Composite solid electrolyte and all-solid-state battery including the same

Abstract

A composite solid electrolyte according to the present disclosure includes a garnet-type solid electrolyte and a Li super ionic conductor-type solid electrolyte including a Cl element. The Li super ionic conductor-type solid electrolyte is represented by Li a M b P c Cl d O e wherein M includes Zn, Al, Ga, Si, Ge, Ti, Mg, or a combination thereof, a, b, c, d, and e are molar ratios of each component, and satisfy 5 ≤ a ≤ 12, 0

Description

Technical Field

[0001] This disclosure relates to a composite solid electrolyte and an all-solid-state battery including the composite solid electrolyte. Background Technology

[0002] Recently, the miniaturization and long-term use of portable electronic devices have necessitated high-capacity batteries, and the widespread adoption of wearable electronics has also raised safety requirements. Therefore, the development of all-solid-state batteries using solid electrolytes instead of liquid electrolytes is progressing actively.

[0003] Because all-solid-state batteries do not use flammable organic solvents, the additional circuitry required for safety can be simplified. Therefore, all-solid-state batteries hold promise as a technology for manufacturing safe batteries with high capacity per unit volume.

[0004] Furthermore, compared to sulfide all-solid-state batteries that use sulfide electrolytes that react with oxygen and moisture in the air, batteries using sulfide electrolytes have a higher ionic conductivity (10 Ω·cm) than sulfide electrolytes. -2 Lower ionic conductivity (S / cm) (10 -4 S / cm to 10 -6 Oxide all-solid-state batteries with oxide electrolytes (S / cm) require a high-temperature sintering process but exhibit excellent stability.

[0005] Compared to lithium metal (vs. Li / Li+), oxide electrolytes, which typically use materials including vanadium (V), have the problem of inducing redox reactions in the voltage range of 0.5V to 1.5V. This redox reaction of vanadium is a side reaction, which makes it difficult for all-solid-state batteries to function properly, thus limiting their operation to a voltage range of 1.5V or higher.

[0006] In addition, garnet-type electrolytes, as a type of conventional oxide electrolyte, also have the disadvantages of high relative density and high firing temperature. Summary of the Invention

[0007] Solution to the problem

[0008] One aspect of the embodiment provides a composite solid electrolyte that can reduce the firing temperature, does not cause side reactions in the operating voltage range of 0V to 6V, has a high relative density, and has a high lithium-ion conductivity.

[0009] Another aspect of the embodiment provides an all-solid-state battery including the composite solid electrolyte.

[0010] However, the problems to be solved by the embodiments are not limited to those described above, and various extensions can be made within the scope of the technical concepts included in the embodiments.

[0011] Advantages of the invention

[0012] Based on the composite solid electrolyte according to the embodiments, the firing temperature can be reduced, no side reactions occur in the operating voltage range of 0V to 6V, the relative density is high, and the lithium-ion conductivity is high.

[0013] All-solid-state batteries incorporating this composite solid electrolyte have the advantage of being able to operate across the entire voltage range from 0V to 6V, as no side reactions occur within the operating voltage range of 0.75V to 1.5V. Furthermore, since there is no need to avoid the range of side reactions, it offers the advantage of expanding the types of electrode active materials that can be selected.

[0014] However, the various advantages and effects of the present invention are not limited to those described above, and will be more readily understood in the process of describing specific embodiments of the invention. Attached Figure Description

[0015] Figure 1 This is a schematic perspective view of an all-solid-state battery according to an embodiment.

[0016] Figure 2 yes Figure 1 The cross-sectional view of the all-solid-state battery according to an embodiment is shown.

[0017] Figure 3 It is shown schematically. Figure 1 An exploded perspective view of the cell stack structure of an all-solid-state battery according to an embodiment is shown.

[0018] Figure 4 This is a graph showing the side reaction analysis results of Example 1, Example 2, Comparative Example 9 and Comparative Example 10.

[0019] The best way to realize an invention

[0020] A composite solid electrolyte according to an embodiment includes: a garnet-type solid electrolyte; and a Li superionic conductor-type solid electrolyte containing Cl element. The Li superionic conductor-type solid electrolyte is represented by chemical formula 1.

[0021] [Chemical Formula 1]

[0022] Li a M b P c Cl d O e

[0023] M includes Zn, Al, Ga, Si, Ge, Ti, Mg, or combinations thereof, and

[0024] a, b, c, d, and e are the molar ratios of the respective components and satisfy 5 ≤ a ≤ 12, 0 < b ≤ 3, 0 < c ≤ 3, 0 < d ≤ 0.1, and 10 ≤ e ≤ 12.

[0025] M may include Si (silicon) or Ge (germanium).

[0026] M may not include V (vanadium).

[0027] The composite solid electrolyte may further include an oxide containing Li element and B element.

[0028] The oxide containing Li element and B element may include Li3BO3, Li4B2O5, LiBO2, or a combination thereof.

[0029] Based on the total volume of the composite solid electrolyte, the garnet-type solid electrolyte may be included in an amount of 10 vol% to 50 vol%.

[0030] Based on the total volume of the composite solid electrolyte, the Li superionic conductor-type solid electrolyte may be included in an amount of 40 vol% to 80 vol%.

[0031] Based on the total volume of the composite solid electrolyte, the oxide containing Li element and B element may be included in an amount of 5 vol% to 20 vol%.

[0032] The volume ratio of the garnet-type solid electrolyte and the Li superionic conductor-type solid electrolyte may be 10:80 to 45:45.

[0033] The volume ratio of the sum of the garnet-type solid electrolyte and the Li superionic conductor-type solid electrolyte to the oxide containing Li element and B element may be 80:20 to 90:10.

[0034] The composite solid electrolyte may have a relative density (%) of 80% or more.

[0035] The composite solid electrolyte may have a room temperature (25 °C) lithium ion conductivity of 1 × 10 -7 (S / cm) or more.

[0036] Li a M b P c Cl d O e may include Li 10.42 Si 1.5 P 1.5 Cl 0.08 O 11.92 .

[0037] A all-solid-state battery according to another embodiment includes: a solid electrolyte layer; and a positive electrode layer and a negative electrode layer, the solid electrolyte layer being disposed between the positive electrode layer and the negative electrode layer. The solid electrolyte layer includes a composite solid electrolyte, and the composite solid electrolyte includes a garnet (LLZO) type solid electrolyte and a Cl element as well as a Li superionic conductor solid electrolyte, and the Li superionic conductor type solid electrolyte is represented by Chemical Formula 1.

[0038] [Chemical Formula 1]

[0039] Li a M b P c Cl d O e

[0040] M includes Zn, Al, Ga, Si, Ge, Ti, Mg, or a combination thereof, and

[0041] a, b, c, d, and e are the molar ratios of the respective components and satisfy 5 ≤ a ≤ 12, 0 < b ≤ 3, 0 < c ≤ 3, 0 < d ≤ 0.1, and 10 ≤ e ≤ 12.

[0042] The composite solid electrolyte may further include an oxide containing a Li element and a B element.

[0043] A all-solid-state battery according to another embodiment includes: a stack including a plurality of solid electrolyte layers and a plurality of positive electrode layers and a plurality of negative electrode layers, the positive electrode layer and the negative electrode layer being alternately arranged and the plurality of solid electrolyte layers being disposed therebetween; and a first external electrode and a second external electrode, respectively disposed on one surface of the stack and on another surface opposite to the one surface, and respectively connected to the positive electrode layer and the negative electrode layer. The solid electrolyte layer includes a composite solid electrolyte, and the composite solid electrolyte includes a garnet (LLZO) type solid electrolyte and a Li superionic conductor type solid electrolyte containing a Cl element, and the Li superionic conductor type solid electrolyte is represented by Chemical Formula 1.

[0044] [Chemical Formula 1]

[0045] Li a M b P c Cl d O e

[0046] M includes Zn, Al, Ga, Si, Ge, Ti, Mg, or a combination thereof, and

[0047] a, b, c, d, and e are the molar ratios of the respective components and satisfy 5 ≤ a ≤ 12, 0 < b ≤ 3, 0 < c ≤ 3, 0 < d ≤ 0.1, and 10 ≤ e ≤ 12.

[0048] The composite solid electrolyte may further include an oxide containing Li element and B element. Detailed implementation mode

[0049] Hereinafter, various embodiments of the present invention will be described in detail with reference to the accompanying drawings, so that those skilled in the art can easily implement the present invention. The drawings and the description are considered to be illustrative rather than restrictive in nature. Throughout the specification, the same reference numerals represent the same elements. In addition, the drawings are provided only to allow easy understanding of the embodiments disclosed in this specification, and the drawings should not be construed as limiting the spirit disclosed in this specification, and it should be understood that the present invention includes all variations, equivalents, and alternatives without departing from the scope and spirit of the present invention. In addition, some components in the drawings are exaggerated, omitted, or shown schematically, and the dimensions of each component do not fully reflect the actual dimensions.

[0050] In addition, unless explicitly described to the contrary, the word "comprising" and variations such as "including" or "having" will be understood to imply including the stated elements but not excluding any other elements.

[0051] Throughout the specification, the "stacking direction" refers to the direction in which the components are stacked in sequence or the "thickness direction" perpendicular to the large surface (main surface) of the sheet-like component, which corresponds to the T-axis direction in the drawings. In addition, the "lateral direction" refers to the direction extending parallel to the large surface (main surface) from the edge of the sheet-like component or the "plane direction", which corresponds to the L-axis direction in the figure. In addition, the W-axis direction in the drawings can be the "width direction".

[0052] Hereinafter, various embodiments and modification examples will be described in detail with reference to the accompanying drawings.

[0053] The composite solid electrolyte according to an embodiment includes a garnet-type solid electrolyte and a LISICON-type solid electrolyte containing Cl element.

[0054] The garnet-type solid electrolyte is an oxide-based solid electrolyte, and compared with Li metal, it has the advantages of high lithium ion conductivity and high stability even at high temperatures.

[0055] The garnet-type solid electrolyte may mean a lithium-lanthanum-zirconium oxide (LLZO) represented by x La y Zr z A w O 12 ​

[0056] A may include Ga, Gd, Al, Mg, Zn, Sc, Nb, Ta, Bi, or a combination thereof.

[0057] x, y, z, and w are the molar ratios of the respective components and may be 6 < x ≤ 7, 2 < y ≤ 3, 1.5 < z ≤ 2, and 0 ≤ w ≤ 0.5. For example, the garnet-type solid electrolyte may include Li7La3Zr2O 12 , Li 6.25 Al 0.25 La3Zr2O 12 , Li 6.4 Ga 0.2 La3Zr2O 12 , Li 6.75 La3Zr 1.75 Nb 0.25 O 12 , Li 6.75 La3Zr 1.75 Ta 0.25 O 12 , Li 6.75 La3Zr 1.75 Al 0.25 O 12 or Li 6.4 Ga 0.2 La 2.95 Ga 0.05 Zr2O 12 .

[0058] The LISICON-type (Li superionic conductor) solid electrolyte is an oxide containing a Cl element.

[0059] For example, the LISICON-type solid electrolyte may be an oxide containing Li element, Si element, Ge element, P element, and Cl element.

[0060] For example, the LISICON-type solid electrolyte is represented by Chemical Formula 1.

[0061] [Chemical Formula 1]

[0062] Li a M b P c Cl d O e

[0063] M includes Zn, Al, Ga, Si, Ge, Ti, Mg, or a combination thereof.

[0064] For example, M may include Si (silicon) or Ge (germanium), and for example, M may not include V (vanadium).

[0065] a, b, c, d, and e are the molar ratios of the respective components, where 5 ≤ a ≤ 12, 0 < b ≤ 3, 0 < c ≤ 3, 0 < d ≤ 0.1, and 10 ≤ e ≤ 12.

[0066] In Chemical Formula 1, 10 ≤ a ≤ 12 or 10 ≤ a ≤ 11 can be satisfied.

[0067] In Chemical Formula 1, 1 ≤ b ≤ 3 or 1 ≤ b ≤ 1.5 can be satisfied.

[0068] In Chemical Formula 1, 1 ≤ c ≤ 3 or 1 ≤ c ≤ 1.5 can be satisfied.

[0069] In Chemical Formula 1, 0.05 ≤ d ≤ 0.1 can be satisfied.

[0070] In Chemical Formula 1, 11 ≤ e ≤ 12 or 11.5 ≤ e ≤ 12 can be satisfied.

[0071] For example, in Chemical Formula 1, 0 < d + e ≤ 12 can be satisfied.

[0072] For example, the LISICON-type solid electrolyte may include Li 10.42 Ge 1.5 P 1.5 Cl 0.08 O 11.92 or Li 10.42 Si 1.5 P 1.5 Cl 0.08 O 11.92 and, as a more specific example, may include Li 10.42 Si 1.5 P 1.5 Cl 0.08 O 11.92 . For example, the LISICON-type solid electrolyte may not include a LISICON-type solid electrolyte containing V (vanadium) such as Li 3.2 (V 0.8 Si 0.2 )O4.

[0073] Since the LISICON-type solid electrolyte is doped with a Cl element, the lithium ion conductivity is particularly high, and side reactions that hinder battery operation can be suppressed.

[0074] Furthermore, since the LISICON-type solid electrolyte does not contain a V element, an oxidation / reduction reaction of the V element does not occur even when the battery is operating, and side reactions can be suppressed.

[0075] The composite solid electrolyte according to the embodiments may also include oxides containing Li and B elements. The oxides containing Li and B elements may be materials added to regulate the process temperature to a low level during the sintering process. The oxides containing Li and B elements may include Li3BO3, Li4B2O5, LiBO2, or combinations thereof, and specifically, may include Li3BO3.

[0076] Based on the total composite solid electrolyte, garnet-type solid electrolytes can be included in amounts ranging from 10 vol% to 50 vol% or from 20 vol% to 45 vol%. When garnet-type solid electrolytes are included in less than 10 vol% of the total composite solid electrolyte, lithium-ion conductivity may decrease, and when garnet-type solid electrolytes are included in greater than 50 vol%, the relative density of the composite solid electrolyte may decrease.

[0077] Based on the total composite solid electrolyte, LISICON-type solid electrolytes can be included in amounts ranging from 40% to 80% or from 45% to 65% by volume. When less than 40% by volume of LISICON-type solid electrolytes are included based on the total composite solid electrolyte, sinterability may deteriorate, and when more than 80% by volume of LISICON-type solid electrolytes are included, the ionic conductivity of the composite solid electrolyte may decrease.

[0078] Based on the total composite solid electrolyte, oxides containing Li and B elements can be included in amounts ranging from 5 vol% to 20 vol% or from 10 vol% to 15 vol%. When the total composite solid electrolyte includes oxides containing Li and B elements in amounts less than 5 vol%, it is difficult to reduce the firing temperature, and when it includes oxides containing Li and B elements in amounts greater than 20 vol%, the lithium-ion conductivity decreases.

[0079] Based on the total composite solid electrolyte, the volume ratio of garnet-type solid electrolyte to LISICON-type solid electrolyte can be 10:80 to 45:45 or 20:70 to 45:45.

[0080] Based on the total composite solid electrolyte, the volume ratio of the sum of garnet-type solid electrolyte and LISICON-type solid electrolyte to the oxide containing Li and B elements can be 80:20 to 90:10 or 85:15 to 90:10.

[0081] Based on the total composite solid electrolyte, the volume ratio of garnet-type solid electrolyte, LISICON-type solid electrolyte, and oxide containing Li and B elements can be, for example, 45:45:10.

[0082] For example, composite solid electrolytes may include garnet-type solid electrolytes with a volume ratio of 45:45:10, Li10.42 Si 1.5 P 1.5 Cl 0.08 O 11.92 And Li3BO3.

[0083] For example, composite solid electrolytes may include garnet-type solid electrolytes with a volume ratio of 20:65:15, Li 10.42 Si 1.5 P 1.5 Cl 0.08 O 11.92 And Li3BO3.

[0084] The relative density (%) of the composite solid electrolyte according to the embodiment may be greater than or equal to 80%.

[0085] The relative density (%) is calculated by dividing the apparent density by the true density, and the apparent density can be calculated using the volume and apparent volume of the material, while the true density can be obtained from the results of single-crystal X-ray structural analysis.

[0086] When the relative density (%) of the composite solid electrolyte meets the above range, the solid electrolyte layer included in the all-solid-state battery can have a density greater than or equal to 1×10⁻⁶. -7 Ionic conductivity (S / cm).

[0087] The lithium-ion conductivity of the composite solid electrolyte according to the embodiments can be greater than or equal to 1×10⁻⁶. -7 (S / cm), and for example, greater than or equal to 5 × 10 -7 (S / cm).

[0088] The lithium-ion conductivity of the composite solid electrolyte can be measured using alternating current (AC) impedance analysis. First, the solid electrolyte layer in the all-solid-state battery is exposed by ion milling or polishing, and a portion of the solid electrolyte layer is sampled into a rectangular plate. Subsequently, electrodes made of gold (Au) are formed at both ends of the obtained plate to prepare the sample. Then, an impedance measurement device (frequency: from 10...) is used... +6 Hz to 10 -1 The AC impedance of the sample was measured at room temperature (25°C) using a voltage of 50mV to 500mV (Hz measurement). The ionic conductivity was calculated.

[0089] Based on the composite solid electrolyte according to the embodiments, the firing temperature can be reduced, no side reactions occur in the operating voltage range of 0V to 6V, the relative density is high, and the lithium-ion conductivity is high.

[0090] The all-solid-state battery according to an embodiment includes: a solid electrolyte layer; a positive electrode layer and a negative electrode layer, wherein the solid electrolyte layer is disposed between the positive electrode layer and the negative electrode layer, and the solid electrolyte layer includes a composite solid electrolyte.

[0091] A all-solid-state battery according to another embodiment includes: a stack including a plurality of solid electrolyte layers, a plurality of positive electrode layers, and a plurality of negative electrode layers, with the positive electrode layers and the negative electrode layers alternating and the plurality of solid electrolyte layers disposed therebetween; and a first external electrode and a second external electrode respectively disposed on one surface of the stack and on another surface opposite to the one surface, and respectively connected to the positive electrode layer and the negative electrode layer. The solid electrolyte layer includes a composite solid electrolyte.

[0092] The composite solid electrolyte includes a garnet (LLZO) type solid electrolyte and a LISICON type solid electrolyte containing Cl element, and the LISICON type solid electrolyte is represented by Chemical Formula 1.

[0093] [Chemical Formula 1]

[0094] Li a M b P c Cl d O e

[0095] M includes Zn, Al, Ga, Si, Ge, Ti, Mg, or a combination thereof, and

[0096] a, b, c, d, and e are the molar ratios of the respective components, where 5 ≤ a ≤ 12, 0 < b ≤ 3, 0 < c ≤ 3, 0 < d ≤ 0.1, and 10 ≤ e ≤ 12.

[0097] The composite solid electrolyte may further include an oxide containing Li element and B element.

[0098] Since the composite solid electrolyte is the same as described above, its detailed description will be omitted.

[0099] Figure 1 is a perspective view schematically showing the all-solid-state battery according to an embodiment, Figure 2 is Figure 1 a cross-sectional view of the all-solid-state battery according to an embodiment shown in Figure 3 is schematically showing Figure 1 an exploded perspective view of the unit cell stack structure of the all-solid-state battery shown in

[0100] The all-solid-state battery 100 may have, for example, a shape approximately like a hexahedron.

[0101] The all-solid-state battery 100 according to an embodiment includes electrode layers 120 and 140 and a solid electrolyte layer 130 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 mainly include current collectors 123 and 143 and active material layers 121, 122, 141 and 142 coated on at least one surface of the current collectors 123 and 143.

[0102] The positive electrode layer 120 is formed by coating at least one surface of the positive electrode current collector 123 with positive electrode active material layers 121 and 122, and the negative electrode layer 140 is formed by coating at least one surface of the negative electrode current collector 143 with negative electrode active material layers 141 and 142. For example, in the stacking direction, the uppermost electrode layer is formed by coating one surface of the positive electrode current collector 123 with positive electrode active material layer 122, and the lowermost electrode layer is formed by coating one surface of the negative electrode current collector 143 with negative electrode active material layer 141. In addition, the electrode layer between the uppermost and lowermost ends is formed by coating both surfaces of the positive electrode current collector 123 with positive electrode active material layers 121 and 122 or by forming both surfaces of the negative electrode current collector 143 with negative electrode active material layers 141 and 142.

[0103] The positive electrode active material layers 121 and 122 may include a positive electrode active material, and optionally, may include a solid electrolyte. Furthermore, the positive electrode active material layers 121 and 122 may optionally include additives, such as binders or conductive agents.

[0104] For example, there are no particular restrictions on the positive electrode active material, as long as it can ensure 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 combinations thereof.

[0105] For example, the positive electrode active material can be a compound represented by the following chemical formula: Li a A l-b M b D2 (where 0.90≤a≤1.8, 0≤b≤0.5); Li a E l-b M b O 2-c D c (Where, 0.90≤a≤1.8, 0≤b≤0.5, 0≤c≤0.05); LiE 2-b M b O 4-c D c (Where, 0≤b≤0.5, 0≤c≤0.05); Li a Ni 1-b-c Cob M c D α (Where, 0.90≤a≤1.8, 0≤b≤0.5, 0≤c≤0.05, 0<α≤2); Li a Ni 1-b-c Co b M c O 2-α X α (Where, 0.90≤a≤1.8, 0≤b≤0.5, 0≤c≤0.05, 0<α<2); Li a Ni 1-b-c CO b M c O 2-α X² (where 0.90≤a≤1.8, 0≤b≤0.5, 0≤c≤0.05, 0<α<2); Li a Ni 1-b-c Mn b M c D α (Where, 0.90≤a≤1.8, 0≤b≤0.5, 0≤c≤0.05, 0<α≤2); Li a Ni 1-b-c Mn b M c O 2-α X α (Where, 0.90≤a≤1.8, 0≤b≤0.5, 0≤c≤0.05, 0<α<2); Li a Ni 1-b-c Mn b M c O 2-α X² (where 0.90≤a≤1.8, 0≤b≤0.5, 0≤c≤0.05, 0<α<2); Li a Ni b E c G d O2 (where 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 GeO2 (where 0.90≤a≤1.8, 0≤b≤0.9, 0≤c≤0.5, 0≤d≤0.5, 0.001≤e≤0.1); Li a NiGbO2 (where 0.90≤a≤1.8, 0.001≤b≤0.1); Li a CoGbO2 (where 0.90≤a≤1.8, 0.001≤b≤0.1); Lia MnGbO2 (where 0.90≤a≤1.8, 0.001≤b≤0.1); Li a Mn₂GbO₄ (where 0.90≤a≤1.8, 0.001≤b≤0.1); QO₂; QS₂; LiQS₂; V₂O₅; LiV₂O₂; LiRO₂; LiNiVO₄; Li (3-f) J2(PO4)3 (0≤f≤2); Li (3-f) Fe2(PO4)3 (where 0≤f≤2); and LiFePO4, wherein, in the above chemical formulas, 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; and J is V, Cr, Mn, Co, Ni or Cu.

[0106] The positive electrode active material can also be LiCoO2 or LiMn. x O 2x (where x = 1 or 2), LiNi 1-x Mn x O 2x (where 0 < x < 1), LiNi 1-x-y Co x Mn y O2 (where 0≤x≤0.5, 0≤y≤0.5), LiFePO4, TiS2, FeS2, TiS3 or FeS3.

[0107] The positive electrode layer 120 may also include a solid electrolyte. There are no particular limitations on the type of solid electrolyte included in the positive electrode layer 120, but it may include a solid electrolyte of the same type as the aforementioned composite solid electrolyte. Based on the total amount of 100 parts by weight of positive electrode active material, the content of the solid electrolyte may be greater than or equal to 0.1 parts by weight, greater than or equal to 1 part by weight, or greater than or equal to 10 parts by weight, and less than or equal to 80 parts by weight, less than or equal to 60 parts by weight, or less than or equal to 50 parts by weight.

[0108] There are no particular limitations on the conductive agent, as long as it is conductive without causing a chemical change in the all-solid-state battery 100. Examples of conductive agents may include: graphite, such as natural graphite and artificial graphite; carbon-based materials, such as carbon black, acetylene black, Ketjen black, channel black, furnace black, lamp black, and pyrolysis black; conductive fibers, such as carbon fibers and metal fibers; fluorocarbons; metal powders, such as aluminum powder and nickel powder; conductive whiskers, such as zinc oxide and potassium titanate; conductive metal oxides, such as titanium oxide; or conductive materials, such as polyphenylene derivatives.

[0109] Based on 100 parts by weight of positive electrode active material, the content of the conductive agent can be from 1 part by weight to 10 parts by weight, or for example, from 2 parts by weight to 5 parts by weight. When the content of the conductive agent is within the above range, the final electrode can have excellent conductivity.

[0110] Adhesives can be used to improve the bond strength between active materials and conductive agents. Adhesives may include polyvinylidene fluoride, polyvinyl alcohol, carboxymethyl cellulose (CMC), starch, hydroxypropyl cellulose, regenerated cellulose, polyvinylpyrrolidone, polytetrafluoroethylene, polyethylene, polypropylene, ethylene-propylene-diene terpolymer (EPDM), sulfonated EPDM, styrene-butadiene rubber, fluororubber, or various copolymers.

[0111] Based on 100 parts by weight of total positive electrode active material, the binder content can be from 1 part by weight to 50 parts by weight, or for example, from 2 parts by weight to 5 parts by weight. When the binder content meets the above range, the active material layer can have high bonding strength.

[0112] There are no particular limitations on the positive electrode current collector 123, as long as it is conductive without causing a chemical change in the positive electrode or the battery. Examples of positive electrode current collectors include: graphite, such as natural graphite and artificial graphite; carbon-based materials, such as carbon black, acetylene black, Ketjen black, channel black, furnace black, lamp black, and pyrolysis black; and conductive fibers, such as carbon fibers or metal fibers. Additionally, porous materials such as mesh or lattice structures can be used as the positive electrode current collector, and porous metal plates such as stainless steel, nickel, or aluminum can be used. Furthermore, the positive electrode current collector 123 may be coated with an oxidation-resistant metal or alloy film to prevent oxidation.

[0113] The negative electrode active material layers 141 and 142 may include a negative electrode active material, and optionally, may include a solid electrolyte.

[0114] The negative electrode active material may be a carbon-based material, silicon, silicon oxide, silicon-based alloy, silicon-carbon composite, tin, tin-based alloy, tin-carbon composite, metal oxide, or a combination thereof, and may include lithium metal and / or lithium metal alloy.

[0115] The lithium metal alloy may include lithium and a metal / metalloid capable of alloying with lithium. For example, the metal / metalloid capable of alloying with lithium may include Si, Sn, Al, Ge, Pb, Bi, Sb, Si-Y alloy (where Y is an alkali metal, alkaline earth metal, Group 13 to Group 16 element, transition metal, rare earth element, or a combination thereof, and does not include Si), Sn-Y alloy (where Y is an alkali metal, alkaline earth metal, Group 13 to Group 16 element, transition metal, such as a transition metal oxide like lithium titanate (Li4Ti5O 12 ), rare earth element, or a combination thereof, and does not include Sn) or MnO x (0 < x ≤ 2).

[0116] The element Y may be 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.

[0117] In addition, the oxide of the metal / metalloid capable of alloying with lithium may be lithium titanate, vanadium oxide, lithium vanadium oxide, SnO2, SiO x (0 < x < 2), etc. For example, the negative electrode active material may include one or more elements selected from the elements of Group 13 to Group 16 of the periodic table. For example, the negative electrode active material may include one or more elements selected from the group consisting of Si, Ge, and Sn.

[0118] The carbon-based material may be crystalline carbon, amorphous carbon, or a mixture thereof. The crystalline carbon may include graphite, such as natural graphite or artificial graphite in irregular form, plate form, flake form, spherical form, or fibrous form. In addition, the amorphous carbon may include soft carbon (low-temperature calcined carbon) or hard carbon, mesophase pitch carbonization products, calcined coke, graphene, carbon black, fullerene soot, carbon nanotubes, carbon fibers, etc.

[0119] Silicon may be Si, SiO x (0 < x < 2, for example 0.5 to 1.5), Sn, SnO2, a silicon-containing metal alloy, or a mixture thereof. The silicon-containing metal alloy may include, for example, one or more of Al, Sn, Ag, Fe, Bi, Mg, Zn, In, Ge, Pb, and Ti, as well as silicon.

[0120] The negative electrode layer 140 may also include a solid electrolyte. There are no particular limitations on the type of solid electrolyte included in the negative electrode layer 140, but it may include a solid electrolyte of the same type as the aforementioned composite solid electrolyte.

[0121] Optionally, the negative electrode active material layer may further include conductive agents and binders as described in the positive electrode active material layer.

[0122] The negative electrode current collector 143 is not particularly limited, as long as it is conductive without causing a chemical change in the negative electrode or the battery. Examples of negative electrode current collectors include: graphite, such as natural and artificial graphite; carbon-based materials, such as carbon black, acetylene black, Ketjen black, channel black, furnace black, lamp black, and pyrolysis black; and conductive fibers, such as carbon fibers or metal fibers. Additionally, porous materials such as mesh or lattice structures can be used as the negative electrode current collector, and porous metal plates such as stainless steel, nickel, or aluminum can be used. Furthermore, the negative electrode current collector 143 may be coated with an oxidation-resistant metal or alloy film to prevent oxidation.

[0123] A solid electrolyte layer 130 can be disposed and stacked between the positive electrode layer 120 and the negative electrode layer 140. Therefore, the solid electrolyte layer 130 can be disposed adjacently in the stacking direction between 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. Thus, in the all-solid-state battery 100, multiple positive electrode layers 120 and multiple negative electrode layers 140 can be alternately disposed, and multiple solid electrolyte layers 130 can be interposed and stacked between them. In the all-solid-state battery 100, multiple positive electrode layers 120 and multiple negative electrode layers 140 are alternately stacked, and multiple solid electrolyte layers 130 are interposed between them to manufacture a battery stack, which can then be batch-fired to manufacture the stacked all-solid-state battery 100.

[0124] The solid electrolyte layer 130 includes the aforementioned composite solid electrolyte. Since the composite solid electrolyte has already been described in detail above, its description will be omitted.

[0125] By including a composite solid electrolyte with the aforementioned excellent effects in the solid electrolyte layer 130, no side reactions occur within the operating voltage range of 0.75V to 1.5V, thereby enabling operation across the entire operating voltage range from 0V to 6V. Furthermore, since there is no need to avoid the range of side reactions, it has the advantage of expanding the types of selectable electrode active materials.

[0126] An edge layer 150 may be disposed along the edges of the positive electrode layer 120 and the negative electrode layer 140. The edge layer 150 is disposed on the solid electrolyte layer 130 and may be formed laterally adjacent to the edges of the positive electrode active material layers 121 and 122 or the negative electrode active material layers 141 and 142. Therefore, the edge layer 150 may be disposed on the same layer as the positive electrode layer 120 and on the same layer as the negative electrode layer 140.

[0127] The edge layer 150 may include a core with a diameter less than or equal to 1.0 × 10⁻⁶. -10 Insulating materials with an ionic conductivity of S / cm, such as the aforementioned solid electrolyte materials or resin insulating materials.

[0128] For example, the insulating material can be a polyolefin such as polyethylene or polypropylene, a polyester such as polyethylene terephthalate (PET), a polyurethane, or a polyimide.

[0129] Additionally, the edge layer 150 may include an inorganic solid electrolyte, including oxide-based solid electrolytes, sulfide-based solid electrolytes, or combinations thereof used in the solid electrolyte layer 130. However, the edge layer 150 is not limited to this and may include various materials.

[0130] The positive electrode layer 120, the solid electrolyte layer 130, the negative electrode layer 140, and the edge layer 150 can be stacked as described above to form a battery stack of the all-solid-state battery 100. Protective layers (not shown) made of insulating material can be formed on the upper and lower ends of the battery stack of the all-solid-state battery 100.

[0131] Furthermore, the ends of the positive current collector 123 and the negative current collector 143 are exposed on both sides of the battery stack of the all-solid-state battery 100, and the external electrodes 112 and 114 can be connected to and bonded to the exposed ends. That is, the external electrode 112 can be configured to be connected to the end of the positive current collector 123 to have positive polarity, and the external electrode 114 can be connected to the end of the negative current collector 143 to have negative polarity. When the ends of the positive current collector 123 and the negative current collector 143 are configured to face opposite directions, the external electrodes 112 and 114 can also be respectively disposed on both sides.

[0132] The external electrodes 112 and 114 may include conductive metal and glass.

[0133] Conductive metals may include, for example, copper (Cu), nickel (Ni), tin (Sn), palladium (Pd), platinum (Pt), gold (Au), silver (Ag), tungsten (W), titanium (Ti), lead (Pb), or alloys thereof.

[0134] The glass composition included in the external electrodes 112 and 114 may have a composition in which oxides are mixed. The glass composition may include, for example, silicon oxide, boron oxide, aluminum oxide, transition metal oxides, alkali metal oxides, alkaline earth metal oxides, or combinations thereof. Here, the transition metal may be selected from zinc (Zn), titanium (Ti), copper (Cu), vanadium (V), manganese (Mn), iron (Fe), or nickel (Ni); the alkali metal may be selected from 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).

[0135] There are no particular limitations on the methods for forming the external electrodes 112 and 114. For example, the method may include: immersing the battery stack in a conductive paste comprising conductive metal and glass, or screen-printing or gravure-printing the conductive paste onto the surface of the battery stack. Alternatively, various methods may be used, such as applying the conductive paste to the surface of the battery stack, or transferring a dry film obtained by drying the conductive paste onto the battery stack.

[0136] Specific examples of the invention are presented below. However, the examples described below are intended only to illustrate or explain the invention, and the scope of the invention should not be limited thereto.

[0137] [Example]

[0138] (Example 1)

[0139] Li7La3Zr2O 12 (Hereinafter referred to as LLZO), Li 10.42 Si 1.5 P 1.5 Cl 0.08 O 11.92 Li3BO3 was weighed and mixed in a volume ratio of 45:45:10. The mixture was then combined with the binder and binder solvent, and ball-milled at room temperature for 24 hours or longer to ensure thorough and uniform mixing. The solvent was then dried in an oven to obtain a mixed powder coated with the binder.

[0140] Subsequently, a solid electrolyte layer green sheet, a positive electrode layer green sheet, and a negative electrode layer green sheet, comprising a mixed composite solid electrolyte, are fabricated and stacked in the order of positive electrode layer green sheet-solid electrolyte layer green sheet-negative electrode layer green sheet. The stack is then heat-treated at 250°C to 600°C in an oxygen atmosphere to remove the binder. After removing the binder, the stack is fired at 800°C in an oxygen atmosphere to fabricate a cell.

[0141] (Example 2)

[0142] Except for heat treatment at 700°C, the cell is manufactured in the same manner as in Example 1.

[0143] (Example 3)

[0144] In addition to using LLZO and Li 10.42 Si 1.5 P 1.5 Cl 0.08 O 11.92 In addition to preparing a composite solid electrolyte by mixing Li3BO3 in a volume ratio of 20:65:15, a cell battery was manufactured in the same manner as in Example 1.

[0145] (Example 4)

[0146] In addition to using LLZO and Li 10.42 Si 1.5 P 1.5 Cl 0.08 O 11.92 In addition to preparing a composite solid electrolyte by mixing Li3BO3 in a volume ratio of 75:15:10, a cell battery was manufactured in the same manner as in Example 1.

[0147] (Comparative Example 1)

[0148] The cell was manufactured in the same manner as in Example 1, except that a solid electrolyte was prepared by using 100% by volume of LLZO and the firing temperature was set to 1000°C.

[0149] (Comparative Example 2)

[0150] In addition to using 100 vol% Li 10.42 Si 1.5 P 1.5 Cl 0.08 O 11.92 In addition to preparing a solid electrolyte and setting the firing temperature to 1000°C, a cell was manufactured in the same manner as in Example 1.

[0151] (Comparative Example 3)

[0152] The cell was manufactured in the same manner as in Example 1, except that a solid electrolyte was prepared by using 100% by volume of Li3BO3 and the firing temperature was set to 700°C.

[0153] (Comparative Example 4)

[0154] The cell was manufactured in the same manner as in Example 1, except that the composite solid electrolyte was prepared by mixing LLZO and Li3BO3 in a volume ratio of 95:5 and the firing temperature was set to 800°C.

[0155] (Comparative Example 5)

[0156] Except for preparing the composite solid electrolyte by mixing LLZO and Li3BO3 in a volume ratio of 90:10, the unit cell was manufactured in the same manner as in Comparative Example 4.

[0157] (Comparative Example 6)

[0158] Except for preparing the composite solid electrolyte by mixing LLZO and Li3BO3 in a volume ratio of 85:15, the unit cell was manufactured in the same manner as in Comparative Example 4.

[0159] (Comparative Example 7)

[0160] In addition to Li 10.42 Si 1.5 P 1.5 Cl 0.08 O 11.92 In addition to preparing a composite solid electrolyte by mixing Li3BO3 at a volume ratio of 85:15, a cell battery was manufactured in the same manner as in Example 1.

[0161] (Comparative Example 8)

[0162] In addition to using 100 vol% Li 3.2 (V 0.8 Si 0.2 O4 replaces Li 10.42 Si 1.5 P 1.5 Cl 0.08 O 11.92 In addition to preparing the composite solid electrolyte, the unit cell was manufactured in the same manner as in Comparative Example 2.

[0163] (Comparative Example 9)

[0164] In addition to using LLZO and Li 3.2 (V 0.8 Si 0.2 In addition to preparing a composite solid electrolyte by mixing O4 and Li3BO3 in a volume ratio of 45:45:10, a cell was manufactured in the same manner as in Example 1.

[0165] (Comparative Example 10)

[0166] In addition to using LLZO and Li 3.2 (V 0.8 Si 0.2 In addition to preparing a composite solid electrolyte by mixing O4 and Li3BO3 in a volume ratio of 75:15:10, a cell battery was manufactured in the same manner as in Example 1.

[0167] (Comparative Example 11)

[0168] In addition to using 100 vol% Li10.5 Si 1.5 P 1.5 O 12 Replace Li 10.42 Si 1.5 P 1.5 Cl 0.08 O 11.92 In addition to preparing a solid electrolyte, a unit cell was manufactured in the same manner as in Comparative Example 2.

[0169] (Comparative Example 12)

[0170] In addition to using LLZO and Li 10.5 Si 1.5 P 1.5 O 12 In addition to preparing a composite solid electrolyte by mixing Li3BO3 in a volume ratio of 45:45:10, a cell battery was manufactured in the same manner as in Example 1.

[0171] The composition and firing temperature of Examples 1 to 4 and Comparative Examples 1 to 12 are shown in Table 1.

[0172] [Table 1]

[0174] [Experimental Example] (Experimental Example 1: Measurement of Relative Density)

[0175] The cell cells according to Examples 1 to 4 and Comparative Examples 1 to 12 were subjected to ion milling or polishing to expose each solid electrolyte layer, and the exposed solid electrolyte surfaces were subjected to X-ray diffraction analysis to calculate the true density.

[0176] Then, each solid electrolyte layer exposed in the same manner as described above is sampled into rectangular plates.

[0177] The mass of the plate-like sheet was measured and divided by the calculated apparent volume to obtain the apparent density. The apparent density was then divided by the true density to obtain the relative density (%), and these results are shown in Table 2.

[0178] Referring to Table 2, by using LLZO and Li 10.42 Si 1.5 P 1.5 Cl 0.08 O 11.92 Examples 1 to 3, which prepared solid electrolyte layers by mixing Li3BO3 in a specific volume ratio, exhibited a high relative density of 80% or greater.

[0179] On the other hand, Comparative Examples 1 to 12 exhibited low relative densities of less than 80%.

[0180] Here, Comparative Example 9 exhibits a slightly higher relative density, but has side reactions, which results in an overall effect lower than the example.

[0181] (Experimental Example 2: Measurement of Lithium-ion Conductivity)

[0182] The lithium-ion conductivity of the solid electrolytes in Examples 1 to 4 and Comparative Examples 1 to 12 was measured using the AC impedance method. First, each cell was ion-milled or polished to expose its solid electrolyte layer, and a portion of the solid electrolyte layer was sampled into a rectangular plate. Subsequently, electrodes made of gold (Au) were formed at both ends of the obtained plate, thus preparing a sample. The AC impedance (frequency: 10 Hz) of the sample was measured at room temperature (25°C) using an impedance measurement device (for calculating lithium-ion conductivity). +6 Hz to 10 -1 (Hz, voltage: 50mV to 500mV), and the results are shown in Table 2.

[0183] "Less than E-08" indicates that the measurement result is less than 1.0·E-08 S / cm.

[0184] "Unmeasurable" indicates that the lithium-ion conductivity of the sample is too low to be subjected to electrochemical analysis.

[0185] Referring to Table 2, the examples exhibit higher lithium-ion conductivity compared to the comparative examples.

[0186] Comparative Examples 8 and 9 exhibit slightly higher lithium-ion conductivity, but have side reactions, resulting in an overall performance lower than the examples.

[0187] (Experimental Example 3: Side reaction occurs)

[0188] Since the side reactions are redox reactions of elements included in the solid electrolyte (e.g., V(vanadium) in Comparative Examples 8 and 9), the all-solid-state battery may fail to function properly when side reactions occur. The occurrence of these side reactions is checked by electrochemical analysis, specifically cyclic voltammetry (CV) analysis. Since this analysis records whether a current is generated within the voltage range in which the analysis is performed, the generation of a current within a specific voltage range confirms that an electrochemical reaction has occurred within that corresponding voltage range. For example, when a peak appears in the + or - direction on the y-axis of the graph, it confirms that the electrochemical reaction is occurring within the corresponding voltage range. Here, the graph shows a decrease in the range of 0.0 V to 0.5 V, which is caused by the Li metal interface but is not considered a side reaction.

[0189] The analysis was performed in the range of 0.0 V to 6.0 V, compared with Li metal (vs. Li / Li+), and the results are given in Table 2 as “No,” “Yes,” or “Not measurable.” “Not measurable” indicates that the lithium-ion conductivity of the sample was too low for electrochemical analysis. Additionally, the side reaction analysis results for Examples 1 and 2, and Comparative Examples 9 and 10, are presented graphically. Figure 4 middle.

[0190] Referring to Table 2, Examples 1 to 4 have no side reactions, but Comparative Examples 8 to 10, which include LISICON-type solid electrolytes containing V (vanadium), have side reactions.

[0191] Reference Figure 4 Examples 1 and 2 showed no side reactions in the 0.75 to 1.5 V range (the range where side reactions occur), but Comparative Examples 9 and 10 exhibited side reactions in the corresponding range. Compared to Comparative Example 9, Comparative Example 10 exhibited a smaller current peak in the range where side reactions occurred because it included a smaller volume percentage of LISICON-type solid electrolyte compared to Comparative Example 9. Side reactions can manifest different current peak sizes depending on the volume ratio of each solid electrolyte in the composite solid electrolyte, but regardless of how small the side reactions are, the all-solid-state battery may not function properly within the corresponding voltage range.

[0192] [Table 2]

[0194] While the invention has been described in conjunction with what are now considered to be practical exemplary embodiments, it should be understood that the invention is not limited to the disclosed embodiments. Rather, it is intended to cover various modifications and equivalent arrangements included within the spirit and scope of the appended claims.

[0195] Industrial applicability

[0196] This disclosure relates to a composite solid electrolyte and an all-solid-state battery including the composite solid electrolyte, which can reduce the firing temperature, does not cause side reactions in the operating voltage range of 0 to 6V, has a high relative density, and has a high lithium-ion conductivity, and therefore can be used in various electrochemical devices and electronic devices.

[0197] <Explanation of reference numerals in the attached figures>

[0198] 100: All-solid-state battery

[0199] 112, 114: External electrodes

[0200] 120: Positive electrode layer

[0201] 121, 122: Positive electrode active material layer

[0202] 123: Positive current collector

[0203] 130: Solid electrolyte layer

[0204] 140: Negative electrode layer

[0205] 141, 142: Negative electrode active material layer

[0206] 143: Negative electrode current collector

[0207] 150: Edge layer.

Claims

1. A composite solid electrolyte, comprising: A garnet-type solid electrolyte; and A Li superionic conductor-type solid electrolyte containing Cl element.

2. The composite solid electrolyte according to claim 1, wherein The Li superionic conductor-type solid electrolyte is represented by Chemical Formula 1: [Chemical Formula 1] Li a M b P c Cl d O e where M includes Zn, Al, Ga, Si, Ge, Ti, Mg or a combination thereof, and a, b, c, d and e are the molar ratios of each component, and satisfy 5 ≤ a ≤ 12, 0 < b ≤ 3, 0 < c ≤ 3, 0 < d ≤ 0.1 and 10 ≤ e ≤ 12.

3. The composite solid electrolyte according to claim 2, wherein M includes Si (silicon) or Ge (germanium).

4. The composite solid electrolyte according to claim 2, wherein M does not include V (vanadium).

5. The composite solid electrolyte according to claim 1, the composite solid electrolyte further includes an oxide containing Li element and B element.

6. The composite solid electrolyte according to claim 5, wherein Based on the total volume of the composite solid electrolyte, the oxide containing Li element and B element is included in an amount of 5 vol% to 20 vol%.

7. The composite solid electrolyte according to claim 5, wherein The ratio of the sum of the volume of the garnet-type solid electrolyte and the volume of the Li superionic conductor-type solid electrolyte to the volume of the oxide containing Li element and B element is 80:20 to 90:

10.

8. The composite solid electrolyte according to claim 5, wherein The oxide containing Li element and B element includes Li3BO3, Li4B2O5, LiBO2 or a combination thereof.

9. The composite solid electrolyte according to claim 1, wherein Based on the total volume of the composite solid electrolyte, the garnet-type solid electrolyte is included in an amount of 10 vol% to 50 vol%.

10. The composite solid electrolyte according to claim 1, wherein Based on the total volume of the composite solid electrolyte, the Li superionic conductor-type solid electrolyte is included in an amount of 40 vol% to 80 vol%.

11. The composite solid electrolyte according to claim 1, wherein The ratio of the volume of the garnet-type solid electrolyte to the volume of the Li superionic conductor-type solid electrolyte is 10:80 to 45:

45.

12. The composite solid electrolyte according to claim 1, wherein The ratio of the volume of the garnet-type solid electrolyte to the volume of the Li superionic conductor-type solid electrolyte is 10:80 to 75:

15.

13. The composite solid electrolyte according to claim 1, wherein The composite solid electrolyte has a relative density (%) of greater than or equal to 80%. The composite solid electrolyte has a content greater than or equal to 1×10 -7 Lithium-ion conductivity (S / cm) at 25°C room temperature.

14. The composite solid electrolyte according to claim 1, wherein Li a M b P c Cl d ON e including Li 10.42 Yes 1.5 P 1.5 Cl 0.08 ON 11.92 。 15. The composite solid electrolyte according to claim 2, wherein 16. A all-solid-state battery, comprising: A solid electrolyte layer; And A positive electrode layer and a negative electrode layer, the solid electrolyte layer is disposed between the positive electrode layer and the negative electrode layer, Among them, the solid electrolyte layer includes a composite solid electrolyte. The composite solid electrolyte includes a garnet (LLZO) type solid electrolyte and a Li superionic conductor type solid electrolyte containing Cl element.

17. The all-solid-state battery according to claim 16, wherein The Li superionic conductor type solid electrolyte is represented by Chemical Formula 1: [Chemical Formula 1] Li a M b P c Cl d O e wherein M includes Zn, Al, Ga, Si, Ge, Ti, Mg or a combination thereof, and a, b, c, d and e are the molar ratios of the respective components, and satisfy 5 ≤ a ≤ 12, 0 < b ≤ 3, 0 < c ≤ 3, 0 < d ≤ 0.1, and 10 ≤ e ≤ 12.

18. The all-solid-state battery according to claim 16, the all-solid-state battery further includes an oxide containing Li element and B element.

19. The all-solid-state battery according to claim 17, wherein Li a M b P c Cl d ON e including Li 10.42 Yes 1.5 P 1.5 Cl 0.08 ON 11.92 。 20. An all-solid-state battery, comprising: A stack including a plurality of solid electrolyte layers, a plurality of positive electrode layers and a plurality of negative electrode layers, the positive electrode layers and the negative electrode layers are arranged alternately and the plurality of solid electrolyte layers are disposed therebetween; and A first external electrode and a second external electrode, respectively disposed on one surface of the stack and another surface opposite to the one surface, and respectively connected to the positive electrode layer and the negative electrode layer, wherein the solid electrolyte layer includes a composite solid electrolyte, and [[ID=I4]]The composite solid electrolyte includes a garnet (LLZO) type solid electrolyte and a Li superionic conductor type solid electrolyte containing Cl element.

21. The all-solid-state battery according to claim 20, wherein The Li superionic conductor type solid electrolyte is represented by Chemical Formula 1: [Chemical Formula 1] Li a M b P c Cl d O e wherein M includes Zn, Al, Ga, Si, Ge, Ti, Mg or a combination thereof, and a, b, c, d and e are the molar ratios of the respective components, and satisfy 5 ≤ a ≤ 12, 0 < b ≤ 3, 0 < c ≤ 3, 0 < d ≤ 0.1, and 10 ≤ e ≤ 12.

22. The all-solid-state battery according to claim 20, the all-solid-state battery further includes an oxide containing Li element and B element.

23. The all-solid-state battery according to claim 21, wherein Li a M b P c Cl d ON e including Li 10.42 Yes 1.5 P 1.5 Cl 0.08 ON 11.92 。

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