An organic-inorganic hybrid halogen compound molecular solid electrolyte and its preparation and all-solid-state battery

Abstract

This invention relates to a solid-state electrolyte based on an organic-inorganic hybrid halogen compound molecule, its preparation, and an all-solid-state battery, belonging to the field of energy storage battery technology. The chemical formula of the solid-state electrolyte of this invention is M. a N b+e Q c X d Y a+bn+cq+dx Z en Or M a N 2b+e Q c X d Y a+cq+ dx Z en O bn M is selected from one of methylamine, ethylamine, propylamine, butylamine, aniline, benzylamine, and phenethylamine; N, Q, and X are different metallic elements; Y is selected from halogens; Z is a pseudohalogen ion; the values ​​of a, b, c, d, and e are in the range of 0.

Description

Technical Field

[0001] This invention belongs to the field of energy storage battery technology, specifically relating to a solid electrolyte of organic-inorganic hybrid halogen compound molecules, its preparation, and an all-solid-state battery. Background Technology

[0002] In recent years, due to the rapid development of electronic devices such as electric vehicles, computers, and smartphones, traditional liquid electrolyte lithium-ion batteries have struggled to meet the stringent demands for high energy density and high safety, limiting their applications. Therefore, scholars and businesses have focused on all-solid-state batteries to overcome the bottlenecks in electrochemical energy storage technology and meet future development needs. From a long-term perspective, solid-state batteries offer significantly better energy density and thermal stability than liquid lithium-ion batteries, making them more promising for long-term commercialization.

[0003] Currently, academia and industry are continuously researching the following types of batteries: from a capacity perspective, metal-air batteries have been studied, with theoretical capacities comparable to lithium secondary batteries; from a safety perspective, non-flammable all-solid-state batteries have been studied; from a power output perspective, supercapacitors have been studied; from a large-scale perspective, NaS batteries or RFB (redox flow batteries) have been studied; from a miniaturization perspective, thin-film batteries have been studied; and so on.

[0004] Solid-state batteries, in particular, replace the liquid electrolyte used in conventional lithium-ion batteries with a solid electrolyte. Because no flammable solvents are used, safety is significantly improved. Currently, solid-state batteries mainly consist of a positive electrode, a negative electrode, and a solid electrolyte. Based on the electrolyte material, solid-state batteries can be divided into three categories: polymer solid-state batteries, sulfide solid-state batteries, and oxide solid-state batteries. Polymer solid-state batteries have good safety performance, sulfide solid-state batteries are easy to process, and oxide solid-state batteries have the highest conductivity. However, the most advanced solid electrolyte is the sulfide-type solid electrolyte, whose ionic conductivity has reached levels approaching that of organic electrolyte solutions. However, it is known that sulfide-type solid electrolytes typically contain phosphorus (P), which reacts with moisture and oxygen in the atmosphere, leading to deterioration in performance and low atmospheric storage stability, making them difficult to handle. Summary of the Invention

[0005] For the reasons stated above, the purpose of this invention is to provide a solid electrolyte containing organic-inorganic hybrid halogen compound molecules. Its preparation process is simple and efficient, involving sintering followed by ball milling, which facilitates large-scale production. This series of electrolyte materials exhibits high ionic conductivity, good flexibility and processability, and excellent air stability. Batteries constructed with the solid electrolyte material of this invention demonstrate excellent electrochemical performance and have significant application prospects in all-solid-state lithium metal batteries. This solves the technical problem that existing sulfide-type solid electrolytes typically contain phosphorus, which reacts with atmospheric moisture and oxygen, leading to performance degradation, and also suffers from low atmospheric storage stability.

[0006] According to a first aspect of the present invention, an organic-inorganic hybrid halogen compound molecular solid electrolyte is provided, wherein the general chemical formula of the organic-inorganic hybrid halogen compound molecular solid electrolyte is M. a N b+e Q c X d Y a+bn+cq+dx Z en Or M a N 2b+ e Q c X d Y a+cq+dx Z en O bn ;

[0007] Where M is selected from methylamine, ethylamine, propylamine, butylamine, aniline, benzylamine, and phenethylamine; N, Q, and X are different metallic elements; N is selected from Li, Na, K, Ca, Mg, Zn, Al, and Fe; Q is selected from Sc, Y, Al, Ga, In, Tl, Ge, Sn, Pb, Sb, and Bi; and X is selected from Fe, Zn, Ge, Zr, Ca, Mg, Ba, Bi, Ti, V, Cr, Co, Mn, Ni, Nb, Mo, Tc, Ru, Rh, Pd, Cd, Hf, Ta, W, Re, Os, Ir, and Sn.

[0008] Y is selected from one of F, Cl, Br, and I;

[0009] Z is a pseudohalogen ion selected from CN. － SH － OCN － SCN － SeCN － N3 － C(CN)3 － CF3SO3 － One of them;

[0010] The value ranges of a, b, c, d, and e are: 0 < a ≤ 3, 0 < b ≤ 3, 0 < c ≤ 1, 0 < d ≤ 1, 0 < e ≤ 6; n, q, and x are the numerical values of the valence of element N, element Q, and element X respectively.

[0011] Preferably, the organic-inorganic hybrid halogen compound molecular solid electrolyte is in powder form.

[0012] According to another aspect of the present invention, there is provided a method for preparing the organic-inorganic hybrid halogen compound molecular solid electrolyte. Under the atmosphere of a protective gas, the precursors MY, NY n , QY q , XY x , NZ n or MY, N2O n , QY q , XY x , NZ n are mixed in a molar ratio of a:b:c:d:e. After ball milling and sintering, the obtained chemical general formula is M a N b+e Q c X d Y a+bn+cq+dx Z en or M a N 2b+e Q c X d Y a+cq+dx Z en O bn ;

[0013] wherein M is selected from one of methylamine, ethylamine, propylamine, butylamine, aniline, benzylamine, and phenethylamine; N, Q, and X are different metal elements; N is selected from one of Li, Na, K, Ca, Mg, Zn, Al, and Fe; Q is selected from one of Sc, Y, Al, Ga, In, Tl, Ge, Sn, Pb, Sb, and Bi; X is selected from one of Fe, Zn, Ge, Zr, Ca, Mg, Ba, Bi, Ti, V, Cr, Co, Mn, Ni, Nb, Mo, Tc, Ru, Rh, Pd, Cd, Hf, Ta, W, Re, Os, Ir, and Sn;

[0014] Y is selected from one or more of F, Cl, Br, and I; <000't0182> Z is a pseudohalide ion, selected from CN － , SH － , OCN － , SCN － , SeCN － , N3 － , C(CN)3 － , CF3SO3－ one of the following;

[0016] The value ranges of a, b, c, d, and e are: 0 < a ≤ 3, 0 < b ≤ 3, 0 < c ≤ 1, 0 < d ≤ 1, 0 < e ≤ 6; n, q, and x are the numerical values of the valences of element N, element Q, and element X, respectively.

[0017] Preferably, the mass ratio of balls to materials in the ball milling is (10 - 40):1.

[0018] Preferably, the rotation speed of the ball milling is 100 - 1000 r / min.

[0019] Preferably, the time of the ball milling is 2 - 48 h.

[0020] Preferably, the sintering temperature is 100 - 700 °C, and the sintering time is 1 - 12 h.

[0021] Preferably, the sintering is carried out under vacuum conditions, or under argon or nitrogen conditions.

[0022] According to another aspect of the present invention, a all-solid-state battery is provided, including the organic-inorganic hybrid halogen compound molecular solid electrolyte described above.

[0023] Compared with the prior art by the above technical solution conceived by the present invention, the following technical advantages are mainly possessed:

[0024] (1) The main object of the present invention is to provide a solid electrolyte of an organic-inorganic hybrid halogen compound, which improves the uniform distribution of halogen element X inside the crystal grains and avoids the formation of a LiX coating layer on the crystal grain surface; moreover, metastable halogen X (X = F, Cl, Br) atoms in-situ precipitate LiX particles along with Li atoms and are diffusely distributed at the grain boundaries, thereby inhibiting the deposition and growth of metallic lithium inside the electrolyte, enhancing the ability of the electrolyte to inhibit lithium dendrites, and enabling the electrolyte to work at a high current density. In this way, both the high ionic conductivity of the battery can be maintained, and its safety and stability can be improved.

[0025] (2) The present invention doping organic substances into the halogen solid electrolyte can improve the performance of the electrolyte through multiple mechanisms, including increasing the ionic conductivity, enhancing the mechanical properties, improving the chemical stability, broadening the electrochemical window, and improving the interfacial compatibility, thereby playing an important role in high-performance battery systems.

[0026] (3) By introducing organic amine compounds, conductive channels can be formed, thereby increasing the migration rate of lithium ions and thus improving the conductivity of the electrolyte. Introducing organic molecules can increase the flexibility and plasticity of the electrolyte, allowing it to maintain good shape and structural stability under high temperature or high pressure conditions. Furthermore, some organic compounds can form stable complexes with halogens, preventing the electrolyte from decomposing in high-temperature or humid environments and improving chemical stability. The presence of organic matter can broaden the electrochemical window of halogen solid electrolytes, allowing them to remain stable over a wider voltage range, thus making them suitable for higher-voltage battery systems. Doping with organic matter can improve the interfacial compatibility between halogen solid electrolytes and electrode materials, reducing interfacial resistance and thus improving the overall performance of the battery.

[0027] (4) By doping different kinds of metal elements, the present invention can effectively adjust the lattice parameters in the halide solid electrolyte, improve the lithium ion transport channel and enhance the ionic conductivity. At the same time, the halide electrolyte material doped with metal elements has good air stability and structural stability, and can maintain chemical stability for a long time in a dew point environment of -40℃.

[0028] (5) In this invention, pseudohalogen ions refer to anions with properties such as ionic radius similar to those of halide ions. Compared with halide ions, the compounds formed by pseudohalogen ions are less prone to hygroscopicity and deliquescence, thereby significantly reducing the humidity instability caused by halide ions. This results in excellent long-term stability and humidity stability of the electrolyte, making it easier to form sheets and maintain a thin sheet state. Attached Figure Description

[0029] Figure 1 The present invention is based on MALi2In prepared according to Examples 1-4. 0.1 Fe 0.1 Cl 2.5 CN、MALi2In 0.1 Zr 0.1 Cl 2.7 OCN, MALi2Ge 0.1 Fe 0.1 Cl 2.7 SCN, (MA)2Li5Sn 0.5 Ge 0.5 XRD pattern of Cl7(CN)3.

[0030] Figure 2 This is the impedance diagram of the solid electrolyte prepared according to Example 1 of this invention. The room temperature ionic conductivity of Example 1 is 2.9 × 10⁻⁶. -3 S cm -1 .

[0031] Figure 3This is the impedance diagram of the solid electrolyte prepared according to Example 4 of this invention. The room temperature ionic conductivity of Example 4 is 3.2 × 10⁻⁶. -3 S cm -1 . Detailed Implementation

[0032] To make the objectives, technical solutions, and advantages of this invention clearer, the invention will be further described in detail below with reference to the accompanying drawings and embodiments. It should be understood that the specific embodiments described herein are merely illustrative and not intended to limit the invention. Furthermore, the technical features involved in the various embodiments of this invention described below can be combined with each other as long as they do not conflict with each other.

[0033] In this invention, M is selected from methylamine (MA), ethylamine, propylamine, butylamine, aniline, benzylamine, and β-phenylethylamine.

[0034] In this invention, N, Q, and X are different metallic elements; N is selected from Li, Na, K, Ca, Mg, Zn, Al, and Fe; Q is selected from Sc, Y, Al, Ga, In, Tl, Ge, Sn, Pb, Sb, and Bi; X is selected from Fe, Zn, Ge, Zr, Ca, Mg, Ba, Bi, Ti, V, Cr, Co, Mn, Ni, Nb, Mo, Tc, Ru, Rh, Pd, Cd, Hf, Ta, W, Re, Os, Ir, and Sn; and Y is selected from F, Cl, Br, and I.

[0035] In this invention, Z represents a pseudohalogen ion, selected from cyanate ions (CN). － ), hydrosulfide ions (SH) － ), oxycyanate ion (OCN) － ), thiocyanate ion (SCN) － ), selenium cyanate ions (SeCN) － ), azide (N3) － ), cyanoform (C(CN)3) － ), trifluoromethanesulfonate (CF3SO3) － One of them.

[0036] The following are specific embodiments.

[0037] Example 1

[0038] This embodiment provides a solid electrolyte MALi2In containing organic-inorganic hybrid halogen compound molecules. 0.1 Fe 0.1Cl 2.5 CN, the specific preparation method is as follows:

[0039] (1) In an Ar atmosphere glove box, weigh the precursor powders MACl, LiCl, InCl3, FeCl2 and LiCN in a molar ratio of 1:1:0.1:0.1:1 and place them in an agate mortar. Grind them by hand for 20 minutes using an agate grinding pestle. Add the ground precursor powder to a ZrO2 ball mill jar with a ball-to-material mass ratio of 20:1. Transfer the ball mill jar to a ball mill and grind it at 500 rpm for 10 hours. Then allow it to cool down to room temperature naturally.

[0040] (2) Remove the ball-milled powder from the ball mill jar and store it in an argon glove box. Place the powder in a quartz glass tube under argon atmosphere, evacuate and seal it. Then transfer the quartz tube to a muffle furnace for sintering at 300°C for 2 hours. Allow it to cool naturally to room temperature, remove the quartz tube, transfer it to an argon glove box, and grind it into a uniform powder to obtain a solid electrolyte.

[0041] MALi2In 0.1 Fe 0.1 Cl 2.5 CN.

[0042] Example 2

[0043] This embodiment provides a solid electrolyte MALi2In containing organic-inorganic hybrid halogen compound molecules. 0.1 Zr 0.1 Cl 2.7 The specific preparation method of OCN is as follows:

[0044] (1) In an Ar atmosphere glove box, weigh MACl, LiCl, InCl3, ZrCl4 and LiOCN precursor powders according to the molar ratio of 1:1:0.1:0.1:1 and place them in an agate mortar. Grind them by hand for 20 minutes using an agate grinding pestle. Add the ground precursor powder to a ZrO2 ball mill jar with a ball-to-material mass ratio of 20:1. Transfer the ball mill jar to a ball mill and grind it at 500 rpm for 10 hours. Then allow it to cool down to room temperature naturally.

[0045] (2) Remove the ball-milled powder from the ball mill jar and store it in an argon glove box. Place the powder in a quartz glass tube under argon atmosphere, evacuate and seal it. Then transfer the quartz tube to a muffle furnace for sintering at 300°C for 2 hours. Allow it to cool naturally to room temperature, remove the quartz tube, transfer it to an argon glove box, and grind it into a uniform powder to obtain a solid electrolyte.

[0046] MALi2In 0.1 Zr 0.1 Cl2.7 OCN.

[0047] Example 3

[0048] This embodiment provides a solid electrolyte MALi2Ge with organic-inorganic hybrid halogen compound molecules. 0.1 Fe 0.1 Cl 2.7 The specific preparation method of SCN is as follows:

[0049] (1) In an Ar atmosphere glove box, weigh the precursor powders of MACl, LiCl, GeCl4, FeCl3 and LiSCN in a molar ratio of 1:1:0.1:0.1:1 and place them in an agate mortar. Grind them by hand for 20 minutes using an agate grinding pestle. Add the ground precursor powder to a ZrO2 ball mill jar with a ball-to-material mass ratio of 20:1. Transfer the ball mill jar to a ball mill and grind it at 500 rpm for 10 hours. Then allow it to cool down to room temperature naturally.

[0050] (2) Remove the ball-milled powder from the ball mill jar and store it in an argon glove box. Place the powder in a quartz glass tube under argon atmosphere, evacuate and seal it. Then transfer the quartz tube to a muffle furnace for sintering at 300°C for 2 hours. Allow it to cool naturally to room temperature, remove the quartz tube, transfer it to an argon glove box, and grind it into a uniform powder to obtain a solid electrolyte.

[0051] MALi2Ge 0.1 Fe 0.1 Cl 2.7 SCN.

[0052] Example 4

[0053] This embodiment provides a solid electrolyte (MA)2Li5Sn containing organic-inorganic hybrid halogen compound molecules. 0.5 Ge 0.5 Cl7(CN)3, the specific preparation method is as follows:

[0054] (1) In an Ar atmosphere glove box, weigh the precursor powders MACl, LiCl, SnCl2, GeCl4, and LiCN in a molar ratio of 2:2:0.5:0.5:3 and place them in an agate mortar. Grind them by hand for 20 minutes using an agate grinding pestle. Add the ground precursor powder to a ZrO2 ball mill jar with a ball-to-material mass ratio of 20:1. Transfer the ball mill jar to a ball mill and grind it at 500 rpm for 10 hours. Then allow it to cool naturally to room temperature.

[0055] (2) Remove the ball-milled powder from the ball mill jar and store it in an argon glove box. Place the powder in a quartz glass tube under argon atmosphere, evacuate and seal it. Then transfer the quartz tube to a muffle furnace for sintering at 300°C for 2 hours. Allow it to cool naturally to room temperature, remove the quartz tube, transfer it to an argon glove box, and grind it into a uniform powder to obtain the solid electrolyte (MA)2Li5Sn. 0.5 Ge 0.5 Cl7(CN)3.

[0056] Example 5

[0057] As shown in Examples 1-4, the difference between this example and Example 4 lies in the following: the ratio of the types and amounts of precursor powders is BACl, LiCl, YCl3, NbCl5, LiCN = 2:2:0.5:0.5:3; hand milling for 20 min; ball-to-powder mass ratio of 20:1; ball milling speed of 500 rpm; ball milling time of 10 h; sintering temperature of 300℃; and sintering time of 2 h. All other operations are the same as in Example 4, yielding the solid electrolyte (BA)2Li5Y. 0.5 Nb 0.5 Cl8(CN)3.

[0058] Example 6

[0059] The difference between this embodiment and Example 4 is that the ratio of the types and amounts of precursor powders is: PEACl, LiCl, SbCl5, CrCl6, LiSCN = 2:2:0.5:0.5:3. The mixture is hand-milled for 20 minutes, the ball-to-powder mass ratio is 20:1, the ball milling speed is 600 rpm, the ball milling time is 10 hours, the sintering temperature is 350℃, and the sintering time is 2 hours. All other operations are the same as in Example 4, yielding the solid electrolyte (PEA)2Li5Sb. 0.5 Cr 0.5 Cl 9.5 (SCN)3.

[0060] Example 7

[0061] The difference between this embodiment and Example 4 is that the ratio of the types and amounts of precursor powders is: MACl, LiCl, ScCl3, BiCl3, LiCF3SO3 = 3:3:1:1:6; hand milling for 20 min; ball-to-powder mass ratio of 20:1; ball milling speed of 600 rpm; ball milling time of 10 h; sintering temperature of 350℃; and sintering time of 3 h. All other operations are the same as in Example 4, yielding the solid electrolyte (MA)3Li9ScBiCl. 12 (CF3SO3)6.

[0062] Example 8

[0063] The difference between this embodiment and Example 4 is that the ratio of the types and amounts of precursor powders is: BACl, LiCl, YCl3, TiCl4, LiOCN = 3:3:1:1:6; hand milling for 20 min; ball-to-powder mass ratio of 25:1; ball milling speed of 700 rpm; ball milling time of 15 h; sintering temperature of 400℃; and sintering time of 3 h. All other operations are the same as in Example 4, yielding the solid electrolyte (BA)3Li9YTiCl. 13 (OCN)6.

[0064] Example 9

[0065] The difference between this embodiment and Embodiment 4 is that the ratio of the types and amounts of precursor powders is: PEACl, LiCl, AlCl3, TaCl. 5、 The LiCN ratio was 1:2:0.3:0.7:3. The mixture was hand-milled for 20 minutes at a ball-to-material mass ratio of 25:1 at 700 rpm for 15 hours. The sintering temperature was 400℃ for 3 hours. All other procedures were the same as in Example 4, yielding the solid electrolyte PEALi5Al. 0.3 Ta 0.7 Cl 7.4 (CN)3.

[0066] Example 10

[0067] The difference between this embodiment and Example 4 is that the ratio of the types and amounts of precursor powders is: MACl, LiCl, ZnCl2, FeCl2, LiSH = 1:2:0.3:0.7:3. The mixture is hand-milled for 20 minutes, with a ball-to-powder mass ratio of 25:1, a ball milling speed of 750 rpm, a ball milling time of 15 hours, a sintering temperature of 450℃, and a sintering time of 5 hours. All other operations are the same as in Example 4, yielding the solid electrolyte MALi5Zn. 0.3 Fe 0.7 Cl5(SH)3.

[0068] Example 11

[0069] The difference between this embodiment and Example 4 is that the ratio of the types and amounts of precursor powders is: BACl, MgCl2, GaCl3, CoCl2, Mg(SeCN)2 = 2:1:0.6:0.4:5. The mixture is hand-milled for 20 minutes, the ball-to-powder mass ratio is 30:1, the ball milling speed is 750 rpm, the ball milling time is 20 hours, the sintering temperature is 450℃, and the sintering time is 5 hours. All other operations are the same as in Example 4, yielding the solid electrolyte (BA)2Mg6Ga. 0.6 Co 0.4 Cl6(SeCN)5.

[0070] Example 12

[0071] The difference between this embodiment and Example 4 is that the ratio of the types and amounts of precursor powders is: MAF, LiF, InF3, FeF3, LiCN = 2:1:0.6:0.4:5; hand milling for 20 min; ball-to-powder mass ratio of 30:1; ball milling speed of 800 rpm; ball milling time of 20 h; sintering temperature of 500℃; and sintering time of 5 h. All other operations are the same as in Example 4 to obtain the solid electrolyte (MA)2Li6In. 0.6 Fe 0.4 F6(CN)5.

[0072] Example 13

[0073] The difference between this embodiment and Example 4 is that the ratio of the types and amounts of precursor powders is: MACl, Li₂O, InCl₃, FeCl₂, LiCN = 1:2:0.4:0.6:3. The mixture is hand-milled for 20 minutes, the ball-to-powder mass ratio is 30:1, the ball milling speed is 800 rpm, the ball milling time is 20 hours, the sintering temperature is 500℃, and the sintering time is 5 hours. All other operations are the same as in Example 4 to obtain the solid electrolyte MALi₇In. 0.4 Fe 0.6 Cl 3.4 (CN)3O2.

[0074] Example 14

[0075] The difference between this embodiment and Example 4 is that the ratio of the types and amounts of precursor powders is: MACl, MgO, InCl3, FeCl3, Mg(CN)2 = 1:2:0.3:0.7:3. The mixture is hand-milled for 20 minutes, the ball-to-powder mass ratio is 30:1, the ball milling speed is 800 rpm, the ball milling time is 20 hours, the sintering temperature is 500℃, and the sintering time is 5 hours. All other operations are the same as in Example 4 to obtain the solid electrolyte MAMg5In. 0.3 Fe 0.7 Cl4(CN)6O2.

[0076] Example 15

[0077] The difference between this embodiment and Example 4 is that the ratio of the types and amounts of precursor powders is: MACl, Al2O3, GeCl4, FeCl2, Al(CN)3 = 2:1:0.6:0.4:3. The mixture is hand-milled for 20 minutes, the ball-to-powder mass ratio is 30:1, the ball milling speed is 800 rpm, the ball milling time is 20 hours, the sintering temperature is 500℃, and the sintering time is 5 hours. All other operations are the same as in Example 4 to obtain the solid electrolyte (MA)2Al5Ge.0.6 Fe 0.4 Cl 5.2 (CN)9O3.

[0078] Performance testing

[0079] like Figure 1 As shown, the samples MALi2In obtained in Examples 1-4 0.1 Fe 0.1 Cl 2.5 CN、MALi2In 0.1 Zr 0.1 Cl 2.7 OCN, MALi2Ge 0.1 Fe 0.1 Cl 2.7 SCN, (MA)2Li5Sn 0.5 Ge 0.5 XRD data of Cl7(CN)3 show that the main body of the material is crystalline.

[0080] like Figure 2 As shown, the sample MALi2In obtained in Example 1 0.1 Fe 0.1 Cl 2.5 The ionic conductivity of CN can reach 2.9 × 10⁻⁶. -3 Scm -1 .

[0081] like Figure 3 As shown, the sample (MA)2Li5Sn obtained in Example 4 0.5 Ge 0.5 The ionic conductivity of Cl7(CN)3 can reach 3.2 × 10⁻⁶. -3 S cm -1 .

[0082] 100 mg of electrolyte powder was weighed and placed in a specially made stainless steel mold for solid-state batteries with a diameter of 10 mm. It was then pressurized at 380 MPa for 1 minute and removed. The room-temperature ionic conductivity of the solid electrolyte in each embodiment was tested using the blocking electrode test method at a frequency of 0.1 Hz to 1 MHz. The calculation formula was σ = d / (SR), where d is the thickness of the electrolyte, S is the area of ​​the electrolyte side in contact with the blocking electrode, and R is the resistance obtained from AC impedance testing. The room-temperature ionic conductivity of each embodiment is shown in Table 1.

[0083] MALi2In obtained in Example 1 0.1 Fe 0.1 Cl 2.5 A full cell assembled using CN solid-state electrolyte. The cathode is lithium nickel manganese cobalt oxide (LiNi) material. 0.5 Mn0.3 Co 0.2 A composite electrode of O2 and Li6PS5Cl, with an electrolyte layer of MALi2In. 0.1 Fe 0.1 Cl 2.5 CN was used as the negative electrode to prepare an all-solid-state lithium-ion battery, which was then tested at a 0.2C rate.

[0084] Table 1 Summary of Test Results

[0085]

[0086]

[0087] Those skilled in the art will readily understand that the above description is merely a preferred embodiment of the present invention and is not intended to limit the present invention. Any modifications, equivalent substitutions, and improvements made within the spirit and principles of the present invention should be included within the scope of protection of the present invention.

Claims

1. A solid electrolyte composed of organic-inorganic hybrid halogen compounds, characterized in that, The general chemical formula of the organic-inorganic hybrid halogen compound molecular solid electrolyte is M. a N b+e Q c X d Y a+bn+cq+dx Z en Or M a N 2b+e Q c X d Y a+cq+dx Z en O bn ; Among them, M is selected from one of methylamine, ethylamine, propylamine, butylamine, aniline, benzylamine, and phenethylamine; N, Q, and X are different metal elements; N is selected from one of Li, Na, K, Ca, Mg, Zn, Al, and Fe; Q is selected from one of Sc, Y, Al, Ga, In, Tl, Ge, Sn, Pb, Sb, and Bi; X is selected from one of Fe, Zn, Ge, Zr, Ca, Mg, Ba, Bi, Ti, V, Cr, Co, Mn, Ni, Nb, Mo, Tc, Ru, Rh, Pd, Cd, Hf, Ta, W, Re, Os, Ir, and Sn; Y is selected from one of F, Cl, Br, and I; Z is a pseudohalogen ion selected from CN. － SH － OCN － SCN － SeCN － N3 － C(CN)3 － CF3SO3 － One of them; The value ranges of a, b, c, d, and e are: 0 < a ≤ 3, 0 < b ≤ 3, 0 < c ≤ 1, 0 < d ≤ 1, 0 < e ≤ 6; n, q, and x are the numerical values of the valence of N element, Q element, and X element respectively; The organic-inorganic hybrid halogen compound molecular solid electrolyte is prepared by the following steps: under a protective gas atmosphere, the precursors MY and NY are... n QY q , XY x NZ n Or precursors MY, N2O n QY q , XY x NZ n The mixture is prepared according to the molar ratio a:b:c:d:e, ball-milled, and then sintered to obtain the chemical formula M. a N b+e Q c X d Y a+bn+cq+dx Z en Or M a N 2b+e Q c X d Y a+cq+ dx Z en O bn The ball milling speed is 500-1000 r / min; the ball milling time is 10-48 h; the sintering temperature is 300-700 ℃, and the sintering time is 1-12 h.

2. The organic-inorganic hybrid halogen compound molecular solid electrolyte as described in claim 1, characterized in that, The organic-inorganic hybrid halide molecular solid electrolyte is in powder form.

3. The method for preparing the solid electrolyte of organic-inorganic hybrid halogen compound molecules as described in claim 1 or 2, characterized in that, Under a protective gas atmosphere, the precursors MY and NY are... n QY q , XY x NZ n Or precursors MY, N2O n QY q , XY x NZ n The mixture is prepared according to the molar ratio a:b:c:d:e, ball-milled, and then sintered to obtain the chemical formula M. a N b+e Q c X d Y a+bn+cq+ dx Z en Or M a N 2b+e Q c X d Y a+cq+dx Z en O bn The ball milling speed is 500-1000 r / min; the ball milling time is 10-48 h; the sintering temperature is 300-700 ℃, and the sintering time is 1-12 h.

4. The preparation method according to claim 3, characterized in that, The mass ratio of balls to materials in the ball milling is (10 - 40):

1.

5. The preparation method according to claim 3, characterized in that, The sintering is carried out under vacuum conditions, or under argon or nitrogen conditions.

6. An all-solid-state battery, characterized in that, It includes the organic-inorganic hybrid halide molecular solid electrolyte according to any one of claims 1-2.

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