Preparation method of a solid-state metal battery based on a dynamic supramolecular ionic conductive elastomer

Abstract

A preparation method of a solid-state metal battery based on a dynamic supramolecular ion-conductive elastomer, comprising: dissolving an electrolyte salt and a dynamic supramolecular elastomer in an anhydrous solvent, stirring at room temperature to form a homogeneous precursor solution, and dividing the precursor solution into portions A and B; using a current collector as a substrate, dissolving positive electrode particles, a conductive agent and portion A of the precursor solution in an anhydrous solvent to obtain a slurry and coating the slurry onto the current collector, and drying to volatilize the solvent to obtain a composite positive electrode sheet; respectively coating portion B of the precursor solution on the adhesive layer of the composite positive electrode sheet and the metal negative electrode sheet, and laminating the composite positive electrode sheet and the metal negative electrode sheet together with the coated surfaces as the bonding surfaces to form an integrated positive electrode / solid electrolyte structure; using the formed integrated positive electrode / solid electrolyte structure as a basic battery unit, and performing encapsulation through a battery encapsulation machine to obtain a solid-state metal battery. The solid-state metal battery prepared by the present invention has excellent electrochemical performance, mechanical performance and safety performance, meeting the requirements of various energy storage fields.

Description

Technical Field

[0001] The present invention relates to the technical field of applications of dynamic supramolecular ion conductors, and particularly relates to a preparation method of a solid-state metal battery based on a dynamic supramolecular ion-conducting elastomer. Background Art

[0002] Solid-state batteries have the advantages of high specific energy, high safety, long life, high reliability, small volume, flexibility, etc., and can meet the various requirements of energy storage fields such as electric vehicles, flexible electronic products, and aerospace. They are an important direction for the development of future energy storage power supplies. Solid-state batteries replace liquid electrolytes and diaphragms with solid electrolytes, which can fundamentally solve the safety problems caused by the volatility, leakage, and combustion of traditional liquid electrolytes. At the same time, the volume can be reduced by 40% and the mass can be reduced by 25%. Therefore, it is considered an important way to achieve the goal of increasing the energy density of power batteries to 500 Wh / kg. Among them, solid-state batteries using solid electrolytes instead of liquid organic electrolytes have become a key technology in the next-generation energy storage field. Among common solid electrolytes, polymer solid electrolytes have the advantages of light weight, flexibility, easy processing, safety and reliability, and low price, and have great potential in the practical application of solid-state batteries with high specific energy, long cycle life, and high safety. -1 Polymer solid electrolytes are composed of a polymer matrix and a lithium salt. Their ion transport mainly depends on two processes: the dissociation of lithium salts by polar groups such as C-O, C=O, and C≡N on polymer segments, and the movement of amorphous segments on polymer segments to promote the repetitive "coordination-dissociation" process of Li to achieve ion transport, thereby providing a relatively high ionic conductivity. However, current polymer solid electrolytes still have the following deficiencies: a relatively narrow electrochemical stability window, which limits the energy density of solid-state batteries; poor mechanical properties, unable to prevent metal dendrites from penetrating the electrolyte and causing battery short circuits; and both flexibility and safety performance need to be improved.

[0003] Polymer solid electrolytes are composed of a polymer matrix and a lithium salt. Their ion transport mainly depends on two processes: the dissociation of lithium salts by polar groups such as C-O, C=O, and C≡N on polymer segments, and the movement of amorphous segments on polymer segments to promote the repetitive "coordination-dissociation" process of Li to achieve ion transport, thereby providing a relatively high ionic conductivity. + However, current polymer solid electrolytes still have the following deficiencies: a relatively narrow electrochemical stability window, which limits the energy density of solid-state batteries; poor mechanical properties, unable to prevent metal dendrites from penetrating the electrolyte and causing battery short circuits; and both flexibility and safety performance need to be improved. Summary of the Invention

[0004] Based on this, the present invention provides a preparation method of a solid-state metal battery based on a dynamic supramolecular ion-conducting elastomer to solve the technical problems that the electrochemical performance, mechanical performance, safety performance, etc. of existing polymer solid electrolyte-based metal batteries still need to be further improved.

[0005] To achieve the above object, the present invention provides a preparation method of a solid-state metal battery based on a dynamic supramolecular ion-conducting elastomer, which includes the following steps:

[0006] S1. Prepare a precursor solution of a dynamic supramolecular ion-conducting elastomer:

[0007] Dissolve the electrolyte salt and the dynamic supramolecular elastomer in an anhydrous solvent, stir at room temperature to form a homogeneous precursor solution, and divide the precursor solution into two portions, A and B;

[0008] S2. Prepare a composite positive electrode sheet:

[0009] Using the current collector as a substrate, dissolve the positive electrode particles, the conductive agent and portion A of the precursor solution in an anhydrous solvent and form a uniform slurry through ball milling or stirring, then coat the slurry onto the current collector, and volatilize the solvent to obtain the composite positive electrode sheet. After volatilizing the solvent, portion A of the precursor solution forms a dynamic supramolecular ion-conductive elastomer, and this dynamic supramolecular ion-conductive elastomer is used as a binder to adhere the positive electrode particles to the surface of the current collector to form a bonding layer;

[0010] S3. Prepare a solid electrolyte:

[0011] Coat portion B of the precursor solution on the bonding layer of the composite positive electrode sheet and the metal negative electrode sheet respectively. After the solvent is completely volatilized, stack the composite positive electrode sheet and the metal negative electrode sheet face-to-face with their coated surfaces in contact to form a basic battery unit with an integrated positive electrode / solid electrolyte structure. After volatilizing the solvent, the dynamic supramolecular ion-conductive elastomer formed from portion B of the precursor solution serves as the solid electrolyte, and the thickness of this solid electrolyte is 1 μm to 1 mm;

[0012] S4. Battery encapsulation:

[0013] Encapsulate the basic battery unit through a battery encapsulator to finally form a solid-state metal battery.

[0014] As a further preferred technical solution of the present invention, in step S1, the electrolyte salt is at least one of lithium salts, sodium salts, potassium salts, zinc salts, magnesium salts, and calcium salts, and the electrolyte salt accounts for 5% to 70% of the mass of the dynamic supramolecular elastomer; the anhydrous solvent is one or more of anhydrous tetrahydrofuran, dichloromethane, chloroform, acetonitrile, and N-methylpyrrolidone, and the mass-volume ratio of the dynamic supramolecular elastomer to the anhydrous solvent is 3% to 50%.

[0015] As a further preferred technical solution of the present invention, the lithium salt is lithium bis(trifluoromethanesulfonyl)imide, lithium trifluoromethanesulfonyl-perfluorobutanesulfonylimide, lithium trifluoromethanesulfonyl-perfluoropropylsulfonylimide, lithium bis(fluorosulfonyl)imide, lithium hexafluorophosphate, lithium tetrafluoroborate, lithium bis(oxalato)borate, lithium oxalodifluoroborate, lithium difluorophosphate, 4,5-dicyano-2-trifluoromethylimidazole lithium, lithium perchlorate or lithium chloride; the sodium salt is sodium bis(trifluoromethanesulfonyl)imide, sodium perchlorate, sodium bis(fluorosulfonyl)imide, sodium chloride, sodium nitrate, sodium fluorosilicate or sodium phthalate; the potassium salt is potassium bis(trifluoromethanesulfonyl)imide, potassium bis(fluorosulfonyl)imide, potassium chloride, potassium nitrate or potassium hydrogen phthalate; the ammonium salt is tetraethylammonium tetrafluoroborate, ammonium chloride or ammonium nitrate.

[0016] As a further preferred technical solution of the present invention, in step S2, the mass ratio of the positive electrode particles, the conductive agent and the dynamic supramolecular ionic conductive elastomer formed from A parts of the precursor solution is 2:1:7 to 8:1:1.

[0017] As a further preferred technical solution of the present invention, in step S2, the positive electrode particles are one or more mixtures of lithium cobaltate, lithium iron phosphate, lithium manganate, lithium titanate, nickel cobalt manganese, sodium fluorophosphate vanadate, Prussian blue, potassium fluorophosphate vanadate; the conductive agent is one or more mixtures of super-p, acetylene black, carbon nanotubes, graphene; the anhydrous solvent is one or more mixtures of N,N-dimethylformamide, N,N-dimethylacetamide, dimethyl sulfoxide, dichloromethane, chloroform, tetrahydrofuran, N-methylpyrrolidone.

[0018] As a further preferred technical solution of the present invention, the metal negative electrode sheet is one or more of lithium metal, sodium metal, potassium metal, magnesium metal, calcium metal.

[0019] As a further preferred technical solution of the present invention, the thickness of the solid electrolyte is 1 μm to 100 μm.

[0020] As a further preferred technical solution of the present invention, the dynamic supramolecular elastomer in step S1 is prepared from the following raw materials: polyester / polyether type bifunctional monomer, diisocyanate monomer, anhydrous solvent, chain extender and catalyst, wherein:

[0021] The molar ratio of the polyester / polyether type bifunctional monomer to the diisocyanate monomer is 1:2 to 2:1; the chain extender includes a dynamic disulfide bond monomer and a supramolecular quadruple hydrogen bond monomer, and the molar ratio of the dynamic disulfide bond monomer to the supramolecular quadruple hydrogen bond monomer is 10:0 to 0:10; the catalyst accounts for 0.01% to 1% of the total mass of the polyester / polyether type bifunctional monomer and the diisocyanate monomer;

[0022] The polyester / polyether type bifunctional monomer includes one or more of polycaprolactone diol, poly(tetrahydrofuran-caprolactone) diol, hydroxyl-terminated poly(tetrahydrofuran), amino-terminated poly(tetrahydrofuran), hydroxyl-terminated polyethylene glycol, hydroxyl-terminated polypropylene glycol, hydroxyl-terminated polyethylene glycol-propylene glycol copolymer, amino-terminated polyethylene glycol, amino-terminated polypropylene glycol, amino-terminated polyethylene glycol-propylene glycol copolymer;

[0023] The diisocyanate monomer is one or more of toluene diisocyanate, isophorone diisocyanate, diphenylmethane diisocyanate, dicyclohexylmethane diisocyanate, hexamethylene diisocyanate, and lysine diisocyanate; the dynamic disulfide bond monomer is one or more of 2,2'-dithiobisethanol or 4,4'-bis(hydroxymethyl)-2,2'-bipyridyl disulfide; the supramolecular quadruple hydrogen bond monomer is 2-ureido-4[1H]pyrimidinone; the catalyst is one or more of diisobutyltin dilaurate or triethanolamine; the anhydrous solvent is one or more of N,N-dimethylformamide, N,N-dimethylacetamide, and dimethyl sulfoxide.

[0024] As a further preferred technical solution of the present invention, the solid-state metal battery is a button-type or soft-pack battery, and one, two, or multiple layers of the basic battery units are encapsulated in the solid-state metal battery.

[0025] The preparation method of the solid-state metal battery based on the dynamic supramolecular ion-conductive elastomer of the present invention can achieve the following beneficial effects by adopting the above technical solutions:

[0026] 1) The present invention uses the dynamic supramolecular ion-conductive elastomer as the binder of the solid-state electrolyte and the composite cathode. The binder and the solid-state electrolyte form an integrated cathode / electrolyte structure under the dynamic exchange and recombination effects, enabling the solid-state metal battery to have high ionic conductivity, a wide electrochemical window, a high ion transference number, high strength, excellent toughness, and good interfacial stability with the metal anode.

[0027] 2) The dynamic supramolecular ion-conductive elastomer in the present invention is not only used as the binder of the cathode particles but also as the polymer solid-state electrolyte. The thickness of the solid-state electrolyte is <100 μm. The reversibility of the dynamic supramolecular structure of the binder and the solid-state electrolyte helps to construct a solid-state metal battery with an integrated cathode / ultrathin solid-state electrolyte structure.

[0028] 3) The solid-state metal battery with the integrated cathode / ultrathin solid-state electrolyte structure constructed in the present invention can be stably cycled more than 300 times, and the capacity retention rate can reach more than 80%, and the Coulomb efficiency can reach more than 99%.

[0029] 4) The assembly method of the solid-state battery prepared in the present invention is simple, the structure is controllable, the materials are easy to obtain, the battery has a long cycle life, high safety, high specific capacity, high energy density, and can meet the flexible wearable requirements (foldable, bendable, and rollable), can be batch-produced and assembled, is suitable for industrial biochemical production, and meets the requirements of various energy storage fields at the same time. BRIEF DESCRIPTION OF THE DRAWINGS

[0030] The present invention will be further described in detail below with reference to the accompanying drawings and specific embodiments.

[0031] Figure 1 SEM image of the all-solid-state lithium metal battery of Embodiment 1 of the present invention;

[0032] Figure 2 Long cycle curve graph of the all-solid-state lithium metal battery of Embodiment 1 of the present invention;

[0033] Figure 3 Functional and safety demonstration diagram of the all-solid-state lithium metal battery of Embodiment 1 of the present invention;

[0034] Figure 4 Long cycle curve graph of the solid-state lithium metal battery of Comparative Example 1.

[0035] The realization of the object, functional features and advantages of the present invention will be further described in conjunction with the embodiments with reference to the accompanying drawings. Detailed Description of the Invention

[0036] The following further details the specific embodiments of the present invention with reference to the accompanying drawings. It should be understood that the specific embodiments described herein are only for the purpose of illustrating and explaining the present invention, and are not intended to limit the present invention.

[0037] Unless otherwise defined, the technical terms used in the following embodiments have the same meanings as commonly understood by those skilled in the art to which the present invention pertains. The test reagents used in the following embodiments are all conventional biochemical reagents unless otherwise specified; the experimental methods are all conventional methods unless otherwise specified.

[0038] The dynamic supramolecular ionic conductive elastomer of the present invention can be obtained by compounding a dynamic supramolecular elastomer and an electrolyte salt. The dynamic supramolecular elastomer is prepared by polyaddition reaction of a polyester / polyether type bifunctional monomer, a diisocyanate monomer, an anhydrous solvent, a chain extender, and a catalyst. The specific preparation method can be referred to the journal "Phase-Locked constructing dynamic supramolecular ionic conductive elastomers with superior toughness, autonomous self-healing and recyclability", Jing Chen, Research Square, publication date December 10, 2021", or refer to the Chinese patent with application number 2021116838324. The dynamic supramolecular ionic conductive elastomer has high ionic conductivity, a wide electrochemical window, a high ion transference number, high strength, excellent toughness, and good interfacial stability with a metal negative electrode.

[0039] The dynamic supramolecular ion-conductive elastomer in the present invention is used as a binder for cathode particles in a composite cathode, and also serves as a polymer solid electrolyte between the composite cathode and a metal electrode. The binder and the solid electrolyte are adhered together, and an integrated cathode / ultrathin solid electrolyte solid-state metal battery is constructed relying on the structural reversibility of the dynamic supramolecular ion-conductive elastomer, which can meet the requirements of various energy storage fields such as electric vehicles, flexible electronic products, and aerospace.

[0040] In order to enable those skilled in the art to better understand and implement the technical solutions of the present invention, the present invention will be further described in detail below through specific embodiments.

[0041] Example 1

[0042] The raw materials of the dynamic supramolecular ion-conductive elastomer in this example include: 1 g of dynamic supramolecular elastomer, 350 mg of lithium bis(trifluoromethanesulfonyl)imide, and 30 mL of anhydrous tetrahydrofuran.

[0043] The preparation method of the solid-state metal battery based on the dynamic supramolecular ion-conductive elastomer in this example specifically includes the following steps:

[0044] The first step: Preparation of the dynamic supramolecular elastomer. Take 1 mmol of polytetramethylene ether glycol and add it to a Schlenk flask (maintaining a nitrogen or argon atmosphere in the flask), heat it to 120 °C, perform the vacuum-filling cycle 3 - 5 times to remove the residual moisture in the Schlenk flask, and cool it to 65 °C; dissolve 2.1 mmol of dicyclohexylmethane diisocyanate in a certain amount of anhydrous solvent N,N-dimethylformamide, mix it well and add it to the polytetramethylene ether glycol, then add 0.03 mol of catalyst dibutyltin dilaurate, and stir and react at 65 °C for 1 h; heat it to 80 °C, add an anhydrous dimethyl sulfoxide solution of 0.7 mmol of 2,2'-dithiobisethanol and 0.3 mmol of 2-ureido-4[1H]pyrimidinone to the above reactants, continuously stir at 80 °C for 9 h, and then add a certain amount of methanol and stir for 30 min to ensure that all isocyanate functional groups react completely; pour the reaction product into a glass petri dish or a polytetrafluoroethylene mold, remove a large amount of solvent in a blast oven at 60 °C, and then put it into a vacuum drying oven at 70 °C for 48 h to remove the residual solvent to obtain the dynamic supramolecular elastomer.

[0045] The second step: Preparation of the precursor solution of the dynamic supramolecular ion-conductive elastomer. Take 1 g of dynamic supramolecular elastomer and 350 mg of lithium bis(trifluoromethanesulfonyl)imide, dissolve them in 30 mL of anhydrous tetrahydrofuran, and continuously stir for 24 h to form a transparent, colorless and homogeneous solution.

[0046] Step 3: Preparation of the composite cathode. Lithium iron phosphate cathode particles, super-p, and the precursor solution of the dynamic supramolecular ion-conductive elastomer are dissolved in a certain volume of anhydrous N-methylpyrrolidone according to a solute mass ratio of 7:2:1, and ball-milled for 4 h to form a uniformly dispersed slurry. The slurry is coated on a current collector (aluminum foil or carbon-coated aluminum foil) by processes such as spin coating and blade coating, dried, and cut into pieces to form a composite cathode sheet, or a self-supporting composite cathode sheet. In this step, the dynamic supramolecular ion-conductive elastomer formed by coating the precursor solution and volatilizing the solvent is used as a binder for the lithium iron phosphate cathode particles. The composite cathode sheet is doped with lithium iron phosphate cathode particles and super-p with the binder to form a bonding layer.

[0047] Step 4: Preparation of an all-solid-state lithium metal battery with an integrated cathode / ultrathin solid electrolyte structure. A certain amount of the precursor solution is respectively coated on the surfaces of the composite cathode sheet and the lithium metal anode sheet by processes such as spin coating and blade coating. After the solvent is completely volatilized, a thin layer of dynamic supramolecular ion-conductive elastomer film (also known as a dynamic supramolecular electrolyte film) is formed on the surfaces of the composite cathode sheet and the lithium metal anode sheet respectively. Subsequently, the composite cathode sheet and the lithium metal anode sheet coated with the electrolyte film are face-to-face bonded together with the coated surfaces as the bonding surfaces. The solid electrolyte obtained after bonding is formed by overlapping the two electrolyte films on the composite cathode sheet and the lithium metal anode sheet, with a total thickness of 11 μm (preferably less than 30 μm). Finally, it is encapsulated through a battery encapsulation machine to form a flexible all-solid-state lithium metal battery with an integrated cathode / ultrathin electrolyte structure under the condition that the dynamic supramolecular structure is reversible. In this step, the dynamic supramolecular ion-conductive elastomer formed by coating the precursor solution and volatilizing the solvent is used as the solid electrolyte of the solid-state metal battery.

[0048] In the above steps 3 and 4, the two coatings on the composite cathode sheet are on the same side, which is the bonding surface facing the lithium metal anode sheet. After bonding, based on the reversible characteristics of the dynamic supramolecular ion-conductive elastomer, the binder and the solid electrolyte form an integrated cathode / electrolyte structure under the dynamic exchange and recombination effects.

[0049] It can be seen that Figure 1 in the all-solid-state lithium metal battery prepared in Example 1, the solid electrolyte and the bonding layer form an integrated cathode / electrolyte structure under the dynamic exchange and recombination effects, and a structure in which the solid electrolyte is in close contact with the lithium metal anode; it can be seen that Figure 2 the all-solid-state lithium metal battery prepared in Example 1 can be stably cycled more than 300 times, and the capacity retention rate can reach 80%, and the Coulomb efficiency is more than 99%; it can be seen that Figure 3 the flexible battery prepared in Example 1 based on the dynamic supramolecular ion-conductive elastomer can normally light up an LED lamp, and can still work normally under environments such as folding, rolling, puncturing, and breaking, indicating that the battery has very high safety.

[0050] Example 2

[0051] The raw materials of the dynamic supramolecular ion-conductive elastomer in this example include: 0.5 g of dynamic supramolecular elastomer, 175 mg of lithium bis(fluorosulfonyl)imide, and 15 mL of anhydrous tetrahydrofuran.

[0052] The preparation method of the solid-state metal battery based on the dynamic supramolecular ion-conductive elastomer in this example specifically includes the following steps:

[0053] The first step: Preparation of the dynamic supramolecular elastomer. Take 1 mmol of polytetramethylene glycol and add it to a Schlenk flask (maintaining a nitrogen or argon atmosphere in the flask), heat up to 120 °C, perform vacuum inflation cycles 3 - 5 times to remove residual moisture in the Schlenk flask, and cool down to 65 °C; dissolve 2.1 mmol of isophorone diisocyanate in a certain amount of anhydrous solvent N,N-dimethylformamide, mix well and add it to the polytetramethylene glycol, then add 0.03 mol of catalyst dibutyltin dilaurate, and stir and react at 65 °C for 1 h; heat up to 80 °C, add an anhydrous dimethyl sulfoxide solution of 0.3 mmol of 2,2'-dithiobisethanol and 0.7 mmol of 2-ureido-4[1H]pyrimidinone to the above reactants, continuously stir at 80 °C for 9 h, and then add a certain amount of methanol and stir for 30 min to ensure that all isocyanate functional groups react completely; pour the reaction product into a glass petri dish or a polytetrafluoroethylene mold, remove a large amount of solvent in a 60 °C forced-air oven, and then place it in a vacuum drying oven at 70 °C for 48 h to remove residual solvent, obtaining the dynamic supramolecular elastomer.

[0054] The second step: Preparation of the precursor solution of the dynamic supramolecular ion-conductive elastomer. Take 0.5 g of dynamic supramolecular elastomer and 175 mg of lithium bis(fluorosulfonyl)imide, dissolve them in 15 mL of anhydrous tetrahydrofuran, and continuously stir for 24 h to form a transparent, colorless and homogeneous solution;

[0055] The third step: Preparation of the composite positive electrode. Dissolve lithium iron phosphate positive electrode particles, super-p, and the precursor solution of the dynamic supramolecular ion-conductive elastomer in a certain volume of anhydrous N-methylpyrrolidone according to a solute mass ratio of 6:2:2, ball mill for 4 h to form a uniformly dispersed slurry, coat the slurry on the current collector through a doctor blade, dry it, and cut it into pieces to form a composite positive electrode sheet.

[0056] Step 4: Preparation of an all-solid-state lithium metal battery with an integrated cathode / ultra-thin solid electrolyte structure. A certain amount of precursor solution was respectively coated on the adhesive layer of the composite cathode and the surface of the lithium metal anode. After the solvent completely evaporated, a ultra-thin dynamic supramolecular electrolyte membrane (solid electrolyte) was formed on the surfaces of the composite cathode and the lithium metal anode respectively. Subsequently, the composite cathode with the electrolyte membrane and the lithium metal anode were pasted together, and then the battery was encapsulated by a battery encapsulation machine. Under the condition that the dynamic supramolecular structure was reversible, an all-solid-state lithium metal battery with an integrated cathode / ultra-thin electrolyte structure was formed.

[0057] Example 3

[0058] The raw materials of the dynamic supramolecular ion-conductive elastomer in this example include: 0.5 g of dynamic supramolecular elastomer, 175 mg of sodium bis(trifluoromethanesulfonyl)imide, and 15 mL of anhydrous tetrahydrofuran.

[0059] The preparation method of the solid-state metal battery based on the dynamic supramolecular ion-conductive elastomer in this example specifically includes the following steps:

[0060] Step 1: Preparation of the dynamic supramolecular elastomer. Take 1 mmol of polytetramethylene ether glycol and add it to a Schlenk flask (maintaining a nitrogen or argon atmosphere in the flask), heat it to 120 °C, perform a vacuum-filling cycle 3 - 5 times to remove the residual moisture in the Schlenk flask, and cool it to 65 °C; dissolve 2.1 mmol of dicyclohexyl diisocyanate in a certain amount of anhydrous solvent N,N-dimethylformamide, mix it well and add it to the polytetramethylene ether glycol, then add 0.03 mol of catalyst dibutyltin dilaurate, and stir and react at 65 °C for 1 h; heat it to 80 °C, add an anhydrous dimethyl sulfoxide solution of 0.3 mmol of 2,2'-dithiobisethanol and 0.7 mmol of 2-ureido-4[1H]pyrimidinone to the above reactants, continuously stir at 80 °C for 9 h, and then add a certain amount of methanol and stir for 30 min to ensure that all isocyanate functional groups react completely; pour the reaction product into a glass petri dish or a polytetrafluoroethylene mold, remove a large amount of solvent in a 60 °C forced-air oven, and then put it into a vacuum drying oven at 70 °C for 48 h to remove the residual solvent to obtain the dynamic supramolecular elastomer.

[0061] Step 2: Preparation of the precursor solution of the dynamic supramolecular ion-conductive elastomer. Take 0.5 g of dynamic supramolecular elastomer and 175 mg of sodium bis(trifluoromethanesulfonyl)imide, dissolve them in 15 mL of anhydrous tetrahydrofuran, and continuously stir for 24 h to form a transparent, colorless and homogeneous solution;

[0062] Step 3: Preparation of the composite cathode. Sodium vanadium fluorophosphate cathode particles, super-p, and the precursor solution of the dynamic supramolecular ion-conductive elastomer are dissolved in a certain volume of anhydrous N-methylpyrrolidone according to a solute mass ratio of 7:2:1, and ball-milled for 4 h to form a uniformly dispersed slurry. The slurry is coated on the current collector by a doctor blade, dried, and cut into pieces to form a composite cathode sheet.

[0063] Step 4: Preparation of an all-solid-state sodium metal battery with an integrated cathode / ultrathin solid electrolyte structure. A certain amount of the precursor solution is respectively coated on the adhesive layer of the composite cathode sheet and the surface of the sodium metal anode sheet. After the solvent has completely evaporated, a ultrathin dynamic supramolecular electrolyte membrane (solid electrolyte) is formed on the surfaces of the composite cathode sheet and the sodium metal anode sheet respectively. Subsequently, the composite cathode sheet and the sodium metal anode sheet coated with the electrolyte membrane are pressed together, and then the battery is encapsulated by a battery encapsulation machine, and an all-solid-state sodium metal battery with an integrated cathode / ultrathin electrolyte structure is formed under the condition that the dynamic supramolecular structure is reversible.

[0064] Example 4

[0065] The raw materials of the dynamic supramolecular ion-conductive elastomer in this example include: 1 g of dynamic supramolecular elastomer, 350 mg of lithium bis(trifluoromethanesulfonyl)imide, and 30 mL of anhydrous tetrahydrofuran.

[0066] The preparation method of the solid-state metal battery based on the dynamic supramolecular ion-conductive elastomer in this example specifically includes the following steps:

[0067] Step 1: Preparation of the dynamic supramolecular elastomer. Take 1 mmol of a hydroxyl-terminated polyethylene glycol-propylene glycol copolymer and add it to a Schlenk flask (maintaining a nitrogen or argon atmosphere in the flask), heat to 120 °C, perform 3 - 5 cycles of vacuum pumping and gas filling to remove the residual moisture in the Schlenk flask, and cool to 65 °C; dissolve 2.1 mmol of dicyclohexylmethane diisocyanate in a certain amount of anhydrous solvent N,N-dimethylformamide, mix well and add it to the hydroxyl-terminated polyethylene glycol-propylene glycol copolymer, then add 0.03 mol of the catalyst dibutyltin dilaurate, and stir and react at 65 °C for 1 h; heat to 80 °C, add an anhydrous dimethyl sulfoxide solution of 0.7 mmol of 2,2'-dithiobisethanol and 0.3 mmol of 2-ureido-4[1H]pyrimidinone to the above reactants, continuously stir at 80 °C for 9 h, and then add a certain amount of methanol and stir for 30 min to ensure that all isocyanate functional groups have reacted completely; pour the reaction product into a glass petri dish or a polytetrafluoroethylene mold, remove a large amount of solvent in a 60 °C forced-air oven, and then place it in a vacuum drying oven at 70 °C for 48 h to remove the residual solvent to obtain the dynamic supramolecular elastomer.

[0068] Step 2: Preparation of the precursor solution of the dynamic supramolecular ion-conductive elastomer. Take 1 g of the dynamic supramolecular elastomer and 350 mg of lithium bis(trifluoromethanesulfonyl)imide, dissolve them in 30 mL of anhydrous tetrahydrofuran, and continuously stir for 24 h to form a transparent, colorless and homogeneous solution.

[0069] Step 3: Preparation of the composite cathode. Dissolve lithium cobaltate cathode particles, super-p and the precursor solution of the dynamic supramolecular ion-conductive elastomer in a certain volume of anhydrous N-methylpyrrolidone according to the solute mass ratio of 5:1:4, ball mill for 4 h to form a uniformly dispersed slurry, coat the slurry on the current collector with a doctor blade, dry it, and cut it into pieces to form a composite cathode sheet.

[0070] Step 4: Preparation of the all-solid-state lithium metal battery with an integrated cathode / ultra-thin solid electrolyte structure. Coat a certain amount of the precursor solution on the adhesive layer of the composite cathode sheet and the surface of the lithium metal anode sheet respectively. After the solvent has completely evaporated, a ultra-thin dynamic supramolecular electrolyte membrane (solid electrolyte) is formed on the surface of the composite cathode sheet and the lithium metal anode sheet respectively. Subsequently, the composite cathode sheet and the lithium metal anode sheet covered with the electrolyte membrane are pasted together, and then the battery is encapsulated by a battery encapsulation machine, and an all-solid-state lithium metal battery with an integrated cathode / ultra-thin electrolyte structure is formed under the condition that the dynamic supramolecular structure is reversible.

[0071] Example 5

[0072] The raw materials of the dynamic supramolecular ion-conductive elastomer in this example include: 0.5 g of the dynamic supramolecular elastomer, 175 mg of lithium bis(fluorosulfonyl)imide, and 15 mL of anhydrous tetrahydrofuran.

[0073] The preparation method of the solid-state metal battery based on the dynamic supramolecular ion-conductive elastomer in this example specifically includes the following steps:

[0074] Step 1: Preparation of dynamic supramolecular elastomer. Add 1 mmol of hydroxyl-terminated polyethylene glycol-propylene glycol copolymer into a Schlenk flask (maintaining a nitrogen or argon atmosphere in the flask), heat to 120 °C, perform 3 - 5 cycles of vacuum evacuation and gas filling to remove residual moisture in the Schlenk flask, and then cool to 65 °C; dissolve 2.1 mmol of dicyclohexylmethane diisocyanate in a certain amount of anhydrous solvent N,N-dimethylformamide, mix well and add it to the hydroxyl-terminated polyethylene glycol-propylene glycol copolymer, then add 0.03 mol of catalyst dibutyltin dilaurate, and stir and react at 65 °C for 1 h; heat to 80 °C, add an anhydrous dimethyl sulfoxide solution of 0.7 mmol of 2,2'-dithiobisethanol and 0.3 mmol of 2-ureido-4[1H]pyrimidinone to the above reactants, continuously stir at 80 °C for 9 h, and then add a certain amount of methanol and stir for 30 min to ensure that all isocyanate functional groups react completely; pour the reaction product into a glass petri dish or a polytetrafluoroethylene mold, remove a large amount of solvent in a blast drying oven at 60 °C, and then place it in a vacuum drying oven at 70 °C for 48 h to remove residual solvent, obtaining a dynamic supramolecular elastomer.

[0075] Step 2: Preparation of the precursor solution of dynamic supramolecular ion-conductive elastomer. Take 0.5 g of dynamic supramolecular elastomer and 175 mg of lithium bis(fluorosulfonyl)imide, dissolve them in 15 mL of anhydrous tetrahydrofuran, and continuously stir for 24 h to form a transparent, colorless and homogeneous solution;

[0076] Step 3: Preparation of the composite cathode. Dissolve lithium nickel cobalt manganese oxide cathode particles, super-p and the precursor solution of dynamic supramolecular ion-conductive elastomer in a certain volume of anhydrous N-methylpyrrolidone according to a solute mass ratio of 5:1:4, ball mill for 4 h to form a uniformly dispersed slurry, coat the slurry on the current collector through a doctor blade, dry it, and cut it into pieces to form a composite cathode sheet.

[0077] Step 4: Preparation of an all-solid-state lithium metal battery with an integrated cathode / ultra-thin solid electrolyte structure. Coat a certain amount of the precursor solution on the adhesive layer of the composite cathode sheet and the surface of the lithium metal anode sheet respectively. After the solvent completely volatilizes, a ultra-thin dynamic supramolecular electrolyte membrane (solid electrolyte) is formed on the surfaces of the composite cathode sheet and the lithium metal anode sheet respectively. Then, the composite cathode sheet covered with the electrolyte membrane and the lithium metal anode sheet are pasted together, and then the battery is encapsulated by a battery encapsulator, and under the condition of reversibility of the dynamic supramolecular structure, an all-solid-state lithium metal battery with an integrated cathode / ultra-thin electrolyte structure is formed.

[0078] For the electrochemical performance of the solid-state metal batteries prepared in the above Examples 1 - 5, see Table 1.

[0079] Table 1

[0080] Example Cyclic stability Capacity retention Coulombic efficiency 1 350 81.2％ >99％ 2 325 83％ >99％ 3 400 85％ >99％ 4 350 80.7％ >99％ 5 500 87％ >99％

[0081] Figure 1 It can be seen that the solid-state metal battery of the present application can be stably cycled more than 300 times, and the capacity retention rate can reach 80%, and the Coulomb efficiency is more than 99%. The performance is excellent. Among them, the effect of Example 5 is the best.

[0082] In order to explore the influence of the dynamic supramolecular ion-conducting elastomer on the battery performance, Comparative Example 1 was proposed according to the same preparation method and process parameters as in Example 1. Only the PVDF material was used to replace the dynamic supramolecular ion-conducting elastomer (DSICE) in the present invention as the binder, and the solid electrolyte still used the dynamic supramolecular ion-conducting elastomer. Its electrochemical performance was tested, and the results are as Figure 4 shown. It can be seen that the battery capacity is significantly lower than that when the dynamic supramolecular ion-conducting elastomer is used as the binder.

[0083] It should be noted here that in the process of preparing the solid electrolyte of the present invention, it is the best operation to coat the precursor solution of the dynamic supramolecular ion-conducting elastomer on both the composite positive electrode sheet and the metal negative electrode sheet (double-sided coating), and then after volatilizing the solvent, the composite positive electrode sheet and the metal negative electrode sheet are bonded face to face with their respective coating surfaces together, and the performance of the obtained solid-state metal battery is the best. When the composite positive electrode sheet and the metal negative electrode sheet are coated on a single piece, it must be coated on the surface of the lithium metal negative electrode to improve the interfacial compatibility with the lithium metal negative electrode by using the wettability of the precursor solution. When the composite positive electrode sheet and the metal negative electrode sheet are fixed at a suitable distance, the precursor solution is poured (using the siphon capillary effect) into the gap between the composite positive electrode sheet and the metal negative electrode sheet, and a solid electrolyte can also be formed by volatilizing the solvent. However, this operation will cause the solvent to volatilize incompletely, or there are bubbles in the poured precursor solution, thus affecting the performance of the battery.

[0084] Although the specific embodiments of the present invention have been described above, those skilled in the art should understand that these are only examples, and various changes or modifications can be made to this embodiment without departing from the principle and essence of the present invention. The protection scope of the present invention is only defined by the appended claims.

Claims

1. A preparation method of a solid-state metal battery based on a dynamic supramolecular ion-conductive elastomer, characterized in that, It includes the following steps: S1. Prepare the precursor solution of the dynamic supramolecular ionic conductive elastomer: Dissolve the electrolyte salt and the dynamic supramolecular elastomer in an anhydrous solvent, stir at room temperature to form a homogeneous precursor solution, and divide the precursor solution into two parts, A and B; S2. Prepare the composite positive electrode sheet: Using the current collector as the substrate, dissolve the positive electrode particles, the conductive agent and part A of the precursor solution in an anhydrous solvent and form a uniform slurry through ball milling or stirring, then coat the slurry onto the current collector, and volatilize the solvent to obtain the composite positive electrode sheet. After the solvent of part A of the precursor solution is volatilized, a dynamic supramolecular ionic conductive elastomer is formed, and this dynamic supramolecular ionic conductive elastomer is used as a binder to adhere the positive electrode particles to the surface of the current collector to form a bonding layer; S3. Prepare the solid electrolyte: Coat part B of the precursor solution on the bonding layer of the composite positive electrode sheet and the metal negative electrode sheet respectively. After the solvent is completely volatilized, stack the composite positive electrode sheet and the metal negative electrode sheet with their coated surfaces facing each other to form a basic battery unit of an integrated positive electrode / solid electrolyte structure, where the dynamic supramolecular ionic conductive elastomer formed after the solvent of part B of the precursor solution is volatilized serves as the solid electrolyte, and the thickness of this solid electrolyte is 1 μm to 1 mm; S4. Battery encapsulation: Encapsulate the basic battery unit through a battery encapsulator to finally form a solid-state metal battery; In step S1, the electrolyte salt is at least one of lithium salt, sodium salt, potassium salt, magnesium salt, and calcium salt. The electrolyte salt accounts for 5% - 70% of the mass of the dynamic supramolecular elastomer. The anhydrous solvent is one or more of anhydrous tetrahydrofuran, dichloromethane, chloroform, acetonitrile, and N-methylpyrrolidone. The mass-volume ratio of the dynamic supramolecular elastomer to the anhydrous solvent is 3% - 50%.

2. The preparation method of the solid-state metal battery based on the dynamic supramolecular ion-conductive elastomer according to claim 1, characterized in that, The lithium salt is lithium bis(trifluoromethanesulfonyl)imide, lithium trifluoromethanesulfonyl-perfluorobutanesulfonylimide, lithium trifluoromethanesulfonyl-perfluoropropanesulfonylimide, lithium bis(fluorosulfonyl)imide, lithium hexafluorophosphate, lithium tetrafluoroborate, lithium bis(oxalato)borate, lithium oxalodifluoroborate, lithium difluorophosphate, 4,5-dicyano-2-trifluoromethylimidazole lithium, lithium perchlorate or lithium chloride; the sodium salt is sodium bis(trifluoromethanesulfonyl)imide, sodium perchlorate, sodium bis(fluorosulfonyl)imide, sodium chloride, sodium nitrate, sodium fluorosilicate or sodium phthalate; the potassium salt is potassium bis(trifluoromethanesulfonyl)imide, potassium bis(fluorosulfonyl)imide, potassium chloride, potassium nitrate or potassium hydrogen phthalate.

3. The preparation method of the solid-state metal battery based on the dynamic supramolecular ion-conductive elastomer according to claim 1, characterized in that, In step S2, the mass ratio of the positive electrode particles, the conductive agent to the dynamic supramolecular ionic conductive elastomer formed from part A of the precursor solution is 2:1:7 - 8:1:

1.

4. The preparation method of the solid-state metal battery based on the dynamic supramolecular ion-conductive elastomer according to claim 1, characterized in that, In step S2, the positive electrode particles are one or more mixtures of lithium cobaltate, lithium iron phosphate, lithium manganate, lithium titanate, nickel cobalt manganese, sodium fluorophosphate vanadate, Prussian blue, potassium fluorophosphate vanadate; the conductive agent is one or more mixtures of super-p, acetylene black, carbon nanotubes, and graphene; the anhydrous solvent is one or more mixtures of N,N-dimethylformamide, N,N-dimethylacetamide, dimethyl sulfoxide, dichloromethane, chloroform, tetrahydrofuran, and N-methylpyrrolidone.

5. The preparation method of the solid-state metal battery based on the dynamic supramolecular ion-conductive elastomer according to claim 1, characterized in that, The metal negative electrode sheet is one or more of lithium metal, sodium metal, potassium metal, magnesium metal, and calcium metal.

6. The preparation method of the solid-state metal battery based on the dynamic supramolecular ion-conductive elastomer according to claim 1, characterized in that, The thickness of the solid electrolyte shown is 1 μm to 100 μm.

7. The preparation method of the solid-state metal battery based on the dynamic supramolecular ion-conductive elastomer according to claim 1, characterized in that, The dynamic supramolecular elastomer in step S1 is prepared from the following raw materials: A polyester / polyether type bifunctional monomer, a diisocyanate monomer, an anhydrous solvent, a chain extender, and a catalyst; wherein: The molar ratio of the polyester / polyether type bifunctional monomer to the diisocyanate monomer is 1:2 to 2:1; the chain extender includes a dynamic disulfide bond monomer and a supramolecular quadruple hydrogen bond monomer, and the molar ratio of the dynamic disulfide bond monomer to the supramolecular quadruple hydrogen bond monomer is 10:0 to 0:10; the catalyst accounts for 0.01% to 1% of the total mass of the polyester / polyether type bifunctional monomer and the diisocyanate monomer; The polyester / polyether type bifunctional monomer includes one or more of polycaprolactone diol, poly(tetrahydrofuran-caprolactone) diol, hydroxyl-terminated poly(tetrahydrofuran), amino-terminated poly(tetrahydrofuran), hydroxyl-terminated polyethylene glycol, hydroxyl-terminated polypropylene glycol, hydroxyl-terminated polyethylene glycol-propylene glycol copolymer, amino-terminated polyethylene glycol, amino-terminated polypropylene glycol, amino-terminated polyethylene glycol-propylene glycol copolymer; The diisocyanate monomer is one or more of toluene diisocyanate, isophorone diisocyanate, diphenylmethane diisocyanate, dicyclohexylmethane diisocyanate, hexamethylene diisocyanate, lysine diisocyanate; The dynamic disulfide bond monomer is one or more of 2,2'-dithiobisethanol or 4,4'-bis(hydroxymethyl)-2,2'-bipyridyl sulfide; The supramolecular quadruple hydrogen bond monomer is 2-ureido-4[1H]pyrimidinone; The catalyst is one or more of diisobutyltin dilaurate or triethanolamine; The anhydrous solvent is one or more of N,N-dimethylformamide, N,N-dimethylacetamide, dimethyl sulfoxide.

8. The preparation method of the solid-state metal battery based on the dynamic supramolecular ion-conductive elastomer according to any one of claims 1 to 7, characterized in that, The solid-state metal battery is a coin-type or soft-pack battery, and one, two, or more layers of the basic battery units are encapsulated in the solid-state metal battery.

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