Calcium carbonate grafted lithium ion transmission functional polymer with core-shell structure as well as preparation method and application of calcium carbonate grafted lithium ion transmission functional polymer

Abstract

The invention belongs to the technical field of solid-state batteries, and particularly relates to a calcium carbonate grafted lithium ion transmission functional polymer with a core-shell structure and a preparation method and application thereof. The preparation method comprises the following steps: grafting a lithium ion transmission functional polymer on the surface of calcium carbonate through an atom transfer radical polymerization method to obtain a calcium carbonate grafted lithium ion transmission functional polymer with a core-shell structure, mixing the calcium carbonate grafted lithium ion transmission functional polymer with a solid electrolyte polymer matrix and a lithium salt, and carrying out hot pressing to form the polymer composite solid electrolyte. The prepared calcium carbonate grafted lithium ion transmission functional polymer with the core-shell structure has good interfacial compatibility, and the obtained polymer composite solid electrolyte has the advantages of adjustable and controllable structure, high mechanical strength and the like, has a Ca < 2 + > slow-release effect, can suppress dendritic crystal growth on the surface of lithium metal, and has a good lithium ion transmission performance. In the lithium-sulfur battery, the shuttle flying effect of polysulfide can be suppressed, the cycle life is prolonged, and the material is expected to be widely applied to the field of intelligent lithium batteries.

Description

Technical Field

[0001] This invention belongs to the field of solid-state battery technology, specifically relating to a calcium carbonate-grafted lithium-ion transport polymer with a core-shell structure, its preparation method, and its application. Background Technology

[0002] Polymer electrolytes have attracted widespread attention and application due to their excellent affinity and migration ability for lithium ions and strong adaptability at electrode interfaces. However, polymer electrolytes themselves struggle to simultaneously possess both high ionic conductivity and high mechanical strength, necessitating the combination with other materials to form composite solid-state electrolytes that meet the charge-discharge cycle requirements of solid-state lithium batteries. The introduction of inorganic fillers can suppress the crystallization of polymer electrolytes, thereby improving their ion transport capacity and providing mechanical enhancement. However, conventional inorganic fillers suffer from poor interfacial compatibility with the polymer electrolyte matrix, making it difficult to achieve good dispersion and limiting their performance enhancement effect on solid-state electrolytes, failing to adequately suppress lithium dendrite formation. Especially for lithium-sulfur batteries, conventional composite solid-state electrolytes lack ion transport selectivity, making it difficult to meet the requirements for suppressing the polysulfide shuttle effect.

[0003] Composite solid-state electrolytes typically consist of a polymer matrix, inorganic fillers, and lithium salts. The inorganic fillers include inert and active inorganic fillers. While composite solid-state electrolytes doped with inert inorganic fillers show improved lithium-ion conductivity, the increase is limited because the filler itself cannot conduct lithium ions. Active ceramic inorganic fillers with lithium-ion conductivity can achieve high ionic conductivity, but they face challenges such as poor interfacial compatibility, the need for high-voltage cycling, and high cost. Therefore, developing a novel solid-state electrolyte filler with ion transport activity, good interfacial compatibility, and low cost is crucial for improving the performance of solid-state lithium batteries. Furthermore, the filler also needs to possess selective lithium-ion and polysulfide transport capabilities to meet the needs of solid-state lithium-sulfur battery development.

[0004] Calcium carbonate plays a role in the slow-release of calcium ions in lithium-ion batteries, which can inhibit the growth of lithium dendrites, improve the composition of the solid electrolyte interface layer, suppress membrane perforation and electrolyte decomposition, and enhance battery safety. Slow-release calcium ions in polymer solid electrolytes are expected to improve the strength of the solid electrolyte through coordination crosslinking and also have potential polysulfide trapping effects. However, no research has yet reported the role of modified calcium carbonate in solid electrolytes and polysulfide trapping. Summary of the Invention

[0005] To overcome the shortcomings of the prior art, this invention provides a calcium carbonate-grafted lithium-ion transport polymer with a core-shell structure, its preparation method, and its application. This invention first grafts a lithium-ion transport polymer onto the surface of calcium carbonate using atom transfer radical polymerization to obtain a calcium carbonate-grafted lithium-ion transport polymer with a core-shell structure. This polymer is then mixed with a solid electrolyte polymer matrix and a lithium salt, and hot-pressed to form a polymer composite solid electrolyte. The obtained calcium carbonate-grafted lithium-ion transport polymer with a core-shell structure exhibits good interfacial compatibility. The resulting polymer composite solid electrolyte has advantages such as adjustable and controllable structure, high mechanical strength, and the presence of Ca... 2+ The slow-release effect can suppress dendrite growth on the surface of lithium metal, and in lithium-sulfur batteries it can also suppress the shuttle effect of polysulfides, extending cycle life. It is expected to be widely used in the field of smart lithium batteries.

[0006] To achieve the above objectives, the technical solution adopted by the present invention is as follows: The first aspect of this invention provides a method for preparing a calcium carbonate-grafted lithium-ion transport polymer with a core-shell structure, comprising the following steps: (1) After mixing calcium carbonate and siloxane initiator in the first solvent, react under inert gas protection to form pre-grafted calcium carbonate; (2) After mixing the lithium-ion transport functional monomer with pre-grafted calcium carbonate in the second solvent, copper catalyst, amino ligand, reducing agent and co-initiator are added under inert gas protection to react and obtain calcium carbonate grafted lithium-ion transport functional polymer with core-shell structure.

[0007] Further, in step (1), the calcium carbonate particle size is 0.01-100 μm; the siloxane initiator is 2-bromo-2-methyl-N-(3-(triethoxysilyl)propyl)propionamide, and the amount of the siloxane initiator is 20-200% of the mass of calcium carbonate.

[0008] Further, in step (1), the first solvent is toluene, and the reaction time is 2-108 h.

[0009] Further, in step (2), the lithium-ion transport functional monomer is acrylonitrile, acrylamide, acrylic acid, lithium acrylate, methyl acrylate, ethyl acrylate, ethylene glycol acrylate, polyethylene glycol acrylate, ethylene ethylene carbonate, hydroxyethyl acrylate, hydroxypropyl acrylate, lithium 2-acrylamido-2-methylpropanesulfonate, 2-oxo-1,3-dioxolan-4-yl-2-acrylic acid, trifluoroethyl acrylate, trifluoroethyl methacrylate, bis(trifluoromethanesulfonyl)imide methacrylate, imidazole ethyl methacrylate, (E)-methyl 3-(3-methyl-3H-imidazo[4,5-b]pyridin-6-yl)acrylate, 2-Propenoic acid, 2-Methyl-, (2-oxo-1,3-dioxolan-4-yl)Methyl ester, 2-(3-(4-amino-6-(3-butylureido)-1,3,5-triazin-2-yl) The lithium-ion transport functional monomer is selected from at least one of ureido) ethyl methacrylate and 4-styrenesulfonyl(phenylsulfonyl) lithium imide, the copper catalyst is selected from at least one of copper bromide and cuprous bromide, the amino ligand is 1,1,4,7,10,10-hexamethyltriethylenetetramine, the reducing agent is ascorbic acid, the co-initiator is azobisisobutyronitrile, the mass of the lithium-ion transport functional monomer is 50-10000% of the mass of pre-grafted calcium carbonate, the amount of the reducing agent is 0-0.5% of the mass of the lithium-ion transport functional monomer, the amount of the amino ligand is 0-2% of the mass of the lithium-ion transport functional monomer, and the amount of the initiating agent is 0-2% of the mass of the lithium-ion transport functional monomer.

[0010] Further, in step (2), the second solvent is a mixed solvent of methanol and deionized water, the reaction time is 8-144 h, and the reaction temperature is 20-60 °C. o C.

[0011] A second aspect of the present invention provides a calcium carbonate-grafted lithium-ion transport polymer with a core-shell structure prepared by the above-described preparation method.

[0012] A third aspect of the present invention provides a method for preparing a polymer composite solid electrolyte using the above-mentioned calcium carbonate-grafted lithium-ion transport polymer with a core-shell structure, comprising the following steps: The solid electrolyte polymer matrix, grafted calcium carbonate and lithium salt are mixed evenly and dried, and then hot-pressed after being stacked with a porous substrate.

[0013] Further, the solid electrolyte polymer matrix is ​​any one of polyethylene oxide, polyacrylonitrile, polyvinylidene fluoride, polymethyl methacrylate, polymethyl methacrylate, polylactic acid, polyurethane, polyvinyl alcohol, polydopamine, polyimide, polycarbonate, polytetrahydrofuran, polypropylene oxide, and polysiloxane; the lithium salt is at least one of lithium hexafluorophosphate, lithium hexafluoroarsenate, lithium perchlorate, lithium tetrafluoroborate, lithium bis(oxalato)borate, lithium nitrate, lithium iodide, lithium trifluoromethanesulfonate, lithium di(trifluoromethanesulfonate)imide, or lithium tri(trifluoromethanesulfonyl)methyl; the porous substrate is any one of porous polyethylene, porous polypropylene, PP / PE composite membrane, porous polyimide, cellulose membrane, glass fiber filter paper, and asbestos filter paper.

[0014] Furthermore, the amount of grafted calcium carbonate is 1-50% of the mass of the solid electrolyte polymer matrix, the amount of lithium salt is 10-100% of the mass of the solid electrolyte polymer matrix, and the hot pressing temperature is 60-250°C. o C, the pressure of the hot pressing is 5-40 MPa.

[0015] A fourth aspect of the present invention provides a polymer composite solid electrolyte prepared by the above-described method.

[0016] Compared with the prior art, the beneficial effects of the present invention are: This invention provides a calcium carbonate-grafted lithium-ion transport polymer with a core-shell structure, its preparation method, and its applications. The invention first grafts a lithium-ion transport polymer onto the surface of calcium carbonate using atom transfer radical polymerization to obtain a calcium carbonate-grafted lithium-ion transport polymer with a core-shell structure. This polymer is then mixed with a solid electrolyte polymer matrix and a lithium salt, and hot-pressed to form a polymer composite solid electrolyte. The resulting calcium carbonate-grafted lithium-ion transport polymer with a core-shell structure exhibits good interfacial compatibility. The resulting polymer composite solid electrolyte has advantages such as tunable and controllable structure, high mechanical strength, and the presence of Ca2+. 2+ The slow-release effect can suppress dendrite growth on the surface of lithium metal, and in lithium-sulfur batteries it can also suppress the shuttle effect of polysulfides, extending cycle life. It is expected to be widely used in the field of smart lithium batteries.

[0017] Specifically, the present invention has the following advantages: (1) The calcium carbonate-grafted lithium-ion transport functional polymer with core-shell structure designed in this invention optimizes the interfacial lithium-ion transport capability and matrix interfacial compatibility of calcium carbonate. On the one hand, the interfacial lithium-ion conductivity and ion transference number of the polymer composite solid electrolyte are improved by grafting functional polymer. On the other hand, the dispersion of calcium carbonate is improved, which has the effect of strengthening and toughening. It is also more conducive to calcium carbonate breaking the crystal structure of the solid electrolyte polymer matrix and improving the segment ion transport capability of the polymer.

[0018] (2) The present invention uses atom transfer radical polymerization technology to graft calcium carbonate. Atom transfer radical polymerization is a living polymerization reaction without chain transfer side reactions. The resulting calcium carbonate grafted lithium ion transport polymer with core-shell structure has the advantages of adjustable and controllable structure, morphology and function.

[0019] (3) The encapsulation of the lithium-ion transport polymer in this invention enables calcium carbonate to form a calcium ion slow-release effect in the lithium battery. The electrostatic effect of calcium ions can inhibit the growth of lithium dendrites and suppress the polysulfide shuttle in the lithium-sulfur battery. Attached Figure Description

[0020] Figure 1 The infrared spectrum is that of the pre-grafted calcium carbonate in Example 1.

[0021] Figure 2 The infrared spectrum is that of the calcium carbonate-grafted lithium-ion transport polymer with a core-shell structure in Example 1.

[0022] Figure 3 This is a scanning electron microscope image of the calcium carbonate-grafted lithium-ion transport polymer with a core-shell structure in Example 1.

[0023] Figure 4 This is the interfacial impedance spectrum of the polymer composite solid electrolyte in Example 1.

[0024] Figure 5 This is the electrochemical window of the polymer composite solid electrolyte in Example 1.

[0025] Figure 6 The charge-discharge curves of the lithium-sulfur battery in Example 1 are shown.

[0026] Figure 7 This is the interfacial impedance spectrum of the polymer composite solid electrolyte in Example 2.

[0027] Figure 8 This is the interfacial impedance spectrum of the polymer composite solid electrolyte in Example 3.

[0028] Figure 9 This is a scanning electron microscope image of the polymer composite solid electrolyte in Comparative Example 1.

[0029] Figure 10 The charge-discharge curves of the lithium-sulfur battery in Comparative Example 2 are shown.

[0030] Figure 11 The charge-discharge curves of the lithium-sulfur battery in Comparative Example 3 are shown. Detailed Implementation

[0031] The specific embodiments of the present invention will be further described below. It should be noted that these descriptions are for the purpose of aiding understanding the present invention, but do not constitute a limitation thereof. Furthermore, the technical features involved in the various embodiments of the present invention described below can be combined with each other as long as they do not conflict with each other.

[0032] Unless otherwise specified, the experimental methods used in the following embodiments are conventional methods, and the experimental materials used in the following embodiments are all available through conventional commercial channels.

[0033] Example 1 (1) Preparation of pre-grafted calcium carbonate: 1 g of 50 nm calcium carbonate and 40 mL of anhydrous toluene were added to a Schrank flask and ultrasonically dispersed for 15 min; 0.8 g of 2-bromo-2-methyl-N-(3-(triethoxysilyl)propyl)propionamide was dissolved in 10 mL of anhydrous toluene and then slowly added dropwise to the above solution; nitrogen gas was purged three times and the reaction was carried out at room temperature for 2 days; the mixture was separated by centrifugation and washed twice with anhydrous toluene, anhydrous acetone and anhydrous ethanol respectively, and placed in a 40°C container. o After drying in a vacuum oven at temperature C for 24 hours, the pre-grafted calcium carbonate is ready for use. The infrared spectrum of the pre-grafted calcium carbonate prepared in this step is as follows: Figure 1 As shown, this demonstrates the successful synthesis of prebranched calcium carbonate.

[0034] (2) Preparation of a core-shell structured calcium carbonate-grafted lithium-ion transport polymer: 51.8 g of 2-acrylamido-2-methylpropanesulfonic acid was added to a three-necked flask, and 500 mL of methanol / water mixed solvent (methanol:water volume ratio = 1:1) was added. The 2-acrylamido-2-methylpropanesulfonic acid was fully dissolved under magnetic stirring. 21 g of lithium hydroxide monohydrate was added to the above solution and stirred for 30 min to ensure complete reaction. 4 g of pre-grafted calcium carbonate was added to the above solution and ultrasonically dispersed for 20 min. Argon gas was introduced for 15 min to ensure that oxygen in the system was removed. Under argon gas, 0.67 g of copper bromide, 1.36 mL of 1,1,4,7,10,10-hexamethyltriethylenetetramine and 0.88 g of ascorbic acid were added sequentially. The mixture was stirred under argon gas and at 40 °C. o The reaction was carried out at C for 36 h; centrifugation was used to separate the samples, and the mixture was washed three times with deionized water and placed at 40 °C. o After drying in a vacuum oven at C for 24 hours, the polymer with a core-shell structure and lithium-ion transport function obtained in this step has the following infrared spectrum: Figure 2 As shown, this demonstrates the successful synthesis of a calcium carbonate-grafted lithium-ion transport polymer with a core-shell structure. Scanning electron microscope images are shown below. Figure 3 As shown, this demonstrates the successful assembly of a core-shell structured calcium carbonate.

[0035] (3) Preparation of polymer composite solid electrolyte: 1 g polyethylene oxide, 0.2 g calcium carbonate grafted with core-shell structure and lithium-ion transport function polymer, and 0.5 g lithium bis(trifluoromethanesulfonic acid)imide were dissolved in 10 mL tetrahydrofuran and stirred at room temperature for 24 hours; the solution was poured into a 50 mm × 50 mm mold and the solvent was allowed to evaporate naturally under a fume hood to obtain a pre-formed film; the pre-formed film and porous polyimide were subjected to a 10 MPa, 100 o Hot pressing at C causes the polymer composite solid electrolyte to finally solidify. The interfacial impedance spectrum of the polymer composite electrolyte prepared in this embodiment is as follows. Figure 4 As shown, the electrochemical window is as follows Figure 5 As shown, it can be seen that it has high ionic conductivity (0.23 mS / s, 30 mS / s). o C) High electrochemical stability.

[0036] The charge-discharge curve of the lithium-sulfur battery assembled in this embodiment is as follows: Figure 6 As shown, the lithium-sulfur battery assembled using the polymer composite electrolyte prepared in this embodiment has a high specific capacity.

[0037] Example 2 The only difference between Example 2 and Example 1 is that the amount of calcium carbonate-grafted lithium-ion transport polymer with a core-shell structure used in step (3) is 0.3 g, while the rest is the same as in Example 1.

[0038] The interfacial impedance spectrum of the polymer composite solid electrolyte prepared in this embodiment is as follows: Figure 7 As shown, the ionic conductivity of the polymer composite solid electrolyte measured at 30℃ is 0.14 mS / s.

[0039] Example 3 The only difference between Example 3 and Example 1 is that in step (3), lithium perchlorate is used instead of lithium di(trifluoromethanesulfonic acid)imide. The rest is the same as in Example 1.

[0040] The interfacial impedance spectrum of the polymer composite solid electrolyte prepared in this embodiment is as follows: Figure 8 As shown, the ionic conductivity of the polymer composite solid electrolyte measured at 30℃ is 0.19 mS / s.

[0041] Comparative Example 1 The only difference between Comparative Example 1 and Example 1 is that cyclohexane was used instead of anhydrous toluene as the solvent in step (1). Everything else was the same as in Example 1.

[0042] Scanning electron microscope images of the polymer composite solid electrolyte prepared in this comparative example are shown below. Figure 9 As shown, this method cannot adequately graft calcium carbonate and does not improve its dispersibility.

[0043] Comparative Example 2 The only difference between Comparative Example 2 and Example 1 is that step (3) uses ungrafted calcium carbonate for filling, while the rest is the same as Example 1.

[0044] The charge-discharge curves of the lithium-sulfur battery assembled in this comparative example are as follows: Figure 10 As shown, it can be seen that the lithium-sulfur battery assembled using the polymer composite electrolyte prepared in this embodiment cannot be charged and discharged normally.

[0045] Comparative Example 3 The only difference between Comparative Example 3 and Example 1 is that in step (3), the pre-formed thin film is directly assembled into a battery. The rest is the same as in Example 1.

[0046] The charge-discharge curves of the lithium-sulfur battery assembled in this comparative example are as follows: Figure 11 As shown, the thickness of the composite solid electrolyte obtained by this method is uncontrollable, and the specific capacity of the assembled lithium-sulfur battery is low.

[0047] The embodiments of the present invention have been described in detail above, but the present invention is not limited to the described embodiments. For those skilled in the art, various changes, modifications, substitutions, and variations can be made to these embodiments without departing from the principles and spirit of the present invention, and these variations still fall within the protection scope of the present invention.

Claims

1. A method for preparing calcium carbonate having a core-shell structure grafted with a lithium ion transport functional polymer, characterized by, The method comprises the following steps: (1) mixing calcium carbonate and siloxane initiator in a first solvent, and then reacting under inert gas protection to form pre-grafted calcium carbonate; (2) mixing lithium ion transport functional monomer and pre-grafted calcium carbonate in a second solvent, and then adding copper catalyst, amino ligand, reducing assistant and assistant initiator under inert gas protection to obtain calcium carbonate grafted lithium ion transport functional polymer with core-shell structure.

2. The method of claim 1, wherein the calcium carbonate grafted lithium ion transport functional polymer having a core-shell structure is prepared by the following steps of: (a) preparing a calcium carbonate core; (b) preparing a lithium ion transport functional polymer shell; and (c) grafting the lithium ion transport functional polymer shell onto the calcium carbonate core. In step (1), the particle size of the calcium carbonate is 0.01-100 μm; the siloxane initiator is 2-bromo-2-methyl-N-(3(triethoxysil)propyl)propionamide, and the amount of the siloxane initiator is 20-200% of the mass of the calcium carbonate.

3. The method of claim 1, wherein the calcium carbonate grafted lithium ion transport functional polymer having a core-shell structure is prepared by the following steps of: (a) preparing a calcium carbonate core; (b) preparing a lithium ion transport functional polymer shell; and (c) grafting the lithium ion transport functional polymer shell onto the calcium carbonate core. In step (1), the first solvent is toluene, and the reaction time is 2-108 h.

4. The method of claim 1, wherein the calcium carbonate grafted lithium ion transport functional polymer having a core-shell structure is prepared by the steps of: (a) preparing a calcium carbonate core; (b) preparing a lithium ion transport functional polymer shell; and (c) grafting the lithium ion transport functional polymer shell onto the calcium carbonate core. In step (2), the lithium ion transport functional monomer is at least one of acrylonitrile, acrylamide, acrylic acid, lithium acrylate, methyl acrylate, ethyl acrylate, ethylene glycol acrylate, polyethylene glycol acrylate, ethylene carbonate, hydroxyethyl acrylate, hydroxypropyl acrylate, lithium 2-acrylamido-2-methylpropane sulfonate, 2-oxo-1,3-dioxolan-4-yl 2-propenoic acid, trifluoroethyl acrylate, trifluoroethyl methacrylate, bis(trifluoromethylsulfonyl) imide methacrylic acid, imidazole ethyl methacrylate, (E)-methyl 3-(3-methyl-3H-imidazo[4,5-b]pyridine-6-yl) acrylate, 2-propenoic acid, 2-methyl-, (2-oxo-1,3-dioxolan-4-yl) methyl ester, 2-(3-(4-amino-6-(3-butylureido)-1,3,5-triazin-2-yl) ureido) ethyl methacrylate and 4-styrenesulfonyl(phenylsulfonyl) lithium imide, the copper catalyst is at least one of copper bromide and cuprous bromide, the amino ligand is 1,1,4,7,10,10-hexamethyltriethylenetetramine, the reducing assistant is ascorbic acid, the assistant initiator is azobis isobutyronitrile, the mass of the lithium ion transport functional monomer is 50-10000% of the mass of the pre-grafted calcium carbonate, the amount of the reducing assistant is 0-0.5% of the mass of the lithium ion transport functional monomer, the amount of the amino ligand is 0-2% of the mass of the lithium ion transport functional monomer, and the amount of the initiator assistant is 0-2% of the mass of the lithium ion transport functional monomer.

5. The method of claim 1, wherein the calcium carbonate grafted lithium ion transport functional polymer having a core-shell structure is prepared by the following steps of: (a) preparing a calcium carbonate core; (b) preparing a lithium ion transport functional polymer shell; and (c) grafting the lithium ion transport functional polymer shell onto the calcium carbonate core. In step (2), the second solvent is a mixture of methanol and deionized water, the reaction time is 8-144 h, and the reaction temperature is 20-60 o C.

6. The calcium carbonate grafted lithium ion transport functional polymer with core-shell structure prepared by the preparation method of any one of claims 1-5.

7. A method for preparing a polymer composite solid-state electrolyte using the calcium carbonate having a core-shell structure of claim 6 grafted with a lithium ion transport functional polymer, characterized by, The method comprises the following steps: Mixing the solid electrolyte polymer matrix, grafted calcium carbonate and lithium salt uniformly and drying, and then laminating with a porous substrate and hot pressing to form. The method comprises the following steps: Mixing the solid electrolyte polymer matrix, grafted calcium carbonate and lithium salt uniformly and drying, and then laminating with a porous substrate and hot pressing to form.

8. The method of claim 7, wherein the polymer composite solid-state electrolyte is prepared by a process comprising: The solid-state electrolyte polymer matrix is any one of polyethylene oxide, polyacrylonitrile, polyvinylidene fluoride, polymethyl acrylate, polymethyl methacrylate, polylactic acid, polyurethane, polyvinyl alcohol, polydopamine, polyimide, polycarbonate, polytetrahydrofuran, polypropylene oxide, polysiloxane; the lithium salt is at least one of lithium hexafluorophosphate, lithium hexafluoroarsenate, lithium perchlorate, lithium tetrafluoroborate, lithium bis(oxalato)borate, lithium nitrate, lithium iodide, lithium triflate, lithium bis(trifluoromethylsulfonyl)imide or lithium tris(trifluoromethylsulfonyl)methide; the porous substrate is any one of porous polyethylene, porous polypropylene, PP / PE composite membrane, porous polyimide, cellulose separator, glass fiber filter paper, asbestos filter paper.

9. The method of claim 7, wherein the polymer composite solid-state electrolyte is prepared by mixing the polymer and the solid-state electrolyte in a solvent. The amount of the grafted calcium carbonate is 1-50% of the mass of the solid electrolyte polymer matrix, the amount of the lithium salt is 10-100% of the mass of the solid electrolyte polymer matrix, the temperature of the hot pressing is 60-250 o C, and the pressure of the hot pressing is 5-40 MPa.

10. A polymer composite solid-state electrolyte prepared by the method of any one of claims 8-9.

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