized and sifted, obtaining sulfide-based solid electrolyte particles of Li6PS5Cl. This obtained sulfide-based solid electrolyte particles had a size (D50) of 0.85 μm.
100 parts by weight of the prepared sulfide-based solid electrolyte particles and 0.25 parts by weight of lithium-zirconium-oxide (LZO) having D50 of 0.13 μm and being amorphous as a result of X-ray diffraction analysis as a coating agent were mixed with the Henschel mixer. The mixed powder was heat-treated at 250° C. for 5 hours in the tube furnace through which argon gas was flowing at the constant speed of 8 SLM. Through this, a solid electrolyte having the lithium-zirconium-oxide coated on the surface of the sulfide-based solid electrolyte particles was prepared.
A solid electrolyte was prepared in the same manner as in Example 1 except that the content of the coating agent was changed into 0.5 parts by weight.
A solid electrolyte was prepared in the same manner as in Example 2 except that amorphous lithium-aluminum-oxide (LAO; D50=0.06 μm) was used as the coating agent.
A solid electrolyte was prepared in the same manner as in Example 2 except that amorphous lithium-titanium-oxide (LTO; D50=0.06 μm) was used as the coating agent.
A solid electrolyte was prepared in the same manner as in Example 1 except that the content of the coating agent was changed into 1.0 part by weight.
A solid electrolyte was prepared in the same manner as in Example 1 except that the coating process through a heat treatment at 250° C. for 5 hours was performed without the coating agent.
A solid electrolyte was prepared in the same manner as in Example 1 except that the coating process was not performed. In other words, the sulfide-based solid electrolyte particles themselves prepared in the step 1 of Example 1 were used as a solid electrolyte.
Each solid electrolyte of Examples 1 to 5 and Comparative Examples 1 to 2 was designed as shown in Table 1.
The solid electrolytes of Examples 1 to 5 and Comparative Examples 1 to 2 were respectively measured with respect to a particle size distribution. The particle size distribution was measured by using xylene, from which moisture was removed, as a solvent and a particle size analyzer using a laser diffraction.
In addition, in each particle size distribution of the solid electrolytes of Examples 1 to 5 and Comparative Examples 1 to 2, a cumulative volume 10% as D10, a cumulative volume 50% as D50, and a cumulative volume 90% as D90 are shown in Table 2. Furthermore, (D90-D10)/D50 was calculated to compare wideness of each particle size distribution and then, provided as Span in Table 2.
Referring to
On the contrary, Examples 1 to 5, referring to
After performing an X-ray diffraction analysis of the solid electrolytes and LZO of Examples 1, 2, and 5 and Comparative Examples 1 and 2, the results are shown in
Referring to
In addition, in
Referring to
Accordingly, when the sulfide-based solid electrolyte particles were appropriately coated with amorphous lithium-metal-oxides on the surface and heat-treated within a specific temperature range, the solid electrolyte particles were suppressed from aggregation but had an increased crystal size.
0.15 g of each solid electrolyte of Examples 1 to 5 and Comparative Examples 1 to 2 was charged and pressed under a pressure of 40 Kgf/cm2, manufacturing a torque cell. The manufactured cells were calculated with respect to ion conductivity through electrochemical impedance spectroscopy (EIS), and the results are shown as a dotted line graph in
Referring to
The examples exhibited improved ion conductivity, compared with the comparative examples. Examples 2 to 4, in which different types of coating agents were used all in the same amount, exhibited different crystal growth and ion conductivity of the solid electrolytes according to types of coating agent. The reason is that the coating agent of Example 2 had D50=0.13 μm, but the coating agents of Examples 3 and 4 had D50 of 0.06 μm and thus formed coating with a different thickness or shape on the surface of the sulfide-based solid electrolyte particles. Example 5, in which a content of the coating agent was increased, exhibited a little reduced ion conductivity due to agglomeration of the sulfide-based solid electrolyte particles or resistance on the surface thereof
The solid electrolytes of Examples 1 to 5 and Comparative Examples 1 to 2 were allowed to stand in a dry room at a dew point of −45° C. for 3 days and then, measured with respect to ion conductivity in the same manner as in Evaluation Example 3.
Referring to
Referring to
By way of summation and review, doping various elements into positive electrode active material particles used with a solid electrolyte and forming a buffer layer including, e.g., B, Nb, Zr, and the like, on the surface of the positive electrode active material particles have been used. However, these methods may have difficulties in mass production, cause coating and environmental problems, and have limitations in improving performance of the all-solid-state battery.
Accordingly, development of a solid electrolyte having high ion conductivity and an appropriate particle size distribution is desired. Therefore, according to embodiments, a solid electrolyte having a uniform particle size distribution, high crystallinity and high ion conductivity, and improved moisture stability and a method for preparing the same are provided
Example embodiments have been disclosed herein, and although specific terms are employed, they are used and are to be interpreted in a generic and descriptive sense only and not for purpose of limitation. In some instances, as would be apparent to one of ordinary skill in the art as of the filing of the present application, features, characteristics, and/or elements described in connection with a particular embodiment may be used singly or in combination with features, characteristics, and/or elements described in connection with other embodiments unless otherwise specifically indicated. Accordingly, it will be understood by those of skill in the art that various changes in form and details may be made without departing from the spirit and scope of the present invention as set forth in the following claims.
| Number | Date | Country | Kind |
|---|---|---|---|
| 10-2022-0094981 | Jul 2022 | KR | national |
