Preparation method of gradient formation and polymerization solid-state battery

Abstract

The invention provides a preparation method of a gradient formation and polymerization solid-state battery, the solid-state battery is manufactured and produced by using a step-by-step formation and in-situ polymerization method, and the gradient formation and polymerization solid-state battery is prepared by the manufacturing process of injecting a conventional liquid electrolyte, injecting a precursor solution containing a polymer monomer and an initiator for multiple times after formation, and performing in-situ polymerization. Therefore, the gradient formation polymerization solid-state battery is formed. The method can effectively alleviate the problem of polymerization monomer reaction and the problem of fixed gas by-products of polyelectrolyte, is compatible with the existing conventional liquid battery production process, and reduces the production line cost.

Description

Technical Field

[0001] The present invention relates to the technical field of solid-state batteries, and in particular to a method for preparing a gradient-type formation and polymerization solid-state battery. Background Art

[0002] Lithium secondary batteries are widely used in power batteries, military fields and portable energy storage due to their advantages such as high energy density, high output power and excellent long cycle performance. With the increasingly urgent demand for improving the energy density of lithium-ion batteries, traditional lithium-ion batteries have found it difficult to meet the demand for ultra-high specific energy. At present, the energy density of lithium secondary batteries is mainly determined by the capacity of the positive and negative electrode materials. The performance of commercial lithium-ion batteries with graphite as the negative electrode has approached the theoretical limit. In order to better meet the society's demand for energy, electrochemical systems with higher energy density and high conversion efficiency have begun to become the focus of researchers. Among them, the lithium metal negative electrode has a low electrode potential of -3.04V (relative to the standard hydrogen electrode) and a capacity of 3860mAh·g –1 The high theoretical specific capacity of silicon anode makes it a potential material to replace graphite anode. However, the high chemical activity of lithium metal anode, the growth of lithium dendrites during charge and discharge, and the interface problem during the cycle have caused people to worry about the safety of energy storage devices while increasing energy density. Silicon anode has a high theoretical specific capacity (4200mAh g –1 ), but its severe volume expansion and unstable SEI film easily lead to large voltage polarization, capacity loss, and poor cycling stability. Therefore, how to ensure battery safety while pursuing high energy density has become a major challenge for future development.

[0003] Based on the traditional lithium-ion battery system, high-energy-density battery materials still have many safety risks. The material itself has large volume expansion, structural changes, and cycle life and safety risks when paired with liquid electrolytes. Liquid electrolytes cannot effectively suppress the huge expansion of the silicon negative electrode, or the changes in the structure of the lithium metal negative electrode and the growth of metal dendrites, and dendrites may pierce the diaphragm and cause a short circuit inside the battery, causing greater safety problems. Solidification of electrolytes is an effective way to solve battery safety problems, but all-solid-state batteries face some challenges when they are brought to market, such as poor wettability between electrolytes and electrodes, ion transport problems at room temperature, and production process problems. Many teams are working hard to solve these problems, but the technology of all-solid-state batteries is not yet mature, so its application still needs time.

[0004] In-situ polymerization batteries can effectively improve the wettability and ionic conductivity of the electrolyte and electrodes, thereby increasing the energy density of the battery while also reducing the potential safety hazards caused by liquid electrolytes. In addition, highly cross-linked polymerized electrolytes can effectively inhibit changes in the negative electrode structure and the growth of metal dendrites to a certain extent, significantly improving battery safety while increasing specific energy. However, the formation polymerization process of solid-state batteries can have a significant impact on battery performance: during formation, the polymerized monomers present in the electrolyte react with the negative electrode to produce transition metal ions and gaseous byproducts that shuttle between the positive and negative electrodes, hindering the transport of lithium ions and affecting the formation of the SEI. Due to the high chemical / electrochemical reactivity and high-voltage fragility of monomers, initiators, and oligomers, they inevitably react with electrodes with corrosive chemical compositions (such as lithiated cathodes, delithiated graphite, and lithium anodes), resulting in the production of soluble byproducts (such as transition metal ions, etc.), solid byproducts (such as LiROCO2, -(CH2CH2O) n -, etc.), gaseous byproducts (such as H2, C2H4, etc.). Soluble byproducts and gaseous byproducts will shuttle between the cathode and anode, causing further deterioration of the electrode / electrolyte interface; polymerizing and fixing the polymerized monomers before formation will cause the gaseous byproducts generated during SEI formation to be fixed in the electrolyte, affecting lithium ion transport and thus increasing the internal resistance of the battery. Summary of the Invention

[0005] The purpose of the present invention is to overcome the shortcomings and deficiencies of the prior art and to provide a method for preparing a solid-state battery with gradient formation and polymerization.

[0006] The technical solution adopted by the present invention is as follows: A method for preparing a solid-state battery with gradient formation and polymerization, characterized by comprising the following steps:

[0007] S1. Assembly: Assemble the positive electrode sheet, separator and negative electrode sheet into the shell to form a bare battery cell;

[0008] S2, injection: inject liquid electrolyte;

[0009] S3, aging;

[0010] S4, forming to the specified capacity;

[0011] S5, liquid injection: injecting a mixed solution containing liquid electrolyte, polymer monomer and initiator;

[0012] S6, aging;

[0013] S7. When the capacity of the solid-state battery reaches the target formation capacity, in-situ polymerization and curing are performed;

[0014] When the capacity of the solid-state battery does not reach the target formation capacity, steps S4 to S6 are repeated after in-situ polymerization and curing, and then step S7 is continued, or formation and in-situ polymerization and curing are performed simultaneously, and then steps S5 to S6 are repeated and then step S7 is continued;

[0015] S8. Capacity separation to obtain a solid-state battery with gradient formation and polymerization.

[0016] In step S7, formation and in-situ polymerization and curing can be carried out simultaneously or in-situ polymerization and curing can be carried out first and then formation, which does not affect the technical effect of slowing down the polymerization monomer reaction and slowing down the fixation of gas byproducts by the polyelectrolyte through step-by-step formation and polymerization.

[0017] Preferably, the amount of liquid injected for n+1 times is ≤ the amount of liquid injected for n times, where n is a positive integer.

[0018] Preferably, the injection volume of n injections is positively correlated with the specified capacity of n formations.

[0019] Preferably, the injection amount of the second injection is 5-50 wt.% of the injection amount of the first injection, and more preferably 20-30 wt.%.

[0020] Preferably, the polymer monomer includes a multi-branched acrylate compound and / or a single-chain acrylate compound.

[0021] The multi-branched acrylate compound includes at least one of hydroxymethylpropane triacrylate TMPTA, ditrimethylolpropane acrylate DTMPTA, ethoxylated trimethylolpropane triacrylate ETPTA, pentaerythritol triacrylate PETA, and dipentaerythritol hexaacrylate DPHA;

[0022] The single-chain acrylate compound includes at least one of methyl acrylate MA, methyl methacrylate MMA, ethyl acrylate EA, butyl acrylate BA, ethylene glycol dimethacrylate EGDMA, and methoxy polyethylene glycol acrylate MPEGDA;

[0023] The initiator is one or more of 2,2-azobisisobutyronitrile, azobisisoheptanenitrile, dimethyl azobisisobutyrate, and benzoyl peroxide.

[0024] Preferably, the polymer monomer comprises a multi-branched acrylate compound and a single-chain acrylate compound, and the mass ratio of the multi-branched acrylate compound to the single-chain acrylate compound is 10:(1-100), and may further preferably be 4:(1-16).

[0025] Preferably, in step S5, the polymer monomer accounts for 5-20wt.% of the total mixed solution, for example, 5wt.%, 7wt.%, 9wt.%, 12wt.%, 15wt.%, 18wt.%, 20wt.%, and more preferably 5-12wt.%; the initiator accounts for 1-15wt.% of the polymer monomer, for example, 1wt.%, 3wt.%, 5wt.%, 7wt.%, 10wt.%, 12wt.%, 15wt.%, and more preferably 3-10wt.%. If the content of the polymer monomer or initiator is too high, the impedance of the battery will increase significantly; if the content is too low, the electrolyte will be difficult to polymerize, and a solid electrolyte cannot be effectively formed.

[0026] Preferably, in steps S3 and S6, the aging temperature is 20-50° C., and the aging time is 10-26 h.

[0027] Preferably, in step S4, the temperature of the formation is 25±3°C and the pressure of the formation is 5kg / cm 2 -20kg / cm 2 .

[0028] Preferably, in step S7, the in-situ polymerization curing time is 1-10 hours, the temperature is 45-65°C, and the pressure is 0-20 kg / cm 2 ;

[0029] The temperature for simultaneous formation and in-situ polymerization curing is 25-65°C and the pressure is 5kg / cm 2 -20kg / cm 2 .

[0030] Some additives in the electrolyte become unstable under prolonged high temperatures and can easily cause undesirable decomposition reactions with the electrode material. Therefore, it is necessary to control the temperature from being too high and the time from being too long.

[0031] Preferably, the liquid electrolyte in step S2 and step S5 contains a lithium salt, and the lithium salt includes at least one of lithium hexafluorophosphate, lithium bis(fluorosulfonyl)imide, lithium bis(trifluoromethanesulfonyl)imide, lithium trifluoromethanesulfonate, lithium tetrafluoroborate, lithium bis(oxalatoborate), lithium difluorooxalatoborate, and lithium difluorobis(oxalatophosphate).

[0032] Preferably, in step S1, the material of the positive electrode is selected from any one of NCM811, Ni90, NCM111, NCM532, NCM622, NCM712, nickel manganese aluminum material, lithium manganese iron phosphate, and lithium iron phosphate. The structural formula of Ni90 is LiNi x Co y Mn z O2, preferably, x≥0.8.

[0033] Preferably, in step S1, the negative electrode sheet is selected from any one of a graphite negative electrode, a silicon-doped graphite negative electrode, a lithium metal negative electrode, and a metal alloy negative electrode. The metal alloy negative electrode includes a Ga-Sn, Ge-Se, or Sn-Al alloy negative electrode. The silicon-doped graphite negative electrode preferably has a silicon doping content of 3-80 wt.%.

[0034] Preferably, both the positive and negative electrode sheets need to be mixed with a conductive agent, specifically one or more of carbon black (super P), Ketjen black (KB), acetylene black, multi-walled carbon nanotubes (MWCNTs), and single-walled carbon nanotubes (SWCNTs).

[0035] Preferably, a binder is required in both the positive and negative electrode sheets, specifically one or more of PEO (polyethylene oxide), PVDF (polyvinylidene fluoride), CMC (sodium carboxymethyl cellulose), PU (polyurethane), SBR (styrene-butadiene rubber), PVA (polyvinyl alcohol), PAA (polyacrylic acid), and PAN (polyacrylonitrile).

[0036] Preferably, the negative electrode sheet adopts a graphite negative electrode, a silicon-doped graphite negative electrode, a lithium metal negative electrode or a metal alloy negative electrode: the silicon-doped graphite negative electrode has a silicon content of 3-80wt.%, and the metal alloy negative electrode includes a Ga-Sn, Ge-Se or Sn-Al alloy negative electrode.

[0037] The beneficial effects of the present invention are as follows:

[0038] 1. The present invention uses a step-by-step in-situ polymerization method to manufacture and produce solid-state batteries. This involves first injecting a conventional liquid electrolyte, then repeatedly injecting a precursor solution containing polymer monomers and an initiator after formation, and then performing in-situ polymerization to form a gradient-formed solid-state battery. This method effectively mitigates the problems of monomer polymerization and the generation of fixed gas byproducts from the polyelectrolyte, and is compatible with existing conventional liquid battery production processes, reducing production line costs.

[0039] 2. The step-by-step formation capacity adopted by the present invention is positively correlated with the injection volume, thereby slowing down the side reactions caused by highly active polymerization monomers; as the number of injections increases, the content of film-forming additives in the precursor solution decreases, and the content of polymerization monomers and initiators increases, so that gas by-products can be effectively removed without being fixed inside the battery cell.

[0040] 3. The present invention regulates the degree of polymerization during in-situ polymerization by establishing a temperature-pressure-time three-factor coupling model: in-situ polymerization after n injections and in-situ polymerization after n+1 injections use different temperatures and pressures for cross-linking, thereby achieving controllable polymerization degrees at different positions in the battery cell and realizing an in-situ polymerization gradient gel battery. BRIEF DESCRIPTION OF THE DRAWINGS

[0041] In order to more clearly illustrate the embodiments of the present invention or the technical solutions in the prior art, the following briefly introduces the drawings required for use in the embodiments or the description of the prior art. Obviously, the drawings described below are only some embodiments of the present invention. For ordinary technicians in this field, without paying any creative work, other drawings obtained based on these drawings still fall within the scope of the present invention.

[0042] Figure 1 The flowchart of the preparation of the gradient formation and polymerization solid-state battery of the present invention is as follows;

[0043] Figure 2 Schematic diagram of the solid-state battery structure of the present invention with gradient formation and polymerization;

[0044] Figure 3 Graphs showing battery performance of Examples 1-3 of the present invention;

[0045] Figure 4 Graph showing battery performance of Comparative Examples 1-3 of the present invention. DETAILED DESCRIPTION

[0046] In order to make the objectives, technical solutions and advantages of the present invention more clear, the present invention will be described in further detail below with reference to the accompanying drawings.

[0047] like Figure 1 The figure shows a flow chart of the preparation of a solid-state battery with gradient formation and polymerization according to an embodiment of the present invention. Figure 2 Shown is a schematic diagram of the solid-state battery structure with gradient formation and polymerization.

[0048] The bare cells in the embodiments and comparative examples of the present invention were prepared using the following preparation method:

[0049] (1) Preparation of positive electrode slurry: lithium iron phosphate material (LFP), conductive carbon black (Super P), and binder (PVDF-900) were mixed in a mass percentage of 96.5:1.9:1.6 to obtain a positive electrode slurry;

[0050] (2) Preparation of negative electrode slurry: Graphite (BF), conductive carbon black (Super P), binder (sodium carboxymethyl cellulose CMC-500), and binder (styrene-butadiene rubber SBR) were mixed in a mass percentage of 93.5:3.6:1.2:1.7 to obtain a negative electrode slurry;

[0051] (3) Preparation of positive and negative electrode sheets: The positive electrode slurry is applied to aluminum foil, and the negative electrode slurry is applied to copper foil. The foils coated with the slurry are dried, rolled, rolled, and cut to obtain positive and negative electrode sheets.

[0052] (4) Pole core winding: The positive electrode sheet, negative electrode sheet, and separator (12um PP base film) are wound into a pole core. The wound pole core is hot-pressed and the pole ears are welded. Then, the pole core is assembled and placed in an aluminum-plastic film to form a bare cell. After the bare cell is baked, the electrolyte injection process can be carried out.

[0053] Example 1

[0054] S1. One injection: inject 20g of conventional lithium battery liquid electrolyte into the bare cell (in this embodiment, commercial LB002 electrolyte is used);

[0055] S2. Primary aging and formation: After the battery is aged at 25°C for 24 hours, it is placed in a high pressure chamber at room temperature (temperature is 25°C, pressure is controlled by a fixture, and is 10 kg / cm 2 ) conditions to 80% of the standard capacity;

[0056] S3. Secondary injection: The secondary injection volume is 8g, and the secondary injection electrolyte includes commercial LB002 electrolyte, ETPTA, EGDMA, AIBN, and the mass percentage of LB002 electrolyte, ETPTA, EGDMA, and AIBN is 60:20:20:5;

[0057] S4. Secondary aging and polymerization: After the battery is aged at 25°C for 24 hours, it is placed in a high temperature environment of 45°C and pressurized (the pressure is controlled by a fixture and is 10kg / cm 2 ) performing a polymerization reaction for 5 h to polymerize the electrolyte to form an in-situ polymerized electrolyte;

[0058] S5. Capacity separation: Perform capacity separation at room temperature to obtain finished battery cells.

[0059] Example 2

[0060] S1. One injection: inject 18g of conventional lithium battery liquid electrolyte into the bare cell (in this embodiment, commercial LB002 electrolyte is used);

[0061] S2. Primary aging and formation: After the battery is aged at 25°C for 24 hours, it is placed in a high pressure chamber at room temperature (temperature is 25°C, pressure is controlled by a fixture, and is 10 kg / cm 2 ) conditions to 80% of the standard capacity;

[0062] S3. Secondary injection: The secondary injection volume is 3 g. The secondary injection electrolyte includes commercial LB002 electrolyte, TMPTA, MA, and AIBN. The mass percentage of LB002 electrolyte, TMPTA, MA, and AIBN is 90:5:5:1.

[0063] S4. Secondary aging, polymerization, and formation: After the battery is aged at 25°C for 24 hours, it is placed in a high-temperature environment at 45°C and pressurized (the pressure is controlled by a fixture and is 10 kg / cm 2 ) to carry out polymerization reaction for 4 hours to polymerize the electrolyte to form an in-situ polymerized electrolyte, and then under normal temperature and high pressure conditions (temperature is 25±3℃, pressure is controlled by the fixture, and is 10kg / cm 2 ) to 91% of standard capacity;

[0064] S5. Three injections: The three injection volumes are 2 g. The secondary injection electrolyte includes commercial LB002 electrolyte, TMPTA, MA, and AIBN. The mass percentage of LB002 electrolyte, TMPTA, MA, and AIBN is 60:20:20:4.

[0065] S6. Three-stage aging and polymerization: After the battery is aged at 25°C for 24 hours, it is placed in a high-temperature environment at 60°C and pressurized (the pressure is controlled by a fixture and is 15kg / cm 2 ) performing a polymerization reaction for 4 hours to polymerize the electrolyte to form an in-situ polymerized electrolyte;

[0066] S7. Capacity separation: Perform capacity separation at room temperature to obtain finished battery cells.

[0067] Example 3

[0068] S1. One injection: inject 15g of conventional lithium battery liquid electrolyte into the bare cell (in this embodiment, commercial LB002 electrolyte is used);

[0069] S2. Primary aging and formation: After the battery is aged at 25°C for 24 hours, it is placed in a high pressure chamber at room temperature (temperature is 25°C, pressure is controlled by a fixture, and is 10 kg / cm 2 ) conditions to 60% of the standard capacity;

[0070] S3. Secondary injection: The secondary injection volume is 5 g. The secondary injection electrolyte includes commercial LB002 electrolyte, PETA, BA, and AIBN. The mass percentage of LB002 electrolyte, PETA, BA, and AIBN is 90:5:5:0.7.

[0071] S4. Secondary aging, polymerization, and formation: After the battery is aged at 25°C for 24 hours, it is placed in a high-temperature environment at 45°C and pressurized (the pressure is controlled by a fixture and is 10 kg / cm 2 ) to carry out polymerization reaction for 2h, so that the electrolyte is polymerized to form an in-situ polymerized electrolyte, and then under normal temperature and high pressure conditions (temperature is 25±3℃, pressure is controlled by the fixture, and is 10kg / cm 2 ) to 80% of the standard capacity;

[0072] S5. Three injections: The three injection volumes are 5 g, and the secondary injection electrolyte includes commercial LB002 electrolyte, PETA, BA, and AIBN. The mass percentage of LB002 electrolyte, PETA, BA, and AIBN is 80:10:10:1.5.

[0073] S6. Three-stage aging and polymerization: After the battery is aged at 25°C for 24 hours, it is placed in a high-temperature environment at 60°C and pressurized (the pressure is controlled by a fixture and is 20kg / cm 2 ) performing a polymerization reaction for 2 h to polymerize the electrolyte to form an in-situ polymerized electrolyte;

[0074] S7. Capacity separation: Perform capacity separation at room temperature to obtain finished battery cells.

[0075] Comparative Example 1

[0076] S1. Injection: The injection volume is 28 g, and the secondary injection electrolyte includes commercial LB002 electrolyte, ETPTA, mPEGDA, AIBN, and the mass percentage of LB002 electrolyte, ETPTA, mPEGDA, and AIBN is 96:2:2:0.3;

[0077] S2. Aging, polymerization, formation, aging, and capacity separation: After the battery is aged at 25°C for 24 hours, it is placed in a high-temperature environment of 60°C for polymerization reaction for 2 hours to polymerize the electrolyte to form an in-situ polymerized electrolyte. Then, it is placed in a high-temperature and high-pressure environment (temperature of 40±3°C, pressure controlled by a fixture, 10kg / cm 2 ) into;

[0078] The cells were aged at 25°C and capacity divided at room temperature to obtain finished battery cells.

[0079] Comparative Example 2

[0080] The difference between this comparative example and comparative example 1 is that in step S2:

[0081] S2. Aging, formation, aging, polymerization, and capacity separation: After the battery is aged at 25°C for 24 hours, it is placed under normal temperature and high pressure conditions (temperature is 25±3°C, pressure is controlled by a fixture, and is 10kg / cm 2 ) is formed, and then aged at 25°C for 24 hours, and then polymerized in a high-temperature environment of 60°C for 2 hours to polymerize the electrolyte to form an in-situ polymerized electrolyte, and finally the capacity is divided at room temperature to obtain a finished battery cell.

[0082] Comparative Example 3

[0083] The difference between this comparative example and comparative example 1 is that in step S2:

[0084] S2. Aging, simultaneous polymerization, and capacity separation: After the battery is aged at 25°C for 24 hours, it is placed under high temperature and high pressure conditions (temperature of 45±3°C, pressure controlled by a fixture, and 10kg / cm 2 ) is formed and polymerized at the same time, and the electrolyte is polymerized to form an in-situ polymerized electrolyte during the formation, and finally the capacity is divided at room temperature to obtain a finished battery cell.

[0085] Figure 3 The batteries of the embodiment were cycled for 3 cycles at a rate of 0.1 C and then subjected to constant current charge and discharge tests at a rate of 0.5 C. After 50 cycles of charge and discharge, the batteries of the embodiment all had high specific capacity and capacity retention.

[0086] Figure 4 The comparative battery was cycled at a rate of 0.1 C for 3 cycles and then subjected to a constant current charge-discharge test at a rate of 0.5 C. After 50 cycles of charge-discharge, the specific capacity and capacity retention rate of the comparative battery were significantly lower than those of the embodiment.

[0087] The above disclosure is merely a preferred embodiment of the present invention and certainly cannot be used to limit the scope of the present invention. Therefore, equivalent changes made according to the claims of the present invention are still within the scope of the present invention.

Claims

1. A method for preparing a solid-state battery with gradient formation and polymerization, characterized in that: The steps include: S1. Assembly: Assemble the positive electrode sheet, separator and negative electrode sheet into the shell to form a bare battery cell; S2, injection: inject liquid electrolyte; S3, aging; S4, forming to the specified capacity; S5, liquid injection: injecting a mixed solution containing liquid electrolyte, polymer monomer and initiator; S6, aging; S7. When the capacity of the solid-state battery reaches the target formation capacity, in-situ polymerization and curing are performed; When the capacity of the solid-state battery does not reach the target formation capacity, steps S4 to S6 are repeated after in-situ polymerization and curing, and then step S7 is continued, or formation and in-situ polymerization and curing are performed simultaneously, and then steps S5 to S6 are repeated and then step S7 is continued; S8. Capacity separation to obtain a solid-state battery with gradient formation and polymerization.

2. The method for preparing a gradient formation and polymerization solid-state battery according to claim 1, characterized in that: The amount of liquid injected for n+1 times is ≤ the amount of liquid injected for n times, where n is a positive integer.

3. The method for preparing a solid-state battery with gradient formation and polymerization according to claim 1, characterized in that: The injection amount of the second injection is 5-50 wt.% of the injection amount of the first injection.

4. The method for preparing a solid-state battery with gradient formation and polymerization according to claim 1, characterized in that: The polymer monomer includes a multi-branched acrylate compound and / or a single-chain acrylate compound, The multi-branched acrylate compound includes at least one of hydroxymethylpropane triacrylate TMPTA, ditrimethylolpropane acrylate DTMPTA, ethoxylated trimethylolpropane triacrylate ETPTA, pentaerythritol triacrylate PETA, and dipentaerythritol hexaacrylate DPHA; The single-chain acrylate compound includes at least one of methyl acrylate MA, methyl methacrylate MMA, ethyl acrylate EA, butyl acrylate BA, ethylene glycol dimethacrylate EGDMA, and methoxy polyethylene glycol acrylate MPEGDA; The initiator is one or more of 2,2-azobisisobutyronitrile, azobisisoheptanenitrile, dimethyl azobisisobutyrate, and benzoyl peroxide.

5. The method for preparing a gradient formation and polymerization solid-state battery according to claim 1, characterized in that: The polymer monomer comprises a multi-branched acrylate compound and a single-chain acrylate compound, and the mass ratio of the multi-branched acrylate compound to the single-chain acrylate compound is 10:(1-100).

6. The method for preparing a solid-state battery with gradient formation and polymerization according to claim 1, characterized in that: In step S5, the polymer monomer accounts for 5-20 wt.% of the total amount of the mixed solution; the initiator accounts for 1-15 wt.% of the polymer monomer.

7. The method for preparing a solid-state battery with gradient formation and polymerization according to claim 1, characterized in that: In steps S3 and S6, the aging temperature is 20-50° C., and the aging time is 10-26 hours.

8. The method for preparing a gradient formation and polymerization solid-state battery according to claim 1, characterized in that: In step S4, the temperature of the formation is 25±3°C and the pressure of the formation is 5kg / cm 2 -20kg / cm 2 .

9. The method for preparing a solid-state battery with gradient formation and polymerization according to claim 1, characterized in that: In step S7, the in-situ polymerization curing time is 1-10 hours, the temperature is 45-65°C, and the pressure is 0-20kg / cm 2 ; The temperature for simultaneous formation and in-situ polymerization curing is 25-65°C and the pressure is 5kg / cm 2 -20kg / cm 2 .

10. The method for preparing a solid-state battery with gradient formation and polymerization according to any one of claims 1 to 9, characterized in that: The liquid electrolytes in step S2 and step S5 both contain lithium salts, and the lithium salts include at least one of lithium hexafluorophosphate, lithium bis(fluorosulfonyl)imide, lithium bis(trifluoromethanesulfonyl)imide, lithium trifluoromethanesulfonate, lithium tetrafluoroborate, lithium bis(oxalatoborate), lithium difluorooxalatoborate, and lithium difluorobis(oxalatophosphate).

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