Inorganic solid ionic conductor and preparation method and application thereof

Abstract

The invention belongs to the technical field of ion conductors, and particularly relates to an inorganic solid-state ion conductor and a preparation method and application thereof. The chemical formula of the inorganic solid-state ion conductor is A3 (OH) 2XGy, A is Li, Na or K, X is one or two of F, Cl, Br and I, and G is one or more of metal oxide, metal halide, metal hydroxide, metal sulfide and ZrOCl2; the metal elements in G are one or more of Ba, La, Ce, Pr, Nd, Pm, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb, Lu, Y, Sr, Zr and Nb, y is greater than 0 and less than or equal to 0.1, the ionic conductivity of the inorganic solid ionic conductor is improved by doping G, and the inorganic solid ionic conductor has high flame retardance due to low melting point and high boiling point, so that the inflammable risk caused by a liquid ionic conductor can be avoided.

Description

Technical Field

[0001] The invention belongs to the technical field of ion conductors, and in particular relates to an inorganic solid-state ion conductor and a preparation method and application thereof. Background Art

[0002] In recent years, the demand for energy storage has increased exponentially in mobile information terminals, mobile electronic devices, electric vehicles, hybrid electric vehicles, and stationary power storage systems. People need larger capacity energy storage devices, faster charging and discharging speeds, lighter weight, greater energy density, and better safety.

[0003] At present, most energy storage devices such as batteries and capacitors use organic liquid solvents as electrolytes to achieve ionic conduction between the cathode and anode to meet energy storage needs. However, the liquid itself has fluidity, and organic solvents have problems such as toxicity and flammability, which have many adverse effects on the structure and safety of current electronic equipment. People need to design more complex structures for electrical equipment, which invisibly increases the cost of using the product and increases its safety risks. Electronic equipment explosions and car fires occur from time to time.

[0004] Subsequently, people used organic polymers as electrolytes. Although this solved the risks brought by liquid flow, its flammability was still not effectively solved, and the ionic conductivity of organic polymer electrolytes was relatively low. Summary of the invention

[0005] In view of this, the object of the present invention is to provide an inorganic solid ion conductor and a preparation method and application thereof. The inorganic solid ion conductor provided by the present invention has high ion conductivity and is non-flammable.

[0006] In order to achieve the above object, the present invention provides the following technical solutions:

[0007] The present invention provides an inorganic solid ion conductor, the chemical formula of which is A3(OH)2XG y , wherein A is Li, Na or K, X is one or two of F, Cl, Br and I, G is one or more of metal oxides, metal halides, metal hydroxides, metal sulfides and ZrOCl2; the metal element in G is one or more of Ba, La, Ce, Pr, Nd, Pm, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb, Lu, Y, Sr, Zr, Nb, and 0<y≤0.1.

[0008] Preferably, G is ZrOCl2, BaCl2, Ba(OH)2, Sm2O3, SmCl3, La2O3, LaCl3 or CeO2.

[0009] Preferably, X is Cl, Br or I.

[0010] Preferably, A is Li or Na.

[0011] Preferably, 0.001 ≤ y ≤ 0.05.

[0012] The present invention also provides a preparation method of the inorganic solid-state ion conductor described in the above technical solution, including the following steps: sintering a hydroxide containing A, a halide of A, and a precursor of the dopant G to obtain an inorganic solid-state ion conductor.

[0013] Preferably, the sintering temperature is 200 - 400 °C, and the heat preservation time ≥ 4 h.

[0014] Preferably, the molar ratio of the hydroxide of A, the halide of A, and the dopant G is 2:1:y.

[0015] The present invention also provides an application of the inorganic solid-state ion conductor described in the above technical solution or the inorganic solid-state ion conductor prepared by the preparation method described in the above technical solution in electronic devices.

[0016] The present invention provides an inorganic solid-state ion conductor with the chemical formula A3(OH)2XG y , where A is Li, Na or K, X is one or two of F, Cl, Br and I, and G is one or several of metal oxides, metal halides, metal hydroxides, metal sulfides and ZrOCl2; the metal elements in G are one or several of Ba, La, Ce, Pr, Nd, Pm, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb, Lu, Y, Sr, Zr, Nb, 0 < y ≤ 0.1. The present invention improves the ionic conductivity by doping G in the ionic conductor solid electrolyte (lithium-sodium-potassium compound), forms partial defects in the lattice configuration of the ionic conductor through the dopant G, thereby increasing the entropy of the ionic conductor, making the crystal structure of the ionic conductor in a recrystallization process, and thus increasing its ionic conductivity. Moreover, the inorganic solid-state ion conductor provided by the present invention has a low melting point (200 - 450 °C) and a high boiling point (above 1000 °C), and the inorganic solid-state ion conductor itself is non-flammable, resulting in its high flame retardancy, so it can avoid the flammability risk brought by liquid ion conductors. The results of the examples show that the ionic conductivity of the inorganic solid-state ion conductor provided by the present invention reaches 10 -3 -10 -5 S / cm.

[0017] In addition, the present invention also provides a preparation method of the above inorganic solid-state ion conductor. The raw materials selected are inexpensive, easy to obtain, simple to operate, and low in cost, which is conducive to large-scale popularization and application. Description of the Drawings

[0018] Figure 1 XRD patterns of the inorganic solid-state ion conductors prepared in Examples 1-9 of the present invention;

[0019] Figure 2 EIS curve of the inorganic solid-state ion conductor film prepared in Example 1 of the present invention at room temperature;

[0020] Figure 3 EIS curve of the inorganic solid-state ion conductor film prepared in Example 2 of the present invention at room temperature;

[0021] Figure 4 EIS curve of the inorganic solid-state ion conductor film prepared in Example 3 of the present invention at room temperature;

[0022] Figure 5 EIS curve of the inorganic solid-state ion conductor film prepared in Example 4 of the present invention at room temperature;

[0023] Figure 6 EIS curve of the inorganic solid-state ion conductor film prepared in Example 5 of the present invention at room temperature;

[0024] Figure 7 EIS curve of the inorganic solid-state ion conductor film prepared in Example 6 of the present invention at room temperature;

[0025] Figure 8 EIS curve of the inorganic solid-state ion conductor film prepared in Example 7 of the present invention at room temperature;

[0026] Figure 9 EIS curve of the inorganic solid-state ion conductor film prepared in Example 8 of the present invention at room temperature;

[0027] Figure 10 EIS curve of the inorganic solid-state ion conductor film prepared in Example 9 of the present invention at room temperature;

[0028] Figure 11 EIS curve of the inorganic solid-state ion conductor film prepared in Comparative Example 1 of the present invention at room temperature. Detailed implementation manners

[0029] The present invention provides an inorganic solid-state ion conductor with the chemical formula A3(OH)2XG y, where A is Li, Na or K, X is one or two of F, Cl, Br and I, and G is one or more of metal oxides, metal halides, metal hydroxides, metal sulfides and ZrOCl2; the metal element in the G is one or more of Ba, La, Ce, Pr, Nd, Pm, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb, Lu, Y, Sr, Zr, Nb, and 0 < y ≤ 0.1.

[0030] Unless otherwise specified, the present invention has no special requirements for the sources of the raw materials used, and commercially available products well-known to those skilled in the art can be used.

[0031] In the present invention, A is Li, Na or K, preferably Li or K; X is one or two of F, Cl, Br and I, preferably Cl, Br or I; G is one or more of metal oxides, metal halides, metal hydroxides, metal sulfides and ZrOCl2, and the metal element in the G is one or more of Ba, La, Ce, Pr, Nd, Pm, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb, Lu, Y, Sr, Zr, Nb, more preferably Ba, La, Ce, Pm, Sm or Zr; G is preferably ZrOCl2, BaCl2, Ba(OH)2, Sm2O3, SmCl3, La2O3, LaCl3 or CeO2; 0 < y ≤ 0.1, preferably 0.001 ≤ y ≤ 0.05.

[0032] In the embodiment of the present invention, the inorganic solid ion conductor is specifically Li3(OH)2F(Sm2O3) 0.005 , Li3(OH)2Cl(ZrOCl2) 0.005 , Li3(OH)2Cl(Sm2O3) 0.005 , Na3(OH)2Cl(Sm2O3) 0.005 , Na3(OH)2I(Sm2O3) 0.005 , Li3(OH)2Cl(La2O3) 0.005 , Li3(OH)2Cl(Ba(OH)2) 0.005 , Li3(OH)2Cl(BaCl2) 0.005 , Li3(OH)2Br(Sm2O3) 0.005 , Li3(OH)2I(Sm2O3) 0.005 .

[0033] The present invention improves the ionic conductivity by doping G in an ionic conductor solid electrolyte (lithium, sodium and potassium compounds).

[0034] In the present invention, the ionic conductivity of the inorganic solid ion conductor is 10 -3 ~10 -5 S / cm, and the melting point is 200 - 450 °C.

[0035] The inorganic solid ion conductor provided by the present invention has a low melting point (200 - 450 °C) and a high boiling point (above 1000 °C), resulting in relatively high flame retardancy, so it can avoid the flammability risk brought by liquid ion conductors.

[0036] The present invention also provides a preparation method of the inorganic solid ion conductor described in the above technical solution, including the following steps: sintering a hydroxide of A, a halide of A, and a precursor of a dopant G to obtain an inorganic solid ion conductor.

[0037] In the present invention, a hydroxide of A, a halide of A, and a precursor of a dopant G are sintered to obtain a sintered body.

[0038] In the present invention, the preparation method of the precursor preferably includes a liquid phase method, a ball milling method, or a chemical combination method, more preferably the liquid phase method or the ball milling method. In the present invention, the uniformity of the liquid phase method is not as good as the other two methods. The ball milling method has high uniformity, smaller material particle size, and the chemical combination method has higher purity.

[0039] In the present invention, the liquid phase method is preferably: after mixing a hydroxide of A, a halide of A, a dopant G, and a solvent, drying and pulverizing are carried out in sequence to obtain a precursor. In the present invention, the solvent is preferably water or ethanol; the molar ratio of the hydroxide of A, the halide of A, and the dopant G is preferably 2:1:y; the mass ratio of the total mass of the hydroxide of A, the halide of A, the dopant G, and the solvent is preferably 1:(1 - 10), more preferably 1:(1 - 5); the mixing is preferably carried out under stirring; the rotation speed of the stirring is preferably 200 - 1000 rpm, more preferably 300 - 500 rpm; the stirring time is preferably 1 - 24 h, more preferably 16 - 24 h; the drying temperature is preferably 80 - 150 °C, more preferably 100 - 120 °C; the drying time is preferably 12 - 48 h, more preferably 12 - 24 h; the pulverizing is preferably carried out by grinding with a mortar or pulverizing with a pulverizer; the pulverizing is preferably until the particle size of the obtained powder > 80 mesh, more preferably > 500 mesh.

[0040] In the present invention, the ball milling method is as follows: after mixing the hydroxide of A, the halide of A and the dopant G, ball milling, drying and pulverization are carried out in sequence to obtain a precursor. In the present invention, the molar ratio of the hydroxide of A, the halide of A and the dopant G is preferably 2:1:y; the rotation speed of the ball milling is preferably ≥150 rpm, more preferably 300 rpm; the time of the ball milling is preferably ≥24 h, more preferably 24 h; the ball milling is preferably wet milling; the amount of solvent added during the wet milling process is preferably 5-50% of the total mass of the hydroxide of A, the halide of A and the dopant G, more preferably 10-20%; the equipment for the ball milling is preferably a ball milling tank; the drying temperature is preferably 60-180 °C, more preferably 80-120 °C; the drying time is preferably ≥12 h, more preferably 24 h; the pulverization is preferably carried out by grinding with a mortar or pulverizing with a pulverizer; the pulverization is preferably to a particle size of the obtained powder >80 mesh, more preferably >500 mesh.

[0041] In the present invention, the chemical synthesis method is to mix the carbonate of A, calcium hydroxide and water, and filter the obtained mixed solution to obtain a supernatant; after adding hydrohalic acid and dopant G to the supernatant and drying, the obtained white solid is pulverized to obtain a precursor. In the present invention, the hydrohalic acid preferably includes one or more of hydrochloric acid, hydrofluoric acid, hydrobromic acid and hydroiodic acid, more preferably hydrochloric acid; the molar ratio of the carbonate of A to calcium hydroxide is 1:1; the molar ratio of the carbonate of A to the hydrohalic acid is 3:2; the molar ratio of the hydrohalic acid to the dopant G is preferably 1:y; the mass ratio of the carbonate of A to water is preferably 1:(500-1000), more preferably 1:(500-600); the mixing of the carbonate of A, calcium hydroxide and water is preferably to first mix the carbonate of A and water, carry out a first stirring until completely dissolved, and then add calcium hydroxide for a second stirring; the rotation speeds of the first stirring and the second stirring are independently preferably 200-1000 rpm, more preferably 300-500 rpm; the time of the second stirring is preferably 12-48 h, more preferably 24 h; there is no special limitation on the filtration in the present invention, and the solid impurities can be removed by using a filtration process well-known in the art; after adding the hydrohalic acid and the dopant G, the present invention preferably further includes: stirring the mixed solution obtained after adding the hydrohalic acid and the dopant G; the rotation speed of the stirring is preferably 200-1000 rpm, more preferably 300-500 rpm; the time of the stirring is preferably 12-48 h, more preferably 24 h; the drying temperature is preferably 60-180 °C, more preferably 100-120 °C; the drying time is preferably 12-48 h, more preferably 24 h; the pulverization is preferably carried out by grinding with a mortar or pulverizing with a pulverizer; the pulverization is preferably to a particle size of the obtained powder >80 mesh, more preferably >500 mesh.

[0042] In the present invention, the sintering temperature is preferably 200 - 400 °C, more preferably 230 - 350 °C, the heat preservation time is preferably ≥ 4 h, more preferably 4 - 24 h; the sintering is preferably carried out in an inert atmosphere; the inert atmosphere is preferably created with argon; the purity of the argon is preferably ≥ 99.99%, more preferably 99.995%.

[0043] During the sintering process, the material lattice is rearranged to generate a new lattice configuration, and the lattice morphology is stabilized through sintering treatment to ensure the synthesis of the ionic conductor. Tempering treatment can also be appropriately carried out at 220 - 270 °C to promote secondary crystallization of the lattice and reorganize the grain morphology to stabilize the lattice morphology.

[0044] The present invention provides a preparation method of the above inorganic solid-state ionic conductor, which uses raw materials with low price, easy availability, simple operation and low cost, and is conducive to large-scale popularization and application.

[0045] The present invention also provides an application of the inorganic solid-state ionic conductor described in the above technical solution or the inorganic solid-state ionic conductor prepared by the preparation method described in the above technical solution in electronic devices.

[0046] In the present invention, the electronic device is preferably a battery and / or a capacitor, more preferably a solid-state battery and / or a solid-state capacitor; the solid-state battery is preferably a lithium-ion battery and / or a sodium-ion battery.

[0047] The present invention has no special limitation on the application mode of the inorganic solid-state ionic conductor in electronic devices, and the well-known application modes in the art can be adopted.

[0048] Next, the technical solutions in the present invention will be clearly and completely described in conjunction with the examples in the present invention, but they cannot be understood as limiting the protection scope of the present invention.

[0049] Example 1

[0050] The chemical formula of the inorganic solid-state ionic conductor is Li3(OH)2Cl(ZrOCl2) 0.005 , and the preparation method is as follows:

[0051] 4.196 g of lithium hydroxide monohydrate, 2.12 g of anhydrous lithium chloride and 0.08 g of zirconium oxychloride octahydrate are added to 20 mL of deionized water, stirred at 300 rpm for 24 h, then evaporated and crystallized in a blast drying oven at 80 °C for 24 h, and then ground into powder (> 500 mesh) with a mortar and placed in a crucible. After sintering at 280 °C for 4 h in an argon atmosphere (purity 99.995%), it is cooled in air with the furnace to obtain the inorganic solid-state ionic conductor.

[0052] Example 2

[0053] The chemical formula of the inorganic solid-state ion conductor is Li3(OH)2Cl(Sm2O3). 0.005 , and the preparation method is as follows: Add 4.196 g of lithium hydroxide monohydrate, 2.12 g of anhydrous lithium chloride, and 0.087 g of Sm2O3 to 20 mL of deionized water, stir at 300 rpm for 24 h, then evaporate and crystallize at 80 °C in a forced-air oven for 24 h. After that, grind it into powder (>500 mesh) with a mortar and pestle, place it in a crucible, sinter at 280 °C for 4 h in an argon atmosphere (purity 99.995%), and then cool it in the furnace to obtain the inorganic solid-state ion conductor.

[0054] Example 3

[0055] The chemical formula of the inorganic solid-state ion conductor is Na3(OH)2Cl(Sm2O3). 0.005 , and the preparation method is as follows:

[0056] Add 4 g of sodium hydroxide, 2.922 g of anhydrous sodium chloride, and 0.087 g of Sm2O3 to 20 mL of deionized water, stir at 300 rpm for 24 h, then evaporate and crystallize at 80 °C in a forced-air oven for 24 h. After that, grind it into powder (>500 mesh) with a mortar and pestle, place it in a crucible, sinter at 280 °C for 4 h in an argon atmosphere (purity 99.995%), and then cool it in the furnace to obtain the inorganic solid-state ion conductor.

[0057] Example 4

[0058] The chemical formula of the inorganic solid-state ion conductor is Li3(OH)2Cl(La2O3). 0.005 , and the preparation method is as follows:

[0059] Add 4.196 g of lithium hydroxide monohydrate, 2.12 g of anhydrous lithium chloride, and 0.0815 g of La2O3 to 20 mL of deionized water, stir at 300 rpm for 24 h, then evaporate and crystallize at 80 °C in a forced-air oven for 24 h. After that, grind it into powder (>500 mesh) with a mortar and pestle, place it in a crucible, sinter at 280 °C for 4 h in an argon atmosphere (purity 99.995%), and then cool it in the furnace to obtain the inorganic solid-state ion conductor.

[0060] Example 5

[0061] The chemical formula of the inorganic solid-state ion conductor is Li3(OH)2Cl(La2O3). 0.005 , and the preparation method is as follows:

[0062] 4.196 g of lithium hydroxide monohydrate, 2.12 g of anhydrous lithium chloride and 0.0815 g of La2O3 were added to 20 mL of deionized water. After stirring at 300 rpm for 24 h, the mixture was evaporated to crystallization at 80 °C in a forced-air oven for 24 h, then ground into powder (>500 mesh) using a mortar and pestle and placed in a crucible. After sintering at 260 °C for 4 h under an argon atmosphere (purity 99.995%), the sample was cooled in the furnace to obtain an inorganic solid-state ion conductor.

[0063] Example 6

[0064] The chemical formula of the inorganic solid-state ion conductor is Li3(OH)2Cl(Ba(OH)2) 0.005 , and the preparation method is as follows:

[0065] 4.196 g of lithium hydroxide monohydrate, 2.12 g of anhydrous lithium chloride and 0.07885 g of Ba(OH)2·8H2O were added to 20 mL of deionized water. After stirring at 300 rpm for 24 h, the mixture was evaporated to crystallization at 80 °C in a forced-air oven for 24 h, then ground into powder (>500 mesh) using a mortar and pestle and placed in a crucible. After sintering at 280 °C for 4 h under an argon atmosphere (purity 99.995%), the sample was cooled in the furnace to obtain an inorganic solid-state ion conductor.

[0066] Example 7

[0067] The chemical formula of the inorganic solid-state ion conductor is Li3(OH)2Cl(BaCl2) 0.005 , and the preparation method is as follows:

[0068] 4.196 g of lithium hydroxide monohydrate, 2.12 g of anhydrous lithium chloride and 0.0502 g of BaCl2 were added to 20 mL of deionized water. After stirring at 300 rpm for 24 h, the mixture was evaporated to crystallization at 80 °C in a forced-air oven for 24 h, then ground into powder (>500 mesh) using a mortar and pestle and placed in a crucible. After sintering at 280 °C for 4 h under an argon atmosphere (purity 99.995%), the sample was cooled in the furnace to obtain an inorganic solid-state ion conductor.

[0069] Example 8

[0070] The chemical formula of the inorganic solid-state ion conductor is Li3(OH)2Br(Sm2O3) 0.005 , and the preparation method is as follows:

[0071] 1.05 g of lithium hydroxide monohydrate, 1.075 g of LiBr and 0.021 g of Sm2O3 were added to 20 mL of deionized water. After stirring at 300 rpm for 24 h, the mixture was evaporated and crystallized in a forced-air oven at 80 °C for 24 h, then ground into powder (>500 mesh) using a mortar and pestle and placed in a crucible. After sintering at 280 °C for 4 h in an argon atmosphere (purity 99.995%), the sample was cooled in the furnace to obtain an inorganic solid-state ion conductor.

[0072] Example 9

[0073] The chemical formula of the inorganic solid-state ion conductor is Li3(OH)2I(Sm2O3) 0.005 , and the preparation method is as follows:

[0074] 1.05 g of lithium hydroxide monohydrate, 1.66 g of LiI and 0.021 g of Sm2O3 were added to 20 mL of deionized water. After stirring at 300 rpm for 24 h, the mixture was evaporated and crystallized in a forced-air oven at 80 °C for 24 h, then ground into powder and placed in a crucible. After sintering at 280 °C for 4 h in an argon atmosphere (purity 99.995%), the sample was cooled in the furnace to obtain an inorganic solid-state ion conductor.

[0075] Comparative Example 1

[0076] The chemical formula of the inorganic solid-state ion conductor is Li3(OH)2Cl, and the preparation method is as follows:

[0077] 4.196 g of lithium hydroxide monohydrate and 2.12 g of anhydrous lithium chloride were added to 20 mL of deionized water. After stirring at 300 rpm for 24 h, the mixture was evaporated and crystallized in a forced-air oven at 80 °C for 24 h, then ground into powder (>500 mesh) using a mortar and pestle and placed in a crucible. After sintering at 280 °C for 4 h in an argon atmosphere (purity 99.995%), the sample was cooled in the furnace to obtain an inorganic solid-state ion conductor.

[0078] Performance Test

[0079] (1) X-ray diffraction tests were performed on the inorganic solid-state ion conductors prepared in Examples 1-4, 7-9, and the results are as Figure 1 shown.

[0080] From Figure 1 it can be seen that according to Bragg's equation 2dsinθ = nλ, when λ is fixed, the smaller the 2θ angle, the larger the interplanar spacing d. Through doping with dopants, the appearance of some obvious or unobvious peaks at 2θ below 15° indicates that lattice defects have been successfully increased by the dopants, and the presence of these lattice defects in the lattice promotes the continuous rearrangement of the lattice to form a regular lattice, thereby increasing the ionic conductivity.

[0081] (2) The powder of the inorganic solid ion conductor obtained in Example 1 was added with 0.5% polytetrafluoroethylene (PTFE) and rolled into a thin film. A circular piece with a radius of 7.5 mm was cut out using a 15-mm-diameter cutter for electrochemical impedance spectroscopy (EIS) testing. The results are as Figure 2 shown.

[0082] As can be Figure 2 seen, the impedance of the Li3(OH)2Cl(ZrOCl2) 0.005 thin film with a thickness of 0.175 mm and a radius of 7.5 mm at room temperature is 9.41 Ω, and its ionic conductivity is calculated to be 1.05 mS / cm.

[0083] (3) The powder of the inorganic solid ion conductor obtained in Example 2 was added with 0.5% polytetrafluoroethylene (PTFE) and rolled into a thin film. A circular piece with a radius of 8 mm was cut out using a 16-mm-diameter cutter for electrochemical impedance spectroscopy (EIS) testing. The results are as Figure 3 shown.

[0084] As can be Figure 3 seen, the impedance of the Li3(OH)2Cl(Sm2O3) 0.005 thin film with a thickness of 0.198 mm and a radius of 8 mm at room temperature is 8.93 Ω, and its ionic conductivity is calculated to be 1.103 mS / cm.

[0085] (4) The powder of the inorganic solid ion conductor obtained in Example 3 was added with 0.5% polytetrafluoroethylene (PTFE) and rolled into a thin film. A circular piece with a radius of 8 mm was cut out using a 16-mm-diameter cutter for electrochemical impedance spectroscopy (EIS) testing. The results are as Figure 4 shown.

[0086] As can be Figure 4 seen, the impedance of the Na3(OH)2Cl(Sm2O3) 0.005 thin film with a thickness of 0.36 mm and a radius of 8 mm at room temperature is 50 Ω, and its ionic conductivity is calculated to be 0.35 mS / cm.

[0087] (5) The powder of the inorganic solid ion conductor obtained in Example 4 was added with 0.5% polytetrafluoroethylene (PTFE) and rolled into a thin film. A circular piece with a radius of 8 mm was cut out using a 16-mm-diameter cutter for electrochemical impedance spectroscopy (EIS) testing. The results are as Figure 5 shown.

[0088] As can be Figure 5 seen, the impedance of the Li3(OH)2Cl(La2O3) 0.005The impedance of the thin film at room temperature is 101.81 Ω, and its ionic conductivity is calculated to be 0.956 mS / cm.

[0089] (6) The powder of the inorganic solid ion conductor obtained in Example 5 was added with 0.5% polytetrafluoroethylene (PTFE) and rolled into a thin film. A disc with a radius of 7.5 mm was cut out using a 15-mm-diameter punch for electrochemical impedance spectroscopy (EIS) testing. The results are as Figure 6 shown.

[0090] From Figure 6 it can be seen that the impedance of the Li3(OH)2Cl(La2O3) 0.005 thin film with a thickness of 0.27 mm and a radius of 7.5 mm at room temperature is 53.06 Ω, and its ionic conductivity is calculated to be 0.288 mS / cm.

[0091] (7) The powder of the inorganic solid ion conductor obtained in Example 6 was added with 0.5% polytetrafluoroethylene (PTFE) and rolled into a thin film. A disc with a radius of 7.5 mm was cut out using a 15-mm-diameter punch for electrochemical impedance spectroscopy (EIS) testing. The results are as Figure 7 shown.

[0092] From Figure 7 it can be seen that the impedance of the Li3(OH)2Cl(Ba(OH)2) 0.005 thin film with a thickness of 0.385 mm and a radius of 7.5 mm at room temperature is 48.08 Ω, and its ionic conductivity is calculated to be 0.4 mS / cm.

[0093] (8) The powder of the inorganic solid ion conductor obtained in Example 7 was added with 0.5% polytetrafluoroethylene (PTFE) and rolled into a thin film. A disc with a radius of 8 mm was cut out using a 16-mm-diameter punch for electrochemical impedance spectroscopy (EIS) testing. The results are as Figure 8 shown.

[0094] From Figure 8 it can be seen that the impedance of the Li3(OH)2Cl(BaCl2) 0.005 thin film with a thickness of 0.188 mm and a radius of 8 mm at room temperature is 12.056 Ω, and its ionic conductivity is calculated to be 0.77 mS / cm.

[0095] (9) The powder of the inorganic solid ion conductor obtained in Example 8 was added with 0.5% polytetrafluoroethylene (PTFE) and rolled into a thin film. A disc with a radius of 8 mm was cut out using a 16-mm-diameter punch for electrochemical impedance spectroscopy (EIS) testing. The results are as Figure 9 shown.

[0096] From Figure 9It can be seen that the impedance of the Li3(OH)2Br(Sm2O3) film with a thickness of 0.195 mm and a radius of 8 mm at room temperature is 62.98 Ω, and its ionic conductivity is calculated to be 0.16 mS / cm. 0.005 The impedance of the Li3(OH)2Br(Sm2O3) film with a thickness of 0.195 mm and a radius of 8 mm at room temperature is 62.98 Ω, and its ionic conductivity is calculated to be 0.16 mS / cm.

[0097] (10) Add the powder of the inorganic solid-state ion conductor obtained in Example 9 to 0.5% polytetrafluoroethylene (PTFE), roll it into a film, cut a circular piece with a radius of 8 mm using a 16-mm-diameter cutter for electrochemical impedance spectroscopy (EIS) testing, and the results are as Figure 10 shown.

[0098] It can be seen from Figure 10 that the impedance of the Li3(OH)2I(Sm2O3) film with a thickness of 0.202 mm and a radius of 8 mm at room temperature is 144.55 Ω, and its ionic conductivity is calculated to be 0.06 mS / cm. 0.005 The impedance of the Li3(OH)2I(Sm2O3) film with a thickness of 0.202 mm and a radius of 8 mm at room temperature is 144.55 Ω, and its ionic conductivity is calculated to be 0.06 mS / cm.

[0099] (11) Add the powder of the inorganic solid-state ion conductor obtained in Comparative Example 1 to 0.5% polytetrafluoroethylene (PTFE), roll it into a film, cut a circular piece with a radius of 8 mm using a 16-mm-diameter cutter for electrochemical impedance spectroscopy (EIS) testing, and the results are as Figure 11 shown.

[0100] It can be seen from Figure 11 that the impedance of the Li3(OH)2Cl film with a thickness of 0.37 mm and a radius of 8 mm at room temperature is 103 Ω, and its ionic conductivity is calculated to be 0.178 mS / cm.

[0101] Although the above embodiments have described the present invention in detail, they are only a part of the embodiments of the present invention rather than all of them. People can also obtain other embodiments based on these embodiments without creative efforts, and these embodiments all fall within the protection scope of the present invention.

Claims

1. An inorganic solid ion conductor, characterized in that, Its chemical formula is A3(OH)2XG y , where A is Li, Na or K, X is one or two of F, Cl, Br and I, and G is one or several of metal oxides, metal halides, metal hydroxides, metal sulfides and ZrOCl2; the metal element in the said G is one or several of Ba, La, Ce, Pr, Nd, Pm, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb, Lu, Y, Sr, Zr, Nb, and 0 < y ≤ 0.

1.

2. The inorganic solid-state ion conductor according to claim 1, wherein G is ZrOCl2, BaCl2, Ba(OH)2, Sm2O3, SmCl3, La2O3, LaCl3 or CeO2.

3. The inorganic solid-state ion conductor according to claim 1, characterized in that, X is Cl, Br or I.

4. The inorganic solid-state ion conductor according to claim 1, wherein A is Li or Na.

5. The inorganic solid-state ion conductor according to claim 1, wherein 0.001≤y≤0.05。 6. The preparation method of the inorganic solid ion conductor according to any one of claims 1 to 5, characterized in that, It includes the following steps: sintering a hydroxide containing A, a halide of A and a precursor of the dopant G to obtain an inorganic solid-state ion conductor.

7. The preparation method according to claim 6, characterized in that, The temperature of the sintering is 200-400 °C, and the heat preservation time is ≥4 h.

8. The preparation method according to claim 6, characterized in that, The molar ratio of the hydroxide of A, the halide of A and the dopant G is 2:1:y.

9. Application of the inorganic solid-state ion conductor according to any one of claims 1-5 or the inorganic solid-state ion conductor prepared by the preparation method according to any one of claims 6-8 in an electronic device.

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