A method of making an in-situ solidified battery

Abstract

The application provides a preparation method of an in-situ solidified battery, monomer A in a polyaddition reaction is mixed into a positive electrode slurry or a negative electrode slurry or a separator coating slurry, the monomer A is uniformly prepositioned into an electrode sheet or a separator through homogenizing coating, monomer B is injected into the battery cell in a liquid injection mode, and the monomer B is polymerized with the monomer A uniformly prepositioned in the electrode sheet or the separator to obtain an in-situ solidified battery. The application solves the uneven polymerization caused by uneven temperature distribution of the battery cell or different local microenvironments in the traditional in-situ solidification method, improves the uniformity of the in-situ solidified electrolyte, and further improves the overall performance of the solidified battery.

Description

TECHNICAL FIELD

[0001] The present application relates to the technical field of solid-state lithium batteries and lithium-sulfur batteries, and more particularly to a preparation method of an in-situ solidified battery. BACKGROUND

[0002] Currently, large-scale commercialized lithium secondary batteries contain a large amount of organic carbonate liquid electrolyte. Due to its low boiling point and flammability, deformation or even electrolyte leakage may occur when the battery is squeezed or collided during use, which may cause the battery to burn or explode, posing a significant safety hazard. Solid-state batteries are considered an effective means to solve the safety performance of the battery core. Among them, polymer electrolytes have become a research hotspot in recent years due to their small interfacial impedance and flame retardancy. However, due to the complex process, they have not quickly entered mass production.

[0003] To improve the preparation process of polymer lithium batteries and improve production efficiency, researchers have proposed an in-situ solidification technology. For example, Chinese Patent Publication No. CN105914405A discloses a preparation method for preparing a full-solid-state polymer electrolyte by in-situ ring-opening polymerization of an epoxy compound and its application in a full-solid-state lithium battery. The patent proposes using liquid epoxy compounds, lithium salts, and battery additives as precursors, which are injected into the battery interior. Then, under heating conditions, the precursors are in-situ ring-opening solidified into an integrated full-solid-state polymer battery. Chinese Patent Publication No. CN108493486A discloses a preparation method for in-situ solidification of a solid-state battery. Acrylate and initiator are dissolved in electrolyte and injected into the battery interior. Under heating conditions, the initiator initiates the polymerization of the original substance into an integrated gel polymer battery. Chinese Patent Publication No. CN111533851A discloses a preparation method for a polymer electrolyte and its application in a full-solid-state battery. Small molecules containing double bonds, ethylene glycol acrylate, and initiators are mixed and injected into the interface of a solid-state battery. The mixture is heated to initiate polymerization, forming an electrode-electrolyte integrated full-solid-state battery. Chinese Patent Publication No. CN111540956A discloses an in-situ solidification electrode micro-interface processing technology. Isocyanate and polypropylene glycol are dissolved in electrolyte and injected into the battery interior to polymerize into an integrated battery, reducing the electrode-electrolyte interfacial impedance.

[0004] In summary, the traditional in-situ solidification method introduces one or more monomer solutions into the battery interior and initiates the self-polymerization, copolymerization, or blending of the monomers through heat, electricity, or other methods. However, due to the uneven distribution of the thermal field and the different local micro-environments inside the battery, the polymerization of the monomers is difficult to maintain uniformity, leading to local overcharging or overdischarging of the battery, which affects the overall performance of the solid-state battery core. SUMMARY

[0005] Therefore, the present application aims to provide a preparation method of in-situ solidified battery, which mixes monomer A in the polyaddition reaction into the positive and negative electrode slurry or the separator coating slurry, uniformly pre-disposes monomer A into the electrode sheet or the separator through homogenizing coating, and then injects monomer B into the battery cell in the form of liquid injection to polymerize with monomer A uniformly pre-disposed in the electrode sheet or the separator, thereby obtaining the in-situ solidified battery. The present application solves the uneven polymerization caused by uneven temperature distribution or different local micro-environment in the traditional in-situ solidification method, improves the uniformity of in-situ solidified electrolyte, and further improves the overall performance of the solidified battery.

[0006] The present application provides a preparation method of in-situ solidified battery, which comprises the following steps:

[0007] a) pre-disposing monomer A in the battery assembly, and assembling the battery cell;

[0008] b) injecting a solution containing monomer B into the battery cell obtained in step a), and then performing infiltration and polymerization to obtain the in-situ solidified battery; the polymerization is a polyaddition reaction of monomer A and monomer B.

[0009] Preferably, the battery assembly in step a) comprises one or more of the positive electrode sheet, the negative electrode sheet and the separator.

[0010] Preferably, the way of pre-disposing monomer A in the positive electrode sheet is to mix monomer A into the positive electrode slurry to prepare the positive electrode sheet;

[0011] The way of pre-disposing monomer A in the negative electrode sheet is to mix monomer A into the negative electrode slurry to prepare the negative electrode sheet.

[0012] The way of pre-disposing monomer A in the separator is to mix monomer A into the separator coating liquid to prepare the separator.

[0013] The positive electrode active material of the electrode sheet is one or more of lithium cobaltate, lithium nickel cobaltate, lithium manganate, lithium nickel manganate, ternary lithium nickel cobalt manganate, lithium nickel cobalt aluminum, lithium nickel cobalt manganese aluminum, lithium manganese iron phosphate, lithium iron phosphate, sulfur, lithium sulfide; the negative electrode material of the electrode sheet is one or more of metal lithium, metal lithium alloy, graphite, hard carbon, molybdenum disulfide, lithium titanate, graphene, silicon, silicon carbon, silicon oxygen, silicon oxygen carbon negative electrode; and the separator is one or more of commercial PP, PE, PI, cellulose membrane, PET porous membrane and ceramic coating membrane.

[0014] Preferably, monomer A in the polyaddition reaction in step b) is a monomer containing isocyanate group, and monomer B in the polyaddition reaction is a monomer containing active hydrogen group.

[0015] Or,

[0016] The monomer A of the polyaddition reaction is a monomer containing active hydrogen groups, and the monomer B of the polyaddition reaction is a monomer containing isocyanate groups.

[0017] Preferably, the monomer containing isocyanate groups is selected from one or more of toluene diisocyanate, isophorone diisocyanate, diphenylmethane diisocyanate, polymeric diphenylmethane diisocyanate, 4,4'-dicyclohexylmethane diisocyanate, hexamethylene diisocyanate, biuret triisocyanate, lysine diisocyanate, xylylene diisocyanate, tetramethylxylene diisocyanate, 1,5-naphthalene diisocyanate, 3,3'-dimethyl-4,4'-diphenyl diisocyanate, 2,2,4-trimethylcyclohexyl diisocyanate, triphenylmethane triisocyanate, 4,4',4"-triphenylthiophosphoric acid triisocyanate, cyclohexane dimethylene diisocyanate, 4,4'-dicyclohexylmethane diisocyanate, polymethylene polyphenyl polyisocyanate, 4,4'-diphenyl diisocyanate, norbornane diisocyanate, p-phenylene diisocyanate, 3,3'-dimethyl-4,4'-diphenylmethane diisocyanate, and C-MDI polyisocyanate and diisocyanate trimer.

[0018] Preferably, the monomer containing active hydrogen groups is selected from one or more of polyhexanediole glycol, polycarbonate glycol, polyhexanediole-1,4-butanediol glycol, polyethylene glycol, polypropylene glycol, polyethylene-polypropylene glycol copolyether, polytetrahydrofuran ether glycol, polytetrahydrofuran epoxy propane copolyether, trihydroxy polyether, ethylene glycol, diethylene glycol, propylene glycol, glycerol, 1,4-butanediol, diethylene glycol, neopentyl glycol, 1,6-hexanediol, trimethylolpropane, propylene glycol, glycerol, 1,4-cyclohexanediol, hydroquinone bis(beta-hydroxyethyl) ether, hydrogenated bisphenol A, dihydroxyethyl terephthalate, resorcinol dihydroxyethyl ether, glycerol alpha-allyl ether, trimethylolpropane monoallyl ether, pentaerythritol, diethyltoluene diamine, 3,3'-dichloro-4,4-diamino-diphenyl methane, diamino diphenyl methane, 3,5-diamino p-chlorobenzoic acid isobutyl ester, polyether diamine, dimethylthio toluene diamine, diethyl toluene diamine, 4,4'-methylene bis(3-chloro-2,6-diethyl aniline), ethanolamine, diethanolamine, triethanolamine, triisopropanolamine, N,N-bis(2-hydroxypropyl) aniline, polyurethane, adipic acid, azelaic acid, sebacic anhydride, isophthalic acid, terephthalic acid, and dimethyl terephthalate.

[0019] Preferably, the molar ratio of isocyanate groups to active hydrogen groups in the polyaddition reaction is (1-20):1.

[0020] Preferably, the solution components in step b) are monomer B, solvent, and lithium salt, and no solvent can be selected when monomer B is liquid.

[0021] The lithium salt is selected from one or more of lithium bistrifluoromethylsulfonylimide, lithium triflate, lithium bis(oxalato)borate, lithium bisfluorosulfonylimide, lithium hexafluoroarsenate, lithium tetrafluoroborate, lithium perchlorate, and lithium hexafluorophosphate.

[0022] The solvent is selected from one or more of vinyl carbonate, fluorovinyl carbonate, propylene carbonate, dimethyl carbonate, diethyl carbonate, methyl ethyl carbonate, butylene carbonate, methyl propyl carbonate, methyl formate, ethyl formate, propyl formate, butyl formate, ethyl acetate, propyl acetate, butyl acetate, methyl propionate, ethyl propionate, butyl propionate, methyl butyrate, ethyl butyrate, propyl butyrate, delta-valerolactone, tetrahydrofuran, 2-methyltetrahydrofuran, 4-methyl-1,3-dioxolane, 2-methyl-1,3-dioxolane, ethylene glycol dimethyl ether, and 1,3 dioxolane, sulfolane, dimethyl sulfoxide.

[0023] The mass ratio of the polymer, the lithium salt, and the solvent in the solid-state battery is (5-95):(5-30):(0-80).

[0024] Preferably, the infiltration time in step b) is 6h-24h.

[0025] Preferably, the polymerization temperature in step b) is 20℃-85℃, and the time is 10h-30h.

[0026] The purpose of the present application is to provide a preparation method of an in-situ solid-state battery. In the present application, monomer A in a polyaddition reaction is mixed into a positive or negative electrode slurry or a separator coating slurry, monomer A is uniformly prepositioned into an electrode sheet or a separator by homogenizing and coating, and monomer B is injected into the inside of the battery cell in a liquid injection manner, polymerized with monomer A uniformly prepositioned in the electrode sheet or the separator, and an in-situ solid-state battery is obtained. The present application solves the problem of uneven polymerization caused by uneven temperature distribution or different local microenvironments in the traditional in-situ solidification method, improves the uniformity of the in-situ solidified electrolyte, and further improves the overall performance of the solid-state battery. BRIEF DESCRIPTION OF DRAWINGS

[0027] Figures 1-20 The first cycle charge-discharge curves (see a in each figure, respectively) and the capacity and coulombic efficiency retention curves at different cycles (see b in each figure, respectively) of the solid-state batteries of Examples 1-20 and Comparative Examples 1-20 are shown in the following tables:

[0028] Figure 21 The SEM images of the positive electrode material surfaces of the two in-situ solidification methods of Example 1 (see a-1 and a-2) and Comparative Example 1 (see b-1 and b-2) are shown in the following tables:

[0029] Figure 22 The S and N element distribution maps of the positive electrode sheet cross sections of the two in-situ solidification methods of Example 1 and Comparative Example 1 are shown in the following tables:

[0030] Figure 23 The distribution diagrams of S and N elements on the surface of the positive electrode sheet for two in-situ curing methods, Example 1 and Comparative Example 1, are shown. Detailed Implementation

[0031] The technical solution of the present invention will be clearly and completely described below with reference to the embodiments of the present invention. Obviously, the described embodiments are only some embodiments of the present invention, and not all embodiments. Based on the embodiments of the present invention, all other embodiments obtained by those of ordinary skill in the art without creative effort are within the scope of protection of the present invention.

[0032] This invention provides a method for preparing an in-situ solid-state battery, comprising the following steps:

[0033] a) Pre-place cell A in the battery pack and assemble the battery cell;

[0034] b) Inject a solution including monomer B into the cell obtained in step a) for impregnation, and then polymerize to obtain an in-situ solid-state battery; the polymerization is a polyaddition reaction of monomer A and monomer B.

[0035] This invention first pre-places cell A in the battery assembly to assemble the battery cell. In this invention, the battery assembly preferably includes one or more of a positive electrode, a negative electrode, and a separator.

[0036] In a preferred embodiment of the present invention, the battery assembly is a positive electrode sheet. Based on this, the positive electrode sheet is prepared by mixing the monomer A into the positive electrode slurry. The mass ratio of the monomer A to the positive electrode slurry is preferably (0.1~1):10, more preferably (0.3~0.8):10.

[0037] This invention does not impose any particular limitation on the cathode slurry; any cathode slurry well-known to those skilled in the art for preparing solid-state batteries can be used. In a preferred embodiment of this invention, the cathode slurry contains 50 wt% of the solvent NMP, and the solid component ratio is LiCo. 0.1 Ni 0.8 Mn 0.1 O2:PVDF:conductive carbon black = 8:1:1; In this invention, monomer A is mixed into the above positive electrode slurry and stirred evenly, then coated and dried to obtain a blended positive electrode.

[0038] In a preferred embodiment of the present invention, the battery assembly is a negative electrode sheet. Based on this, the method of pre-placing the monomer A on the negative electrode sheet is to prepare the negative electrode sheet by mixing the monomer A into the negative electrode slurry. The mass ratio of the monomer A to the negative electrode slurry is preferably (0.1~1):10, more preferably (0.3~0.8):10.

[0039] The negative electrode slurry of the present application is not particularly limited, and the negative electrode slurry for preparing a solid-state battery known to those skilled in the art can be used. In a preferred embodiment of the present application, the negative electrode slurry contains 50 wt% of solvent NMP, and the ratio of solid components is graphite: PVDF: conductive carbon black = 9:3:7; the monomer A is mixed into the above negative electrode slurry and stirred uniformly, and a blended electrode is obtained after coating, drying, etc.

[0040] In a preferred embodiment of the present application, the battery component is a separator, and the monomer A is fixed on the separator by mixing the monomer A into a separator coating solution to prepare the separator; the mass ratio of the monomer A to the separator coating solution is preferably (0.05-0.5):1.05, and more preferably (0.1-0.3):1.05.

[0041] The separator coating solution of the present application is not particularly limited, and the separator coating solution for preparing a solid-state battery known to those skilled in the art can be used. In a preferred embodiment of the present application, the separator coating solution contains polyvinylidene fluoride (PVDF) and ethylene glycol dimethyl ether (DME) in a mass ratio of 0.05:1; the monomer A is mixed into the above separator coating solution and stirred uniformly, and a monomer-coated separator is prepared by coating on the surface of the separator.

[0042] The monomer A in the polyaddition reaction is mixed into the positive and negative electrode slurries or the separator in the present application, and a pole piece or a separator containing uniformly distributed monomer A is obtained, and the battery cell is further assembled. The process of assembling the battery cell in the present application is not particularly limited, and the technical solution known to those skilled in the art, i.e., assembling in a glove box filled with inert gas, can be used; the inert gas is preferably argon.

[0043] Then, an electrolyte solution containing monomer B and electrolyte salt is injected into the above battery cell, and infiltration is performed, and a solid-state battery in situ is obtained after polymerization.

[0044] In the present application, the polymerization is a polyaddition reaction of the monomer A and the monomer B; the polyaddition reaction has no small molecule by-product.

[0045] In the present application, the monomer A of the polyaddition reaction is a monomer containing an isocyanate group, and the monomer B of the polyaddition reaction is a monomer containing a active hydrogen group.

[0046] Or,

[0047] The monomer A of the polyaddition reaction is a monomer containing an active hydrogen group, and the monomer B of the polyaddition reaction is a monomer containing an isocyanate group.

[0048] That is, the monomers A, B have two cases: ① A is a monomer containing isocyanate group, and B is a monomer containing active hydrogen group; ② A is a monomer containing active hydrogen group, and B is a monomer containing isocyanate group.

[0049] In the present application, the monomer containing isocyanate group is preferably selected from one or more of toluene diisocyanate (TDI), isophorone diisocyanate (IPDI), diphenylmethane diisocyanate (MDI), polymeric MDI (PAPI), 4,4'-dicyclohexylmethane diisocyanate (HMDI), hexamethylene diisocyanate (HDI), biuret triisocyanate produced by reacting HDI with water, lysine diisocyanate (LDI), xylylene diisocyanate (XDI), tetramethylxylene diisocyanate (TMXDI), 1,5-naphthalene diisocyanate (NDI), 3,3'-dimethyl-4,4'-diphenyl diisocyanate (TODI), 2,2,4-trimethylcyclohexyl diisocyanate (TMDI), triphenylmethane triisocyanate (TTI), 4,4',4"-triphenylthiophosphoric acid triisocyanate (TPTI), cyclohexane dimethylene diisocyanate (H6XDI), 4,4'-dicyclohexylmethane diisocyanate (H 12 MDI), polymethylene polyphenyl polyisocyanate (PAPI), 4,4'-diphenyl diisocyanate (DBDI), norbornane diisocyanate (NDI), p-phenylene diisocyanate (PPDI), 3,3'-dimethyl-4,4'-diphenylmethane diisocyanate (DMMDI), C-MDI, and trimers of diisocyanates (such as MDI trimer, trimer of HDI), more preferably isophorone diisocyanate (IPDI), hexamethylene diisocyanate (HDI), diphenylmethane diisocyanate (MDI), toluene diisocyanate (TDI), trimer of toluene diisocyanate (TDI), cyclohexane dimethylene diisocyanate (H6XDI), or trimer of diphenylmethane diisocyanate (MDI). The present application does not have special limitation on the source of the monomer containing isocyanate group, and any commercially available or self-made product of the above diisocyanates, triisocyanates, and self-polymerization products (including dimers, trimers, and polymers) known to those skilled in the art can be used.

[0050] In the present application, the monomer containing active hydrogen group is preferably selected from one or more of polyadipic acid glycol (such as polyethylene adipate, polypropylene adipate, polybutylene adipate, polyhexylene adipate, polyglycerol adipate, polyadipic acid glycol, polyterephthalic acid glycol, etc.), polycarbonate diol (PCDL), polybutylene adipate diol (PBA), polyethylene glycol (PEG), polypropylene glycol (PPG), PEG-PPG copolyether, polytetramethylene ether glycol (PTMG), polytetramethylene ether glycol-propylene oxide copolyether (PTMG-PPG), trihydroxy polyether, ethylene glycol, diethylene glycol, propylene glycol, glycerol, 1,4-butanediol, diethylene glycol, neopentyl glycol, 1,6-hexanediol, trimethylolpropane (TMP), propylene glycol, glycerol, 1,4-cyclohexanediol, hydroquinone bis(β-hydroxyethyl) ether (HQEE), hydrogenated bisphenol A, terephthalic acid dihydroxyethyl ester (BHET), resorcinol dihydroxyethyl ether (HER), glycerol α-allyl ether, trimethylolpropane monoallyl ether, pentaerythritol, diethyltoluene diamine, 3,3'-dichloro-4,4-diamino-diphenyl methane (MOCA), diamino diphenyl methane (MDA), 3,5-diamino-p-chlorobenzoic acid isobutyl ester (DD-1604), polyether diamine, dimethylthio toluene diamine (DMTDA), diethyl toluene diamine (DETDA), 4,4'-methylene bis(3-chloro-2,6-diethyl aniline) (MCDEA), ethanolamine, diethanolamine, triethanolamine, triisopropanolamine, N,N-bis(2-hydroxypropyl) aniline, polyurethane, adipic acid (AA), azelaic acid (AZA), sebacic anhydride (CSA), isophthalic acid, terephthalic acid, and dimethyl terephthalate (DMTP), more preferably polycarbonate diol (PCDL), polybutylene adipate diol (PBA), trihydroxy polyether, polyethylene glycol (PEG), polyether diamine, polyurethane, or terephthalic acid. The present application does not have special limitation on the source of the monomer containing active hydrogen group, and any commercially available or self-made product of the above-mentioned polyol (including -OH and -SH), diamine or polyamine (including primary amine and tertiary amine), alcohol amine, phenol, carboxylic acid group, amide group, urea group, and carbamate group known to those skilled in the art can be used.

[0051] In the present application, the active hydrogen-containing substances are mainly divided into oligomers and small molecule compounds; wherein, the oligomers mainly include: oligomer polyols, such as polyester polyols, polyether polyols, poly-ε-caprolactone polyols, other oligomer polyols, such as grafted polymer polyols or copolymer polyols, castor oil and the corresponding mercapto alcohol oligomers of the above hydroxyl polyol oligomers, such as bis-mercapto-polyethylene glycol (HS-PEG-SH) and the like; the polyester polyols mainly include polyadipic acid diols, such as polyethylene glycol adipate, polypropylene glycol adipate, polybutylene glycol adipate, poly-pentylene glycol adipate, polyhexylene glycol adipate, polyglycerol adipate, polyphthalic acid diol, polyterephthalic acid diol and the like; the polyether polyols mainly include polypropylene oxide ether polyols and polytetrahydrofuran polyols and copolyether polyols, such as polyethylene glycol (PEG), polypropylene glycol (PPG), PEG-PPG copolyether, polytetrahydrofuran ether glycol (PTMG), polytetrahydrofuran epoxy propane copolyether (PTMG-PPG) and the like; the other oligomer polyols mainly include polyolefin polyols, polycarbonate polyols, polyacrylate polyols; the active hydrogen-containing small molecule polyols mainly include ethylene glycol, diethylene glycol, propylene glycol, glycerol, 1,4-butanediol, diethylene glycol, neopentyl glycol, 1,6-hexanediol, trimethylolpropane (TMP), propylene glycol, glycerol, 1,4-cyclohexanediol, hydroquinone bis(β-hydroxyethyl) ether (HQEE), hydrogenated bisphenol A, terephthalic acid dihydroxyethyl ester (BHET), resorcinol dihydroxyethyl ether (HER), glycerol α-allyl ether, trimethylolpropane monoallyl ether, pentaerythritol; the active hydrogen-containing small molecule polyamines mainly include diethyl toluene diamine, 3,3'-dichloro-4,4-diamino-diphenyl methane (MOCA), diamino diphenyl methane (MDA), 3,5-diamino-p-chlorobenzoic acid isobutyl ester (DD-1604), dimethylthio toluene diamine (DMTDA), diethyl toluene diamine (DETDA), 4,4'-methylene bis(3-chloro-2,6-diethyl aniline) (MCDEA) and the like; the active hydrogen-containing small molecule polyol amines mainly include ethanolamine, diethanolamine, triethanolamine, triisopropanolamine, N,N-bis(2-hydroxypropyl) aniline and the like; the active hydrogen-containing small molecule polycarboxylic acids mainly include adipic acid (AA) and also azelaic acid (AZA), sebacic anhydride (CSA), isophthalic acid, terephthalic acid and terephthalic acid dimethyl ester (DMTP) and the like; the monomers containing amide groups, urea groups and carbamate groups are mainly oligomers or polymers containing such groups, including: polyamides, polyimides, polyureas, polyurethanes and the like.

[0052] In the present application, the molar ratio of isocyanate groups to active hydrogen groups in the polyaddition reaction (all of monomer A and monomer B) is preferably (1-20):1.

[0053] In the present application, the lithium salt is preferably selected from one or more of lithium bis-trifluoromethanesulfonylimide (LiTFSI), lithium trifluoromethanesulfonate (LiCF3SO3), lithium diformate borate (LiDFOB), lithium bisfluorosulfonylimide (LiFSI), lithium hexafluoroarsenate, lithium tetrafluoroborate (LiBF4), lithium perchlorate (LiClO4), lithium hexafluorophosphate (LiPF6), more preferably LiDFOB, LiTFSI or LiPF6. The present application does not have special restrictions on the source of the electrolyte salt, and commercially available or self-made products known to those skilled in the art can be used. In the present application, the mass fraction of the electrolyte salt in the electrolyte is preferably 20% to 95%.

[0054] In the present application, when the monomer B is a liquid, the solution can be composed of monomer B and electrolyte salt; in addition, the solution also includes a solvent; the solvent is preferably one or more of ethylene carbonate (EC), propylene carbonate (PC), dimethyl carbonate (DMC), diethyl carbonate (DEC), methyl ethyl carbonate (EMC), ethylene glycol dimethyl ether (DME) and 1,3 dioxolane (DOL); the present application does not have special restrictions on the source of the solvent, and commercially available products known to those skilled in the art can be used. In the present application, the mass fraction of the solvent in the electrolyte is preferably 0 to 80%.

[0055] The electrolyte including monomer B and electrolyte salt is injected into the battery cell in the present application, and the battery assembly fixed with monomer A is fully infiltrated to form a state of monomer A fixation and monomer B uniform distribution in the battery cell. In the present application, the infiltration time is preferably 6h to 24h, more preferably 12h.

[0056] Finally, after polymerization (monomer B is uniformly polymerized around monomer A), an in-situ solidified battery is obtained; the polymerization is a polyaddition reaction of monomer A and monomer B. In the present application, the polymerization temperature is preferably 20°C to 85°C, more preferably 80°C; the polymerization time is preferably 10h to 120h, more preferably 12h to 24h.

[0057] In the present application, in the final solidified battery, the mass ratio of polymer: lithium salt: solvent is preferably (5-80):(20-95):(0-80).

[0058] The purpose of the present application is to provide a preparation method of in-situ solidified battery. In the present application, monomer A in the polyaddition reaction is mixed into the positive and negative electrode slurry or the separator coating slurry, and monomer A is uniformly prepositioned into the electrode sheet or the separator through homogenizing coating. Then, monomer B is injected into the battery in the form of liquid electrolyte, and polymerizes with monomer A uniformly prepositioned in the electrode sheet or the separator to obtain an in-situ solidified battery. The present application solves the problem of uneven polymerization caused by uneven temperature distribution or different local micro-environment in the traditional in-situ solidification method, improves the uniformity of in-situ solidified electrolyte, and further improves the overall performance of the solidified battery.

[0059] In order to further illustrate the present application, the following examples are used for detailed description. The raw materials used in the following examples of the present application are all commercially available.

[0060] Example 1

[0061] (1) 0.5 g of polycarbonate diol (PCDL) with a molecular weight of 2000 was mixed into 10 g of positive electrode slurry and stirred uniformly. The positive electrode slurry contained 50 wt% of solvent NMP, and the solid component ratio was LiCo 0.1 Ni 0.8 Mn 0.1 O2: PVDF: conductive carbon black = 8:1:1; after coating and drying, a blended positive electrode was obtained.

[0062] (2) 0.1 g of isophorone diisocyanate (IPDI) was mixed uniformly with 100 μL of 1 mol / L LiDFOB (DMC:DEC:EC = 1:1:1) to obtain a blended liquid in a flowable state.

[0063] (3) In an argon-filled glove box, the blended positive electrode obtained in step (1) and metallic lithium were used as electrodes, and the blended liquid obtained in step (2) was used as electrolyte to assemble a button cell. After assembly, the button cell was soaked at room temperature for 12 h and cured at 80℃ for 24 h to obtain an in-situ solidified solid-state lithium ion battery.

[0064] Comparative Example 1

[0065] Compared with Example 1, polycarbonate diol (PCDL) and isophorone diisocyanate (IPDI) were directly mixed with the electrolyte to prepare a prepolymer liquid, which was injected into the battery to obtain a solid-state battery through in-situ solidification.

[0066] Further, the solid-state batteries prepared in Example 1 and Comparative Example 1 were subjected to charge-discharge test, and the test procedure was 0.2C cycle after 0.1C formation for two cycles. The results are shown in Table 1, and the first cycle charge-discharge curve is shown in Figure 1 a, and the cycle capacity and coulombic efficiency are shown in Figure 1 b.

[0067] Table 1. Solid-state battery cycling results of Example 1 and Comparative Example 1

[0068]

[0069] Example 2

[0070] (1) 0.3 g of polybutylene adipate diol (PBA) with a molecular weight of 2000 was mixed into 10 g of cathode slurry to be stirred uniformly, and the cathode slurry contained 50 wt% of solvent NMP, and the solid component ratio was LiCo 0.1 Ni 0.8 Mn 0.1 O2: PVDF: conductive carbon black = 8: 1: 1; after coating and drying, a blended cathode was obtained.

[0071] (2) 0.37 g of hexamethylene diisocyanate (HDI) was mixed with 100 μL of 1 mol / L LiTFSI (DOL: DME = 1:1) to obtain a blended liquid in a flowable state.

[0072] (3) In an argon-filled glove box, the blended cathode obtained in step (1) and metal lithium were used as electrodes, and the blended liquid obtained in step (2) was used as electrolyte to assemble a coin cell; after assembly, it was soaked at room temperature for 12 h and cured at 80°C for 12 h to obtain an in-situ cured solid-state lithium ion battery.

[0073] Comparative Example 2

[0074] Compared with Example 2, polybutylene adipate diol (PBA) and hexamethylene diisocyanate (HDI) were directly mixed with the electrolyte to prepare a prepolymer liquid, which was injected into the battery to be cured in-situ to obtain a solid-state battery.

[0075] Further, the solid-state battery prepared in Example 1 and Comparative Example 1 was subjected to charge-discharge test, and the test procedure was 0.2C cycle after 0.1C formation for two cycles, and the results are shown in Table 2, and the first cycle charge-discharge curve is shown in Figure 2 a, the cycle capacity and coulombic efficiency are shown in Figure 2 b.

[0076] Table 2. Solid-state battery cycling results of Example 2 and Comparative Example 2

[0077]

[0078] Example 3

[0079] (1) 0.2 g of polytetramethylene glycol (PTMG) with a molecular weight of 2000 was mixed into 10 g of cathode slurry to be stirred uniformly, and the cathode slurry contained 50 wt% of solvent NMP, and the solid component ratio was LiCo 0.1 Ni0.8 Mn 0.1 O2: PVDF: conductive carbon black = 8: 1: 1; after coating and drying, a blended positive electrode is obtained.

[0080] (2) 0.3 g of xylylene diisocyanate (XDI) was mixed with 100 μL of 1 mol / L LiTFSI (DOL: DME = 1:1) to obtain a blended liquid in a flowing state.

[0081] (3) In an argon-filled glove box, the blended positive electrode obtained in step (1) and metal lithium were used as electrodes, and the blended liquid obtained in step (2) was used as an electrolyte to assemble a coin cell. After assembly, it was soaked at room temperature for 12 h and solidified at 80°C for 12 h to obtain a solid-state lithium ion battery solidified in situ.

[0082] Comparative Example 3

[0083] Compared with Example 3, polytetrahydrofuran ether glycol (PTMG) and xylylene diisocyanate (XDI) were directly mixed with the electrolyte to prepare a prepolymer liquid, which was injected into the battery to solidify in situ to obtain a solid-state battery.

[0084] Further, the solid-state batteries prepared in Example 3 and Comparative Example 3 were subjected to charge-discharge tests, and the test procedure was 0.2C cycle after 0.1C formation for two cycles. The results are shown in Table 3, and the first cycle charge-discharge curve is shown in Figure 3 a, the cycle capacity and coulombic efficiency are shown in Figure 3 b.

[0085] Table 3: Cycle results of solid-state batteries of Example 3 and Comparative Example 3

[0086]

[0087] Example 4

[0088] (1) 0.5 g of toluene diisocyanate (TDI) trimer was mixed into 10 g of positive electrode slurry and stirred uniformly. The positive electrode slurry contained 50 wt% of solvent NMP, and the solid component ratio was LiCo 0.1 Ni 0.8 Mn 0.1 O2: PVDF: conductive carbon black = 8: 1: 1; after coating and drying, a blended positive electrode is obtained.

[0089] (2) 0.3 g of polyether diamine with a molecular weight of 6000 was mixed with 100 μL of 1 mol / L LiTFSI (DOL: DME = 1:1) to obtain a blended liquid in a flowing state.

[0090] (3) In the glove box filled with argon, the blended cathode obtained in step (1) and metal lithium were used as electrodes, and the blended liquid obtained in step (2) was used as electrolyte to assemble a button cell; after assembly, the button cell was soaked at room temperature for 12 h and cured at 80°C for 12 h to obtain a solid-state lithium ion battery cured in situ.

[0091] Comparative Example 4

[0092] Compared with Example 4, toluene diisocyanate (TDI) trimer and polyether diamine were directly mixed with electrolyte to prepare a prepolymer liquid, which was injected into the battery to cure in situ to obtain a solid-state battery.

[0093] Further, the solid-state batteries prepared from Example 4 and Comparative Example 4 were subjected to charge-discharge test, and the test procedure was 0.2C cycle after 0.1C formation for two cycles. The results are shown in Table 4, and the first cycle charge-discharge curve is shown in Figure 4 in a, the cycle capacity and coulombic efficiency are shown in Figure 4 b.

[0094] Table 4: Cycle results of the solid-state batteries of Example 4 and Comparative Example 4

[0095]

[0096] Example 5

[0097] (1) 0.7 g of diphenylmethane diisocyanate (MDI) trimer was mixed into 10 g of cathode slurry to be uniform, and the cathode slurry contained 50 wt% of solvent NMP, and the solid component ratio was LiCo 0.1 Ni 0.8 Mn 0.1 O2: PVDF: conductive carbon black = 8: 1: 1; after coating and drying, a blended cathode was obtained.

[0098] (2) 0.2 g of terephthalic acid was mixed with 100 μL of 1 mol / L LiPF6 (DMC:DEC:EC = 1:1:1) to obtain a blended liquid in a flow state.

[0099] (3) In the glove box filled with argon, the blended cathode obtained in step (1) and metal lithium were used as electrodes, and the blended liquid obtained in step (2) was used as electrolyte to assemble a button cell; after assembly, the button cell was soaked at room temperature for 12 h and cured at 80°C for 12 h to obtain a solid-state lithium ion battery cured in situ.

[0100] Comparative Example 5

[0101] Compared with Example 5, diphenylmethane diisocyanate (MDI) trimer and terephthalic acid were directly mixed with electrolyte to prepare a prepolymer liquid, which was injected into the battery to cure in situ to obtain a solid-state battery.

[0102] Further, the solid-state battery prepared from Example 5 and Comparative Example 5 was subjected to charge-discharge test, and the test procedure was 0.2C cycle after 0.1C formation for two cycles. The results are shown in Table 5, and the first cycle charge-discharge curve is shown in Figure 5 The cycle capacity and coulombic efficiency are shown in Figure 5 b.

[0103] Table 5 Cycle results of solid-state battery of Example 5 and Comparative Example 5

[0104]

[0105] Example 6

[0106] (1) 0.8 g of polyurethane with a molecular weight of 5000 was mixed into 10 g of positive electrode slurry to be stirred uniformly, and the positive electrode slurry contained 50 wt% of solvent NMP, and the solid component ratio was LiCo 0.1 Ni 0.8 Mn 0.1 O2: PVDF: conductive carbon black = 8: 1: 1; and the blended positive electrode was obtained after coating and drying.

[0107] (2) 0.2 g of cyclohexane dimethylene diisocyanate (H6XDI) was mixed with 100 μL of 1 mol / L LiPF6 (DMC:DEC:EC = 1:1:1) to obtain a blended liquid in a flow state.

[0108] (3) In an argon-filled glove box, the blended positive electrode obtained in step (1) and metal lithium were used as electrodes, and the blended liquid obtained in step (2) was used as electrolyte to assemble a button cell; after assembly, it was soaked at room temperature for 12 h, and cured at 80°C for 12 h to obtain an in-situ cured solid-state lithium ion battery.

[0109] Comparative Example 6

[0110] Compared with Example 6, polyurethane and cyclohexane dimethylene diisocyanate (H6XDI) were directly mixed with electrolyte to prepare a prepolymer liquid, which was injected into the battery to be cured in-situ to obtain a solid-state battery.

[0111] Further, the solid-state battery prepared from Example 6 and Comparative Example 6 was subjected to charge-discharge test, and the test procedure was 0.2C cycle after 0.1C formation for two cycles. The results are shown in Table 6, and the first cycle charge-discharge curve is shown in Figure 6 The cycle capacity and coulombic efficiency are shown in Figure 6 b.

[0112] Table 6 Cycle results of solid-state battery of Example 6 and Comparative Example 6

[0113]

[0114] Example 7

[0115] (1) 0.2 g of diphenylmethane diisocyanate (MDI) and 0.05 g of polyvinylidene fluoride (PVDF) were dissolved in 1 g of ethylene glycol dimethyl ether (DME) to prepare a coating liquid, which was coated on the surface of a separator to prepare a coated monomer separator.

[0116] (2) 0.1 g of a trihydroxy polyether with a molecular weight of 1000 was uniformly mixed with 100 μL of 1 mol / L LiTFSI (DOL:DME = 1:1) to obtain a blended liquid in a flowable state.

[0117] (3) In an argon-filled glove box, the coated monomer separator obtained in step (1), LiCo 0.1 Ni 0.8 Mn 0.1 O2 positive electrode, a metal lithium negative electrode, and the blended liquid obtained in step (2) were assembled into a coin cell. After assembly, the coin cell was soaked at room temperature for 12 h and cured at 80°C for 24 h to obtain a solid-state lithium ion battery cured in situ.

[0118] Comparative Example 7

[0119] In comparison with Example 7, diphenylmethane diisocyanate (MDI) and trihydroxy polyether were directly mixed with an electrolyte to prepare a prepolymer liquid, which was injected into the interior of a battery to obtain a solid-state battery cured in situ.

[0120] Further, the solid-state batteries obtained in Example 7 and Comparative Example 7 were subjected to charge-discharge tests, and the test procedure was 0.2C cycling after 0.1C formation for two cycles. The results are shown in Table 7, and the first cycle charge-discharge curves are shown in FIG. 1. Figure 7 The cycle capacity and coulombic efficiency are shown in FIG. 2a. Figure 7

[0121] Table 7 Cycle results of the solid-state batteries of Example 7 and Comparative Example 7

[0122]

[0123] Example 8

[0124] (1) 0.2 g of hexamethylene diisocyanate trimer and 0.05 g of polyvinylidene fluoride (PVDF) were dissolved in 1 g of ethylene glycol dimethyl ether (DME) to prepare a coating liquid, which was coated on the surface of a separator to prepare a coated monomer separator.

[0125] (2) 0.15 g of a polyether diamine with a molecular weight of 900 was uniformly mixed with 100 μL of 1 mol / L LiTFSI (DOL:DME = 1:1) to obtain a blended liquid in a flowable state.

[0126] ​(3) In the glove box filled with argon, the coated monomer separator, LiCo 0.1 Ni 0.8 Mn 0.1 O2 cathode, metal lithium anode, and the blended liquid obtained in step (2) were assembled into a button cell. After assembly, the button cell was immersed at room temperature for 12 h and cured at 80°C for 24 h to obtain a solid-state lithium ion battery cured in situ.

[0127] Comparative Example 8

[0128] Compared with Example 8, the hexamethylene diisocyanate trimer and the polyether diamine were directly mixed with the electrolyte to prepare a prepolymer liquid, which was injected into the inside of the battery to obtain a solid-state battery cured in situ.

[0129] Further, the solid-state batteries obtained in Example 8 and Comparative Example 8 were subjected to charge-discharge tests, and the test procedure was 0.2C cycle after 0.1C formation for two cycles. The results are shown in Table 8, and the first cycle charge-discharge curves are shown in FIG. 2a. Figure 8 The cycle capacity and coulombic efficiency are shown in FIG. 2b. Figure 8

[0130] Table 8. Cycle results of the solid-state batteries of Example 8 and Comparative Example 8

[0131]

[0132] Example 9

[0133] (1) 0.1 g of polyimide (PI) with a molecular weight of 100,000 was prepared into a coating liquid in 1 g of NMP, and was coated on the surface of a separator to prepare a coated monomer separator.

[0134] (2) 0.05 g of triphenylmethane triisocyanate (TTI) was uniformly mixed with 100 μL of 1 mol / L LiTFSI (DOL:DME = 1:1) to obtain a blended liquid in a flowable state.

[0135] (3) In the glove box filled with argon, the coated monomer separator, LiCo 0.1 Ni 0.8 Mn 0.1 O2 cathode, metal lithium anode, and the blended liquid obtained in step (2) were assembled into a button cell. After assembly, the button cell was immersed at room temperature for 12 h and cured at 80°C for 24 h to obtain a solid-state lithium ion battery cured in situ.

[0136] Comparative Example 9

[0137] Compared with Example 9, the polyimide (PI) and triphenylmethane triisocyanate (TTI) were directly mixed with the electrolyte to prepare a prepolymer liquid, which was injected into the inside of the battery to obtain a solid-state battery cured in situ. ​

[0138] Further, the solid-state battery prepared from Example 9 and Comparative Example 9 was subjected to charge-discharge test, and the test procedure was 0.2C cycle after 0.1C formation for two cycles. The results are shown in Table 9, and the first cycle charge-discharge curve is shown in FIG. 6a. Figure 9 The cycle capacity and coulombic efficiency are shown in FIG. 6b. Figure 9

[0139] Table 9 Cycle results of solid-state battery of Example 9 and Comparative Example 9

[0140]

[0141] Example 10

[0142] (1) 0.5 g of polyethylene glycol (PEG) with a molecular weight of 2000 was mixed into 10 g of negative electrode slurry to obtain a uniform mixture, and the negative electrode slurry contained 50 wt% of solvent NMP, and the solid component ratio was graphite: PVDF: conductive carbon black = 90:3:7. After coating and drying, a blended electrode was obtained.

[0143] (2) 0.1 g of toluene diisocyanate (TDI) was mixed with 100 μL of 1 mol / L LiPF6 (DMC:DEC:EC = 1:1:1) to obtain a blended liquid in a flowable state.

[0144] (3) In an argon-filled glove box, the blended negative electrode obtained in step (1) and LiCo 0.1 Ni 0.8 Mn 0.1 O2 positive electrode were used as electrodes, and the blended liquid obtained in step (2) was used as electrolyte to assemble a coin battery. After assembly, the coin battery was immersed at room temperature for 12 h and cured at 80°C for 24 h to obtain an in-situ cured solid-state lithium ion battery.

[0145] Comparative Example 10

[0146] Compared with Example 10, polyethylene glycol (PEG) and toluene diisocyanate (TDI) were directly mixed with electrolyte to prepare a prepolymer liquid, which was injected into the battery to obtain an in-situ cured solid-state battery.

[0147] Further, the solid-state battery prepared from Example 10 and Comparative Example 10 was subjected to charge-discharge test, and the test procedure was 0.2C cycle after 0.1C formation for two cycles. The results are shown in Table 10, and the first cycle charge-discharge curve is shown in FIG. 7a. Figure 10 The cycle capacity and coulombic efficiency are shown in FIG. 7b. Figure 10

[0148] Table 10 Cycle results of solid-state battery of Example 10 and Comparative Example 10

[0149] ​​

[0150] Example 11

[0151] (1) 0.3 g TDI trimer was mixed into 10 g negative electrode slurry, which contained 50 wt% solvent NMP, and the solid component ratio was graphite: PVDF: conductive carbon black = 90:3:7. After coating and drying, a blended electrode was obtained.

[0152] (2) 0.4 g polyethylene glycol dimethyl ether (PEG) with a molecular weight of 600 was mixed with 100 μL 1 mol / L LiPF6(DMC:DEC:EC = 1:1:1) to obtain a blended liquid in a flowable state.

[0153] (3) In an argon-filled glove box, the blended negative electrode obtained in step (1) and LiCo 0.1 Ni 0.8 Mn 0.1 O2 positive electrode were used as electrodes, and the blended liquid obtained in step (2) was used as electrolyte to assemble a coin cell. After assembly, the coin cell was soaked at room temperature for 12 h and cured at 80°C for 24 h to obtain a solid-state lithium ion battery cured in situ.

[0154] Comparative Example 11

[0155] Compared with Example 11, polyethylene glycol (PEG) and TDI trimer were directly mixed with electrolyte to prepare a pre-polymer liquid, which was injected into the battery to cure in situ to obtain a solid-state battery.

[0156] Further, the solid-state batteries prepared in Example 11 and Comparative Example 11 were subjected to charge-discharge tests, and the test procedure was 0.2C cycling after 0.1C formation for two cycles. The results are shown in Table 10, and the first cycle charge-discharge curves are shown in Figure 11 a, and the cycle capacity and coulombic efficiency are shown in Figure 11 b.

[0157] Table 11 Cycle results of the solid-state batteries of Example 11 and Comparative Example 11

[0158]

[0159] Example 12

[0160] (1) 0.5 g polytetrahydrofuran propylene oxide copolyether (PTMG-PPG) with a molecular weight of 2000 was mixed into 10 g negative electrode slurry, which contained 50 wt% solvent NMP, and the solid component ratio was graphite: PVDF: conductive carbon black = 90:3:7. After coating and drying, a blended electrode was obtained.

[0161] (2) 0.2 g of lysine diisocyanate (LDI) was mixed with 100 μL of 1 mol / L LiPF6 (DMC:DEC:EC = 1:1:1) to obtain a blended liquid in a flowable state.

[0162] (3) In an argon-filled glove box, the blended electrode obtained in step (1) and LiCo 0.1 Ni 0.8 Mn 0.1 O2 positive electrode as the electrode, the blended liquid obtained in step (2) as the electrolyte, a button cell was assembled; after being assembled, it was soaked at room temperature for 12 h and cured at 80°C for 24 h to obtain a solid-state lithium ion battery cured in situ.

[0163] Comparative Example 12

[0164] Compared with Example 12, polytetrahydrofuran propylene oxide copolyether (PTMG-PPG) and lysine diisocyanate (LDI) were directly mixed with the electrolyte to prepare a prepolymer liquid, which was injected into the battery to cure in situ to obtain a solid-state battery.

[0165] Further, the solid-state batteries prepared from Example 12 and Comparative Example 12 were subjected to charge-discharge tests, and the test procedure was 0.2C cycle after 0.1C formation for two cycles. The results are shown in Table 12, and the first cycle charge-discharge curves are shown in Figure 12 a, the cycle capacity and coulombic efficiency are shown in Figure 12 b.

[0166] Table 12 Cycle results of the solid-state batteries of Example 12 and Comparative Example 12

[0167]

[0168] Example 13

[0169] (1) 0.3 g of polybutylene adipate glycol (PBA) with a molecular weight of 2000 was mixed into 10 g of positive electrode slurry to obtain a blended positive electrode. 0.1 Ni 0.8 Mn 0.1 O2: PVDF: conductive carbon black = 8:1:1.

[0170] 0.3 g of polypropylene glycol (PPG) with a molecular weight of 10000 was mixed into 10 g of negative electrode slurry to obtain a blended electrode.

[0171] 0.2 g of polyethylene glycol (PEG) with a molecular weight of 10000, 0.05 g of polyvinylidene fluoride (PVDF) were dissolved in 1 g of ethylene glycol dimethyl ether (DME) to prepare a coating liquid, which was coated on the surface of the separator to prepare a coated monomer separator.

[0172] (2) 0.3 g of cyclohexane dimethylene diisocyanate (H6XDI) was uniformly mixed with 100 μL of 1 mol / L LiPF6 (DMC:DEC:EC=1:1:1) to obtain a blended liquid in a flow state.

[0173] (3) In an argon-filled glove box, the blended electrode obtained in step (1) and the separator were used as battery components, and the blended liquid obtained in step (2) was used as the electrolyte to assemble a button cell. After assembly, it was soaked at room temperature for 12 h and cured at 80°C for 24 h to obtain a solid-state lithium ion battery cured in situ.

[0174] Comparative Example 13

[0175] Compared with Example 13, polybutylene adipate-1,4-butylene glycol (PBA), polypropylene glycol (PPG), and cyclohexane dimethylene diisocyanate (H6XDI) were directly mixed with the electrolyte to prepare a prepolymer liquid, which was injected into the battery to cure in situ to obtain a solid-state battery.

[0176] Further, the solid-state batteries prepared in Example 13 and Comparative Example 13 were subjected to charge-discharge tests, and the test procedure was 0.2C cycling after 0.1C formation for two cycles. The results are shown in Table 13, and the first cycle charge-discharge curves are shown in Figure 13 a, the cycle capacity and coulombic efficiency are shown in Figure 13 b.

[0177] Table 13 Cycle results of solid-state batteries of Example 13 and Comparative Example 13

[0178]

[0179] Example 14

[0180] (1) 0.2 g of polypropylene glycol (PPG) with a molecular weight of 10000 was mixed into 10 g of positive electrode slurry and stirred uniformly. The positive electrode slurry contained 50 wt% of solvent NMP, and the solid component ratio was LiCo 0.1 Ni 0.8 Mn 0.1 O2: PVDF: conductive carbon black = 8:1:1; after coating and drying, a blended positive electrode was obtained.

[0181] 0.2 g of polypropylene glycol (PPG) with a molecular weight of 10000 was mixed into 10 g of negative electrode slurry to be stirred uniformly, the negative electrode slurry contained 50 wt% of solvent NMP, and the solid component ratio was graphite: PVDF: conductive carbon black = 90:3:7; after coating and drying, a blended electrode was obtained.

[0182] 0.1 g of polypropylene glycol (PPG) with a molecular weight of 10000 and 0.05 g of polyvinylidene fluoride (PVDF) were dissolved in 1 g of ethylene glycol dimethyl ether (DME) to prepare a coating liquid, which was coated on the surface of a separator to prepare a coated monomer separator.

[0183] (2) 0.3 g of 4,4'-dicyclohexyl methane diisocyanate (HMDI) was uniformly mixed with 100 μL of 1 mol / L LiPF6 (DMC:DEC:EC = 1:1:1) to obtain a blended liquid in a flowing state.

[0184] (3) In an argon-filled glove box, the blended electrode obtained in step (1) and the separator were used as battery components, and the blended liquid obtained in step (2) was used as the electrolyte to assemble a button cell; after assembly, it was soaked at room temperature for 12 h and solidified at 80°C for 24 h to obtain a solid-state lithium ion battery solidified in situ.

[0185] Comparative Example 14

[0186] Compared with Example 14, polypropylene glycol (PPG) and 4,4'-dicyclohexyl methane diisocyanate (HMDI) were directly mixed with the electrolyte to prepare a prepolymer liquid, which was injected into the battery to be solidified in situ to obtain a solidified battery.

[0187] Further, the solidified batteries prepared in Example 14 and Comparative Example 14 were subjected to charge-discharge tests, and the test procedure was 0.2C cycle after 0.1C formation for two cycles, and the results are shown in Table 14, and the first cycle charge-discharge curve is shown in Figure 14 a, the cycle capacity and coulombic efficiency are shown in Figure 14 b.

[0188] Table 14 Cycle results of solidified batteries of Example 14 and Comparative Example 14

[0189]

[0190] Example 15

[0191] (1) 0.15 g of polyethylene glycol (PEG) with a molecular weight of 10000 was mixed into 10 g of positive electrode slurry to be stirred uniformly, the positive electrode slurry contained 50 wt% of solvent NMP, and the solid component ratio was LiCo 0.1 Ni 0.8 Mn 0.1 O2: PVDF: conductive carbon black = 8:1:1; after coating and drying, a blended positive electrode was obtained.

[0192] 0.15 g of polyethylene glycol (PEG) with a molecular weight of 10,000 was mixed into 10 g of negative electrode slurry to be stirred uniformly, the negative electrode slurry contained 50 wt% of solvent NMP, and the solid component ratio was graphite: PVDF: conductive carbon black = 90:3:7; after coating and drying, a blended electrode was obtained.

[0193] 0.1 g of polyethylene glycol (PEG) with a molecular weight of 10,000 and 0.05 g of polyvinylidene fluoride (PVDF) were dissolved in 1 g of ethylene glycol dimethyl ether (DME) to prepare a coating liquid, which was coated on the surface of a separator to prepare a coated monomer separator.

[0194] (2) 0.1 g of 4,4'-dicyclohexyl methane diisocyanate (HMDI) and 0.2 g of isophorone diisocyanate (IPDI) were uniformly mixed with 100 μL of 1 mol / L LiPF6 (DMC:DEC:EC = 1:1:1) to obtain a blended liquid in a flowing state.

[0195] (3) In an argon-filled glove box, the blended electrode obtained in step (1) and the separator were used as battery components, and the blended liquid obtained in step (2) was used as the electrolyte to assemble a button cell; after assembly, the button cell was soaked at room temperature for 12 h and solidified at 80°C for 24 h to obtain a solid-state lithium ion battery solidified in situ.

[0196] Comparative Example 15

[0197] Compared with Example 15, polyethylene glycol (PEG), 4,4'-dicyclohexyl methane diisocyanate (HMDI), and isophorone diisocyanate (IPDI) were directly mixed with the electrolyte to prepare a prepolymer liquid, which was injected into the battery to solidify in situ to obtain a solid-state battery.

[0198] Further, the solid-state batteries prepared in Example 15 and Comparative Example 15 were subjected to charge-discharge tests, and the test procedure was 0.2C cycling after 0.1C formation for two cycles. The results are shown in Table 15, and the first cycle charge-discharge curve is shown in Figure 15 a, the cycle capacity and coulombic efficiency are shown in Figure 15 b.

[0199] Table 15 Cycle results of the solid-state batteries of Example 15 and Comparative Example 15

[0200]

[0201] Example 16

[0202] (1) 0.15 g of polybutylene adipate glycol (PBA) with a molecular weight of 2,000 was mixed into 10 g of positive electrode slurry to be stirred uniformly, the positive electrode slurry contained 50 wt% of solvent NMP, and the solid component ratio was LiCo0.1 Ni 0.8 Mn 0.1 O2: PVDF: conductive carbon black = 8: 1: 1; after coating and drying, a blended positive electrode is obtained.

[0203] 0.15 g of polyethylene glycol (PEG) with a molecular weight of 10,000 is mixed into 10 g of negative electrode slurry to be stirred uniformly, the negative electrode slurry contains 50 wt% of solvent NMP, and the solid component ratio is graphite: PVDF: conductive carbon black = 90: 3: 7; after coating and drying, a blended electrode is obtained.

[0204] 0.1 g of trihydroxy polyether with a molecular weight of 10,000 and 0.05 g of polyvinylidene fluoride (PVDF) are dissolved in 1 g of ethylene glycol dimethyl ether (DME) to prepare a coating liquid, which is coated on the surface of a separator to prepare a coated monomer separator.

[0205] (2) 0.3 g of isophorone diisocyanate (IPDI), 0.08 g of polyethylene glycol (PEG) with a molecular weight of 600, and 0.287 g of LiTFSI are mixed uniformly to obtain a blended liquid in a flow state.

[0206] (3) In an argon-filled glove box, the blended electrode obtained in step (1) and the separator are used as battery components, and the blended liquid obtained in step (2) is used as an electrolyte to assemble a button cell; after assembly, it is soaked at room temperature for 12 h and cured at 80°C for 24 h to obtain a solid-state lithium ion battery that is cured in situ.

[0207] Comparative Example 16

[0208] Compared with Example 16, polybutylene adipate glycol (PBA), polyethylene glycol (PEG) with a molecular weight of 10,000, polyethylene glycol (PEG) with a molecular weight of 600, trihydroxy polyether with a molecular weight of 10,000, and isophorone diisocyanate (IPDI) are directly mixed with LiTFSI to prepare a prepolymer liquid, which is injected into the battery to be cured in situ to obtain a solid-state battery.

[0209] Further, the solid-state batteries prepared in Example 16 and Comparative Example 16 are subjected to charge-discharge tests, and the test procedure is 0.2C cycling after 0.1C formation for two cycles. The results are shown in Table 16, and the first cycle charge-discharge curves are shown in Figure 16 a, the cycle capacity and coulombic efficiency are shown in Figure 16 b.

[0210] Table 16 Cycle results of solid-state batteries of Example 16 and Comparative Example 16

[0211]

[0212] Example 17

[0213] (1) 0.05 g of diphenylmethane diisocyanate (MDI) trimer was mixed into 10 g of positive electrode slurry and stirred uniformly. The positive electrode slurry contained 50 wt% of solvent NMP, and the solid component ratio was LiCo 0.1 Ni 0.8 Mn 0.1 O2: PVDF: conductive carbon black = 8:1:1; after coating and drying, a blended positive electrode was obtained.

[0214] 0.03 g of diphenylmethane diisocyanate (MDI) was mixed into 10 g of negative electrode slurry and stirred uniformly. The negative electrode slurry contained 50 wt% of solvent NMP, and the solid component ratio was graphite: PVDF: conductive carbon black = 90:3:7; after coating and drying, a blended electrode was obtained.

[0215] 0.1 g of isophorone diisocyanate trimer and 0.05 g of polyvinylidene fluoride (PVDF) were dissolved in 1 g of ethylene glycol dimethyl ether (DME) to prepare a coating liquid, which was coated on the surface of the separator to prepare a coated monomer separator.

[0216] (2) 0.5 g of polyethylene glycol (PEG) with a molecular weight of 600, 0.3 g of glycerol, and 0.287 g of LiTFSI were mixed uniformly to obtain a blended liquid in a flowable state.

[0217] (3) In an argon-filled glove box, the blended electrode obtained in step (1) and the separator were used as battery components, and the blended liquid obtained in step (2) was used as the electrolyte to assemble a coin cell. After assembly, it was soaked at room temperature for 12 h and solidified at 80°C for 24 h to obtain a solid-state lithium ion battery solidified in situ.

[0218] Comparative Example 17

[0219] In comparison with Example 17, diphenylmethane diisocyanate (MDI) trimer, diphenylmethane diisocyanate (MDI), isophorone diisocyanate trimer, polyethylene glycol (PEG) with a molecular weight of 600, and glycerol were directly mixed with LiTFSI to prepare a prepolymer liquid, which was injected into the battery to solidify in situ to obtain a solid-state battery.

[0220] Further, the solid-state batteries prepared in Example 17 and Comparative Example 17 were subjected to charge-discharge tests, and the test procedure was 0.2C cycling after 0.1C formation for two cycles. The results are shown in Table 17, and the first cycle charge-discharge curves are shown in Figure 17 a, and the cycle capacity and coulombic efficiency are shown in Figure 17 b.

[0221] Table 17 Cycle results of the solid-state batteries of Example 17 and Comparative Example 17

[0222]

[0223] Example 18

[0224] (1) 0.05 g of diphenylmethane diisocyanate (MDI) trimer was mixed into 10 g of positive electrode slurry to be stirred uniformly, and the positive electrode slurry contained 50 wt% of solvent NMP, and the solid component ratio was LiCo 0.1 Ni 0.8 Mn 0.1 O2: PVDF: conductive carbon black = 8: 1: 1; after coating and drying, a blended positive electrode was obtained.

[0225] 0.1 g of isophorone diisocyanate trimer and 0.05 g of polyvinylidene fluoride (PVDF) were dissolved in 1 g of ethylene glycol dimethyl ether (DME) to prepare a coating liquid, which was coated on the surface of the separator to prepare a coated monomer separator.

[0226] (2) 0.02 g of triethanolamine, 0.3 g of 1,4-butanediol, 0.8 g of polyethylene glycol (PEG) with a molecular weight of 600, and 0.287 g of LiTFSI were mixed uniformly to obtain a blended liquid in a flowable state.

[0227] (3) In an argon-filled glove box, the blended positive electrode obtained in step (1), the separator, and metallic lithium were used as battery components, and the blended liquid obtained in step (2) was used as the electrolyte to assemble a coin cell battery; after assembly, the coin cell battery was immersed at room temperature for 12 h and solidified at 80°C for 24 h to obtain a solid-state lithium ion battery solidified in situ.

[0228] Comparative Example 18

[0229] Compared with Example 18, diphenylmethane diisocyanate (MDI) trimer, isophorone diisocyanate trimer, triethanolamine, 1,4-butanediol, polyethylene glycol (PEG) with a molecular weight of 600, and 0.287 g of LiTFSI were mixed to prepare a prepolymer liquid, which was injected into the battery to solidify in situ to obtain a solid-state battery.

[0230] Further, the solid-state batteries prepared in Example 18 and Comparative Example 18 were subjected to charge-discharge tests, and the test procedure was 0.2C cycling after 0.1C formation for two cycles. The results are shown in Table 18, and the first cycle charge-discharge curves are shown in FIG. 1a, the cycle capacity and coulombic efficiency are shown in FIG. 1b, and the discharge curves of the 10th cycle are shown in FIG. 1c. Figure 18 Figure 18

[0231] Table 18 Cycle results of the solid-state batteries of Example 18 and Comparative Example 18

[0232]

[0233] Example 19

[0234] ​​(1) 0.2 g polycarbonate diol (PCDL) with molecular weight of 2000 was mixed into 10 g cathode slurry to stir evenly, the cathode slurry contained 50 wt% solvent NMP, the solid component ratio was LiCo 0.1 Ni 0.8 Mn 0.1 O2: PVDF: conductive carbon black = 8: 1: 1; after coating and drying, a blended cathode was obtained.

[0235] 0.1 g polyethylene glycol (PEG) with molecular weight of 10000, 0.05 g polyvinylidene fluoride (PVDF) were dissolved in 1 g ethylene glycol dimethyl ether (DME) to prepare a coating liquid, which was coated on the surface of the separator to prepare a coated monomer separator.

[0236] (2) 0.2 g isophorone diisocyanate (IPDI), 0.1 g hexamethylene diisocyanate (HDI), 0.2 g polyether diamine with molecular weight of 900 were mixed with 0.287 g LiTFSI to obtain a blended liquid in a flow state.

[0237] (3) In an argon-filled glove box, the blended cathode obtained in step (1), the separator, and the metal lithium were used as battery components, and the blended liquid obtained in step (2) was used as the electrolyte to assemble a coin cell battery; after assembly, the coin cell battery was soaked at room temperature for 12 h and cured at 80 °C for 24 h to obtain a solid-state lithium ion battery cured in situ.

[0238] Comparative Example 19

[0239] Compared with Example 19, polycarbonate diol (PCDL) with molecular weight of 2000, polyethylene glycol (PEG) with molecular weight of 10000, isophorone diisocyanate (IPDI), hexamethylene diisocyanate (HDI), and polyether diamine with molecular weight of 900 were mixed with 0.287 g LiTFSI to prepare a prepolymer liquid, which was injected into the battery to cure in situ to obtain a solid-state battery.

[0240] Further, the solid-state batteries prepared in Example 19 and Comparative Example 19 were subjected to charge-discharge tests, and the test procedure was 0.2C cycling after 0.1C formation for two cycles. The results are shown in Table 19, and the first cycle charge-discharge curves are shown in FIG. 1a, the cycle capacity and coulombic efficiency are shown in FIG. 1b. Figure 19 Figure 19

[0241] Table 19 Cycle results of solid-state batteries of Example 19 and Comparative Example 19

[0242]

[0243] Example 20

[0244] ​​(1) 0.2 g of polyethylene glycol (PEG) with a molecular weight of 10000 was mixed into 10 g of positive electrode slurry to be stirred uniformly, and the positive electrode slurry contained 50 wt% of solvent NMP, and the solid component ratio was LiCo 0.1 Ni 0.8 Mn 0.1 O2: PVDF: conductive carbon black = 8: 1: 1; after coating and drying, a blended positive electrode was obtained.

[0245] 0.05 g of diphenyl methane diisocyanate (MDI) and 0.05 g of polyvinylidene fluoride (PVDF) were dissolved in 1 g of ethylene glycol dimethyl ether (DME) to prepare a coating liquid, which was coated on the surface of the separator to prepare a coated monomer separator.

[0246] (2) 0.1 g of 4,4'-diphenyl diisocyanate (DBDI), 0.1 g of polyethylene glycol (PEG) with a molecular weight of 2000, and 100 μL of 1 mol / L LiTFSI (DOL: DME = 1:1) were mixed uniformly to obtain a blended liquid in a flow state.

[0247] (3) In an argon-filled glove box, the blended positive electrode obtained in step (1), the separator, and metallic lithium were used as battery components, and the blended liquid obtained in step (2) was used as the electrolyte to assemble a coin cell battery; after assembly, the coin cell battery was immersed at room temperature for 12 h and solidified at 80°C for 24 h to obtain a solid-state lithium ion battery solidified in situ.

[0248] Comparative Example 20

[0249] Compared with Example 20, polyethylene glycol (PEG) with a molecular weight of 2000, polyethylene glycol (PEG) with a molecular weight of 10000, 4,4'-diphenyl diisocyanate (DBDI), and diphenyl methane diisocyanate (MDI) were mixed uniformly with 100 μL of 1 mol / L LiTFSI (DOL: DME = 1:1) to prepare a prepolymer liquid, which was injected into the battery to be solidified in situ to obtain a solid-state battery.

[0250] Further, the solid-state batteries prepared from Example 20 and Comparative Example 20 were subjected to charge-discharge tests, and the test procedure was 0.2C cycling after 0.1C formation for two cycles. The results are shown in Table 20, and the first cycle charge-discharge curves are shown in Figure 20 a, the cycle capacity and coulombic efficiency are shown in Figure 20 b.

[0251] Table 20: Cycle results of the solid-state batteries of Example 20 and Comparative Example 20

[0252]

[0253] It can be seen from the comparison result that the method of pre-setting a monomer into a battery assembly and then injecting a monomer reacting with the monomer into the battery in a liquid injection manner to heat initiate polymerization can improve the uniform distribution of the in-situ solidified electrolyte in the battery, and further improve the cycle stability of the in-situ solidified battery.

[0254] The above description of disclosed embodiments enables one of ordinary skill in the art to make and use the application. Various modifications to these embodiments will be readily apparent to those skilled in the art, and the generic principles defined herein can be applied to other embodiments without departing from the spirit or scope of the application. Thus, the present application is not intended to be limited to the embodiments shown herein but is to be accorded the widest scope consistent with the principles and novel features disclosed herein.

Claims

1. A method for preparing an in-situ solidified battery, comprising the following steps: a) prepositioning monomer A in a battery component, assembling a battery cell; b) injecting a solution comprising monomer B into the battery cell obtained in step a), infiltrating, and then polymerizing to obtain an in-situ solidified battery; wherein the polymerization is a polyaddition reaction of monomer A and monomer B; wherein the battery component in step a) comprises a positive electrode sheet and a separator; wherein the prepositioning of monomer A in the positive electrode sheet is achieved by mixing monomer A into a positive electrode slurry to prepare the positive electrode sheet; wherein the prepositioning of monomer A in the separator is achieved by mixing monomer A into a separator coating solution to prepare the separator; wherein monomer A in the polyaddition reaction in step b) is an isocyanate group-containing monomer, and monomer B in the polyaddition reaction is a reactive hydrogen group-containing monomer; or wherein monomer A in the polyaddition reaction is a reactive hydrogen group-containing monomer, and monomer B in the polyaddition reaction is an isocyanate group-containing monomer; wherein the isocyanate group-containing monomer is selected from the group consisting of diphenylmethane diisocyanate trimer, isophorone diisocyanate trimer, cyclohexane dimethylene diisocyanate, 4,4'-diphenyl diisocyanate, 4,4'-dicyclohexylmethane diisocyanate, diphenylmethane diisocyanate, isophorone diisocyanate, and hexamethylene diisocyanate; wherein the solution in step b) comprises monomer B, a solvent, and a lithium salt, and when monomer B is a liquid, no solvent is added. 3.The method of claim 1, wherein the prepositioning of monomer A in the negative electrode sheet is achieved by mixing monomer A into a negative electrode slurry to prepare the negative electrode sheet; wherein the reactive hydrogen group-containing monomer is selected from one or more of polyhexanediole, polyethylene glycol, polypropylene glycol, polyethylene glycol-polypropylene glycol copolyether, polytetrahydrofuran ether glycol, polytetrahydrofuran epoxy propane copolyether, ethylene glycol, diethylene glycol, propylene glycol, glycerol, 1,4-butanediol, diethylene glycol, neopentyl glycol, 1,6-hexanediol, trimethylolpropane, propylene glycol, glycerol, 1,4-cyclohexanediol, hydroquinone bis(β-hydroxyethyl) ether, hydrogenated bisphenol A, terephthalic acid dihydroxyethyl ester, resorcinol dihydroxyethyl ether, glycerol α-allyl ether, trimethylolpropane monoallyl ether, pentaerythritol, diethyltoluene diamine, 3,3'-dichloro-4,4-diamino-diphenyl methane, diamino diphenyl methane, 3,5-diamino-p-chlorobenzoic acid isobutyl ester, dimethylthio toluene diamine, diethyl toluene diamine, 4,4'-methylene bis(3-chloro-2,6-diethyl aniline), ethanolamine, diethanolamine, triethanolamine, triisopropanolamine, N,N-bis(2-hydroxypropyl) aniline, adipic acid, azelaic acid, sebacic anhydride, isophthalic acid, terephthalic acid, and dimethyl terephthalate; wherein the molar ratio of isocyanate groups to reactive hydrogen groups in the polyaddition reaction is (1-20) : 1; and wherein the lithium salt is selected from one or more of lithium bistrifluoromethylsulfonylimide, lithium trifluoromethylsulfonate, lithium bisoxalate borate, lithium bisfluorosulfonylimide, lithium hexafluoroarsenate, lithium tetrafluoroborate, lithium perchlorate, and lithium hexafluorophosphate. ​ ​ ​ ​ ​ ​ ​ ​ 2. The production method according to claim 1, characterized by, ​ ​ ​ 4. The method of claim 1, wherein, ​ 5. The preparation method according to claim 1, characterized in that, ​ 6. The preparation method according to claim 2, characterized in that, ​ 7. The preparation method according to claim 2, characterized in that, The solvent is selected from one or more of ethylene carbonate, fluoroethylene carbonate, propylene carbonate, dimethyl carbonate, diethyl carbonate, ethyl methyl carbonate, butylene carbonate, methyl propyl carbonate, methyl formate, ethyl formate, propyl formate, butyl formate, ethyl acetate, propyl acetate, butyl acetate, methyl propionate, ethyl propionate, butyl propionate, methyl butyrate, ethyl butyrate, propyl butyrate, delta-valerolactone, tetrahydrofuran, 2-methyltetrahydrofuran, 4-methyl-1,3-dioxolane, 2-methyl-1,3-dioxolane, ethylene glycol dimethyl ether, and 1,3 dioxolane, sulfolane, dimethyl sulfoxide.

8. The preparation method according to claim 2, characterized in that, The mass ratio of the polymer, the lithium salt and the solvent in the solid-state battery is (5-95):(5-30):(0-80).

9. The method of claim 1, wherein, The positive active material of the pole piece is one or more of lithium cobaltate, lithium nickel cobaltate, lithium manganate, lithium nickel manganate, ternary lithium nickel cobalt manganate, lithium nickel cobalt aluminum, lithium nickel cobalt manganese aluminum, lithium manganese iron phosphate, lithium iron phosphate, sulfur, lithium sulfide; the negative material of the pole piece is one or more of metal lithium, metal lithium alloy, graphite, hard carbon, molybdenum disulfide, lithium titanate, graphene, silicon, silicon carbon, silicon oxygen, silicon oxygen carbon negative electrode; the separator is one or more of commercial PP, PE, PI, cellulose membrane, PET porous membrane and ceramic coating membrane.

10. The method of claim 1, wherein, The infiltration time in step b) is 6h-24h.

11. The method of claim 1, wherein, The polymerization temperature in step b) is 20℃-85℃, and the time is 10h-120h.

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