An inorganic solid-state ion conductor and a preparation method and application thereof

Abstract

The application 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. y The inorganic solid-state ion conductor has a chemical formula of A3(OH)2XG, wherein 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 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 and Nb, 0 < y < 0.1, the ion conductivity of G is improved by doping, and the inorganic solid-state ion conductor has low melting point and high boiling point, so that the inorganic solid-state ion conductor has high flame retardance, and thus the risk of flammability caused by liquid ion conductors can be avoided.

Description

Technical Field

[0001] This invention belongs to the field of ion conductor technology, specifically relating to an inorganic solid-state ion conductor, its preparation method, and its application. Background Technology

[0002] In recent years, the demand for energy storage has been increasing in devices such as mobile information terminals, mobile electronic devices, electric vehicles, hybrid electric vehicles, and stationary energy storage systems. People need energy storage devices with larger capacity, faster charging and discharging speeds, lighter weight, higher energy density, and better safety.

[0003] Currently, most energy storage devices, such as batteries and capacitors, use organic liquid solvents as electrolytes to achieve ion conduction between the anode and cathode, thus meeting energy storage requirements. However, liquids themselves are fluid, and organic solvents have problems such as toxicity and flammability, which have had many adverse effects on the structure and safety of current electronic devices. People need to design more complex structures for electrical equipment, which increases the cost of using the products and increases their safety hazards. Incidents of electronic equipment explosions and car fires occur frequently.

[0004] Subsequently, people used organic polymers as electrolytes, which solved the risks associated with liquid flow, but their flammability was not effectively addressed, and the ionic conductivity of organic polymer electrolytes was relatively low. Summary of the Invention

[0005] In view of this, the purpose of this invention is to provide an inorganic solid-state ionic conductor, its preparation method and application. The inorganic solid-state ionic conductor provided by this invention has high ionic conductivity and is non-flammable.

[0006] To achieve the above objectives, the present invention provides the following technical solution:

[0007] This invention provides an inorganic solid-state ionic 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 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, and 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 method for preparing the inorganic solid-state ionic conductor described in the above technical solution, comprising the following steps: sintering a precursor containing A hydroxide, A halide and dopant G to obtain an inorganic solid-state ionic conductor.

[0013] Preferably, the sintering temperature is 200–400°C, and the holding time is ≥4 hours.

[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 the 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.

[0016] This invention provides an inorganic solid-state ionic 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 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, and Nb, and 0 < y ≤ 0.1. This invention improves the ionic conductivity of an ionic conductor solid electrolyte (containing lithium, sodium, and potassium compounds) by doping it with G. The dopant G creates partial defects in the crystal lattice of the ionic conductor, increasing its entropy and inducing a recrystallization process, thereby increasing its ionic conductivity. Furthermore, the inorganic solid-state ionic conductor provided by this invention has a low melting point (200–450°C) and a high boiling point (above 1000°C). As it is non-flammable, it possesses high flame retardancy, thus avoiding the flammability risks associated with liquid ionic conductors. The results of the embodiments show that the ionic conductivity of the inorganic solid-state ionic conductor provided by this invention reaches 10. -3 ~10 -5 S / cm.

[0017] Furthermore, this invention also provides a method for preparing the aforementioned inorganic solid-state ionic conductor, which uses inexpensive and readily available raw materials, is simple to operate, and has low cost, making it conducive to large-scale promotion and application. Attached Figure Description

[0018] Figure 1 The XRD patterns are of the inorganic solid-state ionic conductors prepared in Examples 1-9 of this invention.

[0019] Figure 2 The image shows the EIS curve of the inorganic solid-state ion conductor film prepared in Example 1 of this invention at room temperature.

[0020] Figure 3 The image shows the EIS curve of the inorganic solid-state ion conductor film prepared in Example 2 of this invention at room temperature.

[0021] Figure 4 The image shows the EIS curve of the inorganic solid-state ion conductor film prepared in Example 3 of this invention at room temperature.

[0022] Figure 5 The image shows the EIS curve of the inorganic solid-state ion conductor film prepared in Example 4 of this invention at room temperature.

[0023] Figure 6 The image shows the EIS curve of the inorganic solid-state ion conductor film prepared in Example 5 of this invention at room temperature.

[0024] Figure 7 The image shows the EIS curve of the inorganic solid-state ion conductor film prepared in Example 6 of this invention at room temperature.

[0025] Figure 8 The image shows the EIS curve of the inorganic solid-state ion conductor film prepared in Example 7 of this invention at room temperature.

[0026] Figure 9 The image shows the EIS curve of the inorganic solid-state ion conductor film prepared in Example 8 of this invention at room temperature.

[0027] Figure 10 The image shows the EIS curve of the inorganic solid-state ion conductor film prepared in Example 9 of this invention at room temperature.

[0028] Figure 11 The image shows the EIS curve of the inorganic solid-state ionic conductor film prepared in Comparative Example 1 of this invention at room temperature. Detailed Implementation

[0029] This invention provides an inorganic solid-state ionic conductor with the chemical formula A3(OH)2XG. yWhere 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 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, and Nb, and 0 < y ≤ 0.1.

[0030] Unless otherwise specified, the present invention does not have special requirements on the source of raw materials used, and commercially available products well known to those skilled in the art can be used.

[0031] In this 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, wherein 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, and 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 this embodiment of the invention, the inorganic solid-state ionic 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] This invention improves the ionic conductivity of an ionic conductor solid electrolyte (containing lithium, sodium, and potassium compounds) by doping it with G.

[0034] In this invention, the ionic conductivity of the inorganic solid-state ionic conductor is 10. -3 ~10 -5 S / cm, melting point is 200~450℃.

[0035] The inorganic solid ionic conductor provided by this invention has a low melting point (200-450°C) and a high boiling point (above 1000°C), which results in its high flame retardancy and thus avoids the flammability risk associated with liquid ionic conductors.

[0036] The present invention also provides a method for preparing the inorganic solid-state ionic conductor described in the above technical solution, comprising the following steps: sintering a precursor containing A hydroxide, A halide and dopant G to obtain an inorganic solid-state ionic conductor.

[0037] The present invention involves sintering a precursor containing A hydroxide, A halide, and dopant G to obtain a sintered body.

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

[0039] In this invention, the liquid phase method is preferably: mixing the hydroxide of A, the halide of A, the dopant G and the solvent, and then drying and pulverizing them sequentially to obtain the precursor. In this 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, and the dopant G to the mass of the solvent is preferably 1:(1-10), more preferably 1:(1-5); the mixing is preferably carried out under stirring conditions; the stirring speed 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℃, more preferably 100-120℃; the drying time is preferably 12-48 h, more preferably 12-24 h; the pulverization is preferably performed using a mortar and pestle or a pulverizer; the pulverization is preferably performed until the particle size of the obtained powder is >80 mesh, more preferably >500 mesh.

[0040] In this invention, the ball milling method comprises: mixing the hydroxide of A, the halide of A, and the dopant G, and then sequentially ball milling, drying, and pulverizing to obtain a precursor. In this invention, the molar ratio of the hydroxide of A, the halide of A, and the dopant G is preferably 2:1:y; the ball milling speed is preferably ≥150 rpm, more preferably 300 rpm; the ball milling time 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 ball milling equipment is preferably a ball milling jar; the drying temperature is preferably 60-180℃, more preferably 80-120℃; the drying time is preferably ≥12 h, more preferably 24 h; the pulverization is preferably performed using a mortar and pestle or a pulverizer; the pulverization is preferably performed until the particle size of the obtained powder is >80 mesh, more preferably >500 mesh.

[0041] In this invention, the chemical reaction method involves mixing the carbonate of A, calcium hydroxide, and water, filtering the resulting mixture to obtain a supernatant, adding hydrohalic acid and dopant G to the supernatant, drying it, and pulverizing the resulting white solid to obtain the precursor. In this 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 carbonate of A to calcium hydroxide is 1:1; the molar ratio of carbonate of A to hydrohalic acid is 3:2; the molar ratio of hydrohalic acid to dopant G is preferably 1:y; the mass ratio of carbonate of A to water is preferably 1:(500-1000), more preferably 1:(500-600); the mixing of carbonate of A, calcium hydroxide, and water is preferably done by first mixing carbonate of A and water, stirring until completely dissolved, and then adding calcium hydroxide for a second stirring; the stirring speeds of the first and second stirrings are preferably 200-1000 rpm, more preferably 300-500 rpm; the second stirring time is preferably... The drying time is preferably 12-48 hours, more preferably 24 hours; the present invention does not have a special limitation on the filtration, and a filtration process well known in the art can be used to remove solid impurities; after adding hydrohalic acid and dopant G, the present invention preferably further includes: stirring the mixture obtained after adding hydrohalic acid and dopant G; the stirring speed is preferably 200-1000 rpm, more preferably 300-500 rpm; the stirring time is preferably 12-48 hours, more preferably 24 hours; the drying temperature is preferably 60-180℃, more preferably 100-120℃; the drying time is preferably 12-48 hours, more preferably 24 hours; the pulverization is preferably performed by grinding with a mortar and pestle or by pulverizing with a pulverizer; the pulverization is preferably performed until the particle size of the obtained powder is >80 mesh, more preferably >500 mesh.

[0042] In this invention, the sintering temperature is preferably 200–400°C, more preferably 230–350°C, and the holding time is preferably ≥4h, more preferably 4–24h; the sintering is preferably carried out under an inert atmosphere; the inert atmosphere is preferably created using argon; the purity of the argon is preferably ≥99.99%, more preferably 99.995%.

[0043] During sintering, the material's crystal lattice rearranges to produce a new lattice configuration. Sintering stabilizes the lattice morphology, ensuring the synthesis of ionic conductors. Alternatively, tempering at 220–270℃ can promote secondary crystallization, reshaping the grain morphology and stabilizing the lattice.

[0044] This invention provides a method for preparing the above-mentioned inorganic solid-state ionic conductor. The raw materials used are inexpensive and readily available, the operation is simple and the cost is low, which is conducive to large-scale promotion and application.

[0045] The present invention also provides the 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 this 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 does not impose any particular limitation on the application of the inorganic solid ionic conductor in electronic devices; any application method known in the art can be used.

[0048] The technical solutions of the present invention will be clearly and completely described below with reference to the embodiments of the present invention, but they should not be construed as limiting the scope of protection 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 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 were added to 20 mL of deionized water and stirred at 300 rpm for 24 h. The mixture was then evaporated and crystallized in an 80 °C oven for 24 h. After that, it was ground into powder (>500 mesh) in a mortar and placed in a crucible. The powder was then sintered at 280 °C for 4 h in an argon atmosphere (purity 99.995%) and then air-cooled in the furnace to obtain an inorganic solid ionic conductor.

[0052] Example 2

[0053] The chemical formula of the inorganic solid-state ionic conductor is Li3(OH)2Cl(Sm2O3). 0.005 The preparation method is as follows: 4.196g of lithium hydroxide monohydrate, 2.12g of anhydrous lithium chloride and 0.087g of Sm2O3 were added to 20mL of deionized water and stirred at 300rpm for 24h. After evaporation and crystallization in an 80℃ forced-air oven for 24h, the mixture was ground into powder (>500 mesh) in a mortar and placed in a crucible. The powder was then sintered at 280℃ for 4h under an argon atmosphere (purity of 99.995%) and then air-cooled in the furnace to obtain an inorganic solid ionic conductor.

[0054] Example 3

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

[0056] 4g of sodium hydroxide, 2.922g of anhydrous sodium chloride and 0.087g of Sm2O3 were added to 20mL of deionized water and stirred at 300rpm for 24h. The mixture was then evaporated and crystallized in an 80℃ forced-air oven for 24h. After that, it was ground into powder (>500 mesh) in a mortar and placed in a crucible. The powder was then sintered at 280℃ for 4h in an argon atmosphere (purity 99.995%) and then air-cooled in the furnace to obtain an inorganic solid ionic conductor.

[0057] Example 4

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

[0059] 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 and stirred at 300 rpm for 24 h. The mixture was then evaporated and crystallized in an 80 °C oven for 24 h. After that, it was ground into powder (>500 mesh) in a mortar and placed in a crucible. The powder was then sintered at 280 °C for 4 h in an argon atmosphere (purity 99.995%) and then cooled in the furnace to obtain an inorganic solid ionic conductor.

[0060] Example 5

[0061] The chemical formula of the inorganic solid-state ionic conductor is Li3(OH)2Cl(La2O3). 0.005 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 and stirred at 300 rpm for 24 h. The mixture was then evaporated and crystallized in an 80 °C oven for 24 h. The mixture was then ground into powder (>500 mesh) in a mortar and placed in a crucible. The powder was sintered at 260 °C for 4 h under an argon atmosphere (purity 99.995%) and then air-cooled in the furnace to obtain an inorganic solid ionic conductor.

[0063] Example 6

[0064] The chemical formula of the inorganic solid-state ionic conductor is Li3(OH)2Cl(Ba(OH)2). 0.005 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 and stirred at 300 rpm for 24 h. The mixture was then evaporated and crystallized in an 80 °C oven for 24 h. After that, the mixture was ground into powder (>500 mesh) in a mortar and placed in a crucible. The powder was then sintered at 280 °C for 4 h under an argon atmosphere (purity 99.995%) and then air-cooled in the furnace to obtain an inorganic solid ionic conductor.

[0066] Example 7

[0067] The chemical formula for the inorganic solid-state ionic conductor is Li3(OH)2Cl(BaCl2). 0.005 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 and stirred at 300 rpm for 24 h. The mixture was then evaporated and crystallized in an 80 °C oven for 24 h. After that, it was ground into powder (>500 mesh) in a mortar and placed in a crucible. The powder was then sintered at 280 °C for 4 h in an argon atmosphere (purity 99.995%) and then cooled in the furnace to obtain an inorganic solid ionic conductor.

[0069] Example 8

[0070] The chemical formula of the inorganic solid-state ionic conductor is Li3(OH)2Br(Sm2O3). 0.005 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 and stirred at 300 rpm for 24 h. The mixture was then evaporated and crystallized in an 80 °C oven for 24 h. The powder was then ground into powder (>500 mesh) in a mortar and placed in a crucible. The powder was sintered at 280 °C for 4 h under an argon atmosphere (purity 99.995%) and then air-cooled in the furnace to obtain an inorganic solid ionic conductor.

[0072] Example 9

[0073] The chemical formula of the inorganic solid-state ionic conductor is Li3(OH)2I(Sm2O3). 0.005 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 and stirred at 300 rpm for 24 h. The mixture was then evaporated and crystallized in an 80 °C oven for 24 h. After that, it was ground into powder in a mortar and placed in a crucible. The powder was then sintered at 280 °C for 4 h in an argon atmosphere (purity 99.995%) and then cooled in the furnace to obtain an inorganic solid ionic conductor.

[0075] Comparative Example 1

[0076] The inorganic solid-state ionic conductor has the chemical formula Li3(OH)2Cl, and its 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 and stirred at 300 rpm for 24 h. The mixture was then evaporated and crystallized in an 80 °C oven for 24 h. After that, it was ground into powder (>500 mesh) in a mortar and placed in a crucible. The powder was then sintered at 280 °C for 4 h in an argon atmosphere (purity 99.995%) and then air-cooled in the furnace to obtain an inorganic solid ionic conductor.

[0078] Performance testing

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

[0080] Depend on Figure 1 It can be seen that, according to the Bragg equation 2dsinθ=nλ, when λ is fixed, the smaller the 2θ angle, the larger the interplanar spacing d. Through doping, the appearance of some obvious or indistinct peaks of 2θ below 15° indicates that the dopant has successfully increased the lattice defects and provided some lattice defects. 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 inorganic solid ionic conductor powder obtained in Example 1 was mixed with 0.5% polytetrafluoroethylene (PTFE) and rolled into a thin film. A circular disc with a radius of 7.5 mm was cut using a 15 mm diameter gun and subjected to electrochemical impedance spectroscopy (EIS) testing. The results are as follows: Figure 2 As shown.

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

[0083] (3) The powder of the organic solid-state ion conductor obtained in Example 2 was mixed with 0.5% polytetrafluoroethylene (PTFE) and rolled into a thin film. A circular piece with a radius of 8 mm was cut using a 16 mm diameter gun and subjected to electrochemical impedance spectroscopy (EIS) testing. The results are as follows: Figure 3 As shown.

[0084] Depend on Figure 3 It can be seen that the thickness is 0.198 mm and the radius is 8 mm. 0.005 The impedance of the thin film at room temperature is 8.93Ω, and its ionic conductivity is calculated to be 1.103mS / cm.

[0085] (4) The inorganic solid-state ionic conductor powder obtained in Example 3 was mixed with 0.5% polytetrafluoroethylene (PTFE) and rolled into a thin film. A circular disc with a radius of 8 mm was cut using a 16 mm diameter gun and subjected to electrochemical impedance spectroscopy (EIS) testing. The results are as follows: Figure 4 As shown.

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

[0087] (5) The inorganic solid-state ionic conductor powder obtained in Example 4 was mixed with 0.5% polytetrafluoroethylene (PTFE) and rolled into a thin film. A circular disc with a radius of 8 mm was cut using a 16 mm diameter gun and subjected to electrochemical impedance spectroscopy (EIS) testing. The results are as follows: Figure 5 As shown.

[0088] Depend on Figure 5 It can be seen that Li3(OH)2Cl(La2O3) has a thickness of 1.1 mm and a radius of 8 mm. 0.005The impedance of the thin film at room temperature is 101.81Ω, and its ionic conductivity is calculated to be 0.956mS / cm.

[0089] (6) The inorganic solid-state ionic conductor powder obtained in Example 5 was mixed with 0.5% polytetrafluoroethylene (PTFE) and rolled into a thin film. A circular disc with a radius of 7.5 mm was cut using a 15 mm diameter gun and subjected to electrochemical impedance spectroscopy (EIS) testing. The results are as follows: Figure 6 As shown.

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

[0091] (7) The inorganic solid-state ionic conductor powder obtained in Example 6 was mixed with 0.5% polytetrafluoroethylene (PTFE) and rolled into a thin film. A circular disc with a radius of 7.5 mm was cut using a 15 mm diameter gun and subjected to electrochemical impedance spectroscopy (EIS) testing. The results are as follows: Figure 7 As shown.

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

[0093] (8) The inorganic solid-state ionic conductor powder obtained in Example 7 was mixed with 0.5% polytetrafluoroethylene (PTFE) and rolled into a thin film. A circular disc with a radius of 8 mm was cut using a 16 mm diameter gun and subjected to electrochemical impedance spectroscopy (EIS) testing. The results are as follows: Figure 8 As shown.

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

[0095] (9) The inorganic solid-state ionic conductor powder obtained in Example 8 was mixed with 0.5% polytetrafluoroethylene (PTFE) and rolled into a thin film. A circular disc with a radius of 8 mm was cut using a 16 mm diameter gun and subjected to electrochemical impedance spectroscopy (EIS) testing. The results are as follows: Figure 9 As shown.

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

[0097] (10) The inorganic solid-state ionic conductor powder obtained in Example 9 was mixed with 0.5% polytetrafluoroethylene (PTFE) and rolled into a thin film. A circular disc with a radius of 8 mm was cut using a 16 mm diameter gun and subjected to electrochemical impedance spectroscopy (EIS) testing. The results are as follows: Figure 10 As shown.

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

[0099] (11) The inorganic solid ionic conductor powder obtained in Comparative Example 1 was mixed with 0.5% polytetrafluoroethylene (PTFE) and rolled into a thin film. A circular disc with a radius of 8 mm was cut using a 16 mm diameter gun and subjected to electrochemical impedance spectroscopy (EIS). The results are as follows: Figure 11 As shown.

[0100] Depend on Figure 11 It can be seen 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 provided a detailed description of the present invention, they are only some embodiments of the present invention and not all embodiments. People can obtain other embodiments based on these embodiments without creative effort, and these embodiments all fall within the protection scope of the present invention.

Claims

1. An inorganic solid state ion conductor, characterized by, 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 several of metal oxides, metal halides, metal hydroxides, metal sulfides and ZrOCl2; the metal element in 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, 0 2. The inorganic solid-state ion conductor according to claim 1, characterized by The 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 by The X is Cl, Br or I.

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

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

7. The production method according to claim 6, characterized by, The sintering temperature is 200-400℃, and the holding time is ≥4h.

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. Use of the inorganic solid-state ion conductor according to any one of claims 1-5 or prepared by the method according to any one of claims 6-8 in electronic devices.

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