KR20230157235A - Lithium ion conductor and all solid state baterry comprising the same - Google Patents

Abstract

The lithium ion conductor for an all-solid-state battery according to the present disclosure contains an oxide containing lithium (Li), silicon (Si), and boron (B), and has a crystallinity of 25.5% or less.

Description

Lithium ion conductor and all-solid-state battery containing the same {LITHIUM ION CONDUCTOR AND ALL SOLID STATE BATERRY COMPRISING THE SAME}

The present disclosure relates to lithium ion conductors and all-solid-state batteries containing the same.

Recently, as portable electronic devices are required to be miniaturized and used for long periods of time, higher capacity batteries are required, and with the spread of wearable electronic devices, ensuring battery safety is required. Therefore, the development of all-solid-state batteries that use solid electrolytes instead of liquid electrolytes is actively underway.

All-solid-state batteries do not use flammable organic solvents, so additional circuits for safety can be simplified. Therefore, it is expected to be a technology that can produce safe batteries with high capacity per unit volume.

In addition, oxide all-solid-state batteries using oxide electrolytes have lower ionic conductivity of the electrolyte (10 ^-4 S/cm to 10 ^-6 S/cm) than sulfide (10 -2 S/cm), and require a ^high -temperature sintering process. However, its stability is superior to that of sulfide all-solid-state batteries that use sulfide electrolytes that react with oxygen and moisture in the air.

The stacked oxide all-solid-state battery is an ultra-small battery that can be mounted on a board like a passive device and is stable even when exposed to high temperatures during the reflow process.

One aspect of the embodiment provides a lithium ion conductor in which ionic conductivity can be freely adjusted, the amount of ionic conductivity reduction can be minimized during the manufacturing process of a stacked all-solid-state battery, and thus ionic conductivity can be predicted in a stacked all-solid-state battery.

Another aspect of the embodiment provides a method of manufacturing the lithium ion conductor.

Another aspect of the embodiment provides an all-solid-state battery including the lithium ion conductor.

However, the problems that the embodiments seek to solve are not limited to the above-described problems and can be expanded in various ways within the scope of the technical ideas included in the embodiments.

The lithium ion conductor according to one embodiment includes an oxide containing lithium (Li), silicon (Si), and boron (B), and has a crystallinity degree calculated by Equation 1 below of 25.5% or less.

[Equation 1]

Crystallinity (%) = [Ic/(Ic+Ia)] × 100

In Equation 1, Ic is the sum of the scattering intensity integrals of the crystalline peak in the X-ray diffraction analysis spectrum of the lithium ion conductor, and Ia is the scattering intensity of the amorphous halo in the X-ray diffraction analysis spectrum of the lithium ion conductor. It is the sum of the integral values of .

The lithium ion conductor may have a crystallinity of 0% to 12.5%.

Lithium ion conductors may have a porosity of 1% or less.

The lithium ion conductor may have a porosity of 0% to 0.5%.

The lithium ion conductor contains 45 mol% to 80 mol% of lithium (Li) oxide, 5 mol% to 20 mol% of silicon (Si) oxide, and 15 mol% to 50 mol% of boron (B) oxide relative to the entire lithium ion conductor. It can be included as a %.

The lithium ion conductor may contain 50 mol% to 70 mol% of lithium (Li) oxide relative to the entire lithium ion conductor.

Lithium ion conductors are Na (sodium), Mg (magnesium), Al (aluminium), P (phosphorus), K (potassium), Ca (calcium), Ti (titanium), V (vanadium), Cr (chromium), Mn. (Manganese), Fe (Iron), Co (Cobalt), Ni (Nickel), Cu (Copper), Zn (Zinc), Ga (Gallium), Ge (Germanium), Se (Selenium), Rb (Rubidium), S (sulfur), Y (yttrium), Zr (zirconium), Nb (niobium), Mo (molybdenum), Ag (silver), In (indium), Sn (tin), Sb (antimony), Cs (cesium), Ba (vanadium), Hf (hafnium), Ta (tantalum), W (tungsten), Pb (lead), Bi (bismuth), Au (gold), La (lanthanum), Nd (neodymium), Eu (europium), or Additional oxides including combinations thereof may be further included.

The lithium ion conductor may further include additional oxides including phosphorous (P) and germanium (Ge).

The lithium ion conductor may contain 5 mol% or less of additional oxide based on the total lithium ion conductor.

The lithium ion conductor may contain 1 mol% or less of additional oxide based on the total lithium ion conductor.

A method of manufacturing a lithium ion conductor according to another embodiment includes the step of calcining oxide powder containing lithium (Li), silicon (Si), and boron (B) while pressing, calculated by Equation 1 below: Crystallinity is less than 25.5%.

[Equation 1]

Crystallinity (%) = [Ic/(Ic+Ia)] × 100

In Equation 1, Ic is the sum of the scattering intensity integrals of the crystalline peak in the X-ray diffraction analysis spectrum of the lithium ion conductor, and Ia is the scattering intensity of the amorphous halo in the X-ray diffraction analysis spectrum of the lithium ion conductor. It is the sum of the integral values of .

The firing temperature may be 300°C to 550°C.

Pressurization may apply a pressure of 1 MPa to 200 MPa.

An all-solid-state battery according to another embodiment includes a solid electrolyte layer and an anode and a cathode disposed with the solid electrolyte layer interposed, and any selected from the group consisting of a solid electrolyte layer, an anode, a cathode, and a combination thereof. One includes a lithium ion conductor containing an oxide containing lithium (Li), silicon (Si), and boron (B), and the lithium ion conductor has a crystallinity of 25.5% or less calculated by Equation 1 below.

[Equation 1]

Crystallinity (%) = [Ic/(Ic+Ia)] × 100

In Equation 1, Ic is the sum of the scattering intensity integrals of the crystalline peak in the X-ray diffraction analysis spectrum of the lithium ion conductor, and Ia is the scattering intensity of the amorphous halo in the X-ray diffraction analysis spectrum of the lithium ion conductor. It is the sum of the integral values of .

Lithium ion conductors may have a porosity of 1% or less.

The lithium ion conductor contains 45 mol% to 80 mol% of lithium (Li) oxide, 5 mol% to 20 mol% of silicon (Si) oxide, and 15 mol% to 50 mol% of boron (B) oxide relative to the entire lithium ion conductor. It can be included as a %.

Lithium ion conductors are Na (sodium), Mg (magnesium), Al (aluminium), P (phosphorus), K (potassium), Ca (calcium), Ti (titanium), V (vanadium), Cr (chromium), Mn. (Manganese), Fe (Iron), Co (Cobalt), Ni (Nickel), Cu (Copper), Zn (Zinc), Ga (Gallium), Ge (Germanium), Se (Selenium), Rb (Rubidium), S (sulfur), Y (yttrium), Zr (zirconium), Nb (niobium), Mo (molybdenum), Ag (silver), In (indium), Sn (tin), Sb (antimony), Cs (cesium), Ba (vanadium), Hf (hafnium), Ta (tantalum), W (tungsten), Pb (lead), Bi (bismuth), Au (gold), La (lanthanum), Nd (neodymium), Eu (europium), or Additional oxides including combinations thereof may be further included.

An all-solid-state battery according to another embodiment includes a laminate including a plurality of solid electrolyte layers and a plurality of anodes and cathodes alternately disposed with the plurality of solid electrolyte layers interposed therebetween, and one surface of the laminate and one surface thereof. It includes first and second external electrodes disposed on opposite surfaces and connected to the anode and the cathode, respectively, and any one selected from the group consisting of a solid electrolyte layer, an anode, a cathode, and a combination thereof is lithium (Li), It includes a lithium ion conductor containing an oxide containing silicon (Si) and boron (B), and the lithium ion conductor has a crystallinity of 25.5% or less calculated by Equation 1 below.

[Equation 1]

Crystallinity (%) = [Ic/(Ic+Ia)] × 100

In Equation 1, Ic is the sum of the scattering intensity integrals of the crystalline peak in the X-ray diffraction analysis spectrum of the lithium ion conductor, and Ia is the scattering intensity of the amorphous halo in the X-ray diffraction analysis spectrum of the lithium ion conductor. It is the sum of the integral values of .

Lithium ion conductors may have a porosity of 1% or less.

The lithium ion conductor contains 45 mol% to 80 mol% of lithium (Li) oxide, 5 mol% to 20 mol% of silicon (Si) oxide, and 15 mol% to 50 mol% of boron (B) oxide relative to the entire lithium ion conductor. It can be included as a %.

Lithium ion conductors are Na (sodium), Mg (magnesium), Al (aluminium), P (phosphorus), K (potassium), Ca (calcium), Ti (titanium), V (vanadium), Cr (chromium), Mn. (Manganese), Fe (Iron), Co (Cobalt), Ni (Nickel), Cu (Copper), Zn (Zinc), Ga (Gallium), Ge (Germanium), Se (Selenium), Rb (Rubidium), S (sulfur), Y (yttrium), Zr (zirconium), Nb (niobium), Mo (molybdenum), Ag (silver), In (indium), Sn (tin), Sb (antimony), Cs (cesium), Ba (vanadium), Hf (hafnium), Ta (tantalum), W (tungsten), Pb (lead), Bi (bismuth), Au (gold), La (lanthanum), Nd (neodymium), Eu (europium), or Additional oxides including combinations thereof may be further included.

According to the lithium ion conductor according to the embodiment, ionic conductivity can be freely adjusted, and the amount of ionic conductivity reduction can be minimized during the manufacturing process of a stacked all-solid-state battery, and thus ionic conductivity can be predicted in the stacked all-solid-state battery.

1 is a perspective view schematically showing an all-solid-state battery according to an embodiment.
FIG. 2 is a cross-sectional view of an all-solid-state battery according to the embodiment shown in FIG. 1.
FIG. 3 is an exploded perspective view schematically showing the unit cell stacked structure of the all-solid-state battery according to the embodiment shown in FIG. 1.
Figure 4 is an ion milling cross-sectional scanning electron microscope (SEM) photograph of Li ₂ OB ₂ O ₃ -SiO ₂ amorphous lithium ion conductor cullet.
Figure 5 is a scanning electron microscope (SEM) photograph of the ion milling cross-section of the lithium ion conductor pellet according to Example 1.
Figure 6 is a scanning electron microscope (SEM) photograph of the ion milling cross-section of the lithium ion conductor pellet according to Comparative Example 1.
Figure 7 is a scanning electron microscope (SEM) photograph of the ion milling cross-section of a lithium ion conductor pellet according to Comparative Example 3.
Figure 8 is a scanning electron microscope (SEM) photograph of the ion milling cross-section of a lithium ion conductor pellet according to Comparative Example 4.
Figure 9 shows the results of determining the thermal behavior of cullet and frit containing 50 mol% Li ₂ O through DSC analysis.
Figure 10 shows the results of analyzing the crystalline states of cullet, frit, and lithium ion conductor through XRD analysis.
Figure 11 shows the results of SEM-EDAX mapping analysis of a lithium ion conductor.
Figure 12 is a cole-cole plot result of the lithium ion conductor manufactured in Example 1 and Comparative Example 1.
Figure 13 is a voltage-capacitance graph in a symmetric cell of the lithium ion conductor prepared in Example 1 and Comparative Example 1.

Hereinafter, with reference to the attached drawings, the present invention will be described in detail so that those skilled in the art can easily implement it. In order to clearly explain the present invention in the drawings, parts not related to the description are omitted, and identical or similar components are given the same reference numerals throughout the specification. In addition, the attached drawings are only for easy understanding of the embodiments disclosed in this specification, and the technical idea disclosed in this specification is not limited by the attached drawings, and all changes included in the spirit and technical scope of the present invention are not limited. , should be understood to include equivalents or substitutes. In addition, in the accompanying drawings, some components are exaggerated, omitted, or schematically shown, and the size of each component does not entirely reflect the actual size.

Throughout the specification, when a part is said to “include” a certain element, this means that it may further include other elements rather than excluding other elements, unless specifically stated to the contrary.

Throughout the specification, the 'stacking direction' refers to the direction in which the components are sequentially stacked, and may also be the 'thickness direction' perpendicular to the wide surface (main surface) of the components on the sheet. In the drawings, it corresponds to the T-axis direction. . Also, the 'side' refers to the direction extending parallel to the wide surface (main surface) from the edge of the sheet-like component, which can be a 'plane direction', and corresponds to the L-axis direction in the drawing.

Hereinafter, various embodiments and modifications will be described in detail with reference to the drawings.

A lithium ion conductor according to one embodiment includes an oxide containing lithium (Li), silicon (Si), and boron (B). Lithium ion conductors can be used as battery materials for all-solid-state batteries, for example, solid electrolytes, electrode binders, or coating agents.

As an example, the lithium ion conductor may include lithium (Li) oxide (Li ₂ O), silicon (Si) oxide (SiO ₂ ), and boron (B) oxide (B ₂ O ₃ ).

The lithium ion conductor contains 45 mol% to 80 mol% of lithium (Li) oxide, 5 mol% to 20 mol% of silicon (Si) oxide, and 15 mol% to 50 mol% of boron (B) oxide relative to the entire lithium ion conductor. %, for example, 50 mol% to 70 mol% of lithium (Li) oxide, 5 mol% to 15 mol% of silicon (Si) oxide, and 35 mol% to 45 mol% of boron (B) oxide. It can be included as a %. If the lithium (Li) oxide content is less than 45 mol%, lithium ion conductivity may be low, and if it exceeds 80 mol%, devitrification of the glass may occur. If the amount of silicon (Si) oxide is less than 5 mol%, it may become vulnerable when exposed to a high humidity environment, and if it exceeds 20 mol%, ionic conductivity may decrease and devitrification may occur. If the amount of boron (B) oxide is less than 15 mol%, ionic conductivity may decrease and devitrification may occur, and if it exceeds 50 mol%, it may become vulnerable when exposed to a high humidity environment.

Optionally, the lithium ion conductor may further comprise additional oxides. For example, additional oxides include Na (sodium), Mg (magnesium), Al (aluminum), P (phosphorus), K (potassium), Ca (calcium), Ti (titanium), V (vanadium), and Cr (chromium). , Mn (manganese), Fe (iron), Co (cobalt), Ni (nickel), Cu (copper), Zn (zinc), Ga (gallium), Ge (germanium), Se (selenium), Rb (rubidium) , S (sulfur), Y (yttrium), Zr (zirconium), Nb (niobium), Mo (molybdenum), Ag (silver), In (indium), Sn (tin), Sb (antimony), Cs (cesium) , Ba (vanadium), Hf (hafnium), Ta (tantalum), W (tungsten), Pb (lead), Bi (bismuth), Au (gold), La (lanthanum), Nd (neodymium), Eu (europium) , or a combination thereof, for example, the lithium ion conductor may further include additional oxides including P (phosphorus) and Ge (germanium).

The lithium ion conductor may contain 5 mol% or less of additional oxide, for example, 1 mol% or less based on the total lithium ion conductor. If the content of additional oxide exceeds 5 mol%, devitrification may occur during glass production or secondary crystal phases may occur during sintering, resulting in a decrease in ionic conductivity.

The lithium ion conductor may have a crystallinity of 25.5% or less, for example, 0% to 12.5%, or 0% to 5%, as calculated by Equation 1 below.

[Equation 1]

Crystallinity (%) = [Ic/(Ic+Ia)] × 100

In Equation 1, Ic is the sum of the scattering intensity integrals of the crystalline peak in the X-ray diffraction analysis spectrum of the lithium ion conductor, and Ia is the scattering intensity of the amorphous halo in the X-ray diffraction analysis spectrum of the lithium ion conductor. It is the sum of the integral values of .

As an example, the crystallinity of a lithium ion conductor can be calculated based on a graph obtained by X-ray diffraction spectroscopy. In the X-ray diffraction analysis spectrum, a relationship of 2d·sin θ=nλ is established between the wavelength λ and incident angle θ of the incident X-ray and the lattice spacing d, and this relationship is called the Bragg equation. Accordingly, once the angle of incidence is determined, the lattice spacing d can be obtained. However, in amorphous materials, a random arrangement rather than a regular atomic arrangement appears, so multiple X-ray diffraction does not appear at a specific wavelength, and a wide halo pattern appears in the area where the diffraction angle is 15° to 35°. do. If there is no peak that appears at a specific angle in the diffraction angle range of 10° to 60° and a diffuse halo pattern appears, it can be judged to be an amorphous material with a crystallinity of 0%. However, the side of the lithium ion conductor exposed to X-rays must not contain any contaminants other than organic matter. Reliability is high only for results measured under conditions where there are no factors affecting the diffraction pattern. If crystals exist in the lithium ion conductor, one or more crystalline peaks will exist in the measured diffraction angle range. At this time, if the crystallinity is high, the halo region is reduced, and in a material with 100% crystallinity, the halo region does not exist. If crystalline and amorphous are mixed, the degree of crystallinity can be calculated by calculating the relative ratio of the area of the crystalline peak and the area of the halo region in the graph consisting of intensity and diffraction angle range.

The degree of crystallinity of the lithium ion conductor can be adjusted by changing the content of lithium (Li) oxide. For example, as the content of lithium (Li) oxide increases, the overall crystallization temperature may gradually decrease and the degree of crystallinity may increase. In this way, the ionic conductivity can be freely adjusted by adjusting the crystallinity of the lithium ion conductor.

If the crystallinity of the lithium ion conductor exceeds 25.5%, ionic conductivity may decrease. For example, if the crystallinity exceeds 50.0%, ionic conductivity may be lost and insulator-like characteristics may appear.

Additionally, the lithium ion conductor may have a porosity of 1% or less, for example, 0% to 0.5%.

The porosity of lithium ion conductors can be measured through scanning electron microscopy (SEM) photographs. As an example, a sample with the surface of a lithium ion conductor etched very smoothly is prepared, and a scanning electron microscope photograph is taken. It is possible to use precision sandpaper to etch the surface of a lithium ion conductor, but since the sample may be damaged and the information distorted, ultra-precision etching equipment such as plasma etching or reactive ion etching should be used. Available. A scanning electron microscope measures at 30 K or 50 K magnification so that the pores of the lithium ion conductor are visible, and the porosity can be measured in an image measuring, for example, 40 ㎛ width × 30 ㎛ length.

At this time, if pores exist in the lithium ion conductor, they appear dark in the scanning electron microscope photo and can be distinguished. The ratio value of bright and dark areas can be calculated using an image program such as an electron beam microanalyzer (EPMA). For the electron beam microanalyzer (EPMA), an energy dispersive spectrometer (EDS) or a wavelength dispersive spectrometer (WDS) can be used. You can. At this time, the dark area of the contrast is assumed to be an air gap, and the bright area of the contrast is judged to be a lithium ion conductive area. For example, the porosity of a lithium ion conductor can be calculated by binarizing a scanning electron microscope image using EDS or the like and calculating the ratio of the area of the portion with different contrast to the entire area of the measurement field of view. Additionally, the measurements may be made at at least 3, 5, or 10 different points or cross sections and the arithmetic average may be calculated.

As the lithium ion conductor has a porosity of 1% or less, the density of the lithium ion conductor increases, thereby minimizing the amount of decrease in ionic conductivity during the manufacturing process of a stacked all-solid-state battery, and thus predicting ionic conductivity in a stacked all-solid-state battery. This is possible.

If the porosity of a lithium ion conductor exceeds 1%, the ionic conductivity may decrease or it may become vulnerable to the external environment. As porosity increases, ionic conductivity decreases and becomes more sensitive to the external environment.

A method of manufacturing a lithium ion conductor according to another embodiment includes the step of calcining oxide powder containing lithium (Li), silicon (Si), and boron (B) while pressing.

First, various types of amorphous materials are mixed as raw materials.

As amorphous materials, network former (NWF), network modifier, and, if necessary, intermediate oxide can be used.

The mesh-forming oxide can be vitrified by itself. Although the modified oxide cannot be amorphized in itself, it can be amorphized within the network structure formed by the mesh-shaped oxide, that is, it can modify the mesh.

SiO ₂ and B ₂ O ₃ may be used as the mesh-forming oxide. Li ₂ O may be used as the modified oxide.

Intermediate oxides are raw materials with properties intermediate between network-forming oxides and modified oxides, and have effects such as lowering the thermal expansion coefficient among the thermal properties of glass, for example.

Examples of intermediate oxides include Na (sodium), Mg (magnesium), Al (aluminum), P (phosphorus), K (potassium), Ca (calcium), Ti (titanium), V (vanadium), and Cr (chromium). ), Mn (manganese), Fe (iron), Co (cobalt), Ni (nickel), Cu (copper), Zn (zinc), Ga (gallium), Ge (germanium), Se (selenium), Rb (rubidium) ), S (sulfur), Y (yttrium), Zr (zirconium), Nb (niobium), Mo (molybdenum), Ag (silver), In (indium), Sn (tin), Sb (antimony), Cs (cesium) ), Ba (vanadium), Hf (hafnium), Ta (tantalum), W (tungsten), Pb (lead), Bi (bismuth), Au (gold), La (lanthanum), Nd (neodymium), Eu (europium) ), or oxides containing combinations thereof may be used.

The amount of Li ₂ O relative to the total amount of Li ₂ O, SiO ₂ and B ₂ O ₃ may be 45 mol% to 80 mol%, or 50 mol% to 70 mol%. The blended amount of SiO ₂ relative to the total amount of Li ₂ O, SiO ₂ and B ₂ O ₃ may be 5 mol% to 20 mol%. The blended amount of B 2 O ₃ relative _to the total amount of Li ₂ O, SiO ₂ and B ₂ O ₃ may be 15 mol% to 50 mol%.

When using an intermediate oxide as an amorphous material, the blending amount of the intermediate oxide relative to the total amount of the network-forming oxide, modified oxide, and intermediate oxide may be 5 mol% or less.

By vitrifying the raw material, a precursor (glass) of a lithium ion conductor is manufactured. Methods for vitrifying raw materials include, for example, melting the raw materials to a melt and allowing to cool, pressing the melt with a metal plate, dropping into mercury, strip furnace, splat quenching, and roll method ( In addition to single, twin), mechanical milling method, sol/gel method, vapor deposition method, sputtering method, laser ablation method, PLD (pulse laser deposition) method, or plasma method can be used.

A lithium ion conductor can be manufactured by firing a precursor of a lithium ion conductor while applying pressure. At this time, the firing temperature may be 300°C to 550°C, for example, 400°C to 500°C, and the pressurization may be performed by applying a pressure of 1 MPa to 200 MPa, for example, 1 MPa to 50 MPa.

A lithium ion conductor manufactured by firing a precursor of a lithium ion conductor while applying pressure may have a crystallinity of 25.5% or less and a porosity of 1% or less.

Optionally, the produced lithium ion conductor can be powdered. Examples of the powder manufacturing method include the mechanochemical method.

An all-solid-state battery according to another embodiment includes a solid electrolyte layer and an anode and a cathode disposed with the solid electrolyte layer interposed, and any one selected from the group consisting of a solid electrolyte layer, an anode, a cathode, and a combination thereof. includes a lithium ion conductor according to one embodiment.

FIG. 1 is a perspective view schematically showing an all-solid-state battery according to another embodiment, FIG. 2 is a cross-sectional view of the all-solid-state battery according to the embodiment shown in FIG. 1, and FIG. 3 is a schematic view of an all-solid-state battery according to the embodiment shown in FIG. 1. This is an exploded perspective view schematically showing the unit cell stacked structure of an all-solid-state battery. Hereinafter, the all-solid-state battery will be described in detail with reference to FIGS. 1 to 3.

As an example, the all-solid-state battery 100 may have a roughly hexahedral shape.

In this embodiment, for convenience of explanation, the two surfaces opposing each other in the thickness direction (T-axis direction) of the all-solid-state battery 100 are referred to as the first surface and the second surface, and are connected to the first surface and the second surface and have a length of The two sides facing each other in the direction (L direction) will be defined as the third side and the fourth side. For example, the first and second sides of the all-solid-state battery 100 that face each other may be the third and fourth sides.

The all-solid-state battery 100 according to this embodiment includes electrode layers 120 and 140 and a solid electrolyte layer 130 disposed adjacent to the electrode layers 120 and 140 in the stacking direction. The electrode layers 120 and 140 include a positive electrode layer 120 and a negative electrode layer 140, and basically include current collectors 123 and 143 and an active material layer 121 applied to at least one surface of the current collectors 123 and 143. , 122, 141, 142).

The positive electrode layer 120 is formed by applying the positive electrode active material layers 121 and 122 on at least one side of the positive electrode current collector 123, and the negative electrode layer 140 is formed by applying a negative electrode active material layer ( 141, 142) can be applied. For example, the electrode layer located at the top based on the stacking direction is formed by applying the positive electrode active material layer 122 to one side of the positive electrode current collector 123, and the electrode layer located at the bottom is formed by applying the positive electrode layer 122 to one side of the negative electrode current collector 143. The active material layer 141 may be formed by being applied. And the electrode layers located between the top and bottom are formed by applying the positive electrode active material layers 121 and 122 on both sides of the positive electrode current collector 123, or the negative electrode active material layers 141 and 142 are applied on both sides of the negative electrode current collector 143. It can be formed by applying.

The positive electrode active material layers 121 and 122 may include a positive electrode active material and, optionally, a solid electrolyte. Additionally, the positive active material layers 121 and 122 may optionally further include additives such as a binder or a conductive agent.

For example, the positive electrode active material is not particularly limited as long as it can secure sufficient capacity of the all-solid-state battery 100. For example, the positive electrode active material may include lithium cobalt oxide, lithium nickel cobalt manganese oxide, lithium nickel cobalt aluminum oxide, lithium iron phosphate, lithium manganese oxide, or a combination thereof.

For example, the positive electrode active material may be a compound represented by the following formula: Li _a A _lb M _b D ₂ (wherein 0.90≤a≤1.8, 0≤b≤0.5); Li _a E _lb M _b O _2-c D _c (wherein 0.90≤a≤1.8, 0≤b≤0.5, 0≤c≤0.05); LiE _2-b M _b O _4-c D _c (wherein 0≤b≤0.5, 0≤c≤0.05); Li _a Ni _1-bc Co _b M _c D _α (wherein 0.90≤a≤1.8, 0≤b≤0.5, 0≤c≤0.05, 0<α≤2); Li _a Ni _1-bc Co _b M _c O _{2- α} Li _a Ni _1-bc CO _b M _c O _{2- α} Li _a Ni _1-bc Mn _b M _c D _α (wherein 0.90≤a≤1.8, 0≤b≤0.5, 0≤c≤0.05, 0<α≤2); Li _a Ni _1-bc Mn _b M _c O _{2- α} Li _a Ni _{1-bc Mn b} M _c O _2-α Li _a Ni _b E _c G _d O ₂ (wherein 0.90≤a≤1.8, 0≤b≤0.9, 0≤c≤0.5, 0.001≤d≤0.1); Li _a Ni _b Co _c Mn _d GeO ₂ (wherein, 0.90≤a≤1.8, 0≤b≤0.9, 0≤c≤0.5, 0≤d≤0.5, 0.001≤e≤0.1); Li _a NiGbO ₂ (wherein 0.90≤a≤1.8, 0.001≤b≤0.1); Li _a CoGbO ₂ (wherein 0.90≤a≤1.8, 0.001≤b≤0.1); Li _a MnGbO ₂ (wherein, 0.90≤a≤1.8, 0.001≤b≤0.1); Li _a Mn ₂ GbO ₄ (wherein 0.90≤a≤1.8, 0.001≤b≤0.1); QO ₂ ; QS ₂ ; LiQS ₂ ; V ₂ O ₅ ; LiV ₂ O ₂ ; LiRO ₂ ; LiNiVO ₄ ; Li _(3-f) J ₂ (PO ₄ ) ₃ (0≤f≤2); Li _(3-f) Fe ₂ (PO ₄ ) ₃ (wherein 0≤f≤2); and LiFePO ₄ , where A is Ni, Co, or Mn; M is Al, Ni, Co, Mn, Cr, Fe, Mg, Sr, V, or a rare-earth element; D is O, F, S, or P; E is Co or Mn; X is F, S, or P; G is Al, Cr, Mn, Fe, Mg, La, Ce, Sr, or V; Q is Ti, Mo or Mn; R is Cr, V, Fe, Sc, or Y; J is V, Cr, Mn, Co, Ni, or Cu.

The positive electrode active material is also LiCoO ₂ , LiMn _x O _2x (where x = 1 or 2), LiNi _1-x Mn _x O _2x (where 0<x<1), LiNi _1-xy Co _x Mn _y It may be O ₂ (where 0≤x≤0.5, 0≤y≤0.5), LiFePO ₄ , TiS ₂ , FeS ₂ , TiS ₃ , or FeS ₃ .

The solid electrolyte may include a lithium ion conductor according to one embodiment. The content of the solid electrolyte may be 0.1 parts by weight or more, 1 part by weight or more, or 10 parts by weight or more, and 80 parts by weight or less, 60 parts by weight, or 50 parts by weight or less, based on a total of 100 parts by weight of the positive electrode active material. there is.

The conductive agent is not particularly limited as long as it has conductivity without causing chemical changes in the all-solid-state battery 100. For example, the conductive agent includes graphite such as natural graphite or artificial graphite; Carbon-based materials such as carbon black, acetylene black, Ketjen black, channel black, furnace black, lamp black, and summer black; Conductive fibers such as carbon fiber and metal fiber; fluorinated carbon; Metal powders such as aluminum and nickel powder; Conductive whiskeys such as zinc oxide and potassium titanate; Conductive metal oxides such as titanium oxide; Conductive materials such as polyphenylene derivatives may be used.

The content of the conductive agent may be 1 part by weight to 10 parts by weight, for example, 2 parts by weight to 5 parts by weight, based on 100 parts by weight of the positive electrode active material. When the content of the conductive agent is within the above range, the finally obtained electrode may have excellent conductivity characteristics.

A binder can be used to improve the bonding strength between an active material and a conductive agent. The binder is polyvinylidene fluoride, polyvinyl alcohol, carboxymethyl cellulose (CMC), starch, hydroxypropyl cellulose, regenerated cellulose, polyvinylpyrrolidone, polytetrafluoroethylene, polyethylene, poly Examples include propylene, ethylene-propylene-dienter polymer (EPDM), sulfonated EPDM, styrene butadiene rubber, fluorine rubber, or various copolymers.

The content of the binder may be 1 part by weight to 50 parts by weight, for example, 2 parts by weight to 5 parts by weight, based on 100 parts by weight of the total positive electrode active material. When the binder content satisfies the above range, the active material layer can have high bonding strength.

As the positive electrode current collector 123, a porous material such as a network or mesh shape can be used, and a porous metal plate such as stainless steel, nickel, or aluminum can be used. Additionally, the positive electrode current collector 123 may be coated with an oxidation-resistant metal or alloy film to prevent oxidation.

The negative electrode active material layers 141 and 142 may include a negative electrode active material and, optionally, a solid electrolyte. Additionally, the negative electrode active material layers 141 and 142 may optionally further include additives such as a binder or a conductive agent.

The negative electrode active material may be carbon-based material, silicon, silicon oxide, silicon-based alloy, silicon-carbon-based material composite, tin, tin-based alloy, tin-carbon composite, metal oxide, or a combination thereof, and may be lithium metal and/or lithium metal. May contain alloys.

The lithium metal alloy may include lithium and metals/metalloids capable of alloying with lithium. For example, metals/metalloids that can be alloyed with lithium include Si, Sn, Al, Ge, Pb, Bi, Sb, Si-Y alloy (Y is an alkali metal, an alkaline earth metal, a group 13 to 16 element, a transition metal, Rare earth elements or combination elements thereof, not including Si), Sn-Y alloy (Y is an alkali metal, alkaline earth metal, group 13 to 16 element, transition metal, lithium titanium oxide (Li ₄ Ti ₅ O ₁₂ ) It may be a transition metal oxide, a rare earth element, or a combination thereof, but does not include Sn) or M _n O _x (0<x≤2).

Element Y includes Mg, Ca, Sr, Ba, Ra, Sc, Y, Ti, Zr, Hf, Rf, V, Nb, Ta, Db, Cr, Mo, W, Sg, Tc, Re, Bh, Fe, Pb. , Ru, Os, Hs, Rh, Ir, Pd, Pt, Cu, Ag, Au, Zn, Cd, B, Al, Ga, Sn, In, Tl, Ge, P, As, Sb, Bi, S, Se , Te, Po, or a combination thereof.

Additionally, oxides of metals/metalloids that can be alloyed with lithium may be lithium titanium oxide, vanadium oxide, lithium vanadium oxide, SnO ₂ , SiO _x (0<x<2), etc. For example, the negative electrode active material may include one or more elements selected from the group consisting of elements in groups 13 to 16 of the periodic table of elements. For example, the negative electrode active material may include one or more elements selected from the group consisting of Si, Ge, and Sn.

The carbon-based material may be crystalline carbon, amorphous carbon, or mixtures thereof. Crystalline carbon may be graphite, such as natural graphite or artificial graphite, in the form of amorphous, plate-shaped, flake, spherical or fibrous shapes. In addition, amorphous carbon is soft carbon (low-temperature calcined carbon) or hard carbon, mesophase pitch carbide, calcined coke, graphene, carbon black, fullerene soot, and carbon. It may be nanotube, carbon fiber, etc.

Silicon may be _Si , _SiO The silicon-containing metal alloy may include, for example, silicon and one or more of Al, Sn, Ag, Fe, Bi, Mg, Zn, in, Ge, Pb, and Ti.

The solid electrolyte may include a lithium ion conductor according to one embodiment. The content of the solid electrolyte is 0.1 part by weight or more, 1 part by weight or more, or 10 parts by weight or more, and 80 parts by weight or less, 60 parts by weight, or 50 parts by weight or less, based on a total of 100 parts by weight of the negative electrode active material. there is.

The negative electrode active material layer may also optionally include a conductive agent and a binder as described in the positive electrode active material layer.

As the negative electrode current collector 143, a porous material such as a network or mesh shape can be used, and a porous metal plate such as stainless steel, nickel, or aluminum can be used. Additionally, the negative electrode current collector 143 may be coated with an oxidation-resistant metal or alloy film to prevent oxidation.

The solid electrolyte layer 130 may be stacked between the anode layer 120 and the cathode layer 140. Accordingly, the solid electrolyte layer 130 may be disposed adjacent to the positive electrode active material layers 121 and 122 of the positive electrode layer 120 and the negative electrode active material layers 141 and 142 of the negative electrode layer 140 in the stacking direction. Accordingly, in the all-solid-state battery 100, a plurality of positive electrode layers 120 and negative electrode layers 140 may be alternately arranged and stacked with a plurality of solid electrolyte layers 130 interposed between them. The all-solid-state battery 100 is manufactured by alternately stacking a plurality of positive electrode layers 120 and negative electrode layers 140, and interposing a plurality of solid electrolyte layers 130 between them to produce a cell stack. It may be a stacked all-solid-state battery (100) manufactured by batch firing.

The solid electrolyte layer 130 may include an inorganic solid electrolyte including an oxide-based solid electrolyte, a sulfide-based solid electrolyte, or a combination thereof. As an example, the solid electrolyte layer 130 may include a lithium ion conductor according to one embodiment.

The oxide-based solid electrolyte is Garnet-type, Nasicon-type, LISICON-type, perovskite-type, LiPON-type, or amorphous type. (Glass) It may be an electrolyte, etc.

The garnet-based solid electrolyte may refer to lithium-lanthanum zirconium oxide (LLZO) represented by Li _a La _b Zr _c O ₁₂ , such as Li ₇ La ₃ Zr ₂ O ₁₂ , and is a nasicon-based solid. The electrolyte is Li _1+x Al _x Ti with Ti introduced into a Li 1+x Al _x M _2-x (PO ₄ ) ₃ (LAMP) (0<x<2, M _is Zr, Ti, or Ge) type compound Lithium-aluminum-titanium-phosphate (LATP) of _2-x (PO ₄ ) ₃ (0<x<1), Li _1+x of Li _1.3 Al _0.3 Ti _1.7 (PO ₄ ) ₃ with excess lithium introduced, etc. Lithium-aluminium-germanium _{- phosphate} (LAGP) and/or lithium-zirconium-phosphate ₍ LZP) of LiZr ₂ (PO ₄ ) _{3 ,} denoted by Al It can mean.

In addition, the risicon-based solid electrolyte may be represented by xLi ₃ AO ₄ -(1-x)Li ₄ BO ₄ (A is P, As, or V, etc., B is Si, Ge, or Ti, etc.), and Li ₄ Solid solution oxides including Zn(GeO ₄ ) ₄ , Li ₁₀ GeP ₂ O ₁₂ (LGPO), Li _3.5 Si _0.5 P _0.5 O ₄ , Li _10.42 Si(Ge) _1.5 P _1.5 Cl _0.08O11.92 , or Li ₄ Li 2 SP 2 S 5 _{, Li 2} S-SiS 2 , _{Li 2} , denoted as _-x M _1-y M' _y S ₄ (M _is Si, Ge, and M' is P, Al, Zn, or Ga) It may refer to a solid solution sulfide containing S-SiS ₂ -P ₂ S ₅ , or Li ₂ S-GeS ₂ .

The perovskite-based solid electrolyte is lithium-lanthanum-titanium-oxide expressed as Li _3x La _2/3-x1/3-2x TiO ₃ (0<x<0.16), such as Li _1/8 La _5/8 TiO ₃ (lithium lanthanum titanate, LLTO), and the lipon-based solid electrolyte may refer to a nitride such as lithium phosphorous oxynitride such as Li _2.8 PO _3.3 N _0.46 .

Amorphous electrolytes include Li ₂ OB ₂ O ₃ -SiO ₂ , Li ₂ OB ₂ O ₃ -P ₂ O ₅ , Li ₃ BO ₃ -Li ₂ SO ₄ , or Li ₃ BO ₃ -Li ₂ CO ₃ . there is.

The sulfide-based solid electrolyte contains sulfur atoms among the electrolyte components and is not particularly limited to specific components, and may include one or more of a crystalline solid electrolyte, an amorphous solid electrolyte (glassy solid electrolyte), or a glass ceramic solid electrolyte. there is.

For example, the sulfide-based solid electrolyte is an LPS-type sulfide containing sulfur and phosphorus (for example, Li ₂ SP ₂ S ₅ ), Li _4-x Ge _1-x P _x S ₄ (x is 0.1 to 2, or x may be 3/4 _{, or 2/3} ), Li _10±1 MP _{2 0.166} S ₄ , Li ₄ SnS ₄ , Li _3.25 Ge _0.25 P _0.75 S ₄ , Li ₂ SP ₂ S ₅ , B ₂ S ₃ -Li ₂ S, xLi ₂ S-(100-x)P ₂ S ₅ (x is 70 to 80), Li ₂ S-SiS ₂ -Li ₃ N, Li ₂ SP ₂ S ₅ -LiI, Li ₂ S-SiS ₂ -LiI, Li ₂ SB ₂ S ₃ -LiI, Li ₁₀ SnP ₂ S ₁₂ , It may be a Thio-LISICON type compound such as Li _3.25 Ge _0.25 P _0.75 S ₄ .

The ionic conductivity of the solid electrolyte may be 1X10 ^-6 S/cm or more. Ion conductivity may be a value measured at a temperature of 25°C. ^{Ion conductivity is more than 1} It may be more than this, and the upper limit is not particularly limited. When a solid electrolyte that satisfies the ionic conductivity in the above range is used, the all-solid-state battery 100 can exhibit high output.

A margin insulating layer 150 may be disposed along the edges of the anode layer 120 and the cathode layer 140. The margin insulating layer 150 is located on the solid electrolyte layer 130 and may be formed laterally adjacent to the edge of the positive electrode active material layers 121 and 122 or the negative electrode active material layers 141 and 142. Accordingly, the margin insulating layer 150 may be located on the same layer of the anode layer 120 and the cathode layer 140, respectively.

The margin insulating layer 150 may include an insulating material having an ionic ^conductivity of ^1.0 May include insulating material.

For example, the insulating material may be polyolefin such as polyethylene or polypropylene, polyester such as polyethylene terephthalate (PET), polyurethane, or polyimide.

Additionally, the margin insulating layer 150 may include an inorganic solid electrolyte including an oxide-based solid electrolyte, a sulfide-based solid electrolyte, or a combination thereof used in the solid electrolyte layer 130. However, the material included in the margin insulating layer 150 is not limited to this and may include various materials.

The anode layer 120, the solid electrolyte layer 130, the cathode layer 140, and the margin insulating layer 150 may be stacked as described above to form a cell stack of the all-solid-state battery 100. A protective layer may be formed with an insulating material on the top and bottom of the cell stack of the all-solid-state battery 100.

In addition, the terminals of the positive electrode current collector 123 and the terminals of the negative electrode current collector 143 are exposed on both sides of the cell stack of the all-solid-state battery 100, and external electrodes 112 and 114 are connected to these exposed terminals. These can be connected and combined. That is, the external electrodes 112 and 114 may be configured to be connected to the terminal of the positive electrode current collector 123 to have a positive electrode, and to be connected to the terminal of the negative electrode current collector 143 to have a negative electrode. If the terminals of the positive electrode current collector 123 and the terminals of the negative electrode current collector 143 are configured to face opposite directions, the external electrodes 112 and 114 may also be located on both sides, respectively.

The external electrodes 112 and 114 may include conductive metal and glass.

Conductive metals include, for example, copper (Cu), nickel (Ni), tin (Sn), palladium (Pd), platinum (Pt), gold (Au), silver (Ag), tungsten (W), and titanium (Ti). It may be a conductive metal containing , lead (Pb), or an alloy thereof.

The glass component included in the external electrodes 112 and 114 may be a mixture of oxides. The glass component may include, for example, silicon oxide, boron oxide, aluminum oxide, transition metal oxide, alkali metal oxide, alkaline earth metal oxide, or combinations thereof. Here, the transition metal is selected from zinc (Zn), titanium (Ti), copper (Cu), vanadium (V), manganese (Mn), iron (Fe), or nickel (Ni), and the alkali metal is lithium (Li). ), sodium (Na), or potassium (K), and the alkaline earth metal may be selected from magnesium (Mg), calcium (Ca), strontium (Sr), or barium (Ba).

The method of forming the external electrodes 112 and 114 is not particularly limited. For example, the cell stack can be formed by dipping it into a conductive paste containing conductive metal and glass, or it can be formed by printing the conductive paste on the surface of the cell stack using a screen printing method or gravure printing method. Additionally, various methods can be used, such as applying the conductive paste to the surface of the cell stack or forming a dry film by drying the conductive paste onto the cell stack.

Below, specific embodiments of the invention are presented. However, the examples described below are only for illustrating or explaining the invention in detail, and should not limit the scope of the invention.

[Manufacturing example]

(Preparation Example 1: Preparation of lithium ion conductor cullet)

Lithium borosilicate glass is manufactured using lithium oxide (Li ₂ O), boron oxide (B ₂ O ₃ ), and silica (SiO ₂ ) as raw materials. If necessary, additional oxides such as phosphorus oxide (P ₂ O ₅ ) and germanium oxide (GeO ₂ ) are included in a total amount of about 5 mol%.

The raw materials are mixed homogeneously and placed in a platinum crucible and melted at 900°C to 1100°C. Colorless and transparent cullets are obtained by rapidly quenching the molten glass liquid in an environment below the temperature at which crystallization occurs. Frit is obtained by pulverizing cullet through a coarse grinding and fine grinding process. The average particle diameter of the frit is 1.0 ㎛ to 10 ㎛, and the particle size range is adjusted differently as needed.

An ion milling cross-sectional scanning electron microscope (SEM) photograph of the prepared Li ₂ OB ₂ O ₃ -SiO ₂ amorphous lithium ion conductor cullet is shown in FIG. 4 .

(Preparation Example 2: Preparation of lithium ion conductor pellets)

To evaluate the manufactured glass frit, it is processed into pellets of circular shape. At this time, pressure firing equipment is used for firing to reduce porosity. The pressure is sufficient under any conditions as long as it can reduce the porosity to 1% or less in the range of 1 MPa to 200 MPa. The temperature range can be set to an appropriate temperature range depending on the glass composition through thermal analysis (Tg-DTA or DSC). To manufacture a lithium ion conductor with a crystallinity of 25.5% or less, it is fired below the crystallization temperature. The crystallization temperature depends on the composition ratio of the glass, decreases as the content of Li ₂ O and B ₂ O ₃ increases, and tends to increase as the content ratio of SiO ₂ increases. However, the crystallization temperature may vary depending on the type of additional oxide. Lithium ion conductors according to Examples and Comparative Examples were manufactured by adjusting the pressurizing conditions and firing conditions as shown in Tables 1 and 2 below.

Ion milling cross-sectional scanning electron microscopy (SEM) photographs of the lithium ion conductor pellets prepared in Example 1, Comparative Example 1, Comparative Example 3, and Comparative Example 4 are shown in FIGS. 5 to 8, respectively.

[Experimental example]

(Experimental Example 1: Synthesis evaluation of lithium ion conductor)

Figure 9 shows the results of determining the thermal behavior of cullet and frit containing 50 mol% Li ₂ O through DSC analysis. Referring to FIG. 9, it can be seen that densification of the lithium ion conductor occurs under limited conditions between Tg and Tx.

Figure 10 shows the results of analyzing the crystalline states of cullet, frit, and lithium ion conductor through XRD analysis. Referring to Figure 10, it can be seen that, unlike the amorphous cullet and frit, the lithium ion conductor was crystallized to a level of crystallinity of 25.5% or less.

Figure 11 shows the results of SEM-EDAX mapping analysis of a lithium ion conductor. Referring to FIG. 11, in the manufactured lithium ion conductor, it can be proven by matching the XRD results that the seed has grown into a crystal containing Si.

(Experimental Example 2: Evaluation of electrochemical properties of lithium ion conductor)

Electrochemical analysis is performed to evaluate the lithium ion conduction performance of lithium ion conductors.

Figure 12 is a cole-cole plot result of the lithium ion conductor manufactured in Example 1 and Comparative Example 1. Referring to FIG. 12, it can be seen that the lithium ion conductor prepared in Example 1 has superior ionic conductivity compared to the lithium ion conductor prepared in Comparative Example 1. In addition, it can be seen that the resistance of the lithium ion conductor prepared in Comparative Example 1 in which crystallization was performed increased by two times.

Figure 13 is a voltage-capacitance graph in a symmetric cell of the lithium ion conductor prepared in Example 1 and Comparative Example 1. Referring to FIG. 13, the lithium ion conductor prepared in Example 1 shows an overvoltage of 30 mV even when reacted at 10 μA·cm ^-2 to 1 mAh·cm ^-2 (over 200 h), which is similar to the electric current of the liquid electrolyte. It can be seen that chemical properties can be secured. On the other hand, it can be seen that the lithium ion conductor prepared in Comparative Example 1 suffers from crystallization and deteriorates overall performance.

(Experimental Example 3: Characteristic analysis of lithium ion conductor)

High transparency manufactured through high temperature and high pressure firing The electrode surface is formed by coating 100 nm or more of platinum or gold on both sides of the lithium ion conductor pellet. At this time, the two sides must not be electrically connected. A cole-cole plot is obtained in the frequency range of 1 MHz to 0.01 Hz using electrochemical impedance analysis equipment to obtain ionic conductivity considering the area and thickness of the lithium ion conductor, and the results are summarized in Tables 1 and 2.

Furtherance Pressure firing Firing temperature (℃) decision state Crystallinity (%) Porosity (%) Ion conductivity (S/cm) Example 1 Li ₂ OB ₂ O ₃ -SiO ₂ practice 415 amorphous 0 0 2.33E-07 Example 2 Li ₂ OB ₂ O ₃ -SiO ₂ practice 430 Amorphous + Crystal 25.13 0 1.34E-07 Example 3 Li ₂ OB ₂ O ₃ -SiO ₂ -P ₂ O ₅ -GeO ₂ practice 475 Amorphous + Crystal 14.27 0.1 1.67E-07 Comparative Example 1 Li ₂ OB ₂ O ₃ -SiO ₂ practice 450 decision 100 0.97 1.59E-08

Furtherance Pressure firing Firing temperature (℃) decision state Crystallinity (%) Porosity (%) Ion conductivity (S/cm) Comparative Example 2 Li ₂ OB ₂ O ₃ -SiO ₂ Not implemented 450 amorphous 0 31.24 1.72E-09 Comparative Example 3 Li ₂ OB ₂ O ₃ -SiO ₂ Not implemented 460 Amorphous + Crystal 27.23 3.26 2.63E-08 Comparative Example 4 Li ₂ OB ₂ O ₃ -SiO ₂ -P ₂ O ₅ -GeO ₂ Not implemented 475 Amorphous + Crystal 29.61 2.85 1.09E-08 Comparative Example 5 Li ₂ OB ₂ O ₃ -SiO ₂ -P ₂ O ₅ -GeO ₂ Not implemented 500 decision 100 4.68 1.42E-08

Referring to Tables 1 and 2, it can be seen that as the crystallinity of the lithium ion conductor is 25.5% or less, the ion conductivity is 1.0X10 ^-7 S/cm or more.

Although the preferred embodiments of the present invention have been described above, the present invention is not limited thereto, and can be implemented with various modifications within the scope of the claims, the detailed description of the invention, and the accompanying drawings. It is natural that it falls within the scope of the invention.

100: All-solid-state battery
112, 114: external electrode
120: anode layer
121, 122: positive active material layer
123: Anode current collector
130: solid electrolyte layer
140: cathode layer
141, 142: Negative active material layer
143: negative electrode current collector
150: Margin insulating layer

Claims (18)

Contains oxides containing lithium (Li), silicon (Si), and boron (B),
The crystallinity calculated by Equation 1 below is 25.5% or less,
Lithium ion conductor for all-solid-state batteries.
[Equation 1]
Crystallinity (%) = [Ic/(Ic+Ia)] × 100
(In Equation 1, Ic is the sum of the integral values of the scattering intensity of the crystalline peak in the X-ray diffraction analysis spectrum of the lithium ion conductor,
Ia is the sum of the integral values of the scattering intensity of the amorphous halo in the X-ray diffraction spectrum of the lithium ion conductor) In paragraph 1:
The lithium ion conductor is a lithium ion conductor for an all-solid-state battery having a crystallinity of 0% to 12.5%. In paragraph 1:
The lithium ion conductor is a lithium ion conductor for an all-solid-state battery having a porosity of 1% or less. In paragraph 3,
The lithium ion conductor is a lithium ion conductor for an all-solid-state battery having a porosity of 0% to 0.5%. In paragraph 1:
The lithium ion conductor contains 45 mol% to 80 mol% of the lithium (Li) oxide, 5 mol% to 20 mol% of the silicon (Si) oxide, and 15 mol% of the boron (B) oxide relative to the entire lithium ion conductor. A lithium ion conductor for an all-solid-state battery, comprising from mol% to 50 mol%. In paragraph 5,
The lithium ion conductor is a lithium ion conductor for an all-solid-state battery, comprising 50 mol% to 70 mol% of lithium (Li) oxide relative to the entire lithium ion conductor. In paragraph 1:
The lithium ion conductor is Na (sodium), Mg (magnesium), Al (aluminium), P (phosphorus), K (potassium), Ca (calcium), Ti (titanium), V (vanadium), Cr (chromium), Mn (manganese), Fe (iron), Co (cobalt), Ni (nickel), Cu (copper), Zn (zinc), Ga (gallium), Ge (germanium), Se (selenium), Rb (rubidium), S (sulfur), Y (yttrium), Zr (zirconium), Nb (niobium), Mo (molybdenum), Ag (silver), In (indium), Sn (tin), Sb (antimony), Cs (cesium), Ba (vanadium), Hf (hafnium), Ta (tantalum), W (tungsten), Pb (lead), Bi (bismuth), Au (gold), La (lanthanum), Nd (neodymium), Eu (europium), Or a lithium ion conductor for an all-solid-state battery, further comprising an additional oxide including a combination thereof. In paragraph 7:
The lithium ion conductor further includes additional oxides including P (phosphorus) and Ge (germanium). In paragraph 7:
The lithium ion conductor is a lithium ion conductor for an all-solid-state battery, wherein the lithium ion conductor contains 5 mol% or less of the additional oxide relative to the entire lithium ion conductor. In paragraph 9:
The lithium ion conductor is a lithium ion conductor for an all-solid-state battery, wherein the lithium ion conductor contains 1 mol% or less of the additional oxide relative to the entire lithium ion conductor. It includes the step of calcining oxide powder containing lithium (Li), silicon (Si), and boron (B) while pressurizing,
The crystallinity calculated by Equation 1 below is 25.5% or less,
Method for manufacturing lithium ion conductors for all-solid-state batteries.
[Equation 1]
Crystallinity (%) = [Ic/(Ic+Ia)] × 100
(In Equation 1, Ic is the sum of the integral values of the scattering intensity of the crystalline peak in the X-ray diffraction analysis spectrum of the lithium ion conductor,
Ia is the sum of the integral values of the scattering intensity of the amorphous halo in the X-ray diffraction spectrum of the lithium ion conductor) In paragraph 11:
A method for producing a lithium ion conductor for an all-solid-state battery, wherein the firing temperature is 300°C to 550°C. In paragraph 11:
A method of manufacturing a lithium ion conductor for an all-solid-state battery, wherein the pressurization applies a pressure of 1 MPa to 200 MPa. It includes a solid electrolyte layer and an anode and a cathode disposed between the solid electrolyte layer,
Any one selected from the group consisting of a solid electrolyte layer, an anode, a cathode, and a combination thereof includes a lithium ion conductor containing an oxide containing lithium (Li), silicon (Si), and boron (B),
The lithium ion conductor has a crystallinity of 25.5% or less calculated by Equation 1 below,
All-solid-state battery.
[Equation 1]
Crystallinity (%) = [Ic/(Ic+Ia)] × 100
(In Equation 1, Ic is the sum of the integral values of the scattering intensity of the crystalline peak in the X-ray diffraction analysis spectrum of the lithium ion conductor,
Ia is the sum of the integral values of the scattering intensity of the amorphous halo in the X-ray diffraction spectrum of the lithium ion conductor) In paragraph 14:
The lithium ion conductor is an all-solid-state battery with a porosity of 1% or less. In paragraph 14:
The lithium ion conductor contains 45 mol% to 80 mol% of the lithium (Li) oxide, 5 mol% to 20 mol% of the silicon (Si) oxide, and 15 mol% of the boron (B) oxide relative to the entire lithium ion conductor. An all-solid-state battery comprising from mol% to 50 mol%. In paragraph 14:
The lithium ion conductor is Na (sodium), Mg (magnesium), Al (aluminium), P (phosphorus), K (potassium), Ca (calcium), Ti (titanium), V (vanadium), Cr (chromium), Mn (manganese), Fe (iron), Co (cobalt), Ni (nickel), Cu (copper), Zn (zinc), Ga (gallium), Ge (germanium), Se (selenium), Rb (rubidium), S (sulfur), Y (yttrium), Zr (zirconium), Nb (niobium), Mo (molybdenum), Ag (silver), In (indium), Sn (tin), Sb (antimony), Cs (cesium), Ba (vanadium), Hf (hafnium), Ta (tantalum), W (tungsten), Pb (lead), Bi (bismuth), Au (gold), La (lanthanum), Nd (neodymium), Eu (europium), or an all-solid-state battery further comprising an additional oxide including a combination thereof. In paragraph 14:
The all-solid-state battery includes a laminate including a plurality of the solid electrolyte layers and a plurality of the anodes and the cathodes alternately disposed with the plurality of solid electrolyte layers interposed therebetween, and one surface of the laminate and the one surface. An all-solid-state battery comprising first and second external electrodes disposed on opposing surfaces and connected to the positive and negative electrodes, respectively.