Composite polymer solid electrolyte material and preparation method and application thereof
Patent Information
- Authority / Receiving Office
- CN · China
- Patent Type
- Applications(China)
- Current Assignee / Owner
- CHONGQING UNIV
- Filing Date
- 2026-03-11
- Publication Date
- 2026-05-29
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Abstract
Description
Technical Field
[0001] This invention belongs to the field of solid electrolyte materials technology, and particularly relates to a composite polymer solid electrolyte material, its preparation method and application. Background Technology
[0002] In recent years, with the rapid development of rechargeable battery technology, metal-ion batteries, represented by lithium-ion and sodium-ion batteries, have gradually achieved technological maturity and large-scale commercialization. However, the organic electrolytes commonly used in traditional liquid metal-ion batteries are highly susceptible to leakage, combustion, and even explosion under abnormal conditions such as overcharging or mechanical impact, posing serious safety hazards. Against this backdrop, replacing traditional liquid electrolytes with solid-state electrolytes is considered one of the most promising solutions for fundamentally improving battery safety.
[0003] Polymer solid electrolytes, with their excellent flexibility and mechanical strength, can adapt to the volume changes of the electrode during cycling and, to some extent, suppress the growth of lithium dendrites, thereby significantly improving battery safety and cycle stability. Among them, polyvinylidene fluoride-hexafluoropropylene copolymer (PVDF-HFP) based electrolytes, due to their excellent film-forming properties, simple preparation process, and relatively low cost, show good potential for large-scale production and are more suitable for commercialization. However, these polymer electrolytes generally suffer from low ionic conductivity at room temperature (typically below 10⁻⁻⁶). 4 The S / cm ratio limits ion transport efficiency, severely restricting its application performance in high-power batteries.
[0004] Currently, the ionic conductivity of polymer solid-state electrolytes is often improved by adding inorganic fillers (such as silica, titanium dioxide, lithium fast ion conductors, or sodium fast ion conductors), mainly by disrupting the polymer's crystalline structure and increasing the content of amorphous regions. However, these inorganic fillers often have limited effect on promoting the dissociation of electrolytes such as lithium and sodium salts, and it is difficult to construct continuous and efficient ion transport channels. Therefore, the improvement in ionic conductivity still cannot meet the needs of practical applications. Thus, developing polymer solid-state electrolytes that combine high safety, good mechanical properties, and high room-temperature ionic conductivity is of significant scientific research and industrial application value for promoting the large-scale commercialization of various solid-state batteries, including lithium and sodium batteries. Summary of the Invention
[0005] In view of this, the purpose of the present invention is to provide a composite polymer solid electrolyte material, its preparation method and application, wherein the composite polymer solid electrolyte material has high ionic conductivity.
[0006] This invention provides a composite polymer solid electrolyte material, which, by mass parts, is prepared from raw materials including 500-1500 parts of solvent, 1-40 parts of calcium copper titanate, 20-70 parts of electrolyte salt, and 100 parts of polymer matrix.
[0007] Preferably, the calcium copper titanate is selected from one or more of granular calcium copper titanate, flake calcium copper titanate, fibrous calcium copper titanate, and rod-shaped calcium copper titanate.
[0008] Preferably, the mass ratio of the calcium copper titanate to the polymer matrix is 0.01 to 0.4:1.
[0009] Preferably, the electrolytic salt includes one or more of electrolyte lithium salt, electrolyte sodium salt, and electrolyte potassium salt.
[0010] Preferably, the electrolyte lithium salt is selected from one or more of lithium bis(trifluoromethanesulfonyl)imide, lithium bis(fluorosulfonyl)imide, lithium hexafluorophosphate, lithium difluorooxalate borate, lithium difluorophosphate, lithium tetrafluoroborate, and lithium bis(oxalate borate).
[0011] Preferably, the electrolyte sodium salt is selected from one or more of sodium hexafluorophosphate, sodium perchlorate, sodium difluorosulfonamide, sodium difluoromethanesulfonamide, sodium difluorooxalate borate, and sodium dioxalate borate.
[0012] Preferably, the electrolyte potassium salt is selected from one or more of potassium hexafluorophosphate, potassium perchlorate, potassium difluorosulfonyl imide, potassium difluoromethanesulfonyl imide, potassium difluorooxalate borate, and potassium dioxalate borate.
[0013] Preferably, the polymer matrix is selected from one or more of polyethylene oxide, polyvinylidene fluoride, polyvinylidene fluoride-hexafluoropropylene copolymer, polyacrylonitrile, and polyacrylate.
[0014] Preferably, the solvent is selected from one or more of tetrahydrofuran, acetonitrile, N,N-dimethylformamide and N-methylpyrrolidone.
[0015] This invention provides a method for preparing the composite solid electrolyte material described in the above technical solution, comprising the following steps:
[0016] A slurry is obtained by mixing a polymer matrix, an electrolyte salt, calcium copper titanate, and a solvent and stirring.
[0017] The slurry is cast into a film and then vacuum dried to obtain a composite polymer solid electrolyte material.
[0018] Preferably, the stirring treatment time is 2~36 hours;
[0019] The vacuum drying temperature is 40℃~90℃, and the time is 12h~48h.
[0020] This invention provides a solid-state battery, comprising a positive electrode, a negative electrode, and the composite polymer solid electrolyte material described in the above technical solution.
[0021] Preferably, the positive electrode is a lithium iron phosphate positive electrode, a ternary positive electrode, a sodium battery positive electrode, or a potassium battery positive electrode;
[0022] The negative electrode is an alkali metal negative electrode, graphite negative electrode, hard carbon negative electrode, silicon-carbon negative electrode, or phosphorus material negative electrode.
[0023] This invention provides a composite polymer solid electrolyte material. The raw materials, by mass, include 500-1500 parts solvent, 1-40 parts calcium copper titanate, 20-70 parts electrolyte salt, and 100 parts polymer matrix. The composite polymer solid electrolyte material prepared using calcium copper titanate as a filler exhibits excellent conductivity due to its extremely high dielectric constant, which greatly promotes the dissociation of the electrolyte salt. Simultaneously, calcium copper titanate can form a three-dimensional structure, acting as an ion transporter and bridge, further enhancing ionic conductivity and strengthening the electrolyte matrix. The prepared composite polymer solid electrolyte shows excellent matching with the positive electrode, and the assembled solid-state full cell exhibits superior rate performance and cycle performance. Attached Figure Description
[0024] Figure 1 The images show the XRD patterns of the composite polymer electrolyte membrane prepared in Example 1 of the present invention and the pure polymer membrane prepared in Comparative Example 1.
[0025] Figure 2 SEM images of the composite polymer electrolyte membrane prepared in Example 1 of the present invention and the pure polymer membrane prepared in Comparative Example 1;
[0026] Figure 3 Electrochemical impedance spectroscopy (EIS) diagrams of the polymer electrolyte membrane-assembled steel sheet batteries prepared in Examples 1, 2, 3, and Comparative Example 1 of this invention.
[0027] Figure 4 Linear scan voltammetry diagrams of the composite polymer electrolyte membrane prepared in Example 1 of the present invention and the pure polymer membrane prepared in Comparative Example 1.
[0028] Figure 5 For Example 1 of the present invention, at 0.1 mA cm -2 Voltage-time curves at current density;
[0029] Figure 6 This is a capacity curve of the LFP cathode matched in Comparative Example 1 of the present invention at a 1C rate.
[0030] Figure 7This is a capacity curve of the LFP cathode matched in Embodiment 1 of the present invention at a 1C rate.
[0031] Figure 8 This is a capacity curve of the LFP cathode matched in Embodiment 1 of the present invention at a 2C rate.
[0032] Figure 9 This is a rate performance diagram of the LFP cathode matched in Embodiment 1 of the present invention;
[0033] Figure 10 This is a capacity curve of the NCM811 positive electrode matched in Embodiment 1 of the present invention at a 1C rate.
[0034] Figure 11 Linear scanning voltammetry diagrams of the sodium and potassium ion composite polymer electrolyte membranes prepared in Examples 4 and 5 of this invention are shown.
[0035] Figure 12 The electrochemical impedance spectroscopy diagrams are for steel sheet batteries assembled with sodium and potassium ion composite polymer electrolyte membranes prepared in Examples 4 and 5 of this invention. Detailed Implementation
[0036] This invention provides a composite polymer solid electrolyte material, which, by mass parts, is prepared from raw materials including 500-1500 parts of solvent, 1-40 parts of calcium copper titanate, 20-70 parts of electrolyte salt, and 100 parts of polymer matrix.
[0037] The raw materials for preparing the composite polymer solid electrolyte material provided by the present invention, by mass parts, include 100 parts of a polymer matrix; the polymer matrix is selected from one or more of polyethylene oxide, polyvinylidene fluoride, polyvinylidene fluoride-hexafluoropropylene copolymer (PVDF-HFP) and polyacrylonitrile, preferably polyvinylidene fluoride-hexafluoropropylene.
[0038] The raw materials for preparing the composite polymer solid electrolyte material provided by this invention include 1 to 40 parts of calcium copper titanate (CCTO), specifically 1 part, 2 parts, 3 parts, 4 parts, 5 parts, 6 parts, 7 parts, 8 parts, 9 parts, 10 parts, 11 parts, 12 parts, 13 parts, 14 parts, 15 parts, 16 parts, 17 parts, 18 parts, 19 parts, 20 parts, 21 parts, 22 parts, 23 parts, 24 parts, 25 parts, 26 parts, 27 parts, 28 parts, 29 parts, 30 parts, 31 parts, 32 parts, 33 parts, 34 parts, 35 parts, 36 parts, 37 parts, 38 parts, 39 parts, or 40 parts; preferably 5 to 30 parts. The calcium copper titanate described in this invention is selected from one or more of granular calcium copper titanate, flake calcium copper titanate, fibrous calcium copper titanate, and rod-shaped calcium copper titanate.
[0039] The calcium copper titanate used as a filler in this invention can greatly promote the dissociation of electrolyte salts, improve the ionic conductivity of the composite polymer solid electrolyte material, and have cycle stability; thus enabling the assembled solid-state full battery to have excellent electrochemical performance.
[0040] The raw materials for preparing the composite solid electrolyte material provided by the present invention include 20 to 70 parts of electrolyte salt, specifically 20, 25, 30, 35, 40, 45, 50, 55, 60, 65 or 70 parts; preferably 40 to 65 parts.
[0041] The electrolyte salts described in this invention include one or more of lithium electrolyte salts, sodium electrolyte salts, and potassium electrolyte salts. In this invention, the lithium electrolyte salt is selected from one or more of lithium bis(trifluoromethanesulfonyl)imide (LiTFSI), lithium bis(fluorosulfonyl)imide, lithium hexafluorophosphate, lithium difluorooxalate borate, lithium difluorophosphate, lithium tetrafluoroborate, and lithium bis(oxalate borate). The sodium electrolyte salt is selected from one or more of sodium hexafluorophosphate, sodium perchlorate, sodium bis(fluorosulfonyl)imide, sodium bis(fluoromethanesulfonyl)imide, sodium difluorooxalate borate, and sodium bis(oxalate borate). The potassium electrolyte salt is selected from one or more of potassium hexafluorophosphate, potassium perchlorate, potassium bis(fluorosulfonyl)imide, potassium bis(fluoromethanesulfonyl)imide, potassium difluorooxalate borate, and potassium bis(oxalate borate).
[0042] The raw materials for preparing the composite polymer solid electrolyte material provided by this invention include 500-1500 parts of solvent, specifically 500 parts, 550 parts, 600 parts, 650 parts, 700 parts, 750 parts, 800 parts, 850 parts, 900 parts, 950 parts, 1000 parts, 1050 parts, 1100 parts, 1150 parts, 1200 parts, 1250 parts, 1300 parts, 1350 parts, 1400 parts, 1450 parts, or 1500 parts; preferably 800-1300 parts. The solvent used in this invention is selected from one or more of tetrahydrofuran, acetonitrile, N,N-dimethylformamide (DMF), and N-methylpyrrolidone.
[0043] The raw materials for preparing the composite polymer solid electrolyte material described in this invention specifically include:
[0044] The mixture consists of 60 parts of electrolyte salt, 100 parts of polymer matrix, 875 parts of solvent, and 7 parts of calcium copper titanate.
[0045] This invention provides a method for preparing the composite polymer solid electrolyte material described in the above technical solution, comprising the following steps:
[0046] The polymer matrix, electrolyte salt, calcium copper titanate, and solvent are mixed and thoroughly stirred to obtain a homogeneous slurry.
[0047] The slurry is cast into a film and then dried under vacuum to obtain a composite polymer solid electrolyte material.
[0048] Specifically, the stirring process is carried out at room temperature, preferably 10℃~30℃; the stirring time is 2h~36h, specifically 2h, 4h, 6h, 8h, 10h, 12h, 14h, 16h, 18h, 20h, 22h, 24h, 26h, 28h, 30h, 32h, 34h or 36h.
[0049] The casting film is preferably formed by injecting the slurry into a mold. After film formation, it is transferred to a vacuum drying oven for drying at a temperature of 40~90℃, specifically 40℃, 45℃, 50℃, 55℃, 60℃, 65℃, 70℃, 75℃, 80℃, 85℃ or 90℃; the drying time is 12~48h, specifically 12h, 14h, 16h, 18h, 20h, 22h, 24h, 26h, 28h, 30h, 32h, 34h, 36h, 38h, 40h, 42h, 44h, 46h or 48h.
[0050] The present invention also provides a solid metal battery, comprising a positive electrode, a negative electrode and the above-mentioned composite polymer solid electrolyte material.
[0051] The positive electrode includes, but is not limited to, lithium iron phosphate positive electrode, NCM ternary positive electrode, sodium battery positive electrode or potassium battery positive electrode; the negative electrode includes alkali metal negative electrode, graphite negative electrode, hard carbon negative electrode, silicon-carbon negative electrode or phosphorus material negative electrode.
[0052] The preferred method for preparing the solid-state metal battery includes the following steps:
[0053] A positive electrode slurry is prepared by mixing the positive electrode material with conductive carbon black and a binder.
[0054] The positive electrode slurry is coated onto the surface of the current collector and dried to obtain the positive electrode.
[0055] The metal negative electrode is attached to one side of the solid electrolyte sheet, and a small amount of electrolyte is dropped onto the other side as an interface wetting layer.
[0056] The positive electrode is attached to the surface of an electrolyte sheet on which electrolyte has been dripped, and the whole assembly yields a solid metal battery.
[0057] Further explanation:
[0058] The adhesive is selected from one or more of polyvinylidene fluoride, polytetrafluoroethylene, sodium carboxymethyl cellulose, and sodium alginate;
[0059] The mass ratio of the positive electrode material, conductive carbon black, and binder is 7.8~8.2:1:1, preferably 8:1:1;
[0060] The current collector is selected from one or more of aluminum foil, carbon cloth, carbon paper, and nickel foam, and is preferably a disc with a diameter of 9 mm;
[0061] For a solid electrolyte sheet with a diameter of 18 mm, the amount of electrolyte used is 5-20 μL / sheet, preferably 8-15 μL / sheet, and more preferably 10 μL / sheet; the electrolyte can be a commercially available electrolyte.
[0062] To further illustrate the present invention, the following detailed description, in conjunction with embodiments, provides a composite polymer solid electrolyte material, its preparation method, and its applications, but these descriptions should not be construed as limiting the scope of protection of the present invention.
[0063] Example 1
[0064] In an argon atmosphere, 0.24 g of lithium bis(trifluoromethanesulfonyl)imide (LiTFSI), 3.5 g of N,N-dimethylformamide (DMF), 0.4 g of polyvinylidene fluoride-hexafluoropropylene copolymer (PVDF-HFP), and 0.028 g of calcium copper titanate (CCTO) were weighed and placed in a sample vial. The mixture was stirred vigorously at room temperature for 24 hours to obtain a homogeneous slurry. The slurry was then injected into a mold and transferred to a vacuum drying oven at 60°C for 24 hours to remove the solvent, forming a self-supporting solid electrolyte film. This film was then cut into 18 mm diameter discs for later use.
[0065] To systematically evaluate electrolyte performance, the following test cells were assembled:
[0066] 1. Using stainless steel (SS) as the blocking electrode, SS||SS symmetrical cells were assembled, and their lithium-ion conductivity was tested by AC impedance method.
[0067] 2. An SS||Li half-cell was assembled using stainless steel as the working electrode and lithium metal as the counter electrode, and its electrochemical stability window was determined by linear sweep voltammetry (LSV).
[0068] 3. Assemble a Li||Li symmetric cell and investigate the interfacial stability and long-term cycling performance between the electrolyte and the lithium metal anode.
[0069] Positive electrode preparation: Lithium iron phosphate (or 811 ternary positive electrode material), conductive carbon black, and polyvinylidene fluoride (PVDF) binder are uniformly mixed at a mass ratio of 8:1:1, and an appropriate amount of N-methylpyrrolidone (NMP) is added to prepare a slurry. The slurry is uniformly coated on the surface of an aluminum foil current collector, and after vacuum drying for 24 hours, it is cut into sheets to obtain the corresponding positive electrode sheets.
[0070] Full cell assembly: A lithium metal sheet is attached to one side of a solid electrolyte disc as the negative electrode; 10 μL of commercial liquid electrolyte is dropped onto the other side of the electrolyte as an interface wetting layer; then the prepared lithium iron phosphate or 811 positive electrode sheet is covered on the surface of the wetting layer, and the corresponding current collectors and shell components are stacked in sequence and encapsulated in a glove box to obtain a solid lithium metal full cell.
[0071] Experimental results show that:
[0072] The addition of calcium copper titanate can disrupt the crystalline regions of the polymer matrix, reduce the crystallinity of the composite polymer solid electrolyte, and promote β-phase transformation. Figure 1 ), while improving the density of the composite electrolyte ( Figure 2 The resulting composite electrolyte exhibits an ionic conductivity of 8.8 × 10⁻⁶. -4 S / cm ( Figure 3 (7%-CCTO curve), the electrochemical stability window is increased to 4.5 V ( Figure 4 ).
[0073] The Li||Li symmetric cell assembled based on this electrolyte achieves a speed of 0.1 mA / cm². -2 Stable cycling for 1800 hours at current density ( Figure 5 The solid-state full cell assembled with a lithium iron phosphate cathode achieved initial discharge specific capacities of 138.07 mAh / g and 125.56 mAh / g at 1C and 2C current densities, respectively, and retained approximately 100% of its capacity after 200 cycles. Figure 7 and Figure 8 The discharge specific capacities at 0.1C, 0.2C, 0.5C, 1C, 2C, and 5C rates were 158 mAh / g, 155 mAh / g, 148 mAh / g, 140 mAh / g, 128 mAh / g, and 104 mAh / g, respectively, demonstrating excellent rate performance. Figure 9 The solid-state battery assembled with the 811 ternary cathode exhibited an initial discharge specific capacity of 146.55 mAh / g under 1C conditions and remained stable for 100 cycles. Figure 10 ).
[0074] Comparative Example 1
[0075] Except for the absence of copper-calcium titanate filler, the other raw materials, preparation methods and battery assembly processes are the same as in Example 1.
[0076] Experimental results show that:
[0077] The surface of a pure polymer solid electrolyte exhibits a porous structure. Figure 2 Its ionic conductivity is only 1.25 × 10⁻ 4 S / cm ( Figure 3The 0%-CCTO curve shows an electrochemical window of 4.25 V. Figure 4 The full battery assembled with this lithium iron phosphate cathode exhibits an initial discharge specific capacity of only 140.81 mAh / g at a 1C rate, and its capacity decays significantly after 100 charge-discharge cycles. Figure 6 ).
[0078] Example 2
[0079] The preparation method is similar to that in Example 1, except that the amount of calcium copper titanate added is adjusted to 0.012 g. The preparation of the corresponding solid electrolyte discs and the assembly of the SS||SS symmetric cells are the same as before.
[0080] Experimental results show that:
[0081] The addition of calcium copper titanate can disrupt the crystalline regions of the polymer matrix, reducing the crystallinity of the composite polymer solid electrolyte to 4.7 × 10⁻⁶. -4 S / cm ionic conductivity ( Figure 3 (3%-CCTO curve).
[0082] Example 3
[0083] The preparation method is similar to that in Example 1, except that the amount of calcium copper titanate added is adjusted to 0.044 g. The preparation of the corresponding solid electrolyte discs and the assembly of the SS||SS symmetric cells are the same as before.
[0084] Experimental results show that:
[0085] The addition of calcium copper titanate can disrupt the crystalline regions of the polymer matrix, reducing the crystallinity of the composite polymer solid electrolyte to 5.3 × 10⁻⁶. -4 S / cm ionic conductivity ( Figure 3 (11%-CCTO curve).
[0086] Example 4
[0087] The lithium salt was replaced with 0.24 g of potassium bis(fluorosulfonyl)imide (KFSI), and the remaining raw materials, preparation methods, and electrolyte membrane treatment were the same as in Example 1. SS||SS symmetric cells and SS||K half-cells were assembled separately to evaluate ionic conductivity and electrochemical window.
[0088] Experimental results show that:
[0089] The introduction of calcium copper titanate effectively disrupted the crystalline regions of the polymer matrix, resulting in a potassium-ion polymer solid electrolyte with a wide electrochemical window (4.0 V). Figure 11 ) and high ionic conductivity (3.6×10⁻ 4 S / cm, Figure 12 ).
[0090] Example 5
[0091] The lithium salt was replaced with 0.24 g of sodium bis(trifluoromethanesulfonyl)imide (NaTFSI), and the remaining raw materials, preparation methods, and electrolyte membrane treatment were the same as in Example 1. SS||SS symmetric cells and SS||Na half-cells were assembled separately to evaluate ionic conductivity and electrochemical window.
[0092] Experimental results show that:
[0093] The introduction of calcium copper titanate effectively disrupted the crystalline regions of the polymer matrix, resulting in a sodium-ion polymer solid electrolyte exhibiting a wide electrochemical window (4.4 V). Figure 11 ) and high ionic conductivity (5.2×10⁻ 4 S / cm, Figure 12 ).
[0094] As can be seen from the above embodiments, the composite polymer solid electrolyte material provided by the present invention has high ionic conductivity and exhibits good stability and cycle performance with a metal anode. This material has excellent compatibility with commercially available lithium iron phosphate cathodes, and the assembled lithium metal full battery possesses outstanding rate performance and long-term cycle stability.
[0095] Experimental results show that the composite polymer solid electrolyte prepared using calcium copper titanate as filler has a lithium-ion conductivity of 8.8 × 10⁻⁻⁻⁶. 4 The S / cm ratio was improved, and the electrochemical window was increased from 4.25 V to 4.5 V compared to Comparative Example 1. The symmetric cell assembled using this electrolyte was able to cycle stably for 1800 hours at a current density of 0.1 mA·cm⁻².
[0096] Meanwhile, this composite polymer solid electrolyte exhibits excellent compatibility with commercially available lithium iron phosphate cathodes. Full cells assembled using both materials demonstrate initial discharge specific capacities of 138.07 mAh / g and 125.56 mAh / g at 1C and 2C current densities, respectively, with approximately 100% capacity retention after 200 cycles. At different rate ratios of 0.1C, 0.2C, 0.5C, 1C, 2C, and 5C, the discharge specific capacities are 158, 155, 148, 140, 128, and 104 mAh / g, respectively, showcasing excellent rate performance. Furthermore, solid-state batteries assembled with 811 ternary cathodes achieve an initial discharge specific capacity of 146.55 mAh / g at 1C and remain stable for 100 cycles.
[0097] The application of calcium copper titanate filler can also be extended to potassium and sodium-based composite polymer solid electrolyte systems, and the prepared electrolytes also exhibit high ionic conductivity and a wide electrochemical window.
[0098] The above description is only a preferred embodiment of the present invention. It should be noted that for those skilled in the art, several improvements and modifications can be made without departing from the principle of the present invention, and these improvements and modifications should also be considered within the scope of protection of the present invention.
Claims
1. A composite polymer solid electrolyte material, wherein the raw materials for preparation, by mass parts, include 500-1500 parts of solvent, 1-40 parts of calcium copper titanate, 20-70 parts of electrolyte salt and 100 parts of polymer matrix.
2. The composite polymer solid electrolyte material according to claim 1, characterized in that, The calcium copper titanate is selected from one or more of granular calcium copper titanate, flake calcium copper titanate, fibrous calcium copper titanate, and rod-shaped calcium copper titanate.
3. The composite polymer solid electrolyte material according to claim 1, characterized in that, The mass ratio of calcium copper titanate to the polymer matrix is 0.01~0.4:
1.
4. The composite polymer solid electrolyte material according to claim 1, characterized in that, The electrolyte salt includes one or more of electrolyte lithium salt, electrolyte sodium salt, and electrolyte potassium salt.
5. The composite polymer solid electrolyte material according to claim 1, characterized in that, The polymer matrix is selected from one or more of polyethylene oxide, polyvinylidene fluoride, polyvinylidene fluoride-hexafluoropropylene copolymer, polyacrylonitrile, and polyacrylate.
6. The composite polymer solid electrolyte material according to claim 1, characterized in that, The solvent is selected from one or more of tetrahydrofuran, acetonitrile, N,N-dimethylformamide and N-methylpyrrolidone.
7. A method for preparing the composite polymer solid electrolyte material according to any one of claims 1 to 6, comprising the following steps: A slurry is obtained by mixing a polymer matrix, an electrolyte salt, calcium copper titanate, and a solvent and stirring. The slurry is cast into a film and then vacuum dried to obtain a composite polymer solid electrolyte material.
8. The preparation method according to claim 7, characterized in that, The stirring process takes 2 to 36 hours. The vacuum drying temperature is 40~90℃, and the time is 12~48h.
9. A solid-state metal battery, comprising a positive electrode, a negative electrode, and a composite polymer solid electrolyte material as described in any one of claims 1 to 6.
10. The solid-state metal battery according to claim 9, characterized in that, The positive electrode is a lithium iron phosphate positive electrode, an NCM ternary positive electrode, a sodium battery positive electrode, or a potassium battery positive electrode. The negative electrode is an alkali metal negative electrode, graphite negative electrode, hard carbon negative electrode, silicon-carbon negative electrode, or phosphorus material negative electrode.
11. The solid-state metal battery according to claim 9, characterized in that, The solid-state metal battery is an alkali metal battery.