Composite solid electrolyte based on organic-inorganic hybrid material and application thereof

Abstract

The invention belongs to the field of electrolytes, and particularly relates to a composite solid electrolyte based on an organic-inorganic hybrid material and application of the composite solid electrolyte based on the organic-inorganic hybrid material. The small organic molecules are combined with the inorganic component substrate through acting force; and the metal salt is dissociated in the electrolyte. The composite solid electrolyte provided by the invention can solve the problems of inorganic filler agglomeration and non-uniform distribution of two components in a traditional composite solid electrolyte membrane; and the normal-temperature ionic conductivity of the composite solid electrolyte disclosed by the invention is remarkably reduced.

Description

Technical Field

[0001] The present invention belongs to the field of electrolytes, and particularly relates to a composite solid electrolyte based on an organic-inorganic hybrid material and its application. Background Art

[0002] Solid electrolytes with high safety are considered an effective means to overcome the thermal runaway risk and thermodynamic instabilities such as volatility of liquid electrolytes. However, inorganic solid electrolytes have poor air stability and complex preparation processes. Polymer solid electrolytes have low ionic conductivity at room temperature, and Li + migrates slowly along the polymer chain segments. Therefore, researchers have introduced inorganic materials into the polymer matrix to prepare composite solid electrolytes, improving their overall mechanical properties and ionic conductivity to achieve large-scale applications of solid-state lithium metal batteries.

[0003] Traditional organic-inorganic composite solid electrolytes use inorganic fillers to enhance ion transport in the polymer matrix. However, the inorganic fillers and the polymer matrix are only simply mechanically mixed, and the high interfacial energy between the inorganic fillers and the polymer can cause agglomeration of the inorganic fillers, seriously hindering the migration of Li + . In addition, the improvement of the ionic conductivity of organic-inorganic composite solid electrolytes is limited by the high coupling of lithium ion transport and polymer chain segment movement, and the ionic conductivity of the composite solid electrolyte at room temperature still fails to reach the expectation. For example, CN202410948509.2 discloses a design scheme of a composite solid electrolyte, which mixes inorganic fillers and polymer components to prepare a composite solid electrolyte. In order to improve the ionic conductivity, the fillers are improved to nanosheets and halogen-containing solid electrolytes. For example, CN202210128482.3 discloses a composite electrolyte membrane and its preparation method, and a composite electrolyte membrane is prepared using an alumina fiber membrane as a skeleton. The electrolyte membrane has low melting point contact characteristics at the interface and can achieve good contact with the electrode. However, the above preparation process is likely to cause uneven distribution of solid fillers in the polymer, resulting in low local mechanical strength of the electrolyte membrane. For example, CN202111412325.7 discloses a nanofiber polyvinylidene fluoride-based composite solid electrolyte, which obtains oxide-type ceramic nanofibers by dispersing oxide-type ceramic nanoparticles in an organic solvent and through electrospinning and high-temperature calcination. The agglomeration problem of inorganic fillers is optimized in this composite solid electrolyte. However, the ion transport still mainly relies on the movement of polymer chain segments, and the improvement of ionic conductivity is limited by the high coupling of lithium ion transport and polymer chain segment movement, and the improvement of the electrolyte ionic conductivity still fails to reach the expectation.

[0004] The existing preparation method of inorganic-polymer composite solid electrolytes is to simply mechanically mix inorganic fillers with a polymer matrix. The contribution of inorganic fillers to conductivity is mainly to reduce the crystallinity of the polymer, enhance the movement of polymer segments, and provide additional transport channels. Although the ionic conductivity of the electrolyte can be improved in the above way, the high interfacial energy between the inorganic fillers and the polymer will cause the inorganic fillers to agglomerate and the transport of lithium ions has not been completely decoupled from the movement of polymer segments, and the conductivity still needs to be improved. Therefore, in order to increase the ionic conductivity of organic-inorganic composite solid electrolytes, it is urgent to explore new combinations of fillers and polymers and change the ionic transport mode in existing composite solid electrolytes. Summary of the Invention

[0005] To improve the deficiencies of the prior art, the object of the present invention is to propose a composite solid electrolyte based on organic-inorganic hybrid materials to solve the problems of uneven component distribution and insufficient ionic conductivity in the composite solid electrolytes of the prior art.

[0006] The technical solutions provided by the present invention are as follows:

[0007] The first object of the present invention is to provide a composite solid electrolyte based on organic-inorganic hybrid materials, mainly to solve the problem of agglomeration of inorganic fillers in traditional composite solid electrolyte membranes; in the present invention, organic small molecule components and inorganic components are combined through forces to form an electrolyte precursor, and further combined with metal ions, thereby obtaining a composite solid electrolyte with uniform component distribution.

[0008] The second object of the present invention is to provide a composite solid electrolyte of organic-inorganic hybrid materials, mainly to solve the problem of too low room temperature ionic conductivity in traditional composite solid electrolyte membranes; in the present invention, the transport of ions is decoupled from the movement of polymer segments, and the ions are transported through organic small molecules combined with inorganic components, obtaining a composite solid electrolyte membrane with high ionic conductivity.

[0009] A composite solid electrolyte based on organic-inorganic hybrid materials, the composite solid electrolyte based on organic-inorganic hybrid materials includes an inorganic component matrix, organic small molecules combined with the inorganic component matrix through forces, and metal salts dissociated in the electrolyte.

[0010] Further, the molar ratio range of the metal element to the organic small molecule is 0.001-10.

[0011] Further, the relative molecular mass of the organic small molecule is ≤1000.

[0012] Further, the binding force between the inorganic component and the organic small molecule is stronger than van der Waals force.

[0013] Further, the organic small molecule serves as a site for transporting ions. Further, the inorganic component contains at least one of the metal elements in the third to sixth periods.

[0014] Further, the inorganic component is one or more of oxides, sulfides, halides, hydroxides, and metal compounds.

[0015] Further, the metal contained in the metal salt is selected from at least one of the metal elements in the first to sixth periods.

[0016] The present invention also provides a preparation method of the above composite solid electrolyte based on the organic-inorganic hybrid material, characterized in that the preparation method includes the following steps: uniformly dispersing the A metal ion solution or the compound containing the A metal element in the organic small molecule solution B, and obtaining an electrolyte precursor containing an organic ligand after the reaction; soaking the electrolyte precursor containing the small molecule ligand in the metal salt solution containing C ions, and obtaining the composite solid electrolyte based on the organic-inorganic hybrid material after removing the solvent.

[0017] Further, in the metal salt solution containing C ions, the concentration of the metal ion is 0-10 mol·L -1 .

[0018] Further, the reaction is a hydrothermal reaction, the temperature of the hydrothermal reaction is 120-200 °C, and the reaction time is 12-24 h.

[0019] Further, the solvent of the metal salt solution containing C ions is selected from at least one of water and organic solvents.

[0020] The present invention also provides an application of the above composite solid electrolyte based on the organic-inorganic hybrid material in the preparation of a battery.

[0021] The present invention also provides a preparation method of a composite solid electrolyte based on an organic-inorganic hybrid material, including the following steps:

[0022] (1) Uniformly dispersing a certain proportion of the ion solution containing A metal or the compound containing this metal element into the small molecule organic matter B, and obtaining an electrolyte precursor containing an organic ligand after the reaction, the molar ratio range of the metal element to the small molecule organic matter is 0.001-10, and the concentration range of C ions is 0-10 mol / L.

[0023] (2) Soaking the precursor in the salt solution containing C ions, and obtaining a composite solid electrolyte based on the organic-inorganic hybrid material after removing the solvent. The Li in this composite solid electrolyte based on the organic-inorganic hybrid material +It can be transported on the surface of the electrolyte or move inside the bulk of the electrolyte; at the same time, the organic component in this electrolyte can only be an organic small molecule with a relative molecular mass of ≤1000; the inorganic component of the electrolyte and the organic small molecule must be combined through a force and cannot be just a physical mixture; in the electrolyte, Li + is transported by relying on organic small molecules.

[0024] Furthermore, the organic small molecule B described in step (1) can be one or several of monovalent, divalent, and trivalent and higher polyvalent organic compounds in any mass ratio mixture.

[0025] Furthermore, the force for the organic small molecule to bind to the inorganic substrate can be at least one of ionic bond, covalent bond, hydrogen bond, and intermolecular force.

[0026] Furthermore, the precursor described in step (1) is at least one of oxides containing metal elements from the third to the sixth period.

[0027] Furthermore, the inorganic substrate of the precursor is one or several of oxides, sulfides, halides, hydroxides, and metal compounds.

[0028] Furthermore, the morphology of the precursor can be a mixture of one or several of 0D (nanoparticles), 1D (nanowires), 2D (nanosheets), and 3D (with macroscopic structure), etc.

[0029] Beneficial effects

[0030] By using the preparation method of the present invention, a composite solid electrolyte based on an organic-inorganic hybrid material can be prepared. The organic small molecules bound through a force on the inorganic substrate can solve the problems of inorganic filler agglomeration and uneven distribution of organic and inorganic components in the traditional composite solid electrolyte membrane. Since the organic small molecule and the inorganic component are bound together by a force, the content of the inorganic component can be increased to more than 80% without agglomeration, which can improve the uniformity and mechanical strength of the electrolyte membrane.

[0031] By using the preparation method of the present invention, a composite solid electrolyte based on an organic-inorganic hybrid material can be prepared, and the room temperature ionic conductivity of the electrolyte is significantly reduced (>10 -4 S cm -1 )

[0032] The preparation method of the present invention is simple, the reaction conditions are mild, the cost is low, the preparation method is simple, the operation controllability is high, and it is suitable for large-scale production. This method can obtain the electrolyte precursor by a simple one-step method, and then a composite solid electrolyte based on an organic-inorganic hybrid material can be obtained by simply soaking in a metal salt solution;

[0033] The composite solid electrolyte prepared by the preparation method of the present invention has reliable stability, is less affected by factors such as water and oxygen, is not prone to flammable and explosive accidents, and is safe and reliable. BRIEF DESCRIPTION OF THE DRAWINGS

[0034] Figure 1 For the electrochemical impedance spectrum, ionic conductivity and battery performance of the composite solid electrolyte based on the organic-inorganic hybrid material with n-butylamine ligand;

[0035] Figure 2 For the electrochemical impedance spectrum, ionic conductivity and battery performance of the composite solid electrolyte based on the organic-inorganic hybrid material with ethylenediamine ligand;

[0036] Figure 3 For the electrochemical impedance spectrum, ionic conductivity and battery performance of the composite solid electrolyte based on the organic-inorganic hybrid material with pentamethyldiethylenetriamine ligand;

[0037] Figure 4 For the electrochemical impedance spectrum, ionic conductivity and battery performance of the composite solid electrolyte based on the organic-inorganic hybrid material with ethylene glycol ligand;

[0038] Figure 5 For the electrochemical impedance spectrum, ionic conductivity and battery performance of the composite solid electrolyte based on the organic-inorganic hybrid material with pentaerythritol ligand;

[0039] Figure 6 For the electrochemical impedance spectrum and ionic conductivity of Comparative Example 1;

[0040] Figure 7 For the electrochemical impedance spectrum and ionic conductivity of Comparative Example 2;

[0041] Figure 8 For the electrochemical impedance spectrum and ionic conductivity of Comparative Example 3;

[0042] Figure 9 For the electrochemical impedance spectrum and ionic conductivity of Comparative Example 4;

[0043] Figure 10 For the electrochemical impedance spectrum and ionic conductivity of Comparative Example 5. DETAILED DESCRIPTION OF THE INVENTION

[0044] In order to more clearly illustrate the technical solutions of the present invention, the present invention will be further described below; obviously, only a part of the embodiments are described below. For those of ordinary skill in the art, without creative efforts, the technical solutions described in the present invention can also be applied to other similar scenarios according to these; in order to more clearly illustrate the technical solutions of the present invention, the technical solutions of the present invention will be further described in detail below.

[0045] Example 1

[0046] This example provides a method for preparing an organic-inorganic hybrid material-based composite solid electrolyte with a n-butylamine ligand, including the following steps:

[0047] Add 0.446 g of Zn(NO3)2·6 H2O and 0.114 g of Na2S·9 H2O to the inner lining (or tank) of an autoclave filled with 80 mL of n-butylamine. The autoclave is heated at 180 °C for 12 hours. The obtained composite solid electrolyte precursor with a n-butylamine ligand (n-butylamine-ZnS nanosheets) is separated by centrifugation after being washed with water and ethanol more than three times. Then, the composite solid electrolyte precursor with a n-butylamine ligand is soaked in a lithium salt water or ethanol solution (1.5 mol L -1 LiTFSI) at room temperature for more than 6 hours, and a composite solid electrolyte containing a n-butylamine ligand is obtained after removing the residual solvent water or ethanol.

[0048] Figure 1 For the electrochemical impedance spectrum, ionic conductivity, and battery performance of the organic-inorganic hybrid material-based composite solid electrolyte with a n-butylamine ligand, the ionic conductivity can be calculated to be 6.7×10 -5 S cm -1 . The solid-state battery can be cycled stably, indicating that the electrolyte has excellent cycle stability and good compatibility with the lithium iron phosphate electrode material.

[0049] Example 2

[0050] This example provides a method for preparing an organic-inorganic hybrid material-based composite solid electrolyte with an ethylenediamine ligand, including the following steps:

[0051] During the synthesis, 15 g of ammonium tungstate and 60 mL of ethylenediamine are mixed and heated and stored at 180 °C for 24 hours. The obtained composite solid electrolyte precursor containing an ethylenediamine ligand (ethylenediamine-WO3 nanowires) is separated by centrifugation after being washed with water and ethanol more than three times. Then, the composite solid electrolyte precursor containing an ethylenediamine ligand is soaked in a lithium salt water or ethanol solution (2 mol L -1 LiTFSI) for more than 6 hours, and a composite solid electrolyte containing a monovalent organic ligand such as ethylenediamine is obtained after removing the residual solvent water or ethanol.

[0052] Figure 2 For the electrochemical impedance spectrum, ionic conductivity, and battery performance of the organic-inorganic hybrid material-based composite solid electrolyte with an ethylenediamine ligand, the ionic conductivity can be calculated to be 2.7×10 -4 S cm-1 The solid-state battery can cycle stably, indicating that the electrolyte has excellent cycle stability and good compatibility with the lithium cobaltate electrode material.

[0053] Example 3

[0054] This example provides a method for preparing a composite solid-state electrolyte based on an organic-inorganic hybrid material with a pentamethyldiethylenetriamine ligand, including the following steps:

[0055] ZnSO4 and Na2SeO3 are added to a mixed solution (35 mL) with a volume ratio of pentamethyldiethylenetriamine: deionized water = 7:8, heated and stored at 180 °C for 12 hours to obtain a composite solid-state electrolyte precursor (pentamethyldiethylenetriamine-ZnSe nanoparticles) containing multiple organic ligands such as pentamethyldiethylenetriamine, and separated by centrifugation after washing with water and ethanol more than three times. Then the composite solid-state electrolyte precursor containing multiple organic ligands such as pentamethyldiethylenetriamine is soaked in an aqueous lithium salt solution (1 mol L -1 LiTFSI) for more than 6 hours, and after removing the residual solvent water, a composite solid-state electrolyte containing multiple organic ligands such as pentamethyldiethylenetriamine is obtained.

[0056] Figure 3 For the electrochemical impedance spectrum, ionic conductivity and battery performance of the composite solid-state electrolyte based on the organic-inorganic hybrid material with a pentamethyldiethylenetriamine ligand, the ionic conductivity can be calculated to be 1.1×10 -5 Scm -1 The solid-state battery can cycle stably, indicating that the electrolyte has excellent cycle stability and good compatibility with the ternary electrode material.

[0057] Example 4

[0058] This example provides a method for preparing a composite solid-state electrolyte based on an organic-inorganic hybrid material with an ethylene glycol ligand, including the following steps:

[0059] 216 mg of niobium pentachloride (NbCl5) is dissolved in 20 mL of ethylene glycol, 448 mg of hexamethylenetetramine is added to 25 mL of deionized water and stirred for 15 min, then the two mixtures are stirred for 15 min and kept at 200 °C for 12 h to obtain a composite solid-state electrolyte precursor (ethylene glycol-Nb2O5 gel macrostructure) containing an ethylene glycol ligand, and separated by centrifugation after washing with water and ethanol more than three times. Then the composite solid-state electrolyte precursor containing an ethylene glycol ligand is soaked in an aqueous lithium salt solution (1mol L -1 LiTFSI) for more than 12 hours, and after removing the residual solvent water, a composite solid-state electrolyte containing an ethylene glycol ligand is obtained.

[0060] Figure 4 For the electrochemical impedance spectrum, ionic conductivity, and battery performance of the organic-inorganic hybrid material-based composite solid electrolyte with ethylene glycol ligand, the ionic conductivity can be calculated to be 1.1×10 -4 S cm -1 . The solid-state battery can be cycled stably, indicating that the electrolyte has excellent cycle stability and good compatibility with the ternary electrode material.

[0061] Example 5

[0062] This example provides a preparation method for an organic-inorganic hybrid material-based composite solid electrolyte with a pentaerythritol ligand, including the following steps:

[0063] Dissolve 1.00 g of pentaerythritol in 18 mL of deionized water to prepare a saturated solution. Then, add the saturated pentaerythritol solution to pure water at a ratio of 15 vol.%, obtaining a mixed solvent. Add NaOH (3.20 g, 0.08 mol) and an aqueous Na2CO3 solution (0.53 g, 0.005 mol) to the previously obtained five solvents with a volume of 30 mL. Then, add Mg(NO3)2 (7.68 g, 0.03 mol) and Al(NO3)3 (3.75 g, 0.01 mol) to the mixed solvent. Subsequently, quickly mix the salt solution and the aqueous solution and stir for 5 minutes. By adding sodium hydroxide solution, the pH value of the mixed solution is maintained above 12.0. Finally, heat all the obtained mixed solutions at 120 °C for 12 h to obtain a composite solid electrolyte precursor containing a pentaerythritol ligand (pentaerythritol-magnesium-aluminum hydroxide nanosheets), and perform centrifugal separation after washing with water and ethanol more than three times. Then soak the composite solid electrolyte precursor containing a pentaerythritol ligand in an aqueous lithium salt solution (1 mol L -1 LiTFSI) for more than 12 hours, and after removing the residual solvent water, obtain a composite solid electrolyte containing a pentaerythritol ligand.

[0064] Figure 5 For the electrochemical impedance spectrum, ionic conductivity, and battery performance of the organic-inorganic hybrid material-based composite solid electrolyte with a pentaerythritol ligand, the ionic conductivity can be calculated to be 6.1×10 -5 S cm -1 . The solid-state battery can be cycled stably, indicating that the electrolyte has excellent cycle stability and good compatibility with the ternary electrode material.

[0065] Due to the difference in whether the inorganic substrates in Examples 1-5 and Comparative Examples 1-5 are combined with organic small molecule ligands, the ionic conductivities of Examples 1-5 are superior to those of Examples 1-5. The reason is that there are ionic transport sites in the examples, indicating that a high ionic conductivity can be obtained by combining an inorganic substrate and an organic small molecule ligand. At the same time, due to the presence of the small molecule ligand, the stability of the organic-inorganic hybrid material-based composite solid electrolyte is enhanced, and the battery has good cycling performance.

[0066] Comparative Example 1

[0067] Mix ZnO solid powder and H2SO4 solution and add them to a reaction kettle. The mass ratio of ZnO solid powder to H2SO4 solution is 1:1.5, and the mass percentage concentration of H2SO4 is 20%. After reacting for 30 min at a temperature of 65 °C, adjust the pH value of the reacted solution to 5.0 to obtain a ZnSO4 solution; then, perform impurity removal treatment on the doped ZnSO4 solution to remove impurities nickel, molybdenum, chromium, copper, lead, and iron in the ZnSO4 solution to obtain a pure ZnSO4 solution with an impurity content of less than 0.02%. React the ZnSO4 solution with Na2S at a mass ratio of 2:1 (the mass percentage concentration of Na2S is 20%) to obtain zinc sulfide.

[0068] Physically mix n-butylamine, zinc sulfide, and LiTFSI. The molar ratio of each component is the same as that of the n-butylamine-ZnS electrolyte in Example 1. The difference is that the organic small molecule n-butylamine in Example 1 is combined with ZnS through a force, while in Comparative Example 1, it is a physical mixture.

[0069] Figure 6 Figure 13 shows the electrochemical impedance spectrum of the composite electrolyte of Comparative Example 1. The ionic conductivity can be calculated as 5.4×10 -6 S cm -1 <6.7×10 -5 S cm -1 , which indicates that the organic small molecule n-butylamine combined through a force exhibits better ionic transport ability.

[0070] Comparative Example 2

[0071] Put tungsten hexachloride into a high-temperature muffle furnace and heat it to 550 °C. During the calcination process, tungsten hexachloride undergoes thermal decomposition at high temperature to generate tungsten trioxide (WO3) and hydrogen chloride (HCl) gas.

[0072] Physically mix ethylenediamine, tungsten oxide, and LiTFSI. The molar ratio of each component is the same as that of the ethylenediamine-WO3 electrolyte in Example 2. The difference is that the organic small molecule ethylenediamine in Example 2 is combined with WO3 through a force, while in Comparative Example 2, it is a physical mixture.

[0073] Figure 7 The electrochemical impedance spectrum of the composite electrolyte of Comparative Example 2. The ionic conductivity can be calculated from the resistance value of EIS to be 1.2×10 -5 S cm -1 <2.7×10 -4 S cm -1 , indicating that the organic small molecule ethylenediamine combined by the acting force exhibits better ionic transport ability.

[0074] Comparative Example 3

[0075] Put 2 mmol of Zn(CH3COO)2·2H2O and 1 mmol of Se powder into 40 mL of ethanolamine solvent, and place it in an oven at 200 °C for reaction for 24 h. After the reaction, it is naturally cooled to room temperature, the sediment is collected, and it is repeatedly washed with absolute ethanol and deionized water. The obtained product is dried at a constant temperature of 60 °C in a vacuum drying oven for 6 h to obtain a ZnSe sample.

[0076] Pentamethyldiethylenetriamine, ZnSe and LiTFSI are physically mixed, and the molar ratio of each component is the same as that of the pentamethyldiethylenetriamine-ZnSe electrolyte in Example 3. The difference is that the organic small molecule pentamethyldiethylenetriamine and ZnSe in Example 3 are combined by the acting force, while in Comparative Example 3 it is a physical mixture.

[0077] Figure 8 The electrochemical impedance spectrum of the composite electrolyte of Comparative Example 3. The ionic conductivity can be calculated from the resistance value of EIS to be 8.3×10 -7 S cm -1 < 1.1×10 -5 S cm -1 , indicating that the organic small molecule combined by the acting force exhibits better ionic transport ability.

[0078] Comparative Example 4

[0079] Under stirring conditions, dissolve niobium pentachloride in deionized water, and the concentration of niobium ions is 0.05 mol / L; add hydrofluoric acid to the above aqueous solution and continue stirring for 0.1 - 24 hours, and the molar ratio of niobium ions to fluoride ions is 1:0.2. The solution reacts at 180 °C for 24 h. The obtained reaction precipitate is centrifuged, washed several times with ethanol and deionized water respectively, and calcined in a tube furnace to obtain the Nb2O5 material.

[0080] Ethylene glycol, Nb2O5 and LiTFSI were physically mixed, and the molar ratio of each component was the same as that of the ethylene glycol-Nb2O5 electrolyte in Example 3. The difference is that in Example 4, the organic small molecule ethylene glycol and Nb2O5 are combined by forces, while in Comparative Example 4, it is a physical mixture.

[0081] Figure 9 Figure 4 shows the electrochemical impedance spectrum of the composite electrolyte of Comparative Example 4. The ionic conductivity can be calculated to be 1.3×10 -7 S cm -1 <1.1×10 -4 S cm -1 from the resistance value of EIS, which indicates that the organic small molecules combined by forces exhibit better ionic transport ability.

[0082] Comparative Example 5

[0083] Magnesium hydroxide and gibbsite were mixed at a molar ratio of 5:1 and then put into a high-speed ball mill for ball milling for 5 h, where the mass ratio of the mixture to the steel balls of the ball mill was 1:3. The ground mixture was placed in a muffle furnace and calcined at 380 - 550 °C for 2 - 5 h to obtain a uniformly dispersed magnesium-aluminum mixed oxide. The above magnesium-aluminum mixed oxide was added to water at 80 °C with a mass more than twice that of the oxide and reacted for 24 h to obtain magnesium-aluminum hydroxide.

[0084] Pentaerythritol, magnesium-aluminum hydroxide and LiTFSI were physically mixed, and the molar ratio of each component was the same as that of the pentaerythritol-magnesium-aluminum hydroxide electrolyte in Example 5. The difference is that in Example 5, the organic small molecule pentaerythritol and magnesium-aluminum hydroxide are combined by forces, while in Comparative Example 5, it is a physical mixture.

[0085] Figure 10 Figure 5 shows the electrochemical impedance spectrum of the composite electrolyte of Comparative Example 5. The ionic conductivity can be calculated to be 7.3×10 -7 S cm -1 <6.1×10 -5 S cm -1 from the resistance value of EIS, which indicates that the organic small molecules combined by forces exhibit better ionic transport ability.

[0086] The above is an illustration of the exemplary embodiments of the present invention. However, the present invention is not limited to the above embodiments. Any modifications, equivalent substitutions, improvements, etc. made by those skilled in the art within the spirit and principles of the present invention shall be included within the protection scope of the present invention.

Claims

1. A composite solid electrolyte based on an organic-inorganic hybrid material, characterized in that, The composite solid electrolyte based on the organic-inorganic hybrid material includes an inorganic component substrate, an organic small molecule combined with the inorganic component substrate through an interaction force, and a metal salt dissociated in the electrolyte.

2. The composite solid electrolyte based on the organic-inorganic hybrid material according to claim 1, wherein The inorganic component is one or more of oxides, sulfides, halides, hydroxides, and metal compounds.

3. The composite solid electrolyte based on the organic-inorganic hybrid material according to claim 1, wherein The relative molecular mass of the organic small molecule is ≤1000.

4. The composite solid electrolyte based on the organic-inorganic hybrid material according to claim 1, characterized in that, The binding force between the inorganic component and the organic small molecule is stronger than the van der Waals force.

5. The composite solid electrolyte based on the organic-inorganic hybrid material according to claim 1, characterized in that, The organic small molecule serves as a site for transporting ions.

6. The composite solid electrolyte based on the organic-inorganic hybrid material according to claim 1, wherein The metal contained in the metal salt is selected from at least one of the metal elements in the first to sixth period.

7. The preparation method of the solid electrolyte with a surface ion transport mechanism according to claim 1, characterized in that, Disperse A metal ions or a compound containing A metal element uniformly into the organic small molecule solution B, and obtain an electrolyte precursor after reaction; immerse the electrolyte precursor in a metal salt solution containing C ions, and obtain a composite solid electrolyte based on the organic-inorganic hybrid material after removing the solvent.

8. The composite solid electrolyte based on the organic-inorganic hybrid material according to claim 7, characterized in that, In the metal salt solution containing C ions, the concentration of metal ions is 0 to 10 mol·L -1 .

9. The preparation method of the composite solid electrolyte based on the organic-inorganic hybrid material according to claim 7, characterized in that, The solvent of the metal salt solution containing C ions is selected from at least one of water or an organic solvent.

10. Use of the composite solid electrolyte based on the organic-inorganic hybrid material according to claim 1 in the preparation of a battery.

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