Charging method of solid-state battery and prepared solid-state battery

Abstract

The invention discloses a solid-state battery charging method and a prepared solid-state battery, and the solid-state battery charging method comprises the following steps: S1, assembling a negative electrode plate, an electrolyte composite material containing an organic solvent, a positive electrode plate and a shell into a battery cell; s2, performing staged formation on the assembled battery cell: in a first stage, under a negative pressure condition, performing constant-current charging to reach a metal lithium deposition starting potential; in the second stage, under the negative pressure condition, charging is performed until the battery reaches 100% SOC, and meanwhile, the organic solvent in the battery electrolyte composite material is discharged until the electrolyte is gelatinized or fully cured; and in the third stage, the battery is discharged to discharge cut-off voltage, and the shell is sealed. The negative electrode, the electrolyte composite material layer and the positive electrode can be integrated, the interface internal resistance of the electrolyte, the positive electrode and the negative electrode is effectively reduced, dendritic crystals are avoided, the power density of the battery is improved, and stable SEI can be formed at the negative electrode through staged formation, so that the cycle life of the battery is prolonged.

Description

Technical Field

[0001] The present invention belongs to the technical field of batteries, and in particular relates to a charging method for a solid-state battery and a solid-state battery manufactured thereby. Background Art

[0002] Solid-state metal batteries have the advantages of high energy density and high safety, and have become one of the main research and development directions of future power and energy storage systems. Among them, metal lithium has an extremely high theoretical capacity (3860mAh g -1 ), also has the lowest standard electrode potential (-3.04V relative to the standard hydrogen electrode) and good conductivity. The lithium metal anode is expected to achieve higher energy density and is an ideal choice for solid-state battery anode.

[0003] However, there are still many problems that need to be solved in metal negative electrode batteries. For example, the metal ion deposition process is difficult to control and the unstable SEI film produced is prone to produce dendrites. The dendrites pierce the diaphragm and cause the battery to short circuit, which is prone to fire and explosion. The lower potential of metallic lithium will cause side reactions with the organic electrolyte, resulting in battery capacity loss and a decrease in the battery's cycle life. During the charge and discharge process, lithium ions are deposited and peeled off on the negative electrode surface, causing the battery volume to expand and contract.

[0004] In order to solve the above problems in the prior art, the present invention is provided. Summary of the invention

[0005] In response to one of the above-mentioned technical problems, the present invention provides a charging method for a solid-state battery and a solid-state battery manufactured thereby.

[0006] The technical solution of the present invention is:

[0007] The present invention relates to a charging method for a solid-state battery, comprising the following steps:

[0008] S1. Assembling a battery cell using a negative electrode sheet, an electrolyte composite material containing an organic solvent, a positive electrode sheet and a shell;

[0009] S2, the assembled battery cells are formed in stages:

[0010] In the first stage, under negative pressure conditions, constant current charging reaches the potential where metal lithium begins to deposit;

[0011] In the second stage, under negative pressure conditions, the battery is charged until it reaches 100% SOC, and at the same time, the organic solvent in the battery electrolyte composite material is discharged until the electrolyte is gelled or fully solidified; this is equivalent to, under charging conditions, the organic solvent in the electrolyte is discharged by means until the electrolyte is gelled or fully solidified, and the extraction of the organic solvent in the electrolyte effectively and significantly reduces the negative reaction between the organic solvent and the alkali metal. After the electrolyte is gelled or fully solidified, the positive electrode, the electrolyte composite material, and the negative electrode are integrated, which effectively reduces the interface contact internal resistance of the electrolyte and the positive and negative electrodes, thereby obtaining a high power density of the solid-state battery;

[0012] In the third stage, the battery is discharged to the discharge cut-off voltage and the shell is sealed.

[0013] Preferably, in the first stage of formation, the battery is charged at a current of 0.01 to 0.5 C under a negative pressure of -80 Kp to 0 Kp to a potential at which metal lithium begins to deposit, and the charging time is 0.1 to 3 h.

[0014] Preferably, in the second stage of formation, the negative pressure condition is -101KPa to 0Kp. The negative pressure in the first and second stages refers to the pressure inside the shell, and the negative pressure is controlled by vacuuming, which helps to remove the solvent.

[0015] Preferably, in the second stage of formation, the method of discharging the organic solvent in the battery electrolyte composite material, gelling the electrolyte and fully curing the electrolyte comprises heating;

[0016] Heating refers to heating the outside of the battery cell, with a heating temperature of 30-100°C.

[0017] Preferably, in the second stage of formation, the method of discharging the organic solvent in the battery electrolyte composite material, gelling the electrolyte and fully curing it further comprises pressurizing;

[0018] Pressurization refers to applying pressure to the outside of the battery cell, with a pressure of 0.1 to 2 MPa.

[0019] Heating and pressurizing are conducive to the gelation or solidification of electrolytes. For cylindrical and aluminum shell batteries, external heating and internal vacuum (negative pressure) treatment can be used; for soft-pack polymer batteries, external pressurization and heating and internal vacuum (negative pressure) treatment can be used.

[0020] Preferably, in the third formation stage, constant current discharge is performed to a discharge cut-off voltage.

[0021] Preferably, the electrolyte composite material further comprises an electrolyte salt, a binder and / or a curing agent.

[0022] Preferably, the mass content of the organic solvent in the electrolyte composite material is 20 to 90%.

[0023] Preferably, the organic solvent is one or more of tetrahydrofuran (THF), 2,2,2-trifluoro-N,N-dimethylacetamide (FDMA), fluoroethylene carbonate (FEC), (1,1,2,2-tetrafluoroethyl-2,2,3,3-tetrafluoropropyl ether) TTE, acetonitrile (AN), N,N-dimethylacetamide (DMAC), ethoxy (pentafluoro) cyclotriphosphazene (EPC), 1,2-difluorobenzene (DFB), ethylene carbonate (EC), dimethyl carbonate (DMC), and diethyl carbonate (DEC).

[0024] Preferably, the raw materials for preparing the positive electrode sheet include positive electrode active material, conductive agent, binder, and / or electrolyte, aluminum or aluminum alloy substrate, wherein the positive electrode active material includes any one or more of lithium, sodium, potassium, magnesium, aluminum, and zinc salt positive electrodes.

[0025] Preferably, the negative electrode sheet has a three-dimensional network structure, the porosity of the three-dimensional network structure is greater than 80%, and the specific surface area is greater than 20m 2 / g; further preferably, a slurry containing nano-carbon fibers is coated on the surface of a metal aluminum / copper substrate and dried to obtain a negative electrode sheet.

[0026] The present invention also relates to a solid-state battery, which is manufactured by adopting the above charging method.

[0027] The beneficial effects of the present invention are:

[0028] The present invention forms the assembled battery cells in stages. In the first stage of formation, a small current is charged to a turning point, metal deposition begins, and a stable SEI is formed under a gel electrolyte to improve the cycle performance of the battery. In the second stage, under charging conditions, the organic solvent in the electrolyte is extracted by heating, pressurizing, vacuuming, etc., and the electrolyte is gelled or fully solidified by in-situ polymerization. The extracted organic solvent effectively and significantly reduces the negative reaction between the organic solvent and the metal, thereby increasing the cycle performance of the battery. In-situ polymerization of the electrolyte composite material integrates the negative electrode, the electrolyte composite material layer, and the positive electrode, thereby preventing lithium dendrites from penetrating the diaphragm or electrolyte membrane, and effectively reducing the interface internal resistance between the electrolyte and the positive and negative electrodes, thereby avoiding the generation of dendrites and obtaining a high power density of the solid-state battery. BRIEF DESCRIPTION OF THE DRAWINGS

[0029] The present invention will be further described below in conjunction with the accompanying drawings and embodiments:

[0030] Figure 1 Li-Cu&Li-CNTp lithium nucleation deposition potential diagram;

[0031] Figure 2 LFP-CNTp charging nucleation potential;

[0032] Figure 3LFP-Cu charge nucleation potential;

[0033] Figure 4 Comparison chart of 5C charge / 5C discharge cycles of Example 1 and Comparative Example 1. DETAILED DESCRIPTION

[0034] The present invention is further described in detail. It should be understood that these descriptions are exemplary only and are not intended to limit the scope of the present invention. In addition, in the following description, the description of well-known structures and technologies is omitted to avoid unnecessary confusion of the concept of the present invention.

[0035] Example 1

[0036] (1) Preparation of negative electrode sheet

[0037] Nanocarbon fiber (CNTp from Suzhou First Element Nanotechnology Co., Ltd.), dispersant PVP, and binder PVDF were added to NMP in a mass ratio of 90:5:5, and prepared into a 10% solid content slurry through ultrasonic dispersion, and then coated on both sides of a composite copper foil with a thickness of 6 μm and dried to obtain a mixed negative electrode sheet with a thickness of 46 μm, a porosity of 92%, a single-sided film thickness of 20 μm, and a specific surface area of ​​21 g / m 2 .

[0038] (2) Preparation of positive electrode sheet

[0039] The positive electrode active material lithium iron phosphate (LFP), solid electrolyte Li3YCl6, conductive agent carbon nanotube CNT (FT6810, Jiangsu Tiannai Technology Co., Ltd.), conductive agent SP, and binder PTFE were mixed in a mass ratio of 84:10:2:1:3, first mixed at a speed of 600 rpm for 8 minutes, and then mixed at a speed of 10000 rpm for 6 minutes to obtain a fiberized material; the fiberized material was rolled by a double roller to obtain a positive electrode film with a thickness of 120 μm; then the positive electrode film was hot-pressed and bonded on both sides of a 10 μm thick aluminum foil by a flat hot press, the hot pressing temperature was 150 ° C, the hot pressing time was 15 s, the thickness of the positive electrode sheet was 188 μm, and the surface density of the charge was 3.41 mAh / cm 2 ;

[0040] (3) Preparation of electrolyte composite materials

[0041] Dissolve lithium bis(trifluoromethanesulfonyl)imide (LiTFSI) salt in tetrahydrofuran (THF) and stir for 2 hours to obtain a solution with a concentration of 1M; continue to add fluoroethylene carbonate (FEC) with a total mass of 10% of LiTFSI and THF and stir for 2 hours; then add polyvinylidene fluoride-hexafluoropropylene copolymer (PVDF-HFP) with a total mass of 30% of LiTFSI and THF and stir for 2 hours.

[0042] (4) Solid-state battery preparation

[0043] The surface of the negative electrode sheet is coated with the electrolyte composite material (wet film thickness 150 μm, dry thickness 15 μm), and then the positive electrode sheet is placed, and the sheets are alternately stacked in sequence to form a soft-pack polymer battery cell.

[0044] In the negative pressure environment of -80Kpa, the first stage of battery formation is 0.03C constant current charging for 1.5h to reach the potential for the deposition of metallic lithium. In the negative pressure environment of -80Kpa, in the second stage, the battery is charged at a constant current of 0.05C to a cut-off voltage of 3.65V, and the constant voltage of 3.65V is limited to 0.03C; during the charging process, the external heating and pressurization conditions of the battery cell are 30℃ and 0.2Mp, and the electrolyte is fully solidified. In the third stage, the battery is discharged at a constant current of 0.5C to a discharge cut-off voltage of 2.5V, and then vacuumized and sealed to complete the preparation of the solid-state battery. The energy density is 351Wh / kg.

[0045] The negative electrode sheet prepared in step (1) of Example 1 is used as the negative electrode, and Li is used as the positive electrode. The prepared battery is denoted as Li-CNTp. The negative electrode sheet in the Li-CNTp battery is replaced with copper foil, and the corresponding battery is denoted as Li-Cu. The Li-Cu&Li-CNTp lithium nucleation deposition potential diagram is shown in FIG. Figure 1 As shown, it can be seen that the Li-CNTp lithium nucleation potential (-28.2mV) is higher than the Li-Cu lithium nucleation deposition potential (-64.8mV), that is, the voltage of the positive electrode active material-CNTp of the whole battery is lower than that of the positive electrode active material-Cu lithium nucleation, and the positive electrode active material-CNTp lithium is easier to deposit at the negative electrode, while avoiding high voltage oxidation of the electrolyte.

[0046] like Figure 2 As shown, the battery prepared in Example 1 is recorded as LFP-CNTp, and the charged lithium nucleation potential of LFP-CNTp is 3.48 V. The negative electrode sheet of the battery prepared in Example 1 is replaced with copper foil, and the corresponding battery is recorded as LFP-Cu. Figure 3 As shown, the charging lithium nucleation potential of LFP-Cu is 3.56 V; compared with LFP-CNTp (3.48 V) in Example 1, the nucleation potential of LFP-Cu (3.56) is higher.

[0047] Example 2

[0048] (1) Preparation of negative electrode sheet

[0049] Nanocarbon fibers (CNTp from Suzhou First Element Nanotechnology Co., Ltd.), dispersant PVP, and binder PVDF were added to NMP in a mass ratio of 90:5:5, and prepared into a slurry with a solid content of 10% through ultrasonic dispersion. The slurry was then double-sidedly coated on a copper foil with a thickness of 6 μm and dried to obtain a negative electrode sheet with a thickness of 56 μm, a porosity of 90.8%, and a single-sided film thickness of 25 μm.

[0050] (2) Preparation of positive electrode sheet

[0051] The positive electrode active material lithium cobalt oxide (LCO), solid electrolyte Li3YCl6, conductive agent CNT (FT6810, Jiangsu Tiannai Technology Co., Ltd.), conductive agent SP, and binder PTFE were mixed in a mass ratio of 84:10:2:1:3, and the mixing process was first carried out at a speed of 500 rpm for 10 min, and then at a speed of 10000 rpm for 8 min to obtain a fibrous material; the fibrous material was rolled by a double roller to obtain a positive electrode film with a thickness of 120 μm; the positive electrode film was hot-pressed and bonded on both sides of an aluminum foil with a thickness of 8 μm by a flat hot press, the hot pressing temperature was 150 ° C, the hot pressing time was 15 s, and finally the positive electrode sheet with a thickness of 138 μm and a surface density of 4.99 mAh / cm 2 .

[0052] (3) Preparation of electrolyte composite materials

[0053] Dissolve lithium bis(trifluoromethanesulfonyl)imide (LiTFSI) and lithium hexafluorophosphate (LiPF6) salts in tetrahydrofuran (THF) and 2,2,2-trifluoro-N,N-dimethylacetamide (FDMA) in a volume ratio of 7:3, and stir for 2 hours to obtain a solution A containing 1M LiTFSI and 1M LiPF6; continue to add 15% fluoroethylene carbonate (FEC) based on the total mass of the above solution A and stir for 2 hours; then add 1.5% polyethylene oxide (PEO) based on the total mass of the above solution A and stir for 2 hours.

[0054] (4) Solid-state battery preparation

[0055] The negative electrode sheets, separators and positive electrode sheets are alternately stacked in sequence to form a soft-pack polymer battery cell, and the electrolyte composite material is injected at a rate of 3 g / Ah.

[0056] Negative pressure -70Kpa environment, open formation, the first stage of battery formation, 0.03C constant current charging for 1.5h, reaching the potential for the start of metal lithium deposition. Negative pressure -70Kpa environment, the second stage, 0.05C current constant current charging to a cut-off voltage of 4.45V, 4.45V constant voltage current limiting to 0.03C; during the charging process, the external heating and pressurization conditions of the battery cell are 45℃ and 0.3Mp, and the electrolyte is fully solidified. In the third stage, 0.5C current constant current discharge to a discharge cut-off voltage of 3.0V, vacuumization, sealing, and completion of solid-state battery preparation. The battery energy density is 530Wh / kg.

[0057] Example 3

[0058] The difference between this embodiment and embodiment 1 is that:

[0059] In the preparation of the negative electrode sheet, the composite copper foil was changed to aluminum foil, and the thickness of the prepared negative electrode was 36 μm. Other conditions remained unchanged.

[0060] Preparation of positive electrode sheet: NFM111 sodium oxide positive electrode material is used as positive electrode active material, solid electrolyte is replaced with Na3YCl6, and other conditions remain unchanged. The thickness of the prepared positive electrode is 135μm, and the surface density of electricity is 2.56 / cm 2 .

[0061] Preparation of electrolyte composite material, replacing lithium bis(trifluoromethanesulfonyl)imide (LiTFSI) with sodium bis(fluorosulfonyl)imide (NaFSI), with other conditions unchanged. The battery energy density of the prepared solid-state battery is 285Wh / kg.

[0062] Example 4

[0063] The difference between this embodiment and embodiment 3 is that:

[0064] Preparation of electrolyte composite materials

[0065] NaFSI salt was dissolved in DMAC at a molar ratio of DMAC:NaFSI=3:1, and the mixture was stirred for 2 h to obtain a solution; 30% of the total mass of PVDF-HFP and 50% of THF of DMAC+NaFSI were added, and the mixture was stirred for 2 h.

[0066] The final battery energy density is 256Wh / kg.

[0067] Comparative Example 1

[0068] (1) Preparation of negative electrode sheet

[0069] Nanocarbon fiber (CNTp from Suzhou First Element Nanotechnology Co., Ltd.), dispersant PVP, and binder PVDF were added to NMP in a mass ratio of 90:5:5, and prepared into a 10% solid content slurry through ultrasonic dispersion, and then coated on both sides of a composite copper foil with a thickness of 6 μm and dried to obtain a mixed negative electrode sheet with a thickness of 46 μm, a porosity of 92%, a single-sided film thickness of 20 μm, and a specific surface area of ​​21 g / m 2 .

[0070] (2) Preparation of positive electrode sheet

[0071] The positive electrode active material lithium iron phosphate (LFP), solid electrolyte Li3YCl6, conductive agent carbon nanotube CNT (FT6810, Jiangsu Tiannai Technology Co., Ltd.), conductive agent SP, and binder PTFE were mixed in a mass ratio of 84:10:2:1:3, first mixed at a speed of 600 rpm for 8 minutes, and then mixed at a speed of 10000 rpm for 6 minutes to obtain a fiberized material; the fiberized material was rolled by a double roller to obtain a positive electrode film with a thickness of 120 μm; then the positive electrode film was hot-pressed and bonded on both sides of a 10 μm thick aluminum foil by a flat hot press, the hot pressing temperature was 150 ° C, the hot pressing time was 15 s, the thickness of the positive electrode sheet was 188 μm, and the surface density of the charge was 3.41 mAh / cm 2 ;

[0072] (3) Preparation of electrolyte composite materials

[0073] Dissolve lithium bis(trifluoromethanesulfonyl)imide (LiTFSI) salt in tetrahydrofuran (THF) and stir for 2 hours to obtain a solution with a concentration of 1M; continue to add fluoroethylene carbonate (FEC) with a total mass of 10% of LiTFSI and THF and stir for 2 hours; then add polyvinylidene fluoride-hexafluoropropylene copolymer (PVDF-HFP) with a total mass of 30% of LiTFSI and THF and stir for 2 hours.

[0074] (4) Solid-state battery preparation

[0075] The surface of the negative electrode sheet is coated with the electrolyte composite material and dried, with a wet film thickness of 150 μm and a dried thickness of 15 μm. The positive electrode sheet is then placed, and the sheets are alternately stacked in sequence to form a battery cell. The battery is evacuated and sealed to complete the assembly of the soft-pack polymer solid-state battery.

[0076] Battery formation, 0.03C constant current charging to a cut-off voltage of 3.65V, 3.65V constant voltage current limiting to 0.03C; 0.5C current constant current discharge to a discharge cut-off voltage of 2.5V, complete the solid-state battery preparation. Energy density is 350Wh / kg.

[0077] The batteries prepared in Example 1 and Comparative Example 1 were cycled at 45°C with a charge and discharge range of 2.5 to 3.65V. The 5C / 5C cycle curves are shown in Table 1. Figure 4 It can be seen that the cycle performance of Example 1 is significantly better than that of Comparative Example 1.

[0078] Comparative Example 2

[0079] 1) Preparation of negative electrode sheet

[0080] Nanocarbon fibers (CNTp from Suzhou First Element Nanotechnology Co., Ltd.), dispersant PVP, and binder PVDF were added to NMP in a mass ratio of 90:5:5, and prepared into a slurry with a solid content of 10% through ultrasonic dispersion. The slurry was then double-sidedly coated on a copper foil with a thickness of 6 μm and dried to obtain a negative electrode sheet with a thickness of 56 μm, a porosity of 90.8%, and a single-sided film thickness of 25 μm.

[0081] (2) Preparation of positive electrode sheet

[0082] The positive electrode active material lithium cobalt oxide (LCO), solid electrolyte Li3YCl6, conductive agent CNT (FT6810, Jiangsu Tiannai Technology Co., Ltd.), conductive agent SP, and binder PTFE were mixed in a mass ratio of 84:10:2:1:3, first mixed at a speed of 500 rpm for 10 min, and then mixed at a speed of 10000 rpm for 8 min to obtain a fibrous material; the fibrous material was rolled by a double roller to obtain a positive electrode film with a thickness of 120 μm; the positive electrode film was hot-pressed and bonded on both sides of an aluminum foil with a thickness of 8 μm by a flat hot press, the hot pressing temperature was 150 ° C, the hot pressing time was 15 s, and finally the positive electrode sheet with a thickness of 138 μm and a surface density of 4.99 mAh / cm 2

[0083] (3) Preparation of electrolyte composite materials

[0084] Dissolve lithium bis(trifluoromethanesulfonyl)imide (LiTFSI) and lithium hexafluorophosphate (LiPF6) salts in tetrahydrofuran (THF) and 2,2,2-trifluoro-N,N-dimethylacetamide (FDMA) in a volume ratio of 7:3, and stir for 2 hours to obtain a solution A containing 1M LiTFSI and 1M LiPF6; continue to add 15% fluoroethylene carbonate (FEC) based on the total mass of the above solution A and stir for 2 hours; then add 1.5% polyethylene oxide (PEO) based on the total mass of the above solution A and stir for 2 hours.

[0085] (4) Solid-state battery preparation

[0086] The surface of the negative electrode sheet is coated with the electrolyte composite material and dried, with a wet film thickness of 150 μm and a dried thickness of 15 μm. The positive electrode sheet is then placed, and the sheets are alternately stacked in sequence to form a battery cell. The battery is evacuated and sealed to complete the assembly of the soft-pack polymer solid-state battery.

[0087] The battery was formed, charged at a constant current of 0.03C to a cut-off voltage of 4.45V, and current limited to 0.03C at a constant voltage of 4.45V; discharged at a constant current of 0.5C to a discharge cut-off voltage of 3.0V, completing the preparation of the solid-state battery. The battery energy density is 531Wh / kg.

[0088] It should be emphasized that the above are only preferred embodiments of the present invention and do not limit the present invention in any form. Any simple modifications, equivalent changes and modifications made to the above embodiments based on the technical essence of the present invention are still within the scope of the technical solution of the present invention.

Claims

1. A charging method for a solid-state battery, characterized in that: The following steps are involved: S1. Assembling a battery cell using a negative electrode sheet, an electrolyte composite material containing an organic solvent, a positive electrode sheet and a shell; S2, the assembled battery cells are formed in stages: In the first stage, under negative pressure conditions, constant current charging reaches the potential where metal lithium begins to deposit; In the second stage, the battery is charged under negative pressure until it reaches 100% SOC, while the organic solvent in the battery electrolyte composite material is discharged until the electrolyte is gelled or fully solidified; In the third stage, the battery is discharged to the discharge cut-off voltage and the shell is sealed.

2. The solid-state battery charging method according to claim 1, characterized in that: In the first stage of formation, under negative pressure of -80Kp to 0Kp, the battery is charged at a current of 0.01 to 0.5C to a potential at which metal lithium begins to deposit, and the charging time is 0.1 to 3h.

3. The solid-state battery charging method according to claim 1, characterized in that: In the second stage of formation, the negative pressure condition is -101KPa~0Kp.

4. The solid-state battery charging method according to claim 1, characterized in that: In the second stage of formation, the method of removing the organic solvent from the battery electrolyte composite material, gelling the electrolyte and fully curing includes heating; Heating refers to heating the outside of the battery cell, with a heating temperature of 30-100°C.

5. The solid-state battery charging method according to claim 4, characterized in that: In the second stage of formation, the method of removing the organic solvent from the battery electrolyte composite material, gelling the electrolyte and fully curing it also includes pressurizing; Pressurization refers to applying pressure to the outside of the battery cell, with a pressure of 0.1 to 2 MPa.

6. The solid-state battery charging method according to claim 1, characterized in that: In the third stage of formation, constant current discharge is performed to the discharge cut-off voltage.

7. The solid-state battery charging method according to claim 1, characterized in that: The electrolyte composite material further includes an electrolyte salt, a binder and / or a curing agent.

8. The solid-state battery charging method according to claim 1, characterized in that: The mass content of the organic solvent in the electrolyte composite material is 20 to 90%.

9. The solid-state battery charging method according to claim 8, characterized in that: The organic solvent is one or more of tetrahydrofuran, 2,2,2-trifluoro-N,N-dimethylacetamide, fluoroethylene carbonate, 1,1,2,2-tetrafluoroethyl-2,2,3,3-tetrafluoropropyl ether, acetonitrile, N,N-dimethylacetamide, ethoxy (pentafluoro) cyclotriphosphazene, 1,2-difluorobenzene, ethylene carbonate, dimethyl carbonate, and diethyl carbonate.

10. A solid-state battery, characterized in that: It is prepared by the solid-state battery charging method described in any one of claims 1 to 9.

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