CN116053595A - A method for the preparation of solid-state metal batteries based on dynamic supramolecular ion-conducting elastomers - Google Patents

Abstract

A preparation method of a solid-state metal battery based on a dynamic supramolecular ion-conducting elastomer, comprising: dissolving an electrolyte salt and a dynamic supramolecular elastomer in an anhydrous solvent, stirring at room temperature to form a uniform precursor solution, and dividing the precursor solution into A , Part B; with the current collector as the substrate, the positive electrode particles, the conductive agent and the precursor solution of Part A are dissolved in an anhydrous solvent to obtain a slurry and coated on the current collector, and the composite positive electrode sheet is obtained after drying the volatile solvent; the composite positive electrode The adhesive layer of the sheet and the metal negative electrode sheet are respectively coated with B parts of the precursor solution, and the composite positive electrode sheet and the metal negative electrode sheet are bonded together with the coated surface as the bonding surface to form an integrated positive electrode/solid electrolyte structure; The positive electrode/solid electrolyte structure is used as the basic battery unit, which is packaged by a battery packaging machine to obtain a solid metal battery. The solid metal battery prepared by the invention has excellent electrochemical performance, mechanical performance and safety performance, and meets the needs of various energy storage fields.

Description

A method for the preparation of solid-state metal batteries based on dynamic supramolecular ion-conducting elastomers

technical field

The invention relates to the application technical field of dynamic supramolecular ion conductors, in particular to a method for preparing a solid metal battery based on dynamic supramolecular ion conductive elastomers.

Background technique

Solid-state batteries have the advantages of high specific energy, high safety, long life, high reliability, small size, and flexibility. They can meet various needs in energy storage fields such as electric vehicles, flexible electronic products, and aerospace. An important direction for the development of energy sources. Solid-state batteries replace liquid electrolytes and separators with solid-state electrolytes, which can fundamentally solve the safety problems caused by the volatility, leakage and combustion of traditional liquid electrolytes, and at the same time reduce the volume by 40% and the mass by 25%. Therefore, it is considered to be the It is an important way to achieve the goal of increasing the energy density of power batteries to 500Wh kg ^-1 . Among them, solid-state batteries, which replace liquid organic electrolytes with solid electrolytes, have become a key technology in the field of next-generation energy storage. Among the common solid-state electrolytes, polymer solid-state 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 and high safety.

The polymer solid-state electrolyte is composed of a polymer matrix and a lithium salt. Its ion transport mainly depends on two processes: polar groups such as CO, C=O, and C≡N on the polymer chain segment dissociate the lithium salt, and The movement of the amorphous segment on the polymer segment promotes Li ⁺ to undergo a repetitive "coordination-dissociation" process to achieve ion transport, thereby providing high ionic conductivity. However, the current polymer solid-state electrolytes still have the following shortcomings: a narrow electrochemical stability window, which limits the energy density of solid-state batteries; poor mechanical properties, which cannot prevent metal dendrites from penetrating the electrolyte and causing battery short circuits; Both compliance and safety performance need to be improved.

Contents of the invention

Based on this, the present invention provides a method for preparing a solid-state metal battery based on a dynamic supramolecular ion-conducting elastomer, to solve the electrochemical performance, mechanical performance, safety performance, etc. Raised technical issues.

To achieve the above object, the invention provides a method for preparing a solid-state metal battery based on a dynamic supramolecular ion-conducting elastomer, which comprises the following steps:

S1. Precursor for preparing dynamic supramolecular ion-conducting elastomers:

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

S2, preparation of composite positive electrode sheet:

Using the current collector as the substrate, dissolve the positive electrode particles, conductive agent and A part of the precursor solution in an anhydrous solvent, and form a uniform slurry by ball milling or stirring, and coat it on the current collector, and volatilize the solvent to obtain a composite positive electrode sheet, in which A part The precursor solution forms a dynamic supramolecular ion-conducting elastomer after volatilizing the solvent, and the dynamic supramolecular ion-conducting 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, preparation of solid electrolyte:

The bonding layer of the composite positive electrode sheet and the metal negative electrode sheet are respectively coated with B parts of the precursor solution. After the solvent is completely volatilized, the composite positive electrode sheet and the metal negative electrode sheet are pasted together with their respective coating surfaces as the bonding faces to form a composite positive electrode sheet. The basic battery unit with an integrated positive electrode/solid electrolyte structure, in which the dynamic supramolecular ion conductive elastomer formed by part B precursor solution after volatilizing the solvent is used as a solid electrolyte, and the thickness of the solid electrolyte is 1 μm to 1 mm;

S4. Battery packaging:

The basic battery unit is packaged by a battery packaging machine to form a solid metal battery.

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

As a further preferred technical solution of the present invention, the lithium salt is lithium bistrifluoromethanesulfonyl imide, lithium trifluoromethanesulfonyl-perfluorobutylsulfonimide, trifluoromethanesulfonyl-perfluoropropane Lithium sulfonyl imide, lithium bisfluorosulfonyl imide, lithium hexafluorophosphate, lithium tetrafluoroborate, lithium dioxalate borate, lithium oxalate difluoroborate, lithium difluorophosphate, 4,5-dicyano-2-trifluoro Methylimidazole lithium, lithium perchlorate or lithium chloride; the sodium salt is sodium bistrifluoromethanesulfonimide, sodium perchlorate, sodium bisfluorosulfonimide, sodium chloride, sodium nitrate, fluorine Sodium silicate or sodium phthalate; the potassium salt is potassium bistrifluoromethylsulfonimide, potassium bisfluorosulfonimide, potassium chloride, potassium nitrate or potassium hydrogen phthalate; the ammonium The salt is tetraethylammonium tetrafluoroborate, ammonium chloride or ammonium nitrate.

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 ion conductive elastomer formed from the precursor solution A is 2:1:7-8:1:1.

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

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, and calcium metal.

As a further preferred technical solution of the present invention, the solid electrolyte shown has a thickness of 1 μm to 100 μm.

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 difunctional monomer, diisocyanate monomer, anhydrous solvent, chain extender and catalyst ,in:

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

The polyester/polyether type difunctional monomers include polycaprolactone diol, polytetrahydrofuran-polycaprolactone diol, hydroxyl-terminated polytetrahydrofuran, amino-terminated polytetrahydrofuran, hydroxyl-terminated polyethylene glycol, and hydroxyl-terminated polytetrahydrofuran One or more of 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 species; the dynamic disulfide bond monomer is one or more of 2,2'-dithiodiethanol or 4,4'-bis(hydroxymethyl)-2,2'-bipyridine 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, and dimethylsulfoxide.

As a further preferred technical solution of the present invention, the solid metal battery is a button or pouch battery, and the solid metal battery is packaged with one, two or more layers of the basic battery unit.

The preparation method of the solid-state metal battery based on the dynamic supramolecular ion-conducting elastomer of the present invention can achieve the following beneficial effects by adopting the above-mentioned technical scheme:

1) The present invention utilizes a dynamic supramolecular ion-conducting elastomer as a binder for a solid electrolyte and a composite positive electrode, and the binder and the solid electrolyte form an integrated positive electrode/electrolyte structure under dynamic exchange and recombination, so that the solid metal battery has High ionic conductivity, wide electrochemical window, high ion migration number, high strength, excellent toughness, and good interface stability with metal negative electrodes;

2) The dynamic supramolecular ion-conducting elastomer in the present invention is not only used as the binding agent of the positive electrode particles, but also as the polymer solid electrolyte, the thickness of the solid electrolyte<100um, the binding agent and the solid electrolyte utilize the dynamic supramolecular structure Reversibility contributes to the construction of solid-state metal batteries with an integrated positive electrode/ultra-thin solid-state electrolyte structure;

3) The solid metal battery with integrated positive electrode/ultra-thin solid electrolyte structure constructed in the present invention can be stably cycled for more than 300 cycles, and the capacity retention rate can reach more than 80%, and the Coulombic efficiency can reach more than 99%;

4) The solid-state battery prepared by the present invention has simple assembly method, controllable structure, easy-to-obtain materials, long battery cycle life, high safety, high specific capacity, high energy density, and can meet the needs of flexible wear (foldable, foldable Bending, rollable), can be prepared and assembled in batches, suitable for industrial biochemical production, and at the same time meet the needs of various energy storage fields.

Description of drawings

The present invention will be further described in detail below in conjunction with the accompanying drawings and specific embodiments.

Fig. 1 is the SEM figure of the all-solid-state lithium metal battery of embodiment 1 of the present invention;

Fig. 2 is the long cycle graph of the all-solid lithium metal battery of embodiment 1 of the present invention;

Fig. 3 is a diagram showing the functionality and safety of the all-solid-state lithium metal battery of Example 1 of the present invention;

FIG. 4 is a long cycle graph of the solid-state lithium metal battery of Comparative Example 1.

The realization of the purpose, function and advantages of the present invention will be further described in conjunction with the embodiments and with reference to the accompanying drawings.

Detailed ways

Specific embodiments of the present invention will be described in detail below in conjunction with the accompanying drawings. It should be understood that the specific embodiments described here are only used to illustrate and explain the present invention, and are not intended to limit the present invention.

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

The dynamic supramolecular ion-conducting elastomer of the present invention can be obtained by compounding a dynamic supramolecular elastomer and an electrolyte salt, wherein the dynamic supramolecular elastomer is composed of a polyester/polyether type difunctional monomer, a diisocyanate monomer, Water solvent, chain extender, and catalyst are prepared by polyaddition reaction. For specific preparation methods, please refer to the journal "Phase-Locked constructing dynamic supramolecular ionic conductive elastomers with superiortoughness, autonomous self-healing and recyclability", Jing Chen, ResearchSquare, open date 2021 December 10, 2011, or refer to the Chinese patent application number 2021116838324. Dynamic supramolecular ion-conducting elastomers have high ionic conductivity, wide electrochemical window, high ion transfer number, high strength, excellent toughness and Good interfacial stability with metal anodes.

The dynamic supramolecular ion-conducting elastomer in the present invention is used as a binder for the positive electrode particles in the composite positive electrode, and also as a polymer solid electrolyte between the composite positive electrode and the metal electric electrode, and the binder and the solid electrolyte are bonded on the At the same time, relying on the structural reversibility of dynamic supramolecular ion-conducting elastomers to build an integrated positive electrode/ultra-thin solid-state electrolyte solid-state metal battery, which can meet the needs of various energy storage fields such as electric vehicles, flexible electronics, and aerospace.

In order to allow those skilled in the art to better understand and realize the technical solution of the present invention, the present invention will be further described in detail through specific examples below.

Example 1

The raw materials of the dynamic supramolecular ion-conducting elastomer in this embodiment include: 1 g of the dynamic supramolecular elastomer, 350 mg of lithium bistrifluoromethylsulfonimide, and 30 mL of anhydrous tetrahydrofuran.

In this embodiment, the method for preparing a solid-state metal battery based on a dynamic supramolecular ion-conducting elastomer specifically includes the following steps:

The first step: preparation of dynamic supramolecular elastomer. Take 1 mmol of polytetramethylene ether glycol and add it to a Schllenk bottle (keep a nitrogen or argon atmosphere in the bottle), raise the temperature to 120°C, vacuumize and inflate for 3 to 5 times, remove the residual moisture in the Schllenk bottle, and cool down to 65°C ; Dissolve 2.1mmol dicyclohexylmethane diisocyanate in a certain amount of anhydrous solvent N,N-dimethylformamide, add in polytetramethylene ether glycol after mixing, then add 0.03mol catalyst dilaurel Acetate diisobutyltin, stirred and reacted at 65°C for 1h; warmed up to 80°C, mixed 0.7mmol of 2,2'-dithiodiethanol and 0.3mmol of 2-ureido-4[1H]pyrimidinone Add the base sulfoxide solution to the above reactants, continue stirring at 80°C for 9 hours, then add a certain amount of methanol and stir for 30 minutes to ensure that all the isocyanate functional groups are completely reacted; ℃ blast oven to remove a large amount of solvent, and then put it into a vacuum drying oven at 70 ℃ for 48h to remove residual solvent to obtain a dynamic supramolecular elastomer.

The second step: the preparation of the precursor solution of the dynamic supramolecular ion-conducting elastomer. Take 1g of dynamic supramolecular elastomer and 350mg of lithium bistrifluoromethanesulfonimide, dissolve in 30mL of anhydrous tetrahydrofuran, and keep stirring for 24h to form a transparent, colorless and uniform solution.

The third step: preparation of the composite positive electrode. Dissolve the precursor solution of lithium iron phosphate cathode particles, super-p and dynamic supramolecular ion-conducting elastomer in a certain volume of anhydrous N-methylpyrrolidone at a solute-mass ratio of 7:2:1, and ball mill for 4 hours to form a dispersed Uniform slurry, the slurry is coated on the current collector (aluminum foil or carbon-coated aluminum foil) by spin coating, scrape coating and other processes, dried, and cut into pieces to form a composite positive electrode sheet, or a self-supporting composite positive electrode sheet. In this step, the dynamic supramolecular ion conductive elastomer formed by coating the precursor solution and volatilizing the solvent is used as the binder of the lithium iron phosphate positive electrode particles, and the binder is doped with the binder on the composite positive electrode sheet. Lithium iron phosphate positive electrode particles, super -p forms a tie layer.

The fourth step: the preparation of an all-solid-state lithium metal battery with an integrated positive electrode/ultra-thin solid-state electrolyte structure. A certain amount of precursor liquid is coated on the surface of the composite positive electrode and the lithium metal negative electrode by spin coating, scrape coating, etc. After the solvent is completely volatilized, an ultra-thin layer is formed on the surface of the composite positive electrode and the lithium metal negative electrode. The dynamic supramolecular ion-conducting elastomer membrane (also known as dynamic supramolecular electrolyte membrane), and then the composite positive electrode sheet covered with the electrolyte membrane and the lithium metal negative electrode sheet are pasted together with the coating surface as the bonding face, and after bonding, the obtained The solid electrolyte is composed of two electrolyte membranes on the composite positive electrode sheet and the lithium metal negative electrode sheet, with a total thickness of 11um (preferably less than 30um), and finally packaged by a battery packaging machine. The dynamic supramolecular structure is reversible Under certain conditions, a soft-pack all-solid-state lithium metal battery with an integrated positive electrode/ultra-thin electrolyte structure is formed. In this step, the dynamic supramolecular ion-conducting elastomer formed by coating the precursor solution and volatilizing the solvent is used as a solid electrolyte for a solid metal battery.

In the third step and the fourth step of the above steps, the two coatings on the composite positive electrode sheet are on the same side, which is the bonding surface facing the lithium metal negative electrode sheet. After bonding, based on the reversible properties of the dynamic supramolecular ion-conducting elastomer, the binder and the solid electrolyte form an integrated positive electrode/electrolyte structure under dynamic exchange and recombination.

It can be seen from Figure 1 that in the solid-state lithium metal battery prepared in Example 1, the solid electrolyte and the bonding layer form an integrated positive electrode/electrolyte structure under the action of dynamic exchange and recombination, and the close contact between the solid electrolyte and the lithium metal negative electrode Structure; It can be seen from Figure 2 that the solid-state lithium metal battery prepared in Example 1 can be stably cycled for more than 300 cycles, and the capacity retention rate can reach 80%, and the Coulombic efficiency can reach more than 99%; it can be seen from Figure 3 that the preparation of Example 1 The pouch battery prepared based on the dynamic supramolecular ion conductive elastomer can normally light up the LED light, and can still work normally in the environment of folding, rolling, puncturing, breaking, etc., which shows that the battery has very high safety .

Example 2

The raw materials of the dynamic supramolecular ion-conducting elastomer in this embodiment include: 0.5 g of the dynamic supramolecular elastomer, 175 mg of lithium bisfluorosulfonyl imide, and 15 mL of anhydrous tetrahydrofuran.

In this embodiment, the method for preparing a solid-state metal battery based on a dynamic supramolecular ion-conducting elastomer specifically includes the following steps:

The first step: preparation of dynamic supramolecular elastomer. Take 1 mmol of polytetramethylene ether glycol and add it to a Schllenk bottle (keep a nitrogen or argon atmosphere in the bottle), raise the temperature to 120°C, vacuumize and inflate for 3 to 5 times, remove the residual moisture in the Schllenk bottle, and cool down to 65°C ; Dissolve 2.1mmol isophorone diisocyanate in a certain amount of anhydrous solvent N,N-dimethylformamide, add in polytetramethylene ether glycol after mixing, then add 0.03mol catalyst dilaurel Acetate diisobutyltin, stirred at 65°C for 1h; warmed up to 80°C, mixed 0.3mmol of 2,2'-dithiodiethanol and 0.7mmol of 2-ureido-4[1H]pyrimidinone in anhydrous dimethyl Add the base sulfoxide solution to the above reactants, continue stirring at 80°C for 9 hours, then add a certain amount of methanol and stir for 30 minutes to ensure that all the isocyanate functional groups are completely reacted; ℃ blast oven to remove a large amount of solvent, and then put it into a vacuum drying oven at 70 ℃ for 48h to remove residual solvent to obtain a dynamic supramolecular elastomer.

The second step: the preparation of the precursor solution of the dynamic supramolecular ion-conducting elastomer. Take 0.5g of dynamic supramolecular elastomer and 175mg of lithium bisfluorosulfonimide, dissolve in 15mL of anhydrous tetrahydrofuran, and keep stirring for 24h to form a transparent, colorless and uniform solution;

The third step: preparation of the composite positive electrode. Dissolve the precursor solution of lithium iron phosphate cathode particles, super-p and dynamic supramolecular ion-conducting elastomer in a certain volume of anhydrous N-methylpyrrolidone according to the solute mass ratio of 6:2:2, and ball mill for 4 hours to form a uniformly dispersed The slurry is coated on the current collector by a scraper, dried, and cut into pieces to form a composite positive electrode sheet.

The fourth step: the preparation of an all-solid-state lithium metal battery with an integrated positive electrode/ultra-thin solid-state electrolyte structure. Apply a certain amount of precursor solution to the bonding layer of the composite positive electrode and the surface of the lithium metal negative electrode, and after the solvent is completely volatilized, a layer of ultra-thin dynamic supramolecular electrolyte is formed on the surface of the composite positive electrode and the lithium metal negative electrode. membrane (solid electrolyte), and then paste the composite positive electrode sheet covered with the electrolyte membrane and the lithium metal negative electrode sheet together, and then use the battery packaging machine to package the battery, and under the condition of reversible dynamic supramolecular structure, an integrated positive electrode/ All-solid-state lithium metal battery with ultra-thin electrolyte structure.

Example 3

The raw materials of the dynamic supramolecular ion-conducting elastomer in this embodiment include: 0.5 g of the dynamic supramolecular elastomer, 175 mg of sodium bistrifluoromethanesulfonimide, and 15 mL of anhydrous tetrahydrofuran.

In this embodiment, the method for preparing a solid-state metal battery based on a dynamic supramolecular ion-conducting elastomer specifically includes the following steps:

The first step: preparation of dynamic supramolecular elastomer. Take 1 mmol of polytetramethylene ether glycol and add it to a Schllenk bottle (keep a nitrogen or argon atmosphere in the bottle), raise the temperature to 120°C, vacuumize and inflate for 3 to 5 times, remove the residual moisture in the Schllenk bottle, and cool down to 65°C ; Dissolve 2.1mmol dicyclohexyl diisocyanate in a certain amount of anhydrous solvent N,N-dimethylformamide, add in polytetramethylene ether glycol after mixing, then add 0.03mol catalyst dilauric acid Diisobutyltin, stirred and reacted at 65°C for 1h; warmed up to 80°C, mixed 0.3mmol of 2,2'-dithiodiethanol and 0.7mmol of 2-ureido-4[1H]pyrimidinone in anhydrous dimethyl Add the sulfoxide solution to the above reactants, stir continuously at 80°C for 9h, then add a certain amount of methanol and stir for 30min to ensure that all the isocyanate functional groups are completely reacted; A large amount of solvent was removed in a blast oven, and then it was placed in a vacuum drying oven at 70°C for 48 hours to remove residual solvent to obtain a dynamic supramolecular elastomer.

The second step: the preparation of the precursor solution of the dynamic supramolecular ion-conducting elastomer. Take 0.5g of dynamic supramolecular elastomer and 175mg of bistrifluoromethanesulfonimide sodium, dissolve it in 15mL of anhydrous tetrahydrofuran, and keep stirring for 24 hours to form a transparent, colorless and uniform solution;

The third step: preparation of the composite positive electrode. Dissolve the precursor solution of sodium vanadium fluorophosphate positive electrode particles, super-p and dynamic supramolecular ion-conducting elastomer in a certain volume of anhydrous N-methylpyrrolidone according to the solute mass ratio of 7:2:1, and ball mill for 4 hours to form a dispersed Uniform slurry, the slurry is coated on the current collector by a scraper, dried, and cut into pieces to form a composite positive electrode sheet.

The fourth step: the preparation of an all-solid-state sodium metal battery with an integrated positive electrode/ultra-thin solid-state electrolyte structure. Apply a certain amount of precursor solution to the bonding layer of the composite positive electrode and the surface of the sodium metal negative electrode, and after the solvent is completely volatilized, a layer of ultra-thin dynamic supramolecular electrolyte is formed on the surface of the composite positive electrode and the sodium metal negative electrode. membrane (solid electrolyte), and then paste the composite positive electrode sheet covered with the electrolyte membrane and the sodium metal negative electrode sheet together, and then perform battery packaging by a battery packaging machine, and form an integrated positive electrode/ All-solid-state sodium metal battery with ultrathin electrolyte structure.

Example 4

The raw materials of the dynamic supramolecular ion-conducting elastomer in this embodiment include: 1 g of the dynamic supramolecular elastomer, 350 mg of lithium bistrifluoromethanesulfonimide, and 30 mL of anhydrous tetrahydrofuran.

In this embodiment, the method for preparing a solid-state metal battery based on a dynamic supramolecular ion-conducting elastomer specifically includes the following steps:

The first step: preparation of dynamic supramolecular elastomer. Take 1 mmol of hydroxyl-terminated polyethylene glycol-propylene glycol copolymer and add it to a Schllenk bottle (keep a nitrogen or argon atmosphere in the bottle), raise the temperature to 120°C, and vacuumize and inflate for 3 to 5 times to remove residual moisture in the Schllenk bottle, then cool down to 65°C; Dissolve 2.1mmol dicyclohexylmethane diisocyanate in a certain amount of anhydrous solvent N,N-dimethylformamide, mix well and add to hydroxyl-terminated polyethylene glycol-propylene glycol copolymer, and then add 0.03 mol catalyst diisobutyltin dilaurate, stirred at 65°C for 1h; heated to 80°C, mixed 0.7mmol of 2,2'-dithiodiethanol and 0.3mmol of 2-ureido-4[1H]pyrimidinone Add anhydrous dimethyl sulfoxide solution to the above-mentioned reactant, continue stirring at 80°C for 9 hours, then add a certain amount of methanol and stir for 30 minutes to ensure that all isocyanate functional groups are completely reacted; 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 in a vacuum drying oven at 70°C for 48h to remove the residual solvent to obtain a dynamic supramolecular elastomer.

The second step: the preparation of the precursor solution of the dynamic supramolecular ion-conducting elastomer. Take 1g of dynamic supramolecular elastomer and 350mg of lithium bistrifluoromethanesulfonimide, dissolve in 30mL of anhydrous tetrahydrofuran, and keep stirring for 24h to form a transparent, colorless and uniform solution.

The third step: preparation of the composite positive electrode. Dissolve the precursor solution of lithium cobaltate cathode particles, super-p and dynamic supramolecular ion-conducting elastomer in a certain volume of anhydrous N-methylpyrrolidone according to the solute mass ratio of 5:1:4, and ball mill for 4 hours to form a uniformly dispersed The slurry is coated on the current collector by a scraper, dried, and cut into pieces to form a composite positive electrode sheet.

The fourth step: the preparation of an all-solid-state lithium metal battery with an integrated positive electrode/ultra-thin solid-state electrolyte structure. Apply a certain amount of precursor solution to the bonding layer of the composite positive electrode and the surface of the lithium metal negative electrode, and after the solvent is completely volatilized, a layer of ultra-thin dynamic supramolecular electrolyte is formed on the surface of the composite positive electrode and the lithium metal negative electrode. membrane (solid electrolyte), and then paste the composite positive electrode sheet covered with the electrolyte membrane and the lithium metal negative electrode sheet together, and then use the battery packaging machine to package the battery, and under the condition of reversible dynamic supramolecular structure, an integrated positive electrode/ All-solid-state lithium metal battery with ultra-thin electrolyte structure.

Example 5

The raw materials of the dynamic supramolecular ion-conducting elastomer in this embodiment include: 0.5 g of the dynamic supramolecular elastomer, 175 mg of lithium bisfluorosulfonyl imide, and 15 mL of anhydrous tetrahydrofuran.

In this embodiment, the method for preparing a solid-state metal battery based on a dynamic supramolecular ion-conducting elastomer specifically includes the following steps:

The first step: preparation of dynamic supramolecular elastomer. Take 1 mmol of hydroxyl-terminated polyethylene glycol-propylene glycol copolymer and add it to a Schllenk bottle (keep a nitrogen or argon atmosphere in the bottle), raise the temperature to 120°C, and vacuumize and inflate for 3 to 5 times to remove residual moisture in the Schllenk bottle, then cool down to 65°C; Dissolve 2.1mmol dicyclohexylmethane diisocyanate in a certain amount of anhydrous solvent N,N-dimethylformamide, mix well and add to hydroxyl-terminated polyethylene glycol-propylene glycol copolymer, and then add 0.03 mol catalyst diisobutyltin dilaurate, stirred at 65°C for 1h; heated to 80°C, mixed 0.7mmol of 2,2'-dithiodiethanol and 0.3mmol of 2-ureido-4[1H]pyrimidinone Add anhydrous dimethyl sulfoxide solution to the above-mentioned reactant, continue stirring at 80°C for 9 hours, then add a certain amount of methanol and stir for 30 minutes to ensure that all isocyanate functional groups are completely reacted; 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 in a vacuum drying oven at 70°C for 48h to remove the residual solvent to obtain a dynamic supramolecular elastomer.

The second step: the preparation of the precursor solution of the dynamic supramolecular ion-conducting elastomer. Take 0.5g of dynamic supramolecular elastomer and 175mg of lithium bisfluorosulfonimide, dissolve in 15mL of anhydrous tetrahydrofuran, and keep stirring for 24h to form a transparent, colorless and uniform solution;

The third step: preparation of the composite positive electrode. Dissolve the precursor solution of nickel-cobalt-manganese-lithium cathode particles, super-p and dynamic supramolecular ion-conducting elastomer in a certain volume of anhydrous N-methylpyrrolidone at a solute mass ratio of 5:1:4, and ball mill for 4 hours to form a dispersed Uniform slurry, the slurry is coated on the current collector by a scraper, dried, and cut into pieces to form a composite positive electrode sheet.

The fourth step: the preparation of an all-solid-state lithium metal battery with an integrated positive electrode/ultra-thin solid-state electrolyte structure. Apply a certain amount of precursor solution to the bonding layer of the composite positive electrode and the surface of the lithium metal negative electrode, and after the solvent is completely volatilized, a layer of ultra-thin dynamic supramolecular electrolyte is formed on the surface of the composite positive electrode and the lithium metal negative electrode. membrane (solid electrolyte), and then paste the composite positive electrode sheet covered with the electrolyte membrane and the lithium metal negative electrode sheet together, and then use the battery packaging machine to package the battery, and under the condition of reversible dynamic supramolecular structure, an integrated positive electrode/ All-solid-state lithium metal battery with ultra-thin electrolyte structure.

See Table 1 for the electrochemical performances of the solid metal batteries prepared in Examples 1-5 above.

Table 1

Example cycle 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%

It can be seen from Fig. 1 that the solid metal battery of the present application can be stably cycled for more than 300 cycles, and the capacity retention rate can reach 80%, the Coulombic efficiency can reach more than 99%, and the performance is excellent. Among them, the effect of Example 5 is the best.

In order to explore the impact of dynamic supramolecular ion-conducting elastomers on battery performance, comparative example 1 is proposed according to the same preparation method and process parameters as in Example 1, and only PVDF materials are used to replace dynamic supramolecular ion-conducting elastomers (DSICE) in the present invention. ) as a binder, the solid electrolyte still uses dynamic supramolecular ion-conducting elastomers, and its electrochemical performance is tested. The results are shown in Figure 4. It can be seen that the battery capacity is significantly lower than that of using dynamic supramolecular ion-conducting elastomers dose capacity.

What needs to be explained here is that in the process of preparing the solid electrolyte in the present invention, the precursor solution of the dynamic supramolecular ion-conducting elastomer is coated (double-sheet coating) with the composite positive electrode sheet and the metal negative electrode sheet, and then after the solvent is volatilized, the The composite positive electrode sheet and the metal negative electrode sheet are pasted together with their respective coated surfaces as bonding faces, which is the optimal operation, and the performance of the obtained solid metal battery is the best. When the composite positive electrode sheet and the metal negative electrode sheet are coated in a single piece, they must be coated on the surface of the lithium metal negative electrode to use the wettability of the precursor solution to improve the interface compatibility with the lithium metal negative electrode. When the composite positive electrode sheet and the metal negative electrode sheet are fixed at an appropriate 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, but , this operation will cause the solvent to evaporate uncleanly, or there will be air bubbles in the perfused precursor solution, which will affect the performance of the battery.

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 the embodiments without departing from the principle and essence of the present invention. The scope of protection is limited only by the appended claims.

Claims (9)

1. A method for preparing a solid-state metal battery based on dynamic supramolecular ion-conducting elastomer, characterized in that, comprising the following steps: S1. Precursor for preparing dynamic supramolecular ion-conducting elastomers: Dissolve the electrolyte salt and dynamic supramolecular elastomer in an anhydrous solvent, stir at room temperature to form a uniform precursor solution, and divide the precursor solution into two parts, A and B; S2, preparation of composite positive electrode sheet: Using the current collector as the substrate, dissolve the positive electrode particles, conductive agent and A part of the precursor solution in an anhydrous solvent, and form a uniform slurry by ball milling or stirring, and coat it on the current collector, and volatilize the solvent to obtain a composite positive electrode sheet, in which A part The precursor solution forms a dynamic supramolecular ion-conducting elastomer after volatilizing the solvent, and the dynamic supramolecular ion-conducting 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, preparation of solid electrolyte: The bonding layer of the composite positive electrode sheet and the metal negative electrode sheet are respectively coated with B parts of the precursor solution. After the solvent is completely volatilized, the composite positive electrode sheet and the metal negative electrode sheet are pasted together with their respective coating surfaces as the bonding faces to form a composite positive electrode sheet. The basic battery unit with an integrated positive electrode/solid electrolyte structure, in which the dynamic supramolecular ion conductive elastomer formed by part B precursor solution after volatilizing the solvent is used as a solid electrolyte, and the thickness of the solid electrolyte is 1 μm to 1 mm; S4. Battery packaging: The basic battery unit is packaged by a battery packaging machine to form a solid metal battery. 2. the preparation method of the solid-state metal battery based on dynamic supramolecular ion conductive elastomer according to claim 1, is characterized in that, in step S1, described electrolyte salt is lithium salt, sodium salt, potassium salt, zinc salt, At least one of magnesium salt and calcium salt, the electrolyte salt accounts for 5% to 70% of the mass of the dynamic supramolecular elastomer; the anhydrous solvent is anhydrous tetrahydrofuran, dichloromethane, chloroform, acetonitrile, N - one or more of methylpyrrolidone, the mass volume ratio of the dynamic supramolecular elastomer to the anhydrous solvent is 3% to 50%. 3. the preparation method of the solid-state metal battery based on dynamic supramolecular ion conductive elastomer according to claim 2, is characterized in that, described lithium salt is two trifluoromethanesulfonylimide lithium, trifluoromethanesulfonyl -Lithium perfluorobutanesulfonimide, lithium trifluoromethanesulfonyl-perfluoropropylsulfonimide, lithium bisfluorosulfonimide, lithium hexafluorophosphate, lithium tetrafluoroborate, lithium dioxalate borate, difluorooxalate Lithium borate, lithium difluorophosphate, lithium 4,5-dicyano-2-trifluoromethylimidazolium, lithium perchlorate or lithium chloride; the sodium salt is bistrifluoromethanesulfonylimide sodium, high Sodium chlorate, sodium bisfluorosulfonimide, sodium chloride, sodium nitrate, sodium fluorosilicate or sodium phthalate; the potassium salt is potassium bistrifluoromethylsulfonimide, potassium bisfluorosulfonyl Potassium amine, potassium chloride, potassium nitrate or potassium hydrogen phthalate; the ammonium salt is tetraethylammonium tetrafluoroborate, ammonium chloride or ammonium nitrate. 4. the preparation method of the solid-state metal battery based on dynamic supramolecular ion-conducting elastomer according to claim 1, is characterized in that, in step S2, the dynamic supramolecular formed by positive electrode particle, conductive agent and by A part precursor solution The mass ratio of the ion conductive elastomer is 2:1:7˜8:1:1. 5. the preparation method of the solid-state metal battery based on dynamic supramolecular ion conductive elastomer according to claim 1, is characterized in that, in step S2, described positive pole particle is lithium cobaltate, lithium iron phosphate, lithium manganate, One or more mixtures of lithium titanate, nickel cobalt manganese, sodium vanadium fluorophosphate, Prussian blue, and potassium vanadium phosphate; the conductive agent is one or more of super-p, acetylene black, carbon nanotubes, and graphene A variety of mixtures; the anhydrous solvent is N,N-dimethylformamide, N,N-dimethylacetamide, dimethyl sulfoxide, dichloromethane, chloroform, tetrahydrofuran, N-methylpyrrolidone one or more mixtures. 6. the preparation method of the solid-state metal battery based on dynamic supramolecular ion conductive elastomer according to claim 1, is characterized in that, described metal negative plate is lithium metal, sodium metal, potassium metal, magnesium metal, calcium metal one or more. 7 . The method for preparing a solid-state metal battery based on a dynamic supramolecular ion-conducting elastomer according to claim 1 , wherein the solid electrolyte has a thickness of 1 μm˜100 μm. 8. The method for preparing a solid-state metal battery based on dynamic supramolecular ion-conducting elastomers according to claim 1, wherein the dynamic supramolecular elastomers in step S1 are prepared from the following raw materials: Polyester/polyether type difunctional monomers, diisocyanate monomers, anhydrous solvents, chain extenders and catalysts; of which: The molar ratio of the polyester/polyether difunctional monomer to the diisocyanate monomer is 1:2 to 2:1; the chain extender includes a dynamic disulfide bond monomer and a supramolecular quartet bond monomer, the molar ratio of the dynamic disulfide bond monomer and the supramolecular quadruple hydrogen bond monomer is 10:0～0:10; the catalyst accounts for the polyester/polyether type bifunctional monomer and the two 0.01% to 1% of the total mass of isocyanate monomer; The polyester/polyether type difunctional monomers include polycaprolactone diol, polytetrahydrofuran-polycaprolactone diol, hydroxyl-terminated polytetrahydrofuran, amino-terminated polytetrahydrofuran, hydroxyl-terminated polyethylene glycol, and hydroxyl-terminated polytetrahydrofuran One or more of 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 kind; The dynamic disulfide bond monomer is one or more of 2,2'-dithiodiethanol or 4,4'-bis(hydroxymethyl)-2,2'-bipyridine 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, and dimethylsulfoxide. 9. according to the preparation method of the solid-state metal battery based on dynamic supramolecular ion conductive elastomer according to any one of claims 1 to 8, it is characterized in that, described solid-state metal battery is button type or pouch battery, and described The basic battery unit is packaged in one layer, two layers or multiple times in the solid metal battery.

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