Fire-inert high energy density sodium ion / lithium ion solid-state battery and production method

Abstract

The application discloses a non-fire high-energy-density sodium ion / lithium ion solid-state battery and a production method. The battery is composed of a negative electrode sheet, a positive electrode sheet, a separator sheet, a powder additive and auxiliary components. The negative electrode sheet is made of silicon material, which is compounded by MOFs, uses MXene as an electronic and ionic conductive agent, is pretreated by sodium or lithium, and is processed by dry mixing, cold pressing and hot pressing. The positive electrode sheet is made of a positive electrode material, a solid-state electrolyte, a conductive agent and a binder by dry mixing, cold pressing and hot pressing. The separator sheet is made of inorganic solid-state electrolyte and polymer solid-state electrolyte by solvent mixing or melt mixing. The powder additive is two or more solid-state powder substances. After the battery is assembled, baked, formed, sealed and divided, the non-fire high-energy-density sodium ion / lithium ion solid-state battery is manufactured. The application can improve the energy density of the battery and effectively alleviate the problem of battery volume expansion.

Description

Technical Field

[0001] This invention relates to the field of solid-state batteries, and in particular to a non-flammable, high-energy-density sodium-ion / lithium-ion solid-state battery. Background Technology

[0002] Solid-state batteries differ from the commonly used lithium-ion and lithium-ion polymer batteries in that they use solid electrodes and solid electrolytes. The principle is the same, except that the electrolyte is solid, and its density and structure allow more charged ions to accumulate at one end, conducting a larger current and thus increasing battery capacity.

[0003] To improve the energy density of batteries, solid-state batteries generally use lithium metal anodes. However, lithium anodes have an inherent defect: they expand significantly during charging. In addition, as the battery cycle life increases, lithium ions are continuously deposited and stripped from the surface of the lithium metal anode, resulting in voids and collapses on the surface. This gradually increases the battery's internal resistance, eventually leading to functional failure.

[0004] Because the solid electrolyte and main material of traditional solid-state batteries are in solid-solid contact, the interface resistance is high and a harmful space charge layer is formed, which limits the charge and discharge rate of the battery to far less than that of conventional liquid batteries. Summary of the Invention

[0005] This invention provides a non-flammable, high-energy-density sodium-ion / lithium-ion solid-state battery that improves battery energy density and alleviates battery volume expansion.

[0006] The objective of this invention is achieved as follows: the solid-state battery comprises a negative electrode, a positive electrode, a separator, powder additives, and auxiliary components; the negative electrode uses silicon material with a higher specific capacity than lithium metal, which is composited with MOFs, uses MXene as an electronic and ionic conductive agent, and is pretreated with sodium or lithium elements, and then dry-mixed, cold-pressed, and heat-applied; the positive electrode is made of positive electrode material, solid electrolyte, conductive agent, and binder through dry mixing, cold pressing, and heat-applied processing; the separator is made of inorganic solid electrolyte and polymer solid electrolyte through solvent mixing or melt mixing; the powder additives are two or more solid powder substances, which are directly added to the gap between the battery core and the casing; the auxiliary components include the casing, large tabs, current collector, and adhesive tape; during battery assembly, the negative electrode, separator, and positive electrode are stacked in sequence, bound with adhesive tape, the tabs on the electrodes are welded together, then welded to the large tabs, then the casing is assembled, then the powder additives are added, and then baked, formed, sealed, and capacity tested to produce a non-flammable high-energy-density sodium-ion / lithium-ion solid-state battery.

[0007] The silicon and MOF composite refers to a material combining silicon compounds and MOFs, where the MOFs are SIFSIX-1-Cu@SiO2, ZIF-8@SiO2, or SiO2@MOF-199 materials.

[0008] The MXene material is a two-dimensional inorganic compound, specifically TiNbC, Ti3C2, or V2N.

[0009] The cathode material is at least one of the following: lithium-rich manganese, lithium nickel cobalt manganese oxide, lithium cobalt oxide, lithium iron phosphate, lithium manganese iron phosphate, lithium manganese oxide, Prussian blue, Prussian white, sodium vanadium phosphate, sodium manganese phosphate, sodium iron copper manganese oxide, sodium iron copper manganese oxide, sodium manganate, and sodium cobalt oxide.

[0010] The inorganic solid electrolyte in the positive electrode and the separator is LLZO, LZSiPO, LPSCl, LLTO, LATP, LAGP, LPS, LGPS, LSiPSCl, LSiPSCl, Na3SbS4, Na4SnS4, or Na3Zr2Si2PO4. 12 At least one of Na3PS4 materials.

[0011] The conductive agent is at least one of conductive carbon black, carbon nanotubes, carbon fibers, and graphene; the binder is at least one of PTFE, SBR, PVDF, PAA, and PAN materials.

[0012] The polymer solid electrolyte in the separator is at least one of PEO, PAN, PVDF, PMMA, and PPO.

[0013] The powder additive is at least two of the following: 1,2-dimethylimidazolium, diethyltetramethylimidazolium, diphenylimidazolium, LiTFSI, LiFSI, NaPF6, NaClO4, NaTFSI, NaFSI, LiPF6, LiClO4, LiBOB, NaCl, LiCl, NaNO3, LiNO3, Na2SO4, and Li2SO4.

[0014] The solvent for the solid electrolyte mixture in the separator is at least one of NMP, acetonitrile, anisole, DMF, THF, acetone, DMAc, TEP, and DMSO.

[0015] Production Method: The manufacturing process for the negative electrode sheet involves first dispersing MOFs in water and ethanol, then ultrasonically and stirring them, followed by adding them to a silicon-containing solution and stirring. The precipitate is then removed, washed, and dried. The resulting silicon MOF composite material is then dry-mixed with MXene. The mixture is pressed into a conductive feed tank, covered with a permeation membrane pre-soaked in solvent. One side of the membrane is wiped off, leaving the dry side facing the mixture. The membrane and feed tank edges are then clamped together with a fixture, pressing down the mixture. A hole is made in the pressure plate, and a sodium-ion-containing solvent is added to the permeation membrane. A graphite electrode is then inserted and connected to the positive terminal of the power supply. The feed tank is connected to the negative terminal. Power is applied to pre-charge the mixture with lithium or sodium. The mixture is then removed, mixed with hard carbon or graphite and a binder, and finally rolled using a rolling mill. The mixture is pressed into sheets, and then the sheets are heat-applied onto the current collector to produce the negative electrode sheet. The solution used to soak the permeation membrane and the sodium or lithium solution added to the feed tank are the same substance, composed of EC, DMC, MEC, PC, ethanol, acetone, pyridine solvent, plus NaPF6, NaClO4, NaTFSI, NaFSI, LiPF6, LiClO4, LiTFSI, LiFSI, LiBOB, NaCl, LiCl, NaNO3, LiNO3, Na2SO4, or Li2SO4. The binder is at least one of PTFE, SBR, PCPU, PVDF, PAA, PAN, etc. The silicon-containing solvent is at least one of tetraethyl orthosilicate, trimethylsilylacetic acid, and 3-trimethylsilylpropionic acid.

[0016] Compared with the prior art, the advantages of this invention are:

[0017] (1) The negative electrode of the present invention uses silicon-containing MOFs material or silicon and MOFs composite material. After being reduced by sodium or lithium, the combined silicon becomes active silicon, thereby having lithium storage and sodium storage performance. Its lithium storage capacity is as high as 4200mAh / g, which is much higher than the 3860mAh / g of lithium. At the same time, the residual metal-organic framework and sodium or lithium compound play a buffering role in silicon volume expansion.

[0018] (2) The negative electrode of this invention uses MXene as the electronic and ionic conductive agent of the negative electrode material, which eliminates the need for conventional liquid electrolyte, thereby realizing the solidification of the negative electrode;

[0019] (3) The solid powder additive used in this invention can alleviate the problem of high solid-solid interface impedance after heating. Attached Figure Description

[0020] Figure 1 This is a schematic diagram of the battery structure of the present invention.

[0021] Figure 2 This is the molecular formula of ZIF-8 in this invention.

[0022] Figure 3 This is a schematic diagram of the material tank used in the production method of the present invention.

[0023] In the diagram: 1-Battery cell; 2-Stacked electrode tab; 3-Large electrode tab; 4-Powder additive; 5-Shell; 6-Pressure plate; 7-Clamp; 8-Permeable membrane; 9-Material tank; 10-Material tank electrode. Detailed Implementation

[0024] Reference Figure 1 The solid-state battery consists of a negative electrode, a positive electrode, a separator, powder additives, and auxiliary components. The negative electrode uses silicon material with a higher specific capacity than lithium metal, which is composited with MOFs, uses MXene as an electronic and ionic conductive agent, and is pretreated with sodium or lithium elements, followed by dry mixing, cold pressing, and hot bonding. The positive electrode is made of positive electrode material, solid electrolyte, conductive agent, and binder through dry mixing, cold pressing, and hot bonding. The separator is made of inorganic solid electrolyte and polymer solid electrolyte through solvent mixing or melt mixing. The powder additives consist of two or more solid powder substances, which are directly added to the gap between the battery cell 1 and the casing 5. The auxiliary components include the casing, large... The battery assembly process involves stacking the negative electrode, separator, and positive electrode in sequence, binding them together with adhesive tape to form the battery core 1. The stacked electrode tabs 2 on the negative and positive electrodes are then welded together and subsequently welded to the large electrode tabs 3. The outer casing 5 is then assembled, followed by the addition of powder additives 4. After baking, formation, sealing, and capacity testing, a non-flammable, high-energy-density sodium-ion / lithium-ion solid-state battery is manufactured. The silicon and MOF composite refers to a material combining silicon compounds and MOFs. The MOFs are SIFSIX-1-Cu@SiO2, ZIF-8@SiO2, or SiO2@MOF-199 materials. The molecular formula of ZIF-8 is [see details]. Figure 2 The MXene material is a two-dimensional inorganic compound, specifically TiNbC, Ti3C2, or V2N. The cathode material is at least one of the following: lithium-rich manganese, lithium nickel cobalt manganese oxide, lithium cobalt oxide, lithium iron phosphate, lithium manganese iron phosphate, lithium manganese oxide, Prussian blue, Prussian white, sodium vanadium phosphate, sodium manganese phosphate, sodium iron copper manganese oxide (a layered oxide), sodium manganate, and sodium cobalt oxide. The inorganic solid electrolyte in the cathode sheet and separator is LLZO, LZSiPO, LPSCl, LLTO, LATP, LAGP, LPS, LGPS, LSiPSCl, LSiPSCl, Na3SbS4, Na4SnS4, or Na3Zr2Si2PO. 12The material is selected from at least one of Na3PS4; the conductive agent is selected from at least one of conductive carbon black, carbon nanotubes, carbon fibers, and graphene; the binder is selected from at least one of PTFE, SBR, PVDF, PAA, and PAN; the polymer solid electrolyte in the separator is selected from at least one of PEO, PAN, PVDF, PMMA, and PPO; the powder additive is selected from at least two of 1,2-dimethylimidazole, diethyltetramethylimidazole, diphenylimidazole, LiTFSI, LiFSI, NaPF6, NaClO4, NaTFSI, NaFSI, LiPF6, LiClO4, LiBOB, NaCl, LiCl, NaNO3, LiNO3, Na2SO4, and Li2SO4; the solvent mixed with the solid electrolyte in the separator is selected from at least one of NMP, acetonitrile, anisole, DMF, THF, acetone, DMAc, TEP, and DMSO.

[0025] Production method: First, MOFs are dispersed in water and ethanol, then ultrasonicated and stirred. Next, a silicon-containing solution is added and stirred. The precipitate is then removed, washed, and dried. The resulting silicon MOF composite material is then dry-mixed with MXene. The mixture is then pressed into a conductive tank, covered with a permeable membrane pre-soaked in solvent. One side of the membrane is wiped off, leaving the dry side facing the mixture. The membrane and tank edges are then clamped together with fixtures to hold the mixture in place. Holes are made in the pressure plate, and sodium-ion-containing solvent is added to the membrane. A graphite electrode is then inserted and connected to the positive terminal of the power supply. The tank is connected to the negative terminal. Power is applied to pre-charge the mixture with lithium or sodium. The mixture is then removed, mixed with hard carbon or graphite and a binder, and finally pressed using a rolling mill. The negative electrode sheet is manufactured by heat-applying the sheet onto the current collector in sheet form. The solution used to soak the permeation membrane and the sodium or lithium solution added to the feed tank are the same substance, composed of EC, DMC, MEC, PC, ethanol, acetone, pyridine solvent, plus NaPF6, NaClO4, NaTFSI, NaFSI, LiPF6, LiClO4, LiTFSI, LiFSI, LiBOB, NaCl, LiCl, NaNO3, LiNO3, Na2SO4, or Li2SO4. The binder is at least one of PTFE, SBR, PCPU, PVDF, PAA, PAN, etc. The silicon-containing solvent is at least one of tetraethyl orthosilicate, trimethylsilylacetic acid, and 3-trimethylsilylpropionic acid.

[0026] Reference Figure 3 A material tank electrode 10 is connected to the material tank 9. A clamp 7 for holding the permeation membrane 8 is provided at the end of the material tank 9. A pressure plate 6 for pressing the mixture is provided on the cavity of the material tank 9.

[0027] Example 1

[0028] Production method of non-flammable high energy density 150Ah lithium-ion solid-state battery

[0029] Add 200L of ethanol and 300L of water to a stirred tank. Add 50kg of anhydrous SIFSIX-1-Cu and 25kg of HMIM to the stirred tank and stir for 1 hour. Simultaneously turn on the ultrasonic generator. Add 15kg of CTBA and continue stirring for 1 hour. Add 80kg of tetraethyl orthosilicate and stir for 3 hours. Remove the precipitate, wash it three times with 300L of methanol, and dry it in a vacuum drying oven at 85℃ for 12 hours to obtain SIFSIX-1-Cu@SiO2.

[0030] 50 kg of SIFSIX-1-Cu@SiO2 and 1.5 kg of TiNbC were placed in a stirred tank and stirred for 2 hours. The mixture was then poured into a conductive tank, leveled, and compacted. A 1.0 mol / L LiCl solution was prepared, with the solvent being EC / DMC 1:1. The permeation membrane was immersed in the LiCl solution for 2 hours. After rinsing, one side was wiped clean and placed in the conductive tank with the wiped side facing the material, ensuring it was tightly adhered. The permeation membrane was fixed with clamps, and the mixture was pressed down with a pressure plate. 1012 L of LiCl solution was placed on the permeation membrane in the tank, and the graphite electrode was inserted and fixed. The tank electrode was connected to the negative terminal of the power supply, and the graphite electrode was connected to the positive terminal. The power was turned on for 5 hours. Then, the power supply and electrodes were removed, and the solution and permeation membrane were taken out. Finally, the active material silicon composite at the bottom of the tank was taken out. This composite has a high lithium storage capacity of 778 mAh / g, which is higher than the maximum specific capacity of graphite.

[0031] Take 45 kg of silicon composite, 5 kg of graphite, and 1.5 kg of SBR, and stir in a mixing tank for 2 hours; then pour into the hopper of a rolling mill, start the rolling mill, press the material into a 50 μm thin sheet, and roll it up; take 6 μm copper foil, load it onto a laminating machine, load the silicon composite sheet on top, heat to 85°C, and pass it through the rolling mill, with a layer of silicon composite sheet on both the top and bottom of the copper foil; start the rollers to press the silicon composite sheet onto the copper foil to obtain a negative electrode sheet; then cut the negative electrode sheet into small pieces of 113 mm × 524 mm, excluding the tab size;

[0032] Take 92 kg of ternary material, 1.5 kg of carbon black, 0.6 kg of carbon nanotubes, 3 kg of PTFE, and 2.9 kg of lithium lanthanum zirconium oxide, and dry mix them for 2 hours; then pour them into the hopper of a rolling mill, start the rolling mill, press the material into an 80 μm thick sheet, and roll it up; take 13 μm aluminum foil, load it onto a laminating machine, then load the positive electrode sheet, heat it to 85°C, and pass it through the rolling mill, with one layer of positive electrode sheet on each side of the aluminum foil. Start the rollers to press the positive electrode sheet onto the aluminum foil to obtain the positive electrode sheet, and then cut the negative electrode sheet into 110 mm × 520 mm small pieces, excluding the tab size;

[0033] Take 9.5 kg of PEO and 0.5 kg of lithium lanthanum zirconium oxide, put them into a mixer and dry mix for 2 hours. Take them out and put them into 150 kg of NMP, stir for 2 hours, take them out and pour them into a mold, and dry them in an oven at 105℃ for 3 hours to obtain the separator sheet. Cut the separator sheet into small pieces of 117 mm × 528 mm.

[0034] 40 negative electrodes, 78 separators, and 39 positive electrodes are stacked into a block in sequence and bound with tape. All positive electrode tabs are welded together using an ultrasonic welding machine, and all negative electrode tabs are welded together. Large electrode tabs are then welded on to form a stacked core. An aluminum-plastic film is taken, stamped into shape, and sealed onto the stacked core.

[0035] The battery was placed in an oven and heated to 85°C under vacuum for 48 hours. Then, 57 grams of 1,2-dimethylimidazole powder and 43 grams of LiTFSI powder were mixed and added to the battery. The battery was pre-sealed and heated to 60°C for 48 hours. The battery was then formed, evacuated, resealed, and capacity tested to obtain a non-flammable, high-energy-density 150Ah lithium-ion solid-state battery.

[0036] Example 2

[0037] Production method of non-flammable high energy density 100Ah sodium-ion solid-state battery

[0038] Add 240L of ethanol and 360L of water to a stirred tank; add 50kg of ZIF-8 and 30kg of HMIM to the stirred tank and stir for 1 hour while simultaneously turning on the ultrasonic generator. Add 18kg of CTBA and continue stirring for 1 hour. Add 182kg of tetraethyl orthosilicate and stir for 3 hours. Remove the precipitate, wash it three times with 300L of methanol, and dry it in a vacuum drying oven at 85℃ for 12 hours to obtain ZIF-8@SiO2.

[0039] Take 50 kg of ZIF-8@SiO2 and 1.5 kg of Ti3C2 and put them into a stirring vessel and stir for 2 hours. Pour the mixture into a conductive tank, spread it evenly, and compact it. Prepare 1.0 mol / L NaClO4 (solvent EC / DMC 1:1). Immerse the permeation membrane in a small amount of NaClO4 solution for 2 hours. Take it out, wipe one side clean, put it into the tank with the wiped side facing the material, and press it tightly. Fix the permeation membrane with a clamp and press the mixture with a pressure plate. Put 1100 L of NaClO4 solution on the permeation membrane, insert and fix the graphite electrode, connect the tank electrode to the negative terminal of the power supply, and connect the graphite electrode to the positive terminal of the power supply. Turn on the power for 5 hours, then remove the power supply and electrodes, take out the solution and permeation membrane, and finally take out the active material silicon composite at the bottom of the tank. The sodium storage capacity of this composite is as high as 460 mAh / g, which is higher than the average storage capacity of hard carbon.

[0040] Take 45 kg of silicon composite, 5 kg of hard carbon, and 1.5 kg of SBR, and stir in a mixing tank for 2 hours; then pour into the hopper of a rolling mill, start the rolling mill, press the material into a 55 μm thin sheet, and roll it up; take 6 μm copper foil, load it onto a laminating machine, then load the silicon composite sheet on top, heat to 85°C, and pass it through the rolling mill, with a layer of silicon composite sheet on both the top and bottom of the copper foil; start the rollers to press the silicon composite sheet onto the copper foil to obtain the negative electrode sheet; then cut the negative electrode sheet into small pieces, 113 mm × 524 mm, excluding the tab size;

[0041] Take 92 kg of sodium iron copper manganese oxide, 1.5 kg of carbon black, 0.6 kg of carbon nanotubes, 3 kg of PTFE, and 2.9 kg of lithium zirconium silicon phosphorus oxide, and dry mix for 2 hours; then pour into the hopper of a rolling mill, start the rolling mill, press the material into an 80 μm thin sheet, and roll it up; take 13 μm aluminum foil, load it onto a laminating machine, then load the positive electrode sheet, heat to 85°C, and pass it through the rolling mill, with one layer of positive electrode sheet on each side of the aluminum foil. Start the rollers to press the positive electrode sheet onto the aluminum foil to obtain the positive electrode sheet; then cut the negative electrode sheet into small pieces, 110 mm × 520 mm, excluding the tab size;

[0042] Take 9.5 kg of PEO and 0.5 kg of lithium zirconium silicon phosphorus oxide, put them into a mixer and dry mix for 2 hours. Take them out and put them into 150 kg of NMP, stir for 2 hours, take them out and pour them into a mold, and dry them in an oven at 105℃ for 3 hours to obtain the separator sheet. Cut the separator sheet into small pieces, 117 mm × 528 mm.

[0043] 35 negative electrodes, 68 separators, and 34 positive electrodes are stacked into a block in sequence and bound with tape. All positive electrode tabs are welded together using an ultrasonic welding machine, and all negative electrode tabs are welded together. Large electrode tabs are then welded on to form a stacked core. An aluminum-plastic film is taken, stamped, and sealed onto the stacked core.

[0044] The battery is placed in an oven and dried under vacuum at 85°C for 48 hours. Then, 35 grams of 1,2-dimethylimidazole powder and 25 grams of NaTFSI powder are mixed and added to the battery. The battery is pre-sealed and dried at 60°C for 48 hours. The battery is then formed, evacuated, re-sealed, and capacity tested to obtain a non-flammable, high-energy-density 100Ah lithium-ion solid-state battery.

[0045] Example 3

[0046] Preparation method of non-flammable high energy density 300Ah lithium-ion solid-state battery

[0047] Add 200L of ethanol and 300L of water to a stirred tank. Add 50kg of SiO2@MOF-199 and 25kg of HMIM to the stirred tank and stir for 1 hour while simultaneously using ultrasound. Add 15kg of CTBA and continue stirring for 1 hour. Add 70kg of tetraethyl orthosilicate and stir for 3 hours. Remove the precipitate, wash it three times with 300L of methanol, and dry it in a vacuum drying oven at 85℃ for 12 hours to obtain MOF-199@SiO2.

[0048] Take 50 kg of MOF-199@SiO2 and 1.5 kg of V2N and put them into a stirring vessel and stir for 2 hours. Pour the mixture into a trough, spread it evenly, and compact it. Prepare 1.0 mol / L LiCl (solvent EC / DMC 1:1).

[0049] Immerse the permeation membrane in a small amount of LiCl solution for 2 hours. Remove it, wipe one side clean, and place it in a conductive tank with the wiped side facing the material, ensuring it is tightly adhered. Secure the permeation membrane with clamps and press down the mixture with a pressure plate. Place 660L of LiCl solution onto the permeation membrane in the tank, insert the graphite electrode, and fix it in place. Connect the tank electrode to the negative terminal of the power supply and the graphite electrode to the positive terminal. Turn on the power for 5 hours. Then remove the power supply and electrodes, remove the solution and permeation membrane, and finally remove the active material silicon composite from the bottom of the tank. This composite has a lithium storage capacity of up to 558mAh / g, which is higher than the maximum capacity of graphite.

[0050] Take 45 kg of silicon composite, 5 kg of graphite, and 1.5 kg of SBR, and stir in a mixing tank for 2 hours; then pour into the hopper of a rolling mill, start the rolling mill, press the material into a 55 μm thin sheet, and roll it up; take 6 μm copper foil, load it onto a laminating machine, then load the silicon composite sheet on top, heat to 85°C, and pass it through the rolling mill, with a layer of silicon composite sheet on both the top and bottom of the copper foil; start the rollers to extrude the silicon composite sheet onto the copper foil to obtain the negative electrode sheet; then cut the negative electrode sheet into small pieces, 113 mm × 524 mm, excluding the tab size;

[0051] Take 92 kg of lithium-rich manganese material, 1.5 kg of carbon black, 0.6 kg of carbon nanotubes, 3 kg of PTFE, and 2.9 kg of LPSCl, and dry mix for 2 hours; then pour into the hopper of a rolling mill, start the rolling mill, press the material into a 70 μm thin sheet, and roll it up; take 13 μm aluminum foil, load it onto a laminating machine, then load the positive electrode sheet, heat to 85°C, and pass it through the rolling mill, with one layer of positive electrode sheet on each side of the aluminum foil. Start the rollers to press and laminate the positive electrode sheet onto the aluminum foil to obtain the positive electrode sheet; cut the negative electrode sheet into small pieces, 110 mm × 520 mm, excluding the tab size;

[0052] Take 9.5 kg of PEO and 0.5 kg of LPSCl, put them into a mixer and dry mix for 2 hours. Take them out and put them into an extruder, heat them to 90℃ for 3-5 minutes, extrude the mixture, cool it, and roll it up to make a release film. Cut the release film into small pieces, 117 mm × 528 mm.

[0053] Take 29 negative electrodes, 56 separators, and 28 positive electrodes, stack them into a block in order, and bind them with tape; use an ultrasonic welding machine to weld all the positive electrode tabs together, weld all the negative electrode tabs together, and then weld the large electrode tabs on each to form a stacked core; take an aluminum shell, insert the two stacked cores side by side into the shell, weld the two positive electrodes together with connecting pieces, weld the two negative electrodes together with connecting pieces, then weld the electrode tabs to the cover plate, and then weld the cover plate to the shell;

[0054] The battery was placed in an oven under vacuum at 85°C for 48 hours. Then, 57 grams of 1,2-dimethylimidazole powder and 43 grams of LiTFSI powder were added to the battery and mixed. The mixture was then added to the battery through the injection hole at 60°C for 48 hours. The battery was then formed, sealed, and tested for capacity to obtain a non-flammable, high-energy-density 300Ah lithium-ion solid-state battery.

Claims

1. A non-flammable, high-energy-density sodium-ion / lithium-ion solid-state battery, comprising a negative electrode, a positive electrode, a separator, powder additives, and auxiliary components, characterized in that: The negative electrode uses silicon material with a higher specific capacity than lithium metal. It is manufactured by combining it with MOFs (Metal-Oxide-Factory Composites), using MXene as an electronic and ionic conductor, and pretreating it with sodium or lithium. The process involves dry mixing, cold pressing, and hot-pressing. The silicon-MOF composite refers to a material combining silicon compounds and MOFs. The MOFs are SIFSIX-1-Cu@SiO2, ZIF-8@SiO2, or SiO2@MOF-199 materials. The MXene material is a two-dimensional inorganic compound, such as TiNbC or Ti3C2. Or V2N material; the positive electrode sheet is made of positive electrode material, solid electrolyte, conductive agent, and binder through dry mixing, cold pressing, and hot pressing; the separator is made of inorganic solid electrolyte and polymer solid electrolyte through solvent mixing or melt mixing; the powder additive consists of two or more solid powder substances, including 1,2-dimethylimidazolium, diethyltetramethylimidazolium, diphenylimidazolium, LiTFSI, LiFSI, NaPF6, NaClO4, NaTFSI, NaFSI, LiPF6, LiClO4, and LiB. At least two of the following are added directly to the gap between the battery cell and the casing: OB, NaCl, LiCl, NaNO3, LiNO3, Na2SO4, and Li2SO4; auxiliary components include casing, large tabs, current collector, and adhesive tape; during battery assembly, the negative electrode, separator, and positive electrode are stacked in sequence, bound with adhesive tape, the tabs on the electrode sheets are welded together, then welded to the large tabs, then the casing is assembled, then powder additives are added, and then the battery is baked, formed, sealed, and capacity tested to produce a non-flammable high-energy-density sodium-ion / lithium-ion solid-state battery.

2. The non-flammable high-energy-density sodium-ion / lithium-ion solid-state battery according to claim 1, characterized in that: The cathode material is at least one of the following: lithium-rich manganese, lithium nickel cobalt manganese oxide, lithium cobalt oxide, lithium iron phosphate, lithium manganese iron phosphate, lithium manganese oxide, Prussian blue, Prussian white, sodium vanadium phosphate, sodium manganese phosphate, sodium iron copper manganese oxide, sodium manganate, and sodium cobalt oxide.

3. The non-flammable high-energy-density sodium-ion / lithium-ion solid-state battery according to claim 1, characterized in that: The inorganic solid electrolyte in the positive electrode and the separator is LLZO, LZSiPO, LPSCl, LLTO, LATP, LAGP, LPS, LGPS, LSiPSCl, LSiPSCl, Na3SbS4, Na4SnS4, or Na3Zr2Si2PO4. 12 At least one of Na3PS4 materials.

4. The non-flammable high-energy-density sodium-ion / lithium-ion solid-state battery according to claim 1, characterized in that: The conductive agent is at least one of conductive carbon black, carbon nanotubes, carbon fibers, and graphene; the binder is at least one of PTFE, SBR, PVDF, PAA, and PAN materials.

5. The non-flammable high-energy-density sodium-ion / lithium-ion solid-state battery according to claim 1, characterized in that: The polymer solid electrolyte in the separator is at least one of PEO, PAN, PVDF, PMMA, and PPO.

6. The non-flammable high-energy-density sodium-ion / lithium-ion solid-state battery according to claim 1, characterized in that: The solvent for the solid electrolyte mixture in the separator is at least one of NMP, acetonitrile, anisole, DMF, THF, acetone, DMAc, TEP, and DMSO.

7. A method for producing a non-flammable high-energy-density sodium-ion / lithium-ion solid-state battery as described in any one of claims 1-6, characterized in that: The manufacturing process for the negative electrode involves first dispersing MOFs in water and ethanol, followed by ultrasonic and stirring treatment, then adding them to a silicon-containing solution and stirring. The precipitate is then removed, washed, and dried. The resulting silicon MOF composite material is then dry-mixed with MXene. The mixture is pressed into a conductive tank, covered with a permeable membrane pre-soaked in solvent. One side of the membrane is wiped off, leaving the dry side facing the mixture. The membrane and tank edges are then clamped together using fixtures to hold the mixture in place. Holes are made in the pressure plate, and solvent is added to the permeable membrane. A graphite electrode is then inserted and connected to the positive terminal of the power supply. The tank is connected to the negative terminal. Power is applied to pre-charge the mixture with lithium or sodium. The mixture is then removed, mixed with hard carbon or graphite and a binder, and finally pressed using a rolling mill. The negative electrode sheet is manufactured by heat-applying the sheet to the current collector in sheet form. The solvent used to soak the permeation membrane and the sodium or lithium-containing solvent added to the permeation membrane in the feed tank are the same substance, composed of EC, DMC, MEC, PC, ethanol, acetone, pyridine solvent plus NaPF6, NaClO4, NaTFSI, NaFSI, LiPF6, LiClO4, LiTFSI, LiFSI, LiBOB, NaCl, LiCl, NaNO3, LiNO3, Na2SO4 or Li2SO4. The binder is at least one of PTFE, SBR, PVDF, PAA, PAN materials. The silicon-containing solvent is at least one of tetraethyl orthosilicate, trimethylsilylacetic acid, and 3-trimethylsilylpropionic acid.

Images