Array type lithium metal negative electrode and preparation method and application thereof

Abstract

The invention provides an array type lithium metal negative electrode as well as a preparation method and application thereof. The preparation method comprises the following steps: coating lithium metal in a molten state on a negative electrode current collector by using a pre-designed mask plate with an array pattern and a certain thickness to obtain a patterned lithium metal negative electrode in array distribution, and accurately quantifying and controlling the amount of the lithium metal through the thickness of the mask plate and the pattern design to obtain the patterned lithium metal negative electrode. Therefore, the equivalent lithium quantity and the area capacity on the negative electrode side unit area current collector are finely regulated and controlled. And meanwhile, alloying of molten lithium and copper at high temperature modifies copper on the surface layer into a three-dimensional porous shape in situ after lithium removal, so that subsequent uniform deposition and stable circulation of lithium are facilitated. The preparation method provided by the invention is low in equipment requirement, quick in preparation and short in time consumption, can be used for large-area preparation, and is expected to assist high-performance application of the lithium metal battery. The negative electrode can be used for a liquid lithium battery and can also be used for a solid-state lithium battery after being matched with a solid-state electrolyte.

Description

TECHNICAL FIELD

[0001] The application belongs to the technical field of lithium metal batteries, and particularly relates to an array type lithium metal negative electrode with accurate and controllable lithium amount and a specific preparation method thereof and application thereof in high-performance liquid lithium batteries and solid-state lithium batteries. BACKGROUND

[0002] The current positive electrode surface capacity of the lithium metal battery is generally 4mAh cm -2 The matching lithium metal negative electrode only needs a thickness of about 30um (6mAh cm -2 , N / P ratio 1.5) to achieve the required capacity matching. However, the current commercialized lithium metal foil is generally 50-750um, which is seriously overcapacity, not only causing lithium waste and potential safety risks, but also greatly weakening the unique advantage of high specific capacity of the lithium metal negative electrode, resulting in a serious reduction in the quality and volume energy density of the battery.

[0003] The current ultra-thin lithium metal strip (<50um) still has many challenges in preparation and performance. In the preparation end, the ultra-thin lithium preparation path mainly by rolling and rolling is limited by the limited mechanical strength of lithium, which is easy to break, difficult to form in large area, low in yield and expensive. The vapor phase preparation path mainly by evaporation and sputtering has high requirements for equipment and site, and low production efficiency, which is difficult to supply in large quantities. In the performance end, the planar lithium metal layer is easy to produce dendrite problem due to the lack of three-dimensional contact interface, and lithium is easy to become dead lithium due to the lack of electrical contact, thereby causing lithium loss and affecting the cycle performance of the battery.

[0004] Therefore, the controllable and low-cost preparation and rapid modification of the ultra-thin lithium metal negative electrode have important practical significance for improving the utilization efficiency of lithium in the lithium metal battery and improving the cycle performance and energy density of the battery. SUMMARY

[0005] To solve the above technical problems, the application provides an array type lithium metal negative electrode and a preparation method and application thereof.

[0006] To achieve the above-mentioned purposes, the technical solutions adopted by the application are as follows:

[0007] The application provides a preparation method of an array type lithium metal negative electrode, which comprises the following steps: preparing a mask plate with an array pattern and a thickness; heating lithium metal to a molten state, and coating the lithium metal in the molten state on the mask plate to obtain the array type lithium metal negative electrode.

[0008] Further, the preparation method specifically comprises: step (1), designing and preparing a mask plate with an array pattern and a certain thickness; wherein the material of the mask plate is stainless steel foil, titanium foil, nickel foil or polyimide film, the thickness is 1-500 microns, and the area ratio of the array pattern on the mask plate is 1-80%; step (2), heating lithium metal to a molten state, transferring the lithium metal in a molten state to the mask plate in a heated state, and the copper foil below the mask plate is in a heated state; continue to heat to maintain the molten state of the lithium metal and uniformly coat the lithium metal on the mask plate, the temperature is 180-350℃, after heat preservation, quickly cool to room temperature, remove the mask plate, and obtain the array lithium metal negative electrode.

[0009] Further, in step (1), the material of the mask plate is stainless steel foil; the area ratio of the array pattern on the mask plate is 20-60%; and the array pattern comprises one or more combined patterns of a circle, a rectangle and a triangle.

[0010] Further, in step (2), the lithium metal comprises pure lithium, lithium-carbon, lithium alloy or lithium-based composite material; the carbon material in the lithium-carbon comprises one or more of acetylene black, ketjen black, Cabot BP2000, Super P, single-walled carbon nanotube, few-walled carbon nanotube, multi-walled carbon nanotube, doped carbon nanotube, graphene, doped graphene, carbon nanofiber or doped carbon nanofiber; the shape of the carbon material comprises one or more of granular, linear or flaky; the lithium alloy comprises an alloy of lithium and magnesium, zinc, aluminum, gallium, indium, silver, tin, bismuth, germanium, antimony or silicon; and the lithium-based composite material comprises a mixture of lithium and a salt or an inorganic solid electrolyte material; wherein the anion of the salt comprises inorganic nitrate, chloride, nitrogen, phosphorus, fluorine, sulfur, oxygen, or organic difluorosulfonyl imide anion, bistrifluoromethylsulfonyl imide anion, difluorophosphoric acid anion, difluoroboric acid oxalate anion, bisoxalate boric acid anion, tetrafluoroboric acid anion, hexafluorophosphoric acid anion, and the cation of the salt is a metal alloyed with lithium, including magnesium, zinc, aluminum, gallium, indium, silver, tin, bismuth, germanium, antimony, silicon; and the inorganic solid electrolyte material comprises garnet-type lithium lanthanum tantalum oxide LLTO and LLZTO and LLATO systems doped with zirconium or aluminum, perovskite-type lithium lanthanum titanium oxide LLTO system, NASICON-type lithium aluminum titanium phosphate LATP system or sulfur-based inorganic solid-state electrolyte.

[0011] Further, the sulfur-based inorganic solid-state electrolyte comprises a (100-x) Li2S-xP2S5 binary system, a ternary system of Li2S-P2S5 doped with GeS2 or other MS2 substances, and a sulfide silver germanite system.

[0012] The application further provides the arrayed lithium metal negative electrode prepared by the preparation method of the arrayed lithium metal negative electrode.

[0013] Further, the equivalent lithium amount of the arrayed lithium metal negative electrode is greater than 0 and less than or equal to 10 mAh cm-2. -2 Correspondingly, the equivalent lithium layer thickness is greater than 0 and less than or equal to 50 μm.

[0014] The application also provides application of the arrayed lithium metal negative electrode in a liquid lithium battery or a solid-state lithium battery.

[0015] The application further provides a preparation method of a solid-state lithium battery, which comprises: coating a solid-state electrolyte slurry on the arrayed lithium metal negative electrode as described above, and drying to obtain the solid-state lithium battery.

[0016] The application provides the solid-state lithium battery prepared by the preparation method of the solid-state lithium battery.

[0017] The application provides an arrayed lithium metal negative electrode, a preparation method and application thereof.

[0018] First, the amount of lithium on the copper foil current collector substrate per unit area can be precisely controlled through the pre-design of the mask plate pattern;

[0019] Second, with the help of the coating method of the mask plate, uniform coating of lithium metal on a large area can be realized, which makes up for the problems of poor thickness uniformity of the lithium layer and uneven distribution of lithium amount caused by direct coating on the copper foil current collector;

[0020] Third, when high-temperature coating, alloying reaction occurs between molten lithium and copper. After delithiation, the surface copper is modified in situ into three-dimensional porous, and the increase of specific surface area and active sites makes lithium ions tend to deposit at the original coating site, which is beneficial to the long-term uniform deposition and stable circulation of lithium.

[0021] Fourth, compared with the traditional continuous lithium film layer, the arrayed lithium metal on the arrayed lithium metal negative electrode prepared has exposed copper blank area, which can provide direct contact and anchoring for solid-state electrolyte and copper foil current collector, and change the contact interface between lithium and electrolyte from traditional plane to three-dimensional nested type, which is beneficial to electron and ion conduction, effectively ensures the physical contact of the electrode in the cycle process, and ensures the cycle stability.

[0022] Fifth, the arrayed lithium metal negative electrode prepared has reserved lithium deposition space in advance, which is beneficial to buffer the volume change of lithium in the repeated deposition process to release stress and stabilize the negative electrode structure. BRIEF DESCRIPTION OF DRAWINGS

[0023] One or more embodiments are illustrated by way of example in the figures that form a part of this patent document, and in which like reference numbers indicate corresponding elements in the drawings, its use in the specification serves to explain embodiments, not to limit them. Unless otherwise indicated, the drawings in the figures are not to scale.

[0024] Figure 1 is a pure lithium array coated on a copper current collector by using a mask plate in Example 1 (equivalent lithium amount 0.5 mAh cm -2 );

[0025] Figure 2 is a Li@LLZTO array coated on a copper current collector by using a mask plate in Example 2 (equivalent lithium amount 2 mAh cm -2 );

[0026] Figure 3 is a Li@LLZTO array coated on a copper current collector by using a mask plate in Example 3 (equivalent lithium amount 4 mAh cm -2 );

[0027] Figure 4 is a FIB-SEM image of the cross section of the lithium array in Example 1;

[0028] Figure 5 is a SEM image of the copper surface at different magnifications after delithiation of the lithium array in Example 1;

[0029] Figure 6is the optical diagram of the secondary lithium intercalation after the lithium array of Example 2 is delithiated;

[0030] Figure 7 is the cycle performance diagram of the liquid lithium battery with the Li@LLZTO array negative electrode and the lithium iron phosphate positive electrode of Example 3;

[0031] Figure 8 is the cycle performance diagram of the solid-state lithium battery with the Li@LLZTO array negative electrode, the PVDF-LLZTO-LITFSI solid-state electrolyte and the lithium iron phosphate positive electrode of Example 3. DETAILED DESCRIPTION

[0032] In view of the prior art, the present application aims to solve the following problems: (1) large-area and uniform forming of ultra-thin lithium and accurate control of the lithium amount; (2) three-dimensional fast modification of the lithium-copper interface to regulate the uniform deposition behavior of lithium ions; and (3) in solid-state batteries, the three-layer stacking of the current collector / lithium metal / electrolyte causes interface deterioration and structural failure due to the frequent intercalation / deintercalation of lithium.

[0033] The present application provides an array lithium metal negative electrode and a preparation method and application thereof. The preparation method comprises: using a pre-designed mask plate with an array pattern and a certain thickness to coat lithium metal in a molten state on a negative electrode current collector to obtain an array distributed patterned lithium metal negative electrode. The thickness of the mask plate and the pattern design can accurately quantify and control the amount of lithium metal, thereby finely regulating the equivalent lithium amount and area capacity of the current collector per unit area on the negative electrode side. The method can accurately prepare an ultra-thin lithium foil with an equivalent lithium amount of 0-10 mAh cm -2 (corresponding to a lithium layer thickness of 0-50 μm). At the same time, the alloying of molten lithium and copper at high temperature modifies the surface layer copper in situ into a three-dimensional porous structure after delithiation, which is beneficial to the uniform deposition and stable cycling of lithium. The negative electrode can be used for liquid lithium batteries and can also be used for solid-state lithium batteries after being matched with a solid-state electrolyte. Especially in a solid-state system, the array lithium metal negative electrode reserves lithium deposition space in advance, which is beneficial to buffering the volume change of lithium during repeated deposition to release stress and stabilize the negative electrode structure. The present application has low equipment requirements, is fast and time-saving to prepare, and can be prepared in a large area, which is expected to help the high-performance application of lithium metal batteries.

[0034] The present application will be described in detail below with reference to the specific embodiments.

[0035] The present application provides a preparation method of an array lithium metal negative electrode, which specifically comprises the following steps:

[0036] Step 1: design and prepare a material mask plate with array arrangement characteristics, adjust the thickness (1 microns to 500 microns), and the proportion of circular, rectangular, triangular and other patterns in the total area (1% to 80%, preferably 20% to 60%). Both control the amount of lithium per unit area on the copper foil after coating, and adjust the dispersion degree of the uniform distribution of lithium metal array.

[0037] Step 2: Heat the lithium metal to a molten state, which can use pure lithium, lithium-carbon, lithium alloy, or lithium-based composite materials, etc. The carbon material in lithium-carbon includes any one or a combination of at least two of granular, linear or sheet carbon materials, including any one or a combination of at least two of acetylene black, ketjen black, cabot BP2000, super P, single-walled carbon nanotubes, few-walled carbon nanotubes, multi-walled carbon nanotubes, doped carbon nanotubes, graphene, doped graphene, carbon nanofibers or doped carbon nanofibers; lithium alloy includes lithium and magnesium, zinc, aluminum, gallium, indium, silver, tin, bismuth, germanium, antimony, silicon, etc. The lithium-based composite material includes a mixture of lithium and salt or inorganic solid electrolyte material, wherein the anion of the salt can be inorganic nitrate, chlorine, nitrogen, phosphorus, fluorine, sulfur, oxygen, or organic difluorosulfonyl imide anion, bistrifluoromethylsulfonyl imide anion, difluorophosphoric acid anion, difluoro oxalic acid borate anion, bisoxalic acid borate anion, tetrafluoroboric acid anion, hexafluorophosphoric acid anion, and the cation can be a metal alloyed with lithium, including magnesium, zinc, aluminum, gallium, indium, silver, tin, bismuth, germanium, antimony, silicon, etc. The inorganic solid electrolyte material includes: garnet-type lithium lanthanum tantalum oxide LLTO and its zirconium or aluminum-doped LLZTO and LLATO systems, perovskite-type lithium lanthanum titanium oxide LLTO system, NASICON-type lithium aluminum titanium phosphate LATP system, sulfur-based inorganic solid-state electrolyte ((100-x)Li2S-xP2S5 binary system, ternary system of Li2S-P2S5 doped with GeS2 or other MS2 substances, and argyrodite system), etc. Transfer the molten pure lithium or composite lithium metal material to the mask plate in a heated state, with a copper foil below in a heated state, continue to heat to maintain the molten state of the lithium material and uniformly coat the lithium metal in this state, and after holding, quickly cool to room temperature to obtain an ultra-thin and array-distributed lithium metal material or lithium metal composite material.

[0038] Step 3: match a variety of conventional positive electrode sheets, assemble a liquid lithium battery, and test the cycle stability, first coulomb efficiency, rate and other indicators of the battery.

[0039] Step 4: Coat the lithium metal material or lithium metal composite foil obtained in Step 2 with a solid electrolyte slurry. The slurry is prepared from inorganic fillers, lithium salts, binders, and solvents in a mass ratio of 3-30:3-40:10-90. The binder is one or more of the following: polyethylene oxide (PEO), polyethylene carbonate (PEC), polytrimethylene carbonate (PTMC), polypropylene carbonate (PPC), polytetrafluoroethylene (PVDF), polyvinylidene fluoride-hexafluoropropylene copolymer (PVDF-HFP), polyacrylic acid (PAA), polyvinyl alcohol (PVA), polyurethane (PU), polystyrene (PS), and polypropylene (PP). The inorganic filler is one or more of the following: garnet-type lithium lanthanum tantalum oxide (LLTO) and its zirconium or aluminum-doped LLZTO and LLATO systems; perovskite-type lithium lanthanum titanium oxide (LLTO) systems; NASICON-type lithium titanium aluminum phosphate (LATP) systems; sulfur-based inorganic solid electrolytes ((100-x)Li₂S-xP₂S₅ binary systems, ternary systems of Li₂S-P₂S₅ doped with GeS₂ or other MS₂ substances, and sulfide-silver germanite systems); alumina (Al₂O₃); zirconium oxide (ZrO₂); titanium oxide (TiO₂); barium sulfate (BaSO₄); etc. The lithium salt includes one or more of the following: lithium bis(fluorosulfonyl)imide, lithium bis(trifluoromethanesulfonyl)imide, lithium difluorophosphate, lithium difluorooxalate borate, lithium bis(oxalate borate), lithium tetrafluoroborate, lithium hexafluorophosphate, and lithium perchlorate; the solvent includes one or more of the following: N-methylpyrrolidone, dimethylformamide, acetonitrile, and tetrahydrofuran. After drying, the solid electrolyte layer completely covers the lithium metal base array, thus obtaining a composite structure of the negative electrode and the solid electrolyte.

[0040] Step 5: Using the composite structure of the negative electrode and solid electrolyte obtained in Step 4, match various positive electrode sheets to assemble a solid lithium battery, and test the battery's cycle stability, initial coulombic efficiency, rate capability, and other indicators.

[0041] Example 1

[0042] Molten lithium metal is coated onto a 10-micrometer-thickness stainless steel mask with a circular pattern covering 25% of the total area. A copper current collector is located beneath the mask. After removing the mask, a lithium array is obtained on the surface of the copper foil.

[0043] Example 1: Pure lithium array coated on copper current collector using a mask. Figure 1 As shown, its equivalent lithium capacity is 0.5 mAh / cm³. -2 .

[0044] Example 1: FIB-SEM image of the lithium array cross-section as shown below. Figure 4 As shown, a three-dimensional lithium-copper alloy is dispersed within the lithium layer.

[0045] Example 1: SEM images of the copper surface after lithium removal from the lithium array at different magnifications are shown below. Figure 5As shown, the copper current collector after three-dimensional in-situ.

[0046] Example 2

[0047] The composite material of molten lithium metal and LLZTO was coated on a mask plate with a thickness of 30 microns, a circular pattern accounting for 40% of the total area of the stainless steel mask plate, and a copper current collector below the mask plate. After removing the mask plate, a Li@LLZTO array was obtained on the surface of the copper foil.

[0048] The Li@LLZTO array coated on the copper current collector using a mask plate in Example 2 is shown in Figure 2 As shown, the equivalent lithium amount is 2 mAh cm -2 .

[0049] The optical image of the secondary lithium intercalation of the lithium array after delithiation in Example 2 is shown in Figure 6 As shown, lithium tends to be deposited again in the position where the original lithium array was coated, demonstrating the regulation effect of the three-dimensional copper current collector on lithium deposition behavior.

[0050] Example 3

[0051] The composite material of molten lithium metal and LLZTO was coated on a mask plate with a thickness of 50 microns, a circular pattern accounting for 45% of the total area of the stainless steel mask plate, and a copper current collector below the mask plate. After removing the mask plate, a Li@LLZTO array was obtained on the surface of the copper foil.

[0052] The Li@LLZTO array coated on the copper current collector using a mask plate in Example 3 is shown in Figure 3 As shown, the equivalent lithium amount is 4 mAh cm -2 .

[0053] The cycle performance chart of the liquid lithium battery with the Li@LLZTO array negative electrode and lithium iron phosphate positive electrode in Example 3 is shown in Figure 7 As shown, the battery has stable cycles and the coulombic efficiency is stable at 99.8%, indicating good cycle performance of the Li@LLZTO array.

[0054] The cycle performance chart of the solid-state lithium battery with the Li@LLZTO array negative electrode, PVDF-LLZTO-LITFSI solid-state electrolyte, and matching lithium iron phosphate positive electrode in Example 3 is shown in Figure 8 As shown, the array negative electrode of the present application has practical application ability in solid-state batteries.

[0055] Those skilled in the art can understand that the above-mentioned embodiments are specific examples for realizing the present application, and in practical applications, various changes can be made in form and details without departing from the spirit and scope of the present application. Any person skilled in the art can make respective changes and modifications without departing from the spirit and scope of the present application, and therefore the protection scope of the present application should be limited by the scope defined in the claims.

Claims

1. A method for preparing an array-type lithium metal anode, characterized in that, The preparation method includes: preparing a mask plate with an array pattern and a thickness; heating lithium metal to a molten state, and then coating the molten lithium metal onto the mask plate to obtain the arrayed lithium metal anode.

2. The method for preparing an array-type lithium metal anode according to claim 1, characterized in that, The preparation method specifically includes: Step (1): Design and fabricate a mask with an array pattern and a certain thickness; wherein the mask is made of stainless steel foil, titanium foil, nickel foil or polyimide film, with a thickness of 1 micrometer to 500 micrometers, and the area ratio of the array pattern on the mask is 1% to 80%. Step (2): Heat the lithium metal to a molten state, transfer the molten lithium metal to the heated mask, with copper foil in the heated state below the mask; continue heating to maintain the molten state of the lithium metal and uniformly coat the lithium metal on the mask, at a temperature of 180°C to 350°C, hold at the temperature and then quickly cool to room temperature, remove the mask to obtain the arrayed lithium metal anode.

3. The method for preparing an array-type lithium metal anode according to claim 2, characterized in that, In step (1), the mask is made of stainless steel foil; the area ratio of the array pattern on the mask is 20% to 60%; the array pattern includes one or more combined patterns of circles, rectangles, and triangles.

4. The method for preparing an array-type lithium metal anode according to claim 2, characterized in that, In step (2), the lithium metal includes pure lithium, lithium carbon, lithium alloy or lithium-based composite material; The carbon material in the lithium-carbon alloy includes one or more of the following: acetylene black, Ketjen black, Cabot BP2000, Super P, single-walled carbon nanotubes, few-walled carbon nanotubes, multi-walled carbon nanotubes, doped carbon nanotubes, graphene, doped graphene, carbon nanofibers, or doped carbon nanofibers; the shape of the carbon material includes one or more of the following: granular, linear, or sheet-like. The lithium alloy includes alloys of lithium with magnesium, zinc, aluminum, gallium, indium, silver, tin, bismuth, germanium, antimony, or silicon. The lithium-based composite material includes a mixture of lithium with salts or inorganic solid electrolyte materials; The anions of the salts include inorganic nitrate, chlorine, nitrogen, phosphorus, fluorine, sulfur, and oxygen, or organic bis(fluorosulfonyl)imide anion, bis(trifluoromethanesulfonyl)imide anion, difluorophosphate anion, difluorooxalate-boronic acid anion, bis(oxalate-boronic acid)-boronic acid anion, tetrafluoroboronic acid anion, and hexafluorophosphate anion. The cations of the salts are metals alloyed with lithium, including magnesium, zinc, aluminum, gallium, indium, silver, tin, bismuth, germanium, antimony, and silicon. The inorganic solid electrolyte materials include garnet-type lithium lanthanum tantalum oxide (LLTO) and zirconium or aluminum doped LLZTO and LLATO systems, perovskite-type lithium lanthanum titanium oxide (LLTO) systems, NASICON-type lithium titanium aluminum phosphate (LATP) systems, or sulfide-based inorganic solid electrolytes.

5. The method for preparing an array-type lithium metal anode according to claim 4, characterized in that, The sulfur-based inorganic solid electrolytes include a (100-x)Li2S-xP2S5 binary system, a ternary system in which GeS2 or other MS2 substances are incorporated into Li2S-P2S5, and a sulfide-silver-germanium ore system.

6. An array-type lithium metal anode prepared by a method according to any one of claims 1 to 5.

7. The array-type lithium metal anode according to claim 6, characterized in that, The equivalent lithium capacity of the array-type lithium metal anode is greater than 0 and less than or equal to 10 mAh cm⁻¹. -2 The corresponding equivalent lithium layer thickness is greater than 0 and less than or equal to 50 μm.

8. The application of an array-type lithium metal anode according to claim 6 in liquid lithium batteries and solid-state lithium batteries.

9. A method for preparing a solid-state lithium battery, characterized in that, The preparation method includes: A solid electrolyte slurry is coated onto the array-type lithium metal anode as described in claim 6, and then dried to obtain the solid lithium battery. The solid electrolyte slurry is prepared from inorganic fillers, lithium salts, binders and solvents in a mass ratio of (3-30):(3-40):(10-90). The inorganic filler is one or more of the following: garnet-type lithium lanthanum tantalum oxide (LLTO) and zirconium or aluminum doped LLZTO and LLATO systems; perovskite-type lithium lanthanum titanium oxide (LLTO) system; NASICON-type lithium titanium aluminum phosphate (LATP) system; sulfur-based inorganic solid electrolyte; alumina Al2O3; zirconium oxide ZrO2; titanium oxide TiO2; barium sulfate BaSO4; etc. The adhesive is one or more of the following: polyethylene oxide (PEO), polyvinyl carbonate (PEC), polytrimethylene carbonate (PTMC), polypropylene carbonate (PPC), polytetrafluoroethylene (PVDF), polyvinylidene fluoride-hexafluoropropylene copolymer (PVDF-HFP), polyacrylic acid (PAA), polyvinyl alcohol (PVA), polyurethane (PU), polystyrene (PS), and polypropylene (PP). The lithium salt includes one or more of lithium bis(fluorosulfonyl)imide, lithium bis(trifluoromethanesulfonyl)imide, lithium difluorophosphate, lithium difluorooxalate borate, lithium bis(oxalate borate), lithium tetrafluoroborate, lithium hexafluorophosphate, and lithium perchlorate. The solvent includes one or more of N-methylpyrrolidone, dimethylformamide, acetonitrile, and tetrahydrofuran.

10. A solid-state lithium battery prepared by the method of preparing a solid-state lithium battery according to claim 9.

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