Lithium borate-doped lithium carbonate-coated cathode active material and sulfide all-solid-state battery containing the same

Abstract

0 <x<0.5である、Li 2+x C 1-x B x A cathode active material (CAM) coated with lithium carbonate doped with lithium borate having a formula of O3, and a method for preparing the same, are disclosed. A cathode layer comprising the coated CAM in particulate form is also disclosed. In one embodiment, an all-solid-state battery comprising the cathode layer exhibits improved stability and cycling performance.

Description

Description of Related Applications

[0001] This application claims priority to U.S. Patent Application No. 18 / 194,145, filed March 31, 2023, and claims the benefit of U.S. Provisional Patent Application No. 63 / 386,183, filed December 6, 2022, the entire contents of which are incorporated herein by reference in their entirety. [Technical Field]

[0002] The present disclosure relates to a lithium carbonate borate-coated positive electrode active material and an sulfide-based all-solid-state battery (ASSB) including the same. [Background technology]

[0003] All-solid-state batteries (ASSBs) are considered promising candidates for future energy storage devices because they enable the use of lithium metal as the anode material, which would result in higher specific energy compared to conventional lithium-ion batteries based on organic liquid electrolytes. Sulfide solid electrolyte (SE) materials are made of elemental sulfur (S) in the -2 oxidation state. -2 ) and have a narrow intrinsic electrochemical window. Thiophosphate-based solid electrolytes (SEs) contain elemental phosphorus (P) and sulfur (S) and are particularly promising due to their high ionic conductivity, good mechanical compatibility, and relatively low cost. Reversible operation of all-solid-state batteries requires passivation of SEs. Specifically, conventional high-capacity positive electrode active materials (CAMs), such as lithium metal oxide CAMs (e.g., LiNi 0.88 Co 0.09 Al 0.03The application of O2--NCA88) to ASSB suffers from interfacial resistance. The interfacial resistance is due to a number of factors, including surface impurities on the CAM surface, violent reactions between lithium metal oxides and sulfide SEs, space charge layer effects, lattice mismatch, and insufficient wetting of the SEs. The formation of surface impurities such as LiOH and Li2CO3 on the CAM surface at ambient atmospheric conditions is known to degrade the electrochemical performance of conventional LIBs. For ASSBs, S / O exchange at the CAM / SE interface and insufficient ionic conductivity of surface impurities are major concerns. Computational modeling by Zhang et al. (Non-Patent Document 1) demonstrated that the LiOH / Li2CO3 interaction in crystalline Li2CO3 + The conductivity is approximately 10 at room temperature. -10 Scm -1 It has been reported that this can result in high interfacial resistance.

[0004] Various protective coatings have been developed to reduce the interface resistance. LiNbO3 has a resistance of about 10 -6 Scm -1 High Li + Due to its conductivity, it is one of the most studied coating materials for sulfide ASSB. Patent document 1 discloses that coating a LiNbO3 layer on CAM can reduce the interface resistance.

[0005] However, such coating materials may not fully address the above challenges. Zhang et al. (2013) reported that transition metals can diffuse from CAMs into thin-film coatings. First-principles calculations also show that the high binding energy of PO groups creates a driving force for S / O exchange between oxygen atoms in lithium transition metal oxide coatings, such as LiNbO3 and LiTaO3, and S atoms in sulfide SEs. In addition, the relatively low oxidation limits of these ternary metal oxide coatings raise stability concerns at high voltages. [Prior art documents] [Patent documents]

[0006] [Patent Document 1] US Patent Application Publication No. 2011 / 0045348A1 [Non-patent literature]

[0007] [Non-Patent Document 1] Zhang, et al. Achieving Both High Ionic Conductivity and High Interfacial Stability with the Li2+xC1-xBxO3 Solid-State Electrolyte: Design from Theoretical Calculations. ACS Appl. Mater. Interfaces 2020, 12, 5, 6007-6014. DOI: 10.1021 / acsami.9b22185. [Non-patent document 2] Zhang, et al. Direct Visualization of the Interfacial Degradation of Cathode Coatings in Solid State Batteries: A Combined Experimental and Computational Study. Adv. Energy Mater.2020, 10, 1903778. DOI: 10.1002 / aenm.201903778 Summary of the Invention [Problem to be solved by the invention]

[0008] Therefore, there remains a need for additional coating materials and solid-state batteries containing the same. [Means for solving the problem]

[0009] 0 <x<0.5である、Li 2+x C 1-x B xA cathode active material (CAM) at least partially coated with lithium carbonate doped with lithium borate having the formula O3, and a method for preparing the same are disclosed herein. A cathode layer including the coated CAM, and a all-solid-state battery including the cathode layer are also disclosed. The CAM disclosed herein having lithium carbonate doped with lithium borate improves discharge specific capacity and / or cycle life stability when incorporated into an all-solid-state battery. In another aspect, a CAM doped with lithium borate on the surface is also disclosed herein.

Brief Description of the Drawings

[0010] [Figure 1] Figure showing a representative structure of a cathode layer including CAM particles (1), a coating (2) around the CAM particles consisting of a thin (1-10 nm) LCBO (Li2+xC1-xBxO3; 0.00 < x < 0.5) layer, conductive carbon fibers (3), and a sulfide SE (4) [Figure 2] Figure showing a typical structure of an all-solid-state battery (ASSB) including a cathode layer (5), a solid electrolyte (6), a anode layer (7), a first current collector (8-1) in contact with the anode layer, and a second current collector (8-2) in contact with the cathode layer [Figure 3] Graph showing the specific capacity versus cycle for a half-cell including a Li metal anode, LPSCl (Li6PS5Cl) SE, and a cathode layer including particles of NCA88 (LiNi0.88Co0.09Al0.03O2) and vapor-grown carbon fibers (VGCF) as the CAM. Cycles 1 and 2 are charge / discharge cycles at 0.1C, cycles 3 and 4 are charge / discharge cycles at 0.33C, cycle 5 is a charge / discharge cycle at 1.0C, and cycles 6-25 are charge / discharge cycles at 0.5C. The cycle plots compare NCA88 CAM coated with approximately 5 nm of Li2+xC1-xBxO3 at x = 0, 0.05, 0.1, 0.15, 0.25, 0.3, 0.5, and 1. [Figure 4]Graph showing the initial 0.1C discharge specific capacity of 5nm LCBO coated CAM for x=0, 0.05, 0.1, 0.15, 0.25, 0.3, 0.5, and 1 (values ​​from Table 1). [Figure 5] Graph showing cycle life capacity retention of 5 nm LCBO coated CAM for x=0, 0.05, 0.1, 0.15, 0.25, 0.3, 0.5, and 1 (values ​​from Table 1). [Figure 6] This graph shows the specific capacity versus cycling at 45°C for a half-cell with a Li metal anode, LPSCl (Li6PS5Cl) SE, and a cathode layer containing NCA88 (LiNi0.88Co0.09Al0.03O2) particles as a CAM with VGCF. Cycles 1 and 2 are 0.1 C charge / discharge cycles, cycles 3 and 4 are 0.33 C charge / discharge cycles, cycle 5 is 1.0 C charge / discharge cycle, and cycles 6 through 100 are 0.5 C charge / discharge cycles. The cycle plot compares the NCA88 CAM coated with approximately 5 nm of Li2+xC1-xBxO3 at x = 0, 0.05, 0.15, and 0.25. [Figure 7] Graph showing the specific capacity versus cycle at 75°C for a half-cell with a Li metal anode, LPSCl (Li6PS5Cl)SE, and a cathode layer containing NCA88 particles and VGCF as the CAM. Cycles 1 and 2 were 0.1C charge / discharge cycles, cycles 3 and 4 were 0.33C charge / discharge cycles, cycles 5 and 6 were 0.5C charge / discharge cycles, cycles 7 and 8 were 1C charge / discharge cycles, cycles 9 and 10 were 2C charge / discharge cycles, cycles 11 and 12 were 5C charge / discharge cycles, and cycles 13–40 were 0.5C charge / discharge cycles. The cycle plot compares NCA88 CAMs coated with approximately 5 nm of Li2+xC1-xBxO3 at x=0, x=0.15, coated using the sol-gel method, and at x=0.15, 0.20, and 0.25, coated using the spray-coating method. DETAILED DESCRIPTION OF THE INVENTION

[0011] In some embodiments, the positive electrode active material (CAM) is <x<0.5である、Li 2+x C 1-x B x The CAM is coated with an LCBO having the formula: O3. Lithium carbonate borate (LCBO) is also known as lithium carbonate doped with lithium borate. In some embodiments, the coated CAM is incorporated into a positive electrode layer, for example, as shown in FIG. 1. The positive electrode layer may include particles of a positive electrode active material (CAM) (1) coated with the LCBO as a CAM coating layer (2), a conductive material (3) such as carbon fiber, and a solid electrolyte (4) such as a sulfur-containing inorganic electrolyte or a sulfide-based solid electrolyte.

[0012] In some embodiments, the CAM comprises Li x MO2, Li x Ni 1-y-z Co y M1 z O2 and Li x Ni 1-y-z Mn y M2 z O2, wherein M is at least one selected from the group consisting of Ni, Co, Mn, Al, B, Fe, Mg, Ca, Sr, Sc, Y, Ti, Zr, V, Nb, Ta, Cr, Mo, W, Rh, Pd, Cu, Zn, Cd, Ga, In, Sn, and rare earth elements; M1 is Mn, Al, B, Fe, Mg, Ca, Sr, Sc, Y, Ti, Zr, V, Nb, Ta, Cr, M2 is at least one selected from the group consisting of Co, Al, B, Fe, Mg, Ca, Sr, Sc, Y, Ti, Zr, V, Nb, Ta, Cr, Mo, W, Rh, Pd, Cu, Zn, Cd, Ga, In, Sn, and rare earth elements, and 0.95≦x≦1.1, 1-yz>0, 0 <y≦0.5、0≦z≦0.5である。

[0013] In some embodiments, the CAM comprises Li xMO2, Li x Ni 1-y-z Co y M1 z O2 and Li x Ni 1-y-z Mn y M2 z O2, wherein M is at least one selected from the group consisting of Al, B, Fe, Mg, Ca, Sr, Sc, Y, Ti, Zr, V, Nb, Ta, Cr, Mo, W, Rh, Pd, Cu, Zn, Cd, Ga, In, Sn, and rare earth elements; and M1 is Mn, Al, B, Fe, Mg, Ca, Sr, Sc, Y, Ti, Zr, V, Nb, Ta, Cr, Mo, W , Rh, Pd, Cu, Zn, Cd, Ga, In, Sn, and rare earth elements, and M2 is at least one selected from the group consisting of Co, Al, B, Fe, Mg, Ca, Sr, Sc, Y, Ti, Zr, V, Nb, Ta, Cr, Mo, W, Rh, Pd, Cu, Zn, Cd, Ga, In, Sn, and rare earth elements, and 0.95≦x≦1.1, 1-yz>0, 0 <y≦0.5、0≦z≦0.5である。

[0014] In some embodiments, the CAM is surface doped with at least one doping element selected from the group consisting of Ni, Co, Mn, Al, B, Fe, Mg, Ca, Sr, Sc, Y, Ti, Zr, V, Nb, Ta, Cr, Mo, W, Rh, Pd, Cu, Zn, Cd, Ga, In, Sn, Si, Ge, S, P, and rare earth elements.

[0015] In some embodiments, the CAM may include, without limitation, Li x Mn 1-y M y A2 (Eq. 1), Li x Mn 1-y M y O 2-z X z (Equation 2), Li x MnO 4-z X z (Equation 3), Li x Mn 2-y M yA4 (Formula 4), Li x Co 1-y M y A2 (Formula 5), Li x Co 1-y M y O 2-z X z (Formula 6), Li x Ni 1-y M y A2 (Formula 7), Li x Ni 1-y M y O 2-z X z (Formula 8), Li x Ni 1-y Co y O 2-z X z (Formula 9), Li x Ni 1-y-z Co y M z A a (Formula 10), Li x Ni 1-y-z Co y M z O 2-a X a (Formula 11), Li x Ni 1-y-z Mn y M z A a (Formula 12), Li x Ni 1-y-z Mn y M z O 2-a X a (Formula 13), Li x Ni 1-y-z Mn y M zO2 (Formula 14) and combinations thereof, wherein 0.95≦x≦1.1, 0≦y≦0.5, 0≦z≦0.5, 0≦a≦2; M is selected from the group consisting of Al, Ni, Co, Mn, Cr, Fe, Mg, Sr, V, and rare earth elements; A is selected from the group consisting of O, F, S, and P; and X is selected from the group consisting of F, S, and P. In some embodiments, the CAM is in the form of particles having an average diameter in the range from about 1 μm to about 15 μm, about 1 μm to about 12 μm, about 1 μm to about 10 μm, about 1 μm to about 7 μm, about 1 μm to about 6 μm, about 3 μm to about 15 μm, about 3 μm to about 12 μm, about 3 μm to about 10 μm, about 3 μm to about 7 μm, about 3 μm to about 6 μm, about 5 μm to about 15 μm, about 5 μm to about 12 μm, about 5 μm to about 10 μm, and all ranges and sub-ranges therebetween. In some embodiments, the coated CAM comprises about 50% to about 99% by weight, about 50% to about 95% by weight, about 50% to about 90% by weight, about 50% to about 85% by weight, about 50% to about 80% by weight, about 55% to about 99% by weight, about 55% to about 95% by weight, about 55% to about 90% by weight, about 55% to about 85% by weight, about 55% to about 80% by weight, about 60% to about 99% by weight, about 60% to about 95% by weight, about 60% to about 90% by weight, about 60% to about 90% by weight, about 60% to about 95% by weight, about 60% to about 90% by weight, about 60% to about 90% by weight, about 60% to about 99% by weight, about 60% to about 95% by weight, about 60% to about 90 ... The CAM particles may have a concentration in the positive electrode layer ranging from about 85% by weight, about 60% by weight to about 80% by weight, about 65% by weight to about 99% by weight, about 65% by weight to about 95% by weight, about 65% by weight to about 90% by weight, about 65% by weight to about 85% by weight, about 65% by weight to about 80% by weight, about 70% by weight to about 99% by weight, about 70% by weight to about 95% by weight, about 70% by weight to about 90% by weight, about 70% by weight to about 85% by weight, about 70% by weight to about 80% by weight, and all ranges and sub-ranges therebetween. In some embodiments, the CAM particles may be polycrystalline or monocrystalline. In some embodiments, the CAM particles may have a single particle size distribution or multiple particle size distributions.

[0016] In some embodiments, the CAM contains the element Ni in a mole fraction of at least 50%, at least 55%, at least 60%, at least 65%, at least 70%, at least 75%, at least 80%, or at least 85% of all metal elements other than lithium.

[0017] In some embodiments, the cathode coating material is Li2CO3 doped with Li3BO3 (LCBO), where the ratio of Li2CO3-Li3BO3 is Li 2+x C 1-x B xO3. In some embodiments, O <x<1、0<x≦0.90、0<x≦0.80、0<x≦0.70、0<x≦0.60、0<x≦0.50、0<x≦0.45、0<x≦0.40、0<x≦0.35、0<x≦0.30、0<x≦0.25、0<x≦0.20、0<x≦0.15、0<x≦0.10、0.10≦x<1、0.10≦x≦0.90、0.10≦x≦0.80、0.10≦x≦0.70、0.10≦x≦0.60、0.10≦x≦0.50、0.10≦x≦0.45、0.10≦x≦0.40、0.10≦x≦0.35、0.10≦x≦0.30、0.10≦x≦0.25、0.10≦x≦0.20、0.15≦x<1、0.15≦x≦0.90、0.15≦x≦0.80、0.15≦x≦0.70、0.15≦x≦0.60、0.15≦x≦0.50、0.15≦x≦0.45、0.15≦x≦0.40、0.15≦x≦0.35、0.15≦x≦0.30、0.15≦x≦0.25、0.20≦x<1、0.20≦x≦0.90、0.20≦x≦0.80、0.20≦x≦0.70、0.20≦x≦0.60、0.20≦x≦0.50、0.20≦x≦0.45、0.20≦x≦0.40、0.20≦x≦0.35、0.20≦x≦0.30、0.25≦x<1、0.25≦x≦0.90、0.25≦x≦0.80、0.25≦x≦0.70、0.25≦x≦0.60、0.25≦x≦0.50、0.25≦x≦0.45、0.25≦x≦0.40、0.25≦x≦0.35、0.30≦x<1、0.30≦x≦0.90、0.30≦x≦0.80、0.30≦x≦0.70、0.30≦x≦0.60、0.30≦x≦0.50、0.30≦x≦0.45、0.30≦x≦0.40、0.35≦x<1、0.35≦x≦0.90、0.35≦x≦0.80、0.35≦x≦0.70、0.35≦x≦0.60、0.35≦x≦0.50、0.35≦x≦0.45、0.40≦x<1、0.40≦x≦0.90、0.40≦x≦0.80、0.40≦x≦0.70、0.40≦x≦0.60、0.40≦x≦0.50、0.45≦x<1、0.45≦x≦0.90、0.45≦x≦0.80、0.45≦x≦0.70、0.45≦x≦0.60、0.50≦x<1、0.50≦x≦0.90、0.50≦x≦0.80、0.50≦x≦0.70、0.50≦x≦0.60、0.70≦x<1, 0.70≦x≦0.90, 0.70≦x≦0.80, and all ranges and subranges therebetween. The range of x disclosed above improves ionic conductivity by doping lithium borate into lithium carbonate, which in turn improves the discharge capacity of all-solid-state batteries. Doping lithium borate into lithium carbonate also results in higher cycle life stability because the B-O bond is stronger than the C-O bond, which reduces the exchange of O-S bonds between the positive electrode active material and the sulfide solid electrolyte. It has been found that doping a large amount of lithium borate into lithium carbonate can decrease ionic conductivity and cycle life stability, resulting in lower discharge capacity. Without intending to be bound by theory, the decreased cycle life capacity of compositions doped with a large amount of lithium borate may be a result of the higher hardness of lithium borate (4 on the Mohs hardness scale) than lithium carbonate (0.6 on the Mohs hardness scale). The harder the lithium borate coating, the more susceptible it is to cracking during volume expansion and contraction of the positive electrode active material during cycling, which will expose the surface of the positive electrode active material to the solid electrolyte. This will reduce cycle life stability.

[0018] In some embodiments, the LCBO coating may have a thickness ranging from 0.5 to 20 nm, 0.8 to 20 nm, 1 to 20 nm, 2 to 20 nm, 4 to 20 nm, 10 to 20 nm, 0.5 to 10 nm, 1.0 to 10 nm, 2 to 10 nm, or 4 to 10 nm. In some embodiments, the thickness is measured by observing the cross-section of a cut particle using a scanning electron microscope (SEM). In some embodiments, the thickness is measured by a transmission electron microscope (TEM). In some embodiments, the thickness is calculated using the mass content of lithium carbonate, the content of doped lithium carbonate borate, and the surface area (e.g., BET specific surface area).

[0019] In some embodiments, the conductive material may be carbon fiber, including but not limited to vapor grown carbon fiber (VGCF), carbon nanotubes (CNT), multi-walled carbon nanotubes (MWCNT), carbon nanofibers, and graphite fibers. In some embodiments, the conductive material may be 1 to 600 mW. 2 / g and / or an electrical resistivity of 0.5 Ω cm or less. In some embodiments, the conductive material may be coated with an oxide material. In some embodiments, oxide materials include, but are not limited to, lithium borate, alumina, lithium zirconate (LiZrO), LiNbO, LiSiO, LiPO, LiSiO, LiPO, LiSO, LiWO, LiMoO, LiAlO, LiTiO, LiTiO. 12 or a complex oxide thereof. In some embodiments, the lithium borate of the conductive material coating includes, without limitation, Li3B 11 O 18 , Li3BO3, Li4B2O5, Li6B4O9, LiBO2, Li2B4O7, Li3B7O 12 and LiB3O5. In some embodiments, the conductive material (coated or uncoated) has a concentration in the positive electrode layer in the range of 0.01% to 5%, 0.01% to 4%, 0.01% to 3%, 0.01% to 2%, 0.5% to 5%, 0.5% to 4%, 0.5% to 3%, 0.5% to 2%, 1% to 5%, 1% to 4%, 1% to 3%, 2% to 5%, 2% to 4%, and any or all ranges and sub-ranges therebetween.

[0020] In some embodiments, the method of preparing the coated positive electrode active material disclosed herein can include determining the mass percentage of lithium carbonate in the uncoated positive electrode active material, for example, by using thermogravimetric analysis (TGA) or titration. A coating solution can be prepared that includes a solvent, a lithium precursor, and a borate precursor, where the amounts of the lithium precursor and the borate precursor are represented by the formula Li 2+x C 1-x B x The coating solution is calculated based on the mass percentage of lithium carbonate previously determined to be present in O3 and the uncoated positive electrode active material. In some embodiments, the solvent for preparing the coating solution is non-aqueous and selected from the group consisting of methanol, ethanol, isopropanol, n-propanol, t-butanol, and mixtures thereof. The coating solution can be applied to the uncoated positive electrode active material, and then the coating solution can be annealed to convert the lithium precursor and borate precursor to lithium carbonate doped with lithium borate and form a coating on the positive electrode active material. In some embodiments, the annealing is performed at a temperature ranging from 150 to 600°C for a period ranging from 0.5 to 3 hours under an oxygen atmosphere. In some embodiments, the coating solution can be applied by spray coating the coating solution onto the uncoated positive electrode active material, which is referred to herein as the spray coating method. In other embodiments, the coating solution can be applied by mixing the uncoated positive electrode active material with the coating solution to form a mixture, which is then formed into a gel by removing the solvent under vacuum, which is referred to herein as a sol-gel process.

[0021] In some embodiments, the solid electrolyte used may be any sulfide solid electrolyte as long as it contains Li and S and has the desired lithium ion conductivity. The sulfide solid electrolyte may be any crystalline material, glass-ceramic, and glass. In some embodiments, the solid electrolyte is a lithium-phosphate-sulfur (LPS) electrolyte. Examples of solid electrolytes include Li2S-P2S5, Li2S-P2S5-LiHa (where "Ha" is one or more halogen elements), Li2S-P2S5-P2O5, Li2S-Li3PO4-P2S5, Li3PS4, Li4P2S6, Li 10 GeP2S 12 、Li 3.25 Ge 0.25 P 0.75 S4, Li7P3S 11 、Li 3.25 P 0.95 S4, and Li 7-x PS 6-x Ha x (Ardillodite-type solid electrolyte, "Ha" is one or more halogen elements, 0.2 < x < 1.8). In some embodiments, the sulfide solid electrolyte may have a concentration in the range of 1% to 35% by mass, 1% to 30% by mass, 1% to 25% by mass, 1% to 20% by mass, 1% to 15% by mass, 1% to 10% by mass, 5% to 35% by mass, 5% to 30% by mass, 5% to 25% by mass, 5% to 20% by mass, 5% to 15% by mass, 10% to 35% by mass, 10% to 30% by mass, 10% to 25% by mass, 10% to 20% by mass, 15% to 35% by mass, 15% to 30% by mass, 15% to 25% by mass, 20% to 30% by mass, and any and all ranges and sub-ranges therebetween in the positive electrode layer.

[0022] In some embodiments, the positive electrode layer is sandwiched between the positive electrode current collector and the solid electrolyte layer. In some embodiments, the positive electrode layer each contains a positive electrode active material (CAM) that requires connectivity of both lithium ions (Li + ) and electrons (e - ) with the solid electrolyte layer and the current collector. Li+ The connectivity is mainly provided by small particles of sulfide-based solid electrolyte in the cathode layer, and e - Connectivity is primarily provided by the conductive material. Sulfide-based solid electrolytes (such as the exemplary sulfide solid electrolytes mentioned above) have high Li + However, they generally exhibit Li / Li conductivity at the CAM / SE, CF / SE, and current collector / SE interfaces. + Decomposition by-products generally occur at potentials below 1.7 V or above 2.1 V relative to Li. + The LCBO coatings disclosed herein have a relatively high Li conductivity, which in turn requires a higher percentage of SE and a lower percentage of CAM in the cathode composite layer. Without intending to be bound by theory, the LCBO coatings disclosed herein may extend the degradation time and provide a relatively high Li + The conductivity is maintained, thus improving the cycling performance.

[0023] The previously disclosed positive electrode layers can be incorporated into all-solid-state batteries. For example, as shown in FIG. 2, the positive electrode layer 5 can function as the positive electrode in an all-solid-state battery (ASSB), which may also include a negative electrode (or negative electrode layer) 7 and a solid electrolyte layer 6 between the positive electrode layer 5 and the negative electrode 7. In some embodiments, the solid electrolyte of the solid electrolyte layer can be the same as or different from the solid electrolyte in the positive electrode layer. In some embodiments, the solid electrolyte layer is an inorganic solid electrolyte layer, such as, but not limited to, Li2S-P2S5, Li2S-P2S5-LiHa (where "Ha" is one or more halogen elements), Li2S-P2S5-P2O5, Li2S-Li3PO4-P2S5, Li3PS4, Li4P2S6, Li 10 GeP2S 12 , Li 3.25 Ge 0.25 P 0.75 S4, Li7P3S 11 , Li 3.25 P 0.95 S4, and Li 7-x PS 6-x Ha x(An argyrodite-type solid electrolyte, where "Ha" is one or more halogen elements, and 0.2 < x < 1.8), is a sulfur-containing inorganic electrolyte.

[0024] In some embodiments, the ASSB has an initial discharge specific capacity of at least 180 mAh / g, at least 185 mAh / g, or at least 190 mAh / g at 45 °C and a discharge rate of 0.5 C.

[0025] In some embodiments, the ASSB has an initial discharge specific capacity of at least 190 mAh / g, at least 195 mAh / g, at least 200 mAh / g, or at least 205 mAh / g at 45 °C and a discharge rate of 0.51.

[0026] In some embodiments, when charging and discharging the ASSB at 45 °C for 20 cycles, at 0.1 C for cycles 1 and 2, at 0.33 C for cycles 3 and 4, at 1.0 C for cycle 5, and at 0.5 C for cycles 6 to 20, and charging to 4.25 V and discharging to 2.8 V in each cycle, the ASSB has a 20-cycle discharge of at least 180 mAh / g, at least 185 mAh / g, or at least 190 mAh / g, and / or a 20th-cycle life retention rate of at least 95%, at least 96%, at least 97%, or at least 98%. The 20th-cycle life retention rate is the ratio of the discharge specific capacity in the 20th cycle to the initial discharge specific capacity at 45 °C and 0.5 C.

[0027] In one embodiment, the present disclosure provides a layer for a positive electrode of a all-solid-state battery, the layer comprising a cathode active material (CAM) coated with LCBO. In one embodiment, LCBO is formed between lithium carbonate and lithium borate or its precursor on the surface of the CAM particles. In some embodiments, lithium borate for doping lithium carbonate on the surface of the CAM includes, without limitation, Li3B 11 O 18 , Li3BO3, Li4B2O5, Li6B4O9, LiBO2, Li2B4O7, Li3B7O12 , and LiB3O5. In some embodiments, the lithium borate is doped with a doping element to dope the lithium carbonate on the CAM surface. In some embodiments, the doping element is fluorine (F), sulfur (S), silicon (Si), germanium (Ge), or a mixture thereof. In some embodiments, the lithium borate comprises one or more undoped or doped lithium borates as described above. In some embodiments, the lithium borate is structurally similar to lithium carbonate such that lithium carbonate doped with lithium borate can be formed on the surface of the CAM.

[0028] In some embodiments, the LCBO formed on the surface of the CAM exhibits less uniformity with respect to the concentrations of lithium carbonate and lithium borate. In some embodiments, the lithium carbonate exhibits a gradient concentration in the LCBO coating on the surface of the CAM particle. In some embodiments, the lithium carbonate concentration is relatively high near or adjacent to the surface of the CAM particle, and / or the lithium carbonate concentration decreases from the surface of the CAM particle to the outer surface of the LCBO coating. In some embodiments, the lithium borate exhibits a gradient concentration in the LCBO coating on the surface of the CAM particle. In some embodiments, the lithium borate concentration is relatively high on or near the outer surface of the LCBO coating, and / or the lithium borate concentration decreases from the outer surface of the LCBO coating to the surface of the CAM particle. In some embodiments, lithium carbonate exposure is minimized to reduce or avoid side reactions between the positive electrode active material and the sulfide electrolyte. In some embodiments, the LCBO is formed based on lithium carbonate on the surface of the CAM particle without an external source of lithium carbonate. The gradient can be determined using high resolution TEM and elemental mapping, such as an energy dispersive spectroscopy (EDS) line scan through the thickness of the coating.

[0029] In some embodiments, the CAM particles coated with an LCBO coating exhibit a core-shell structure, where the core is the CAM particle and the shell is the LCBO coating.

[0030] In one embodiment, the present disclosure provides a all-solid-state battery (ASSB) comprising the above-described cathode layer.

[0031] In some embodiments, the present disclosure provides a cathode active material whose surface is doped with lithium borate.

[0032] In some embodiments, the solid electrolyte layer of the ASSB is an inorganic solid electrolyte layer, such as, but not limited to, Li2S-P2S5, Li2S-P2S5-LiHa (where "Ha" is one or more halogen elements), Li2S-P2S5-P2O5, Li2S-Li3PO4-P2S5, Li3PS4, Li4P2S6, Li 10 GeP2S 12 、Li 3.25 Ge 0.25 P 0.75 S4、Li7P3S 11 、Li 3.25 P 0.95 S4、and Li 7-x PS 6-x Ha x (Ardillodite-type solid electrolyte, "Ha" is one or more halogen elements, 0.2 < x < 1.8), which is a sulfur-containing inorganic electrolyte.

[0033] The present disclosure will be better understood by reference to the following experimental details, but it will be readily recognized by those skilled in the art that the specific experiments described in detail are for illustrative purposes only and are not intended to limit the present disclosure as described herein, which is defined by the claims that follow.

[0034] Note that the transitional phrase "comprising," which is synonymous with "including," "containing," or "characterized by," is inclusive or open-ended and does not exclude additional, unrecited elements or method steps. [Example]

[0035] Example 1 Because Li2CO3 is inherently present on the CAM surface from standard manufacturing processes, the mass percentage of Li2CO3 relative to the CAM can be determined, for example, by using thermogravimetric analysis (TGA). The stoichiometric amount of Li3BO3 required to produce an LCBO coating was further calculated. For an LCBO coating with x = 0.15, stoichiometric amounts of a Li precursor (e.g., lithium acetate or lithium metal) and a B precursor (e.g., triisopropyl borate) were dissolved in a dry solvent (e.g., ethanol) to form a coating solution containing the lithium and boron precursors. The coating solution was added to a predetermined amount of CAM, calculated from the TGA data to give the desired Li3BO3 doping ratio. The mixture was stirred for 30 minutes, and then the solvent was removed under vacuum while sonicating, resulting in a gel of the CAM coated with the Li and B precursors. The gel was then annealed at 300 °C for 1 hour under a flow of oxygen to form the LCBO coating layer.

[0036] The specific discharge capacity and cycle life retention of various LCBO coating compositions for x = 0 to 1.00 are summarized in Table 1. For the LCBO with x = 1.00 (no lithium carbonate in the coating), the CAM was first annealed in air at 600 °C for 16 hours to remove the native Li2CO3 on the surface before coating with the stoichiometric Li3BO3 sol-gel reagent. The positive electrode layer contained 65 wt% CAM (NCA88), 5 wt% carbon fiber, and 30 wt% lithium phosphosulfur chloride (LPSCl) (Li6PS5Cl). The positive electrode layer was electrochemically evaluated in a torque cell using Li metal on copper as the anode and LPSCl (Li6PS5Cl) as the SE. The cells were cycled from 2.8V to 4.25V at 0.1C charge / discharge for cycles 1 and 2, 0.33C charge / discharge for cycles 3 and 4, 1.0C charge / discharge for cycle 5, and 0.5C charge / discharge for cycles 6 through 25.

[0037] The LCBO coating with x = 0.15 reduced the discharge specific capacity fade while maintaining a high initial cell performance. For example, as shown in Table 1 and Figure 4, the initial discharge capacity is 205.95 mAh / g at a 0.1 C discharge rate for a half-cell containing undoped CAM (x = 0.00). When Li3BO3 is doped into Li2CO3 (x = 0.05, 0.10, and 0.15), the initial discharge specific capacities are 211.00 mAh / g, 208.03 mAh / g, and 204.46 mAh / g, respectively. When x = 1.00 (100% Li3BO3), the initial discharge capacity drops to 186.39 mAh / g. The LCBO-coated CAM effectively reduced cell degradation and increased the theoretical capacity of the CAM (NCA88-LiNi 0.88 Co 0.09 Al 0.03 This will be crucial for achieving high capacity SSBs, as evidenced by the increase in initial discharge specific capacity at a discharge rate of 0.1 C, approaching 219.8 mAh / g for O2.

[0038] [Table 1]

[0039] As also shown in Table 1 and Figure 5, the cycle life retention increased from 95.87% for x = 0 to 99.22%, 98.21%, 99.63%, 98.83%, and 99.04% for x = 0.05, 0.10, 0.15, 0.25, and 0.3, respectively. When x is 0.5 or 1.0, the cycle life retention decreased to a level comparable to or lower than that of the uncoated CAM (x = 0). Under some circumstances, an x ​​greater than 0.5 may provide benefits such as short- to intermediate-term cycle life capacity retention.

[0040] Figure 6 is a plot of the specific capacity from cycle 1 to cycle 100. It is shown that x=0.05 and 0.15 have improved cycling performance compared to the uncoated one (x=0). The cycling performance of x=0.25 shows that the specific capacity in the early cycles is higher than that of the uncoated one, but gradually decreases to a lower level.

[0041] Example 2 The LCBO coating was applied to the CAM surface by spray coating using the same method for preparing the coating solution as detailed in Example 1. The coating solution was applied to the CAM particles using a Model FD-MP-01D rolling fluidized bed granulator and coater from Powrex Corporation. The coated CAM was then annealed at 300°C for 1 hour under flowing oxygen to form an LCBO coating layer.

[0042] The 0.1C to 5C charge / discharge specific capacity and cycle life retention of the LCBO coating compositions for x = 0.00, x = 0.15 via the sol-gel method, and x = 0.15, 0.20, and 0.25 are shown in Figure 7 and summarized in Table 2. Comparing the sol-gel and spray-coated x = 0.15 materials, the spray-coated materials exhibit similar rate and discharge performance but higher stability. This is most likely due to more uniform / complete coverage, an inherent benefit of using the spray-coating method over the sol-gel method. Comparing the LCBO spray-coated materials with x = 0.15 and 0.25, the x = 0.15 material exhibited higher specific capacity at 5C charge / discharge, exceeding 200 mAh / g. The x = 0.25 material exhibited lower discharge capacity and rate capability, but showed a slight improvement in cycle life capacity retention. All coated materials showed improved performance compared to the x = 0.00 CAM.

[0043] [Table 2]

[0044] In a first embodiment of the present disclosure, a coated positive electrode active material includes a positive electrode active material (CAM) and a coating in contact with the positive electrode active material, the coating comprising: <x<0.5である、Li 2+x C 1-x B x Lithium borate doped lithium carbonate (LCBO) has the formula O3.

[0045] In a second embodiment according to the first embodiment, the coating has a thickness in the range of 0.5 to 20 nm.

[0046] In a third embodiment according to any preceding embodiment, 0.00 <x≦0.30である。

[0047] In a fourth embodiment according to any previous embodiment, the positive electrode active material is in the form of particles and has an average diameter of 1 to 15 μm.

[0048] In a fifth embodiment according to any previous embodiment, the CAM comprises Li x MO2, Li x Ni 1-y-z Co y M1 z O2 and Li x Ni 1-y-z Mn y M2 z O2, wherein M is at least one selected from the group consisting of Ni, Co, Mn, Al, B, Fe, Mg, Ca, Sr, Sc, Y, Ti, Zr, V, Nb, Ta, Cr, Mo, W, Rh, Pd, Cu, Zn, Cd, Ga, In, Sn, and rare earth elements; M1 is Mn, Al, B, Fe, Mg, Ca, Sr, Sc, Y, Ti, Zr, V, Nb, Ta, Cr, M2 is at least one selected from the group consisting of Co, Al, B, Fe, Mg, Ca, Sr, Sc, Y, Ti, Zr, V, Nb, Ta, Cr, Mo, W, Rh, Pd, Cu, Zn, Cd, Ga, In, Sn, and rare earth elements, and 0.95≦x≦1.1, 1-yz>0, 0 <y≦0.5、0≦z≦0.5である。

[0049] In a sixth embodiment, the CAM comprises Li x MO2, Li x Ni 1-y-z Co y M1 z O2 and Li x Ni 1-y-z Mn y M2 zO2, wherein M is at least one selected from the group consisting of Al, B, Fe, Mg, Ca, Sr, Sc, Y, Ti, Zr, V, Nb, Ta, Cr, Mo, W, Rh, Pd, Cu, Zn, Cd, Ga, In, Sn, and rare earth elements; and M1 is Mn, Al, B, Fe, Mg, Ca, Sr, Sc, Y, Ti, Zr, V, Nb, Ta, Cr, Mo, W , Rh, Pd, Cu, Zn, Cd, Ga, In, Sn, and rare earth elements, and M2 is at least one selected from the group consisting of Co, Al, B, Fe, Mg, Ca, Sr, Sc, Y, Ti, Zr, V, Nb, Ta, Cr, Mo, W, Rh, Pd, Cu, Zn, Cd, Ga, In, Sn, and rare earth elements, and 0.95≦x≦1.1, 1-yz>0, 0 <y≦0.5、0≦z≦0.5である。

[0050] In a seventh embodiment, the CAM is surface doped with at least one doping element selected from the group consisting of Ni, Co, Mn, Al, B, Fe, Mg, Ca, Sr, Sc, Y, Ti, Zr, V, Nb, Ta, Cr, Mo, W, Rh, Pd, Cu, Zn, Cd, Ga, In, Sn, Si, Ge, S, P, and rare earth elements.

[0051] In an eighth embodiment according to any previous embodiment, the CAM contains the element Ni in a mole fraction of at least 70% among all metal elements other than lithium.

[0052] In a ninth embodiment according to any previous embodiment, the positive electrode active material is polycrystalline particles or single crystalline particles.

[0053] In a tenth embodiment according to any previous embodiment, the concentration of lithium carbonate in the coating decreases from the surface of the CAM to the outer surface of the LCBO coating, and the concentration of lithium borate decreases from the outer surface of the LCBO coating to the surface of the CAM.

[0054] In an eleventh embodiment, a method of preparing a coated positive electrode active material according to any previous embodiment comprises: a) determining the mass percentage of lithium carbonate in the uncoated positive electrode active material; b) preparing a coating solution comprising a solvent, a lithium precursor and a borate precursor, the amounts of lithium precursor and borate precursor being calculated based on the formula and the mass percentage of lithium carbonate from step a); c) applying a coating solution to the uncoated positive electrode active material; and d) annealing the coating solution, wherein the lithium precursor and the borate precursor are converted into lithium borate-doped lithium carbonate (LCBO), thereby obtaining the coated positive electrode active material; Includes:

[0055] In a twelfth embodiment according to the eleventh embodiment, the solvent for preparing the coating solution is non-aqueous and is selected from the group consisting of methanol, ethanol, isopropanol, n-propanol, t-butanol, and mixtures thereof.

[0056] In a thirteenth embodiment according to any of the eleventh to twelfth embodiments, the coating solution is annealed at a temperature in the range of 150 to 600° C. for a period in the range of 0.5 to 3 hours under an oxygen atmosphere.

[0057] In a fourteenth embodiment according to any of the eleventh to thirteenth embodiments, the step of applying the coating solution comprises spraying the coating solution onto the positive electrode active material.

[0058] In a fifteenth embodiment according to any of the eleventh to thirteenth embodiments, the step of applying the coating solution comprises mixing the positive electrode active material in the coating solution.

[0059] In a sixteenth embodiment, the positive electrode layer comprises the coated positive electrode active material previously described in any of the first through fifteenth embodiments.

[0060] In a seventeenth embodiment according to the sixteenth embodiment, the coated positive electrode active material has a mass percentage of at least 65% of the positive electrode layer.

[0061] In an eighteenth embodiment according to the sixteenth or seventeenth embodiment, the positive electrode layer further comprises a conductive material.

[0062] In a nineteenth embodiment according to the eighteenth embodiment, the conductive material is selected from carbon fibers, vapor grown carbon fibers, carbon nanotubes, graphite fibers, and mixtures thereof.

[0063] In a twentieth embodiment according to any of the sixteenth to nineteenth embodiments, the positive electrode layer further comprises a sulfur-containing inorganic electrolyte.

[0064] In a twenty-first embodiment according to the twentieth embodiment, the sulfur-containing inorganic electrolyte is Li2S-P2S5, Li2S-P2S5-LiHa, Li2S-P2S5-P2O5, Li2S-Li3PO4-P2S5, Li3PS4, Li4P2S6, Li 10 GeP2S 12 , Li 3.25 Ge 0.25 P 0.75 S4, Li7P3S 11 , Li 3.25 P 0.95 S4, Li 7-x PS 6-x Ha x and mixtures thereof, wherein "Ha" is one or more halogen elements, and 0.2 <x<1である。

[0065] In a twenty-second embodiment, an all-solid-state battery (ASSB) includes a positive electrode layer as previously described in any of the sixteenth to twenty-first embodiments.

[0066] In a twenty-third aspect according to the twenty-second aspect, the ASSB further comprises an inorganic solid electrolyte layer.

[0067] In a twenty-fourth embodiment according to the twenty-third embodiment, the inorganic solid electrolyte layer comprises a sulfur-containing inorganic electrolyte.

[0068] In a twenty-fifth aspect according to the twenty-fourth aspect, the sulfur-containing inorganic electrolyte is Li2S-P2S5, Li2S-P2S5-LiHa, Li2S-P2S5-P2O5, Li2S-Li3PO4-P2S5, Li3PS4, Li4P2S6, Li 10 GeP2S 12 , Li 3.25 Ge 0.25 P 0.75 S4, Li7P3S 11 , Li 3.25 P 0.95 S4, Li 7-x PS 6-x Ha x and mixtures thereof, wherein "Ha" is one or more halogen elements, and 0.2 <x<1である。

[0069] In a 26th aspect according to any of the 22nd to 25th aspects, the LCBO comprises Li 2.05 C 0.95 B 0.05 O3(x=0.05), Li 2.10 C 0.90 B 0.10 O3(x=0.10), Li 2.15 C 0.85 B 0.15 O3(x=0.15), Li 2.25 C 0.75 B 0.25 O3 (x=0.25), and Li 2.30 C 0.70 B 0.30 O3 (x=0.30).

[0070] In a 27th embodiment according to any of the 22nd to 26th embodiments, the ASSB has a 20th cycle life retention of at least 98% when charged and discharged at 45° C. from 2.8 V to 4.25 V for 20 cycles, with 0.1 C for cycles 1 and 2, 0.33 C for cycles 3 and 4, 1.0 C for cycle 5, and 0.5 C for cycles 6 to 20, where the 20th cycle life retention is the ratio of the discharge specific capacity at the 20th cycle to the initial discharge specific capacity at 0.5 C at 45° C., where each cycle is charged to 4.25 V and discharged to 2.8 V.

[0071] In a 28th embodiment according to any of the 22nd to 27th embodiments, the ASSB has an initial discharge specific capacity at 45° C. and 0.1 C of at least 190 mAh / g. [Explanation of symbols]

[0072] 1. Cathode active material (CAM) particles 2 CAM coating layer 3. Conductive materials 4, 6 Solid electrolyte 5 Positive electrode layer 7. Negative electrode layer 8-1 First current collector 8-2 Second current collector

Claims

1. 1. A coated positive electrode active material comprising: a positive electrode active material (CAM), and a coating in contact with the positive electrode active material; Including, The coating is Li, where 0<x<0.

5. ２＋ｘ C １－ｘ B ｘ O ３ 1. A coated positive electrode active material comprising lithium borate doped lithium carbonate (LCBO) having a formula:

2. 10. The coated positive electrode active material of claim 1, wherein the coating has a thickness in the range of 0.5 to 20 nm.

3. 2. The coated positive electrode active material of claim 1, wherein 0<x≦0.

30.

4. 10. The coated positive electrode active material of claim 1, wherein the positive electrode active material is in the form of particles, the particles having an average diameter of 1 to 15 μm.

5. The CAM is Li ｘ MO ２ , Li ｘ Ni １－ｙ－ｚ Co ｙ M1 ｚ O ２ and Li ｘ Ni １－ｙ－ｚ Mn ｙ M2 ｚ O ２ selected from the group consisting of M is at least one selected from the group consisting of Ni, Co, Mn, Al, B, Fe, Mg, Ca, Sr, Sc, Y, Ti, Zr, V, Nb, Ta, Cr, Mo, W, Rh, Pd, Cu, Zn, Cd, Ga, In, Sn, and rare earth elements; M1 is at least one selected from the group consisting of Mn, Al, B, Fe, Mg, Ca, Sr, Sc, Y, Ti, Zr, V, Nb, Ta, Cr, Mo, W, Rh, Pd, Cu, Zn, Cd, Ga, In, Sn, and rare earth elements; M2 is at least one selected from the group consisting of Co, Al, B, Fe, Mg, Ca, Sr, Sc, Y, Ti, Zr, V, Nb, Ta, Cr, Mo, W, Rh, Pd, Cu, Zn, Cd, Ga, In, Sn, and rare earth elements; 2. The coated positive electrode active material of claim 1, wherein 0.95≦x≦1.1, 1−y−z>0, 0<y≦0.5, and 0≦z≦0.

5.

6. The CAM is Li ｘ MO ２ , Li ｘ Ni １－ｙ－ｚ Co ｙ M1 ｚ O ２ and Li ｘ Ni １－ｙ－ｚ Mn ｙ M2 ｚ O ２ selected from the group consisting of M is at least one selected from the group consisting of Al, B, Fe, Mg, Ca, Sr, Sc, Y, Ti, Zr, V, Nb, Ta, Cr, Mo, W, Rh, Pd, Cu, Zn, Cd, Ga, In, Sn, and rare earth elements; M1 is at least one selected from the group consisting of Mn, Al, B, Fe, Mg, Ca, Sr, Sc, Y, Ti, Zr, V, Nb, Ta, Cr, Mo, W, Rh, Pd, Cu, Zn, Cd, Ga, In, Sn, and rare earth elements; M2 is at least one selected from the group consisting of Co, Al, B, Fe, Mg, Ca, Sr, Sc, Y, Ti, Zr, V, Nb, Ta, Cr, Mo, W, Rh, Pd, Cu, Zn, Cd, Ga, In, Sn, and rare earth elements; 2. The coated positive electrode active material of claim 1, wherein 0.95≦x≦1.1, 1−y−z>0, 0<y≦0.5, and 0≦z≦0.

5.

7. 7. The coated positive electrode active material of claim 6, wherein the CAM is surface doped with at least one doping element selected from the group consisting of Ni, Co, Mn, Al, B, Fe, Mg, Ca, Sr, Sc, Y, Ti, Zr, V, Nb, Ta, Cr, Mo, W, Rh, Pd, Cu, Zn, Cd, Ga, In, Sn, Si, Ge, S, P, and rare earth elements.

8. 10. The coated positive electrode active material of claim 1, wherein the CAM contains the element Ni in a mole fraction of at least 70% among all metal elements other than lithium.

9. 10. The coated positive electrode active material of claim 1, wherein the positive electrode active material is polycrystalline particles or single crystal particles.

10. 10. The coated positive electrode active material of claim 1, wherein the concentration of lithium carbonate in the coating decreases from the surface of the CAM to the outer surface of the coating, and the concentration of lithium borate decreases from the outer surface of the coating to the surface of the CAM.

11. 10. The method for preparing the coated positive electrode active material of claim 1, a) determining the mass percentage of lithium carbonate in the uncoated positive electrode active material; b) preparing a coating solution comprising a solvent, a lithium precursor and a borate precursor, wherein the amount of the lithium precursor and the borate precursor is 0<x<0.5; ２＋ｘ C １－ｘ B ｘ O ３ and the mass percentage of lithium carbonate from step a), c) applying the coating solution to the uncoated positive electrode active material; and d) annealing the coating solution, wherein the lithium precursor and the borate precursor are converted into lithium borate-doped lithium carbonate (LCBO), thereby obtaining the coated positive electrode active material; A method comprising:

12. The method of claim 11, wherein the solvent for preparing the coating solution is non-aqueous and selected from the group consisting of methanol, ethanol, isopropanol, n-propanol, t-butanol, and mixtures thereof.

13. 12. The method of claim 11, wherein the coating solution is annealed at a temperature ranging from 150 to 600°C for a period ranging from 0.5 to 3 hours under an oxygen atmosphere.

14. The method of claim 11 , wherein applying the coating solution comprises spraying the coating solution onto the positive electrode active material.

15. The method of claim 11 , wherein applying the coating solution comprises mixing the positive electrode active material in the coating solution.

16. A positive electrode layer comprising the coated positive electrode active material of claim 1.

17. 17. The positive electrode layer of claim 16, wherein the coated positive electrode active material has a mass percentage of at least 65% of the positive electrode layer.

18. The positive electrode layer of claim 16 , further comprising a conductive material.

19. 20. The cathode layer of claim 18, wherein the conductive material is selected from carbon fibers, vapor-grown carbon fibers, carbon nanotubes, graphite fibers, and mixtures thereof.

20. 17. The positive electrode layer of claim 16, further comprising a sulfur-containing inorganic electrolyte.

21. The sulfur-containing inorganic electrolyte is Li ２ S-P ２ S ５ , Li ２ S-P ２ S ５ -LiHa, Li ２ S-P ２ S ５ -P ２ O ５ , Li ２ S-Li ３ P.O. ４ -P ２ S ５ , Li ３ P.S. ４ , Li ４ P ２ S ６ , Li １０ GeP ２ S １２ , Li ３．２５ Ge ０．２５ P ０．７５ S ４ , Li ７ P ３ S １１ , Li ３．２５ P ０．９５ S ４ , Li ７－ｘ P.S. ６－ｘ Ha ｘ 21. The cathode layer of claim 20, wherein "Ha" is one or more halogen elements, and 0.2<x<1.

22. An all-solid-state battery (ASSB) comprising the positive electrode layer of claim 16.

23. 23. The ASSB of claim 22, further comprising an inorganic solid electrolyte layer.

24. 24. The ASSB of claim 23, wherein the inorganic solid electrolyte layer comprises a sulfur-containing inorganic electrolyte.

25. The sulfur-containing inorganic electrolyte is Li ２ S-P ２ S ５ , Li ２ S-P ２ S ５ -LiHa, Li ２ S-P ２ S ５ -P ２ O ５ , Li ２ S-Li ３ P.O. ４ -P ２ S ５ , Li ３ P.S. ４ , Li ４ P ２ S ６ , Li １０ GeP ２ S １２ , Li ３．２５ Ge ０．２５ P ０．７５ S ４ , Li ７ P ３ S １１ , Li ３．２５ P ０．９５ S ４ , Li ７－ｘ P.S. ６－ｘ Ha ｘ 25. The ASSB of claim 24, wherein "Ha" is one or more halogen elements and 0.2<x<1.

26. The LCBO is Li ２．０５ C ０．９５ B ０．０５ O ３ , Li ２．１０ C ０．９０ B ０．１０ O ３ , Li ２．１５ C ０．８５ B ０．１５ O ３ , Li ２．２５ C ０．７５ B ０．２５ O ３ , and Li ２．３０ C ０．７０ B ０．３０ O ３ 23. The ASSB of claim 22 having a formula selected from the group consisting of:

27. 23. The ASSB of claim 22, wherein the ASSB has a 20th cycle life retention of at least 97% when charged and discharged at 45°C from 2.8V to 4.25V for 20 cycles, the 20th cycle life retention being the ratio of the discharge specific capacity at the 20th cycle to the initial discharge specific capacity at 0.5C, when each cycle is charged to 4.25V and discharged to 2.8V.

28. 23. The ASSB of claim 22, wherein the ASSB has an initial discharge specific capacity at 45°C and 0.1C of at least 190 mAh / g.

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