Method for photo-initiation in-situ preparation of integrated silicon solid electrolyte and application

Abstract

The invention belongs to the technical field of material chemistry, and particularly relates to a method for photo-initiation in-situ preparation of an integrated silicon solid electrolyte and application. The preparation method comprises the following steps: firstly, adding PEGDA and UPyMA into DMSO, and carrying out ultrasonic uniform dispersion; and adding a photoinitiator porphyrin COF and a coinitiator TEA, and removing water and oxygen in the solution by a bubbling method. Under the protection of argon, adding LiTFSI and stirring at room temperature to prepare a polymer solid electrolyte precursor solution; and dropwise adding the precursor solution on the surface of a silicon electrode, irradiating with an ultraviolet lamp, and drying after complete polymerization to obtain the silicon negative electrode-polymer integrated solid electrolyte. The synthesis mode is simple and convenient, the yield is high, the effect is good, the composition can effectively solve the problem of a solid-solid interface in a solid electrolyte, the volume expansion of nano silicon is relieved, the ionic conductivity and the transference number are improved, the stability of an electrode material is maintained, and the composition can be used for all-solid-state lithium metal batteries and all-solid-state silicon batteries.

Description

TECHNICAL FIELD

[0001] The application belongs to the technical field of material chemistry, and particularly relates to a method for in-situ preparation of integrated silicon solid-state electrolyte by photoinitiation and application. BACKGROUND

[0002] The development of solid-state polymer electrolyte can effectively solve the safety problems such as electrolyte leakage and flammability in liquid batteries. Compared with lithium metal batteries with high cost and serious dendrite problem, the development of silicon solid-state batteries is particularly important. However, the huge volume expansion of silicon and the instability of the interface SEI are still important factors limiting its development. Therefore, it is necessary to solve the interface problem, eliminate the solid-solid interface in the solid-state electrolyte and design a stable interface layer to solve the problem of the rupture and generation of SEI film caused by the volume expansion of silicon, so as to realize the development and application of silicon solid-state batteries.

[0003] Porphyrin covalent organic framework material (COF) has a large specific surface area, multiple pore sizes and a stable conjugated structure, which is an excellent lithium ion transmission channel and a free radical polymerization initiator. It is an ideal scheme to introduce it into the polymer and use it as an in-situ polymerization photoinitiator. Therefore, how to develop an in-situ technology to directly grow a polymer electrolyte on the surface of a silicon negative electrode and improve the lithium ion migration number and conductivity is a technical problem to be solved by the application. SUMMARY

[0004] In order to overcome the shortcomings of the prior art, the application provides a method for in-situ preparation of integrated silicon solid-state electrolyte by photoinitiation and application. First, polyethylene glycol diacrylate (PEGDA) and 2-(3-(6-methyl-4-oxo-1,4-dihydropyrimidin-2-yl)ureido)ethyl methacrylate (UPyMA) are added to dimethyl sulfoxide (DMSO) and uniformly dispersed by ultrasonic; then a photoinitiator porphyrin COF and a co-initiator triethylamine (TEA) are added, and water and oxygen in the solution are removed by bubbling. Under the protection of argon, lithium bis(trifluoromethanesulfonyl)imide (LiTFSI) is added and stirred at room temperature to prepare a polymer solid-state electrolyte precursor solution; the precursor solution is added dropwise on the surface of a silicon electrode, and irradiated with a UV lamp. After the polymerization is completed, the silicon negative electrode-polymer integrated solid-state electrolyte is obtained by drying. The synthesis method of the application is simple, high-yield and effective. The synthesis product of the application can effectively solve the solid-solid interface problem in the solid-state electrolyte, relieve the volume expansion of nano-silicon, improve the ion conductivity and migration number, and maintain the stability of the electrode material, and can be used in all-solid-state lithium metal batteries and all-solid-state silicon batteries.

[0005] In order to achieve the above purpose, the technical scheme adopted by the application is as follows: The first aspect of the application provides a method for in-situ preparation of integrated silicon solid-state electrolyte by photoinitiation, comprising the following steps: (1) 2-amino-4-hydroxy-6-methylpyrimidine was taken in dimethyl sulfoxide, heated and stirred, then 2-isocyanatoethyl acetate was added, white solid was precipitated under ice water bath stirring, the white solid was collected, washed, dried, and 2-(3-(6-methyl-4-oxo-1,4-dihydropyrimidin-2-yl)ureido)ethyl methacrylate was obtained as a white powder; (2) 2,5-dihydroxyterephthaldehyde (DHA) and 5,10,15,20-tetrakis(4-aminophenyl)-21H,23H-porphyrin (TPH) were taken into a mixed solvent of o-dichlorobenzene and n-butanol, ultrasonic dispersion was performed, a catalyst of glacial acetic acid was added dropwise, and the reaction was performed after oxygen removal, centrifugation was performed to collect and dry to obtain a photoinitiator porphyrin COF; (3) polyethylene glycol diacrylate and 2-(3-(6-methyl-4-oxo-1,4-dihydropyrimidin-2-yl)ureido)ethyl methacrylate were ultrasonic dispersed in dimethyl sulfoxide; (4) the photoinitiator porphyrin COF and a co-initiator triethylamine were added, ultrasonic dispersion was performed and light shielding treatment was performed, oxygen was removed, and then transferred to a glove box; (5) lithium bistrifluoromethanesulfonimide was added, and stirring was performed at room temperature to obtain a solid electrolyte precursor solution; (6) the solid electrolyte precursor solution was added dropwise on the surface of a silicon negative electrode, and irradiated with an ultraviolet lamp, dried after polymerization to obtain an integrated silicon negative electrode-polymer solid electrolyte.

[0006] Further, in step (1), the temperature of the heating and stirring is 150-180 ℃, and the time of the heating and stirring is 10-20 minutes; in step (2), the molar ratio of 2,5-dihydroxyterephthaldehyde and 5,10,15,20-tetrakis(4-aminophenyl)-21H,23H-porphyrin is 0.7:1, the volume ratio of o-dichlorobenzene and n-butanol is 1:1-1:2, the temperature of the reaction is 120-150 ℃, and the time of the reaction is 72-96 h.

[0007] Further, in step (2), the final concentration of glacial acetic acid is 6 M.

[0008] Further, in step (3), the mass ratio of the polyethylene glycol diacrylate and 2-(3-(6-methyl-4-oxo-1,4-dihydropyrimidin-2-yl)ureido)ethyl methacrylate is 5:1-5:3.

[0009] Further, in step (4), the amount of the porphyrin COF added is 0.25-1.5% of the mass of the polyethylene glycol diacrylate.

[0010] Further, in step (4), the oxygen removal refers to argon bubbling method.

[0011] Further, in step (5), the mass ratio of lithium bis(trifluoromethanesulfonylimide) to polyethylene glycol diacrylate is 1:10 to 1:20.

[0012] Furthermore, in step (5), the stirring time is 12~24h and the rotation speed is 400~800 r / min.

[0013] Furthermore, in step (6), the wavelength of the ultraviolet lamp is 245~365 nm, and the irradiation time of the ultraviolet lamp is 12~24 h.

[0014] A second aspect of the present invention provides an integrated silicon solid electrolyte prepared by the above-described method.

[0015] A third aspect of the present invention provides the application of the above-mentioned integrated silicon solid electrolyte in all-solid-state lithium metal batteries and all-solid-state silicon batteries.

[0016] Compared with the prior art, the beneficial effects of the present invention are: The integrated silicon solid electrolyte prepared in situ by photoinitiation in this invention not only improves ionic conductivity and lithium-ion transference number, but also effectively mitigates the significant volume expansion of silicon, thereby improving the cycle life and stability of the electrode material. The integrated silicon solid electrolyte prepared in this invention, due to the presence of porous porphyrin COF as an initiator and filler, can generate a polymer electrolyte layer in situ at the solid-solid interface. The presence of porphyrin COF induces the orderly growth of polymer chains within the framework pores, accelerating lithium-ion transport and improving ionic conductivity. The multi-group effect can bind anions in the lithium salt, thereby increasing the lithium-ion transference number. The high-strength polymer electrolyte alleviates the volume expansion of silicon and promotes the formation of the SEI at the interface, showing great promise in the energy storage field.

[0017] Specifically, the present invention has the following advantages: (1) The preparation method of the present invention is simple and efficient; the composite material is directly synthesized in situ in one step by PEGDA / UPyMA under the photoinitiation of porphyrin COF / TEA. The synthesis steps are simple, the cost is low and the efficiency is high.

[0018] (2) SEM analysis revealed that the synthesized composite material exhibits a uniform morphology, and the electrolyte at the interface is only 30 μm thick and fully bonded to the silicon particles. LSV testing showed that the electrolyte has an electrochemical window as high as 4.7 V, enabling efficient matching with high-voltage cathodes such as NCM811. Furthermore, the electrolyte possesses excellent ionic conductivity, reaching 2.23 × 10⁻⁶ at 25 °C. -4 S cm -1The lithium-ion transference number is as high as 0.92. The assembled Li / / SPE-COF / / Li symmetric cells and Li / / SPE-COF / / Si solid-state half-cells exhibit excellent cycle stability, with a speed of 0.1 mA cm⁻¹. -1 Cycle at 30 °C for 580 h, 100 mA g -1 The capacity retention rate after cycling at 30 °C was 79.55%. Attached Figure Description

[0019] Figure 1 This is a schematic diagram of the synthesis of SPE-COF (0.5wt% COF).

[0020] Figure 2 Scanning electron microscope image of SPE-COF / Si (0.5wt% COF).

[0021] Figure 3 LSV curve of SPE-COF electrode (30 °C) (0.5wt% COF).

[0022] Figure 4 The ionic conductivity curves of SPE-COF (25-80 ℃) (0.5wt% COF) are shown.

[0023] Figure 5 The activation energy of SPE-COF (0.5wt% COF).

[0024] Figure 6 IT curves and corresponding impedance curves of Li / / SPE-COF / / Li under 0.25wt% COF conditions (30 ℃).

[0025] Figure 7 IT curves and corresponding impedance curves of Li / / SPE-COF / / Li under 0.5wt% COF conditions (30 ℃).

[0026] Figure 8 The IT curves and corresponding impedance curves (30 °C) of Li / / SPE-COF / / Li under 1wt% COF conditions are shown.

[0027] Figure 9 IT curves and corresponding impedance curves (30 °C) of Li / / SPE-COF / / Li under 1.5 wt% COF conditions.

[0028] Figure 10 Long cycle curves (30 °C) for Li / / SPE-COF / / Li (0.5wt% COF).

[0029] Figure 11Cyclic performance curves of Li / / SPE-COF / / Si (100 mA g) -1 Current density, 30 °C (0.5 wt% COF). Detailed Implementation

[0030] The specific embodiments of the present invention will be further described below. It should be noted that these descriptions are for the purpose of aiding understanding the present invention, but do not constitute a limitation thereof. Furthermore, the technical features involved in the various embodiments of the present invention described below can be combined with each other as long as they do not conflict with each other.

[0031] Unless otherwise specified, the experimental methods used in the following embodiments are conventional methods, and the experimental materials used in the following embodiments are all available through conventional commercial channels.

[0032] Example 1: Synthesis of SPE-COF / Si and SPE-COF (0.25wt% COF) (1) Take 1 g of 2-amino-4-hydroxy-6-methylpyrimidine in DMSO, stir at 150 °C for 10 minutes, then add 1.32 g of ethyl 2-isocyanate, stir under ice water bath to precipitate white solid, wash, collect and dry to obtain white powder UPyMA; (2) 8.2 mg of 2,5-dihydroxyterephthalaldehyde (DHA) and 15 mg of 5,10,15,20-tetra(4-aminophenyl)-21H,23H-porphyrin (TPH) were added to o-dichlorobenzene / n-butanol (volume ratio 1:1) and ultrasonically dispersed. Subsequently, glacial acetic acid (final concentration 6 M) was added dropwise and transferred to a reaction tube for deoxygenation treatment. The mixture was kept at 120 °C for 72 h, centrifuged, collected, and dried to obtain the initiator porphyrin COF; (3) Take 1g of polyethylene glycol diacrylate (PEGDA) and 200 mg of UPyMA and ultrasonically disperse them in dimethyl sulfoxide (DMSO); (4) Add photoinitiator porphyrin COF (0.25wt% vs PEGDA) and 100 μL co-initiator triethylamine (TEA) to the above solution, disperse by ultrasonication and protect from light, deoxygenate by argon bubbling at room temperature for 15 minutes, and then transfer to a glove box; (5) Take 60 mg of lithium bis(trifluoromethanesulfonyl)imide (LiTFSI) into the above solution and stir at 400 r / min for 12 h at room temperature to obtain a solid electrolyte precursor solution; (6) Take 30 μL of the above precursor solution and drop it onto the surface of the silicon anode, and irradiate it with a 365 nm ultraviolet lamp for 12 h. After polymerization, dry to obtain an integrated silicon anode-polymer solid electrolyte. (7) Take 500 μL of the above precursor solution and add it to the polytetrafluoroethylene mold. Irradiate it with a 365 nm ultraviolet lamp for 12 h. After polymerization, dry to obtain the polymer solid electrolyte.

[0033] Example 2: Synthesis of SPE-COF / Si and SPE-COF (0.5wt% COF) (1) Take 1 g of 2-amino-4-hydroxy-6-methylpyrimidine in DMSO, stir at 150 °C for 10 minutes, then add 1.32 g of ethyl 2-isocyanate, stir under ice water bath to precipitate white solid, wash, collect and dry to obtain white powder UPyMA; (2) 8.2 mg of 2,5-dihydroxyterephthalaldehyde (DHA) and 15 mg of 5,10,15,20-tetra(4-aminophenyl)-21H,23H-porphyrin (TPH) were added to o-dichlorobenzene / n-butanol (volume ratio 1:1) and ultrasonically dispersed. Subsequently, glacial acetic acid (final concentration 6 M) was added dropwise and transferred to a reaction tube for deoxygenation treatment. The mixture was kept at 120 °C for 72 h, centrifuged, collected, and dried to obtain the initiator porphyrin COF; (3) Take 1g of polyethylene glycol diacrylate (PEGDA) and 200 mg of UPyMA and ultrasonically disperse them in dimethyl sulfoxide (DMSO); (4) Add photoinitiator porphyrin COF (0.5wt% vs PEGDA) and 100 μL co-initiator triethylamine (TEA) to the above solution, disperse by ultrasonication and protect from light, deoxygenate by argon bubbling at room temperature for 15 minutes, and then transfer to a glove box; (5) Take 60 mg of lithium bis(trifluoromethanesulfonyl)imide (LiTFSI) into the above solution and stir at 400 r / min for 12 h at room temperature to obtain a solid electrolyte precursor solution; (6) Take 30 μL of the above precursor solution and drop it onto the surface of the silicon anode, then irradiate it with a 365 nm ultraviolet lamp for 12 h. After polymerization and drying, an integrated silicon anode-polymer solid electrolyte is obtained; Figure 2 It can be seen that the surface of the polymer electrolyte is uniform and flat, with a thickness of 30 μm.

[0034] (7) Take 500 μL of the above precursor solution and add it to the polytetrafluoroethylene mold. Irradiate it with a 365 nm ultraviolet lamp for 12 h. After polymerization, dry to obtain the polymer solid electrolyte.

[0035] Example 3: Synthesis of SPE-COF / Si and SPE-COF (1wt% COF) (1) Take 1 g of 2-amino-4-hydroxy-6-methylpyrimidine in DMSO, stir at 150 °C for 10 minutes, then add 1.32 g of ethyl 2-isocyanate, stir under ice water bath to precipitate white solid, wash, collect and dry to obtain white powder UPyMA; (2) 8.2 mg of 2,5-dihydroxyterephthalaldehyde (DHA) and 15 mg of 5,10,15,20-tetra(4-aminophenyl)-21H,23H-porphyrin (TPH) were added to o-dichlorobenzene / n-butanol (volume ratio 1:1) and ultrasonically dispersed. Subsequently, glacial acetic acid (final concentration 6 M) was added dropwise and transferred to a reaction tube for deoxygenation treatment. The mixture was kept at 120 °C for 72 h, centrifuged, collected, and dried to obtain the initiator porphyrin COF; (3) Take 1g of polyethylene glycol diacrylate (PEGDA) and 200 mg of UPyMA and ultrasonically disperse them in dimethyl sulfoxide (DMSO); (4) Add photoinitiator porphyrin COF (1wt% vs PEGDA) and 100 μL co-initiator triethylamine (TEA) to the above solution, disperse by ultrasonication and protect from light, deoxygenate by argon bubbling at room temperature for 15 minutes, and then transfer to a glove box; (5) Take 60 mg of lithium bis(trifluoromethanesulfonyl)imide (LiTFSI) into the above solution and stir at 400 r / min for 12 h at room temperature to obtain a solid electrolyte precursor solution; (6) Take 30 μL of the above precursor solution and drop it onto the surface of the silicon anode, and irradiate it with a 365 nm ultraviolet lamp for 12 h. After polymerization, dry to obtain an integrated silicon anode-polymer solid electrolyte. (7) 500 μL of the above precursor solution was added dropwise to a polytetrafluoroethylene mold and irradiated with a 365 nm ultraviolet lamp for 12 h. After polymerization, the polymer solid electrolyte was obtained by drying. The schematic diagram of the synthesis of SPE-COF in this embodiment is shown below. Figure 1 As shown.

[0036] Example 4: Synthesis of SPE-COF / Si and SPE-COF (1.5wt% COF) (1) Take 1 g of 2-amino-4-hydroxy-6-methylpyrimidine in DMSO, stir at 150 °C for 10 minutes, then add 1.32 g of ethyl 2-isocyanate, stir under ice water bath to precipitate white solid, wash, collect and dry to obtain white powder UPyMA; (2) 8.2 mg of 2,5-dihydroxyterephthalaldehyde (DHA) and 15 mg of 5,10,15,20-tetra(4-aminophenyl)-21H,23H-porphyrin (TPH) were added to o-dichlorobenzene / n-butanol (volume ratio 1:1) and ultrasonically dispersed. Subsequently, glacial acetic acid (final concentration 6 M) was added dropwise and transferred to a reaction tube for deoxygenation treatment. The mixture was kept at 120 °C for 72 h, centrifuged, collected, and dried to obtain the initiator porphyrin COF; (3) Take 1g of polyethylene glycol diacrylate (PEGDA) and 200 mg of UPyMA and ultrasonically disperse them in dimethyl sulfoxide (DMSO); (4) Add photoinitiator porphyrin COF (1.5wt% vs PEGDA) and 100 μL co-initiator triethylamine (TEA) to the above solution, disperse by ultrasonication and protect from light, deoxygenate by argon bubbling at room temperature for 15 minutes, and then transfer to a glove box; (5) Take 60 mg of lithium bis(trifluoromethanesulfonyl)imide (LiTFSI) into the above solution and stir at 400 r / min for 12 h at room temperature to obtain a solid electrolyte precursor solution; (6) Take 30 μL of the above precursor solution and drop it onto the surface of the silicon anode, and irradiate it with a 365 nm ultraviolet lamp for 12 h. After polymerization, dry to obtain an integrated silicon anode-polymer solid electrolyte. (7) Take 500 μL of the above precursor solution and add it to the polytetrafluoroethylene mold. Irradiate it with a 365 nm ultraviolet lamp for 12 h. After polymerization, dry to obtain the polymer solid electrolyte.

[0037] Test case 1. LSV was tested using an electrochemical workstation, with the voltage range set to 0-7 V and the scan rate at 0.5 mV / s. Figure 3 It can be seen that the electrolyte has an electrochemical window of up to 4.7 V, which can be efficiently matched with high-voltage cathodes such as NCM811.

[0038] 2. The ionic conductivity within the range of 25-80 was tested using an electrochemical workstation. The thickness and area of ​​the electrolyte membrane were measured, and the impedance parameters were set as follows. The corresponding impedance value is obtained from Hz, and substituting it into the formula L / (RS) yields the ionic conductivity and activation energy. Figure 4 and Figure 5 It can be seen that this electrolyte has excellent ionic conductivity, reaching as high as 2.23 × 10⁻⁶ at 25 °C. -4 Scm -1 The lithium-ion transference number is as high as 0.92.

[0039] 3. Long-cycle testing of lithium-ion / / SPE-COF / / lithium symmetric batteries, with an electrode area of ​​1.32 cm². -2The current density is set to 0.1 mA cm⁻¹. -2 The charging and discharging time is 1 hour.

[0040] 4. Cyclic testing of lithium / / SPE-COF / / silicon cells; lithium cell area is 1.32 cm². -2 The silicon electrode is 1.54 cm. -2 The active substance mass is 0.5-1 mg, and the current density is set to 0.05 mA g for the first five cycles. -1 Subsequently, it was 0.1 mA g. -1 The charge / discharge voltage window is 0.01-1.6 V.

[0041] Depend on Figure 6-11 It can be seen that the assembled Li / / SPE-COF / / Li symmetric cells and Li / / SPE-COF / / Si solid-state half-cells exhibit excellent cycle stability, with a stability of 0.1 mA cm⁻¹. -1 Cycle at 30 °C for 580 h, 100 mA g -1 The capacity retention rate after cycling at 30 °C was 79.55%.

[0042] The embodiments of the present invention have been described in detail above, but the present invention is not limited to the described embodiments. For those skilled in the art, various changes, modifications, substitutions, and variations can be made to these embodiments without departing from the principles and spirit of the present invention, and these variations still fall within the protection scope of the present invention.

Claims

1. A method for photo-initiated in-situ preparation of an integrated silicon solid electrolyte, characterized in that, Includes the following steps: (1) Take 2-amino-4-hydroxy-6-methylpyrimidine in dimethyl sulfoxide, heat and stir, then add ethyl 2-isocyanate, stir under ice water bath to precipitate white solid, collect white solid, wash, dry to obtain white powder 2-(3-(6-methyl-4-oxo-1,4-dihydropyrimidin-2-yl)ureido)ethyl methacrylate; (2) Take 2,5-dihydroxyterephthalaldehyde and 5,10,15,20-tetra(4-aminobenzene)-21H,23H-porphyrin and add them to a mixed solvent of o-dichlorobenzene and n-butanol. Disperse by ultrasonication, add glacial acetic acid as a catalyst and remove oxygen before reaction. Collect by centrifugation and dry to obtain photoinitiator porphyrin COF; (3) Polyethylene glycol diacrylate and 2-(3-(6-methyl-4-oxo-1,4-dihydropyrimidin-2-yl)ureido)ethyl methacrylate were ultrasonically dispersed in dimethyl sulfoxide; (4) Add the photoinitiator porphyrin COF and the co-initiator triethylamine, disperse by ultrasonication and protect from light to remove oxygen, and then transfer to a glove box; (5) Add lithium bis(trifluoromethanesulfonylimide) and stir at room temperature to obtain a solid electrolyte precursor solution; (6) Take a solid electrolyte precursor liquid droplet and add it to the surface of the silicon anode, and irradiate it with ultraviolet light. After polymerization and drying, an integrated silicon anode-polymer solid electrolyte is obtained.

2. The method for photo-initiated in-situ preparation of integrated silicon solid electrolyte according to claim 1, characterized in that, In step (1), the heating and stirring temperature is 150~180 ℃, and the heating and stirring time is 10~20 minutes; in step (2), the molar ratio of 2,5-dihydroxyterephthalaldehyde and 5,10,15,20-tetra(4-aminobenzene)-21H,23H-porphyrin is 0.7:1, the volume ratio of o-dichlorobenzene and n-butanol is 1:1~1:2, the reaction temperature is 120~150 ℃, and the reaction time is 72~96 h.

3. The method for photo-initiated in-situ preparation of integrated silicon solid electrolyte according to claim 1, characterized in that, In step (3), the mass ratio of polyethylene glycol diacrylate and 2-(3-(6-methyl-4-oxo-1,4-dihydropyrimidin-2-yl)ureido)ethyl methacrylate is 5:1 to 5:

3.

4. The method for photo-initiated in-situ preparation of integrated silicon solid electrolyte according to claim 1, characterized in that, In step (4), the amount of porphyrin COF added is 0.25 to 1.5% of the mass of polyethylene glycol diacrylate.

5. The method for photoinitiated in-situ preparation of integrated silicon solid electrolyte according to claim 1, characterized in that, In step (4), the deoxygenation refers to the deoxygenation by argon bubbling.

6. The method for photo-initiated in-situ preparation of an integrated silicon solid electrolyte according to claim 1, characterized in that, In step (5), the mass ratio of lithium bis(trifluoromethanesulfonylimide) to polyethylene glycol diacrylate is 1:10 to 1:

20.

7. The method for photo-initiated in-situ preparation of integrated silicon solid electrolyte according to claim 1, characterized in that, In step (5), the stirring time is 12~24 h and the rotation speed is 400~800 r / min.

8. The method for photoinitiated in-situ preparation of integrated silicon solid electrolyte according to claim 1, characterized in that, In step (6), the wavelength of the ultraviolet lamp is 245~365 nm, and the irradiation time of the ultraviolet lamp is 12~24 h.

9. An integrated silicon solid electrolyte prepared by the method according to any one of claims 1-8.

10. The application of the integrated silicon solid electrolyte as described in claim 9 in all-solid-state lithium metal batteries and all-solid-state silicon batteries.

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