Solid electrolyte for all-solid-state battery and all-solid-state battery comprising same

Abstract

The present invention relates to a solid electrolyte for an all-solid-state battery and an all-solid-state battery comprising same. The solid electrolyte for an all-solid-state battery, according to one embodiment of the present invention, is composed of an oxide material containing Li, Mo, B, Al, and Cl.

Description

Solid electrolyte for all-solid-state batteries and all-solid-state batteries containing the same

[0001] The present invention relates to a solid electrolyte for an all-solid-state battery and an all-solid-state battery including the same.

[0002] Secondary batteries are used in a variety of fields, from IT devices such as mobile phones to electric vehicles and energy storage devices.

[0003] Lithium-ion batteries, which use liquid electrolytes, are the most widely used secondary batteries. However, liquid electrolytes pose a risk of leakage if the battery is subjected to external shocks, necessitating the use of additional components and devices to ensure safety.

[0004] Recently, active development of all-solid-state lithium-ion batteries using solid electrolytes has been underway to improve the safety of lithium-ion batteries. Solid electrolytes for all-solid-state lithium-ion batteries include polymer electrolytes, oxide electrolytes, and sulfide electrolytes. Sulfide-based solid electrolytes exhibit excellent electrochemical performance due to their high ionic conductivity and particle deformation capabilities. However, they react with moisture in the air to generate toxic hydrogen sulfide gas. Polymer electrolytes have the advantage of a relatively simple process and the ability to utilize existing lithium-ion battery processes, but their significantly low ionic conductivity is a drawback.

[0005] Oxide electrolytes have lower ionic conductivity than sulfide electrolytes, but are relatively high, and have the advantage of excellent safety. Currently, there are 10 types of electrolytes, including LAGP and LLZO. -4 Oxide-based solid electrolytes with high ionic conductivities exceeding S / cm are being developed. However, these solid electrolytes have limitations in enhancing electrochemical performance due to their narrow electrochemical voltage range and high-temperature sintering process (over 1,000°C). This can increase production costs and limit their usability.

[0006] The present invention is intended to solve the problems of the prior art described above, and its purpose is to provide an oxide-based solid electrolyte for an all-solid-state battery that can be sintered at low temperatures and has excellent ionic conductivity, and an all-solid-state battery including the same.

[0007] In one embodiment of the present invention, a solid electrolyte for an all-solid-state battery is composed of an oxide containing Li, Mo, B, Al, and Cl.

[0008] In one embodiment of the present invention, a solid electrolyte for an all-solid-state battery can satisfy, based on a molar ratio, (LiCl + Al2O3) / (Li2O + MoO3 + B2O3) ≥ 0.16.

[0009] In one embodiment of the present invention, a solid electrolyte for an all-solid-state battery can satisfy, based on a molar ratio, 0.01≤ Al2O3 / (Li2O + MoO3+ B2O3)≤ 0.02.

[0010] According to one embodiment of the present invention, the composition ratio of Li2O, MoO3 and B2O3 may be 10:1:14.

[0011] In one embodiment of the present invention, the solid electrolyte for an all-solid-state battery is LCB (Li 10 B 14 Cl2O 25 ) crystal, LBO (LiBO2) crystal, LBA (Li3Al(BO3)2) crystal, and LMO (Li2MoO4) crystal.

[0012] In one embodiment of the present invention, a solid electrolyte for an all-solid-state battery can be manufactured from a precursor powder including Li2CO3, MoO3, B2O3, Al2O3, and LiCl.

[0013] In one embodiment of the present invention, a solid electrolyte for an all-solid-state battery has an ionic conductivity of 9.89×10 -5 It can be more than S / cm.

[0014] An all-solid-state battery according to one embodiment of the present invention includes a cathode layer, a cathode layer, and a solid electrolyte layer. Here, the solid electrolyte layer is made of an oxide containing Li, Mo, B, Al, and Cl.

[0015] In addition, the solid electrolyte for an all-solid-state battery according to the present invention may further include other additional components within a range that does not impair the technical idea of ​​the present invention.

[0016] According to one embodiment of the present invention, a solid electrolyte for an all-solid-state battery is an oxide-based solid electrolyte, which is formed of an oxide containing Li, Mo, B, Al, and Cl, thereby enabling low-temperature sintering and having excellent ionic conductivity.

[0017] Figure 1 is a perspective view schematically showing an all-solid-state battery.

[0018] Figure 2 is a drawing showing an example of a cross-section of an all-solid-state battery.

[0019] FIG. 3 and FIG. 4 are graphs showing the results of XRD analysis of powder before sintering of solid electrolyte according to examples and comparative examples of the present invention.

[0020] Figure 5 is a graph showing the results of XRD analysis after sintering of a solid electrolyte according to an embodiment of the present invention.

[0021] [Explanation of symbols]

[0022] 10: All-solid-state batteries

[0023] 11: Bipolar layer

[0024] 12: Cathode layer

[0025] 13: Solid electrolyte layer

[0026] 14, 15: External electrode

[0027] 16: Case

[0028] Hereinafter, with reference to the attached drawings, a preferred embodiment of the present invention will be described in detail to a degree that a person having ordinary skill in the art to which the present invention pertains can easily practice the present invention.

[0029] To clearly explain the present invention, descriptions of parts irrelevant to the present invention have been omitted, and the same reference numerals are assigned to the same components throughout the specification. It should be understood that specific shapes, structures, and characteristics described in the specification may be modified and implemented from one embodiment to another without departing from the spirit and scope of the present invention, and that the location or arrangement of individual components may also be changed without departing from the spirit and scope of the present invention.

[0030] Accordingly, the detailed description set forth below is not intended to be limiting, and the scope of the present invention should be accepted as encompassing the scope claimed in the claims and all scopes equivalent thereto.

[0031] Fig. 1 is a perspective view schematically illustrating an all-solid-state battery, and Fig. 2 is a drawing schematically illustrating a cross-section of the all-solid-state battery. The all-solid-state battery according to one embodiment of the present disclosure can be formed into a small chip shape as a so-called laminated ceramic battery and can be used in small electronic devices such as wearable electronic devices.

[0032] Referring to FIGS. 1 and 2, the all-solid-state battery (10) includes a positive electrode layer (11), a negative electrode layer (12), and a solid electrolyte layer (13). The solid electrolyte layer (13) is disposed between the positive electrode layer (11) and the negative electrode layer (12), and can be in contact with the positive electrode layer (11) and the negative electrode layer (12), respectively. The positive electrode layer (11) and the negative electrode layer (12) can each have a current collector and an active material layer, and the active material layer of the electrode layer is formed by being applied to at least one surface of each current collector, and can be in contact with the solid electrolyte layer (13).

[0033] In one embodiment, the positive electrode layer (11) may be formed by applying a positive electrode active material layer to at least one surface of the positive electrode collector, and the negative electrode layer (12) may be formed by applying a negative electrode active material layer to at least one surface of the negative electrode collector. For example, the electrode layer located at the uppermost layer based on the stacking direction may be formed by applying a positive electrode active material layer to one surface of the positive electrode collector, and the electrode layer located at the lowermost layer may be formed by applying a negative electrode active material layer to one surface of the negative electrode collector. In addition, the electrode layers located between the uppermost and lowermost layers may be formed by applying a positive electrode active material layer to both surfaces of the positive electrode collector, or by applying a negative electrode active material layer to both surfaces of the negative electrode collector.

[0034] The positive electrode active material layer may include a positive electrode active material and optionally a solid electrolyte. In addition, the positive electrode active material layer may optionally further include additives such as a binder or a conductive agent.

[0035] The cathode active material is not particularly limited as long as it can secure sufficient capacity of the all-solid-state battery (10). For example, the cathode 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.

[0036] The conductive agent of the positive electrode active material layer is not particularly limited as long as it is conductive and does not cause a chemical change in the all-solid-state battery (10). For example, the conductive agent may include 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 or metal fiber; fluorinated carbon; metal powders such as aluminum or nickel powder; conductive whiskey such as zinc oxide or potassium titanate; conductive metal oxides such as titanium oxide; and conductive materials such as polyphenylene derivatives.

[0037] A binder may be used to improve the bonding strength between the active material and the conductive agent. Examples of the binder include polyvinylidene fluoride, polyvinyl alcohol, carboxymethyl cellulose (CMC), starch, hydroxypropyl cellulose, regenerated cellulose, polyvinyl pyrrolidone, polytetrafluoroethylene, polyethylene, polypropylene, ethylene-propylene-dienhe polymer (EPDM), sulfonated EPDM, styrene butadiene rubber, fluoroelastomer, or various copolymers.

[0038] A porous body such as a mesh or mesh-shaped positive electrode collector can be used, and a porous metal plate such as stainless steel, nickel, or aluminum can be used. In addition, the positive electrode collector can be coated with an oxidation-resistant metal or alloy film to prevent oxidation.

[0039] The negative electrode active material layer may include a negative electrode active material and optionally a solid electrolyte. In addition, the negative electrode active material layer may optionally further include additives such as a binder or a conductive agent.

[0040] The negative active material may be a 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 include lithium metal and / or a lithium metal alloy.

[0041] The negative active material layer may also optionally include a conductive agent and a binder, as described for the positive active material layer.

[0042] A porous body such as a mesh or mesh-shaped negative electrode collector can be used, and a porous metal plate such as stainless steel, nickel, or aluminum can be used. In addition, the negative electrode collector can be coated with an oxidation-resistant metal or alloy film to prevent oxidation.

[0043] In one embodiment, a margin insulating layer (not shown) may be additionally disposed along the edges of the positive electrode layer (11) and the negative electrode layer (12). The margin insulating layer is positioned on the solid electrolyte layer (13) and may be formed laterally adjacent to the edges of the positive electrode active material layer or the negative electrode active material layer. Accordingly, the margin insulating layer may be positioned in the same layer of the positive electrode layer (11) and the negative electrode layer (12), respectively.

[0044] The margin insulation layer may include an insulating material having low ionic conductivity. For example, the insulating material may be polyethylene, a polyolefin such as polypropylene, a polyester such as polyethylene terephthalate (PET), polyurethane, or polyimide.

[0045] Additionally, the margin insulating layer may include an oxide-based solid electrolyte used in the solid electrolyte layer (13). However, the material included in the margin insulating layer is not limited thereto and may include various materials.

[0046] The positive electrode layer (11) and the negative electrode layer (12) of the all-solid-state battery (10) can be connected to external electrodes (14, 15), respectively. The external electrodes (14, 15) can be connected to the exposed terminals of the current collectors of the positive electrode layer (11) and the negative electrode layer (12), thereby serving as positive and negative electrodes, respectively.

[0047] According to one embodiment of the present invention, the all-solid-state battery (10) is configured such that a cathode layer (11), a cathode layer (12), and a solid electrolyte layer (13) are each formed of multiple layers and alternately laminated to form a cell stack. In FIG. 2, the cathode layers (11) and the anode layers (12) are alternately arranged and the solid electrolyte layer (13) is arranged between them. However, the arrangement of the cathode layers (11), the cathode layers (12), and the solid electrolyte layer (13) is not limited to what is illustrated. In one embodiment, a protective layer (not shown) made of an insulating material may be formed on the top and bottom of the cell stack.

[0048] According to one embodiment of the present invention, an all-solid-state battery (10) includes a case (16) configured to surround a cell stack. Additionally, external electrodes (14, 15) may be arranged at both ends of the case (16).

[0049] The external electrodes (14, 15) may include a conductive metal and glass. The conductive metal may be, for example, a conductive metal including copper (Cu), nickel (Ni), tin (Sn), palladium (Pd), platinum (Pt), gold (Au), silver (Ag), tungsten (W), titanium (Ti), lead (Pb), or an alloy thereof.

[0050] The glass component included in the external electrode (14, 15) may have a composition of mixed oxides. The glass component may include, for example, silicon oxide, boron oxide, aluminum oxide, a transition metal oxide, an alkali metal oxide, an alkaline earth metal oxide, or a combination 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).

[0051] The method for forming the external electrodes (14, 15) is not particularly limited. For example, they may be formed by dipping the cell stack into a conductive paste containing a conductive metal and glass, or by printing the conductive paste on the surface of the cell stack using a screen printing method or a gravure printing method. In addition, various methods may be used, such as applying the conductive paste on the surface of the cell stack or transferring a dried film of the conductive paste onto the cell stack.

[0052] The case (16) can perform the function of protecting the cell stack including the anode layer (11), the cathode layer (12) and the solid electrolyte layer (13) from being exposed to the outside. The case (16) is required to have moisture permeability, heat resistance, insulation, etc. to protect the internal components from external moisture, heat, electricity, etc., and is also required to have high resistance to chemical corrosion along with long-term stability.

[0053] According to one embodiment of the present invention, an all-solid-state battery (10) can be manufactured by stacking a cathode layer (11), a cathode layer (12), a solid electrolyte layer (13), a case (16), etc. and then sintering them integrally. In order to prevent the characteristics of the electrode layer, etc. from deteriorating during this sintering process, each component including the solid electrolyte layer (13) must be sintered at a low temperature, for example, a temperature of 700°C or lower.

[0054] In this way, the solid electrolyte of the all-solid-state battery (10) is required to have excellent low-temperature characteristics.

[0055] The solid electrolyte layer (13) according to one embodiment of the present invention includes an oxide-based electrolyte as a solid electrolyte.

[0056] As oxide-based solid electrolytes, Nasicon type such as LAGP and Garnet type such as LLZO are known, and through continuous research and development, the ionic conductivity of these oxide-based solid electrolytes has been increased to 10 -4 It is known to have improved to the S / cm level.

[0057] However, there are limits to further improving ionic conductivity with the above-mentioned NASICON-type and garnet-type oxide-based solid electrolytes. Furthermore, these oxide-based solid electrolytes are sintered at high temperatures exceeding 1,000°C. Therefore, even if a certain degree of excellent ionic conductivity can be achieved, as described above, the increased manufacturing costs due to high-temperature sintering inevitably increase. In particular, when high-temperature sintering is performed, it becomes practically impossible to sinter the solid electrolyte integrally with the positive and negative electrode layers.

[0058] In one embodiment of the present invention, a novel oxide-based solid electrolyte is used that overcomes the limitations of conventional oxide-based solid electrolytes, thereby securing excellent ionic conductivity while lowering the sintering temperature.

[0059] A solid electrolyte for an all-solid-state battery according to one embodiment of the present invention may be formed of an oxide containing Li, Mo, B, Al, and Cl. Specifically, the solid electrolyte according to one embodiment of the present invention may contain Li2O, MoO3, B2O3, Al2O3, and LiCl.

[0060] In the composition of the solid electrolyte, Li2O can function as a network modifier and improve ionic conductivity by providing Li ions.

[0061] In the composition of the solid electrolyte, MoO3 and B2O3 can function as network formers and, as low-temperature components, play a role in lowering the sintering temperature.

[0062] In the composition forming a solid electrolyte, Al2O3 can function as an intermediate. That is, Al2O3 can function as a network former or network modifier depending on its concentration in the composition.

[0063] In the composition of a solid electrolyte, LiCl enhances ionic conductivity by increasing the concentration of Li and Cl ions. The increased Cl ions can migrate as free ions within the network structure, increasing the lattice constant of the oxide crystal structure. This, in turn, widens the path for Li ions to migrate within the crystal structure, further enhancing ionic conductivity.

[0064] In one embodiment, the solid electrolyte may satisfy Equation 1 based on the molar ratio.

[0065] [Mathematical Formula 1]

[0066] (LiCl + Al2O3) / (Li2O + MoO3 + B2O3)≥ 0.16

[0067] In another embodiment, the solid electrolyte may satisfy Equation 2 based on the molar ratio.

[0068] [Equation 2]

[0069] 0.01≤ Al2O3 / (Li2O + MoO3+ B2O3)≤ 0.02

[0070] According to one embodiment of the present invention, the composition ratio of Li2O, MoO3 and B2O3 may be 10:1:14.

[0071] A solid electrolyte according to one embodiment of the present invention is LCB (Li 10 B 14 Cl2O 25 ) crystal, LBO (LiBO2) crystal, LBA (Li3Al(BO3)2) crystal, and LMO (Li2MoO4) crystal.

[0072] In this way, the solid electrolyte for an all-solid-state battery according to one embodiment of the present invention is composed of oxides including Li, Mo, B, Al, and Cl, and thus can be sintered at a temperature of approximately 700°C while exhibiting excellent ionic conductivity. Furthermore, since low-temperature sintering is possible, the solid electrolyte layer can be sintered simultaneously with the electrode, thereby simplifying the process and improving quality.

[0073] A solid electrolyte according to one embodiment of the present invention can be manufactured from a precursor powder including Li2CO3, MoO3, B2O3, Al2O3, and LiCl. Specifically, a solid electrolyte according to one embodiment of the present invention can be manufactured through the following process.

[0074] (1) Prepare precursor powder containing Li2CO3, MoO3, B2O3, Al2O3, and LiCl.

[0075] (2) The precursor powder is mixed uniformly through dry or wet mixing.

[0076] (3) The mixture of precursor powders is melted in a platinum crucible at a temperature of approximately 1,000°C for 30 minutes.

[0077] (4) Rapidly cool the melt to room temperature.

[0078] (5) The cooled melt is crushed into fine particles.

[0079] (6) The crushed material is pelletized and sintered at a temperature of approximately 700°C.

[0080] The solid electrolyte obtained through the above process has a density of about 7.20×10 at room temperature. -6 It exhibits an ionic conductivity of more than S / cm. Preferably, the solid electrolyte is 1.48×10 -4 It exhibits an ionic conductivity of more than S / cm.

[0081] Meanwhile, the solid electrolyte according to one embodiment of the present invention possesses excellent ionic conductivity and non-hygroscopicity. Accordingly, even if moisture enters the all-solid-state battery, the battery's performance is not degraded and it maintains stable and excellent performance.

[0082]

[0083] Experimental example

[0084] Precursor powders (batch size 100 g) containing Li2CO3, MoO3, B2O3, Al2O3, and LiCl were prepared. At this time, the mixing ratio of Li2CO3, MoO3, and B2O3 was fixed, and the addition amounts of LiCl and Al2O3 were varied to prepare a total of 10 types of precursor powders.

[0085] To ensure homogeneity of the solid electrolyte, precursor powders were sufficiently mixed through ball milling or mechanical mixing. The precursor powders were then placed in a platinum crucible and melted at approximately 1,000°C for approximately 30 minutes. The melt was rapidly cooled on a quenching roller, pulverized using a planetary ball mill, and then sieved to obtain micro-sized fine powders. The powders were then pelletized and sintered at approximately 700°C for approximately 3 hours, producing 10 different solid electrolytes.

[0086] The composition of the solid electrolyte manufactured as described above is as described in Table 1. The composition ratio of the solid electrolyte was calculated based on the remaining components excluding LiCl and Al2O3 for comparison with the comparative example described below, that is, based on the sum of the remaining components excluding LiCl and Al2O3 being 100 mol%.

[0087] Classification Solid electrolyte composition (mol%) Li2OMoO3B2O3LiClAl2O3Example 140456151Example 240456152Example 340456153Example 440456154Comparative Example 1404563-Comparative Example 2404565-Comparative Example 3404567-Comparative Example 44045610-Comparative Example 54045615-Comparative Example 64045620-

[0088]

[0089] FIGS. 3 and 4 are graphs showing XRD analysis results for pre-sintered powders of solid electrolytes according to embodiments and comparative examples of the present invention. Referring to FIGS. 3 and 4, the XRD graphs for pre-sintered powders of solid electrolytes according to embodiments and comparative examples of the present invention do not show crystalline peaks. This indicates that the pre-sintered powders are in an amorphous state, and in such an amorphous state, it is difficult to form lithium ion paths that enable ion diffusion.

[0090] Figure 5 is a graph showing the results of XRD analysis after sintering of a solid electrolyte according to an embodiment of the present invention.

[0091] Referring to Fig. 5, the XRD graph of the solid electrolyte after sintering shows multiple crystal peaks. Specifically, the solid electrolyte according to the embodiments of the present invention is LCB (lithium chloroborosite, Li 10 B 14 Cl2O 25 ), LBO (lithium metaborate, LiBO2), LBA (lithium aluminum borate, Li3Al(BO3)2), and LMO (lithium molybdate, Li2MoO4). In such a crystal structure, ion flow is smooth, resulting in excellent ionic conductivity.

[0092] Next, the results of the transition temperature and crystallization temperature measurement through DTA analysis of the solid electrolyte according to each example and comparative example are as shown in Table 2.

[0093] Classification DTA Transition Temperature (Tg, ℃) Crystallization Temperature (Tc, ℃) Example 1 391468 Example 2 395484 Example 3431481 Example 4 384470 Comparative Example 1 416501 Comparative Example 2 411499 Comparative Example 3406481 Comparative Example 4 380471 Comparative Example 5 380457 Comparative Example 6 372461

[0094]

[0095] Referring to Table 2, the examples generally exhibit low transition temperatures and crystallization temperatures. In particular, the solid electrolytes of Examples 1 and 2 exhibit excellent low-temperature characteristics, with transition temperatures and crystallization temperatures of approximately 395°C or lower and approximately 484°C or lower, respectively. Next, the sintering temperature, softening point, and half-ball temperature measurements of the solid electrolytes according to each example, measured through HTM analysis, are as shown in Table 3.

[0096] Distinction HTM sintering temperature (T sint , ℃) softening point (T soft , ℃)Half Ball(T half-ball , ℃)Example 1766795-Example 2452778789Example 3447778780Example 4721754776

[0097]

[0098] Referring to Table 3, the examples generally exhibit low sintering temperatures of approximately 760°C. This means that the solid electrolytes can be sintered at significantly lower temperatures compared to conventional oxide-based solid electrolytes, which are sintered at high temperatures of over 1,000°C. Next, the ionic conductivity measurement results of the solid electrolytes according to each example and comparative example are as shown in Table 4.

[0099]

[0100] Ionic conductivity (S / cm) Example 19.89×10 -5 Example 21.48×10 -4 Example 37.20×10 -6 Example 43.09×10 -5 Comparative example 14.46×10 -6 Comparative example 23.53×10 -7 Comparative example 39.34×10 -8 Comparative example 45.75×10 -5 Comparative example 53.83×10 -5 Comparative example 67.62×10 -5

[0101]

[0102] Referring to Table 4, the examples generally show higher ionic conductivity than the comparative examples. Among the examples, examples 1 and 2 each have ionic conductivity of 9.89×10 -5 S / cm and 1.48×10 -4 It shows a high ionic conductivity of S / cm, and in particular, the solid electrolyte of Example 2 has a conductivity of 10 -4 It can be confirmed that it has a very high ionic conductivity of the order of S / cm, which is much higher than that of the comparative examples. In this way, it can be confirmed that the ionic conductivity is improved as the solid electrolyte further includes Al2O3 and LiCl in addition to Li2O, MoO3, and B2O3. Furthermore, it can be confirmed that the ionic conductivity of the solid electrolyte is significantly improved when the ratio of Al2O3 and LiCl to the sum of Li2O, MoO3, and B2O3 based on the molar ratio is 0.16 or more (Examples 1 and 2).

[0103] As described above, this is presumed to be a result of improved ion mobility as the lattice constant of the crystals included in the solid electrolyte increases with the addition of LiCl.

[0104] Although the present invention has been described above with specific details such as specific components and limited examples, the above examples are provided only to help a more general understanding of the present invention, and the present invention is not limited thereto, and those with ordinary knowledge in the technical field to which the present invention pertains can make various modifications and variations based on this description.

[0105] Therefore, the idea of ​​the present invention should not be limited to the embodiments described above, and all things that are modified equally or equivalently to the claims described below as well as the claims are considered to fall within the scope of the idea of ​​the present invention.

Claims

1. As a solid electrolyte for all-solid-state batteries, Composed of oxides containing Li, Mo, B, Al and Cl. Solid electrolyte.

2. In paragraph 1, Based on the molar ratio, Satisfying (LiCl + Al2O3) / (Li2O + MoO3+ B2O3)≥ 0.16, Solid electrolyte.

3. In paragraph 2, Based on the molar ratio, Satisfying 0.01≤ Al2O3 / (Li2O + MoO3+ B2O3)≤ 0.02, Solid electrolyte.

4. In paragraph 2, The composition ratio of Li2O, MoO3 and B2O3 is 10:1:

14. Solid electrolyte.

5. In paragraph 1, LCB(Li 10 B 14 Cl2O 25 ) crystals, LBO (LiBO2) crystals, LBA (Li3Al(BO3)2) crystals and LMO (Li2MoO4) crystals, Solid electrolyte.

6. In paragraph 1, Manufactured from precursor powders containing Li2CO3, MoO3, B2O3, Al2O3 and LiCl, Solid electrolyte.

7. In paragraph 1, Ionic conductivity is 9.89×10 -5 S / cm or more, Solid electrolyte.

8. Bipolar layer, Cathode layer and Contains a solid electrolyte layer, The above solid electrolyte layer is made of an oxide containing Li, Mo, B, Al and Cl. All-solid-state battery.

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