All-solid-state battery electrolyte as well as preparation method and application thereof

Abstract

The invention provides an all-solid-state battery electrolyte as well as a preparation method and application thereof. The electrolyte comprises a lithium salt, a low-melting-point halide and an inorganic halide modifier, the softening point of the low-melting-point halide is 20-70 DEG C. The electrolyte has a low melting point and high ionic conductivity, and has certain fluidity or viscoelasticity at room temperature due to the low solid melting point, so that when the material is used as an electrolyte material in an all-solid-state battery, the material can be stacked under the condition that only extremely low external stacking pressure is needed; and long-term, tight and self-adaptive contact with the electrode is realized, so that the low-pressure all-solid-state battery with high interface stability, high rate performance and excellent safety is constructed.

Description

Technical Field

[0001] This invention relates to the field of battery technology, and in particular to an all-solid-state battery electrolyte, its preparation method, and its application. Background Technology

[0002] With the increasing demands for energy density and safety from electric vehicles, large-scale energy storage, and portable electronic devices, traditional liquid lithium-ion batteries, due to their flammable organic electrolytes and inherent energy density limitations, are finding it difficult to meet future needs. All-solid-state batteries (ASSBs), which use non-flammable solid electrolytes instead of liquid electrolytes, are widely recognized as one of the ultimate solutions for next-generation energy storage technologies, offering advantages such as high intrinsic safety, high energy density potential, wide operating temperature range, and long cycle life.

[0003] However, the commercialization of all-solid-state batteries is severely limited by the solid-solid interface problem. Unlike liquid electrolytes, which can wet and penetrate the electrode pores to form a perfect contact, the contact between the solid electrolyte and the solid electrode is a rigid point-to-point contact. This contact is very fragile during battery cycling and is easily damaged by changes in electrode volume or uneven lithium deposition / stripping, leading to a surge in interfacial impedance and battery failure. To solve this problem, the current mainstream technical approach is to apply enormous external stacking pressure to the battery to mechanically force the interface to maintain contact. However, this brings many drawbacks as mentioned above. Therefore, developing new solid electrolyte systems that can achieve "low-pressure" or even "pressure-free" operation has become crucial for academia and industry to overcome the technical challenges of all-solid-state batteries.

[0004] Iodine ion interface-controlled low-pressure sulfide solid-state battery technology can solve the above problems to some extent. This approach introduces iodine ions (I₂O₃) into the sulfide solid electrolyte. -One approach utilizes the directional migration characteristics of iodine ions under an electric field to form an "iodine-rich adaptive layer" at the lithium metal anode-electrolyte interface. This layer actively fills the microscopic voids at the interface, suppresses lithium dendrite growth, and buffers volume changes during electrode charging and discharging, thus maintaining stable solid-solid interface contact under low external pressure conditions and reducing reliance on mechanical pressurization devices. Another solution is a polymer-inorganic composite solid electrolyte. This approach uses a flexible polymer matrix (such as polyethylene oxide (PEO), polycarbonate, etc.) as the continuous phase, providing flexibility and adhesion to the electrode. Simultaneously, high-ionic-conductivity inorganic fillers (such as LLZO, LATP, etc.) are dispersed within the polymer matrix, aiming to combine the good processability and flexibility of polymers with the high ionic conductivity and mechanical strength of inorganic materials. Its working principle is attributed to the viscoelasticity and certain plastic deformation capacity of polymers, enabling relatively good contact with the electrode under relatively low pressure. In addition to improving the overall ionic conductivity, the addition of inorganic fillers is also believed to inhibit the crystallization of polymer segments and increase their mechanical modulus, thereby suppressing lithium dendrites to a certain extent.

[0005] However, on the one hand, existing iodine-ion interface-controlled low-pressure sulfide solid-state battery schemes have inherent limitations in the interfacial stability mediated by iodine ions. The chemical stability of the iodine-rich layer depends on maintaining the iodine ion concentration. After a certain number of cycles, iodine ions will diffuse towards the positive electrode, causing the interfacial layer thickness to decrease from 5-10 nm to 2-3 nm, resulting in a loss of void-filling capacity. Simultaneously, when the battery operating voltage exceeds 4.2 V (a necessary condition for adapting to high-nickel positive electrodes NCM811 and NCA), iodine ions are easily oxidized to elemental iodine. The volatilization of elemental iodine or its reaction with the electrolyte will generate insulating iodides, leading to a sharp decrease in battery capacity. On the other hand, in existing polymer-inorganic composite solid-state electrolyte implementation schemes, the polymer content cannot be too low to achieve sufficient flexibility. This limits the proportion of inorganic fillers, resulting in the room-temperature ionic conductivity of the composite electrolyte typically only reaching 10. -5 ~10 -4 The S / cm range limits the rate performance of the battery. Furthermore, its interface adaptability is limited. Although superior to pure inorganic electrolytes, existing composite electrolytes still have a high elastic modulus, limiting their deformation capacity. When faced with drastic volume changes, interface delamination may still occur, and they cannot achieve "self-healing" to repair the resulting microcracks, resulting in insufficient long-term cycle stability. Summary of the Invention

[0006] The present invention aims to solve at least one of the aforementioned technical problems existing in the prior art. Therefore, the object of the present invention is to provide an all-solid-state battery electrolyte, its preparation method, and its application.

[0007] To achieve the above objectives, the technical solution adopted by the present invention is as follows: This invention provides an electrolyte comprising a lithium salt, a low-melting-point halide, and an inorganic halide modifier; wherein the low-melting-point halide has a softening point of 20-70 °C.

[0008] In this invention, the electrolyte is designed as a ternary composite system of lithium salt, low-melting-point halide, and inorganic halide modifier. This design achieves synergistic optimization of interfacial interaction mechanisms, structural characteristics, and ion transport efficiency at the molecular / atomic scale, ultimately resulting in stable operation without the need for high voltage. The core mechanism is as follows: (1) Softening and flow characteristics of low-melting-point halides: Low-melting-point halides undergo solid-state softening at the normal operating temperature of the battery (25-60℃), exhibiting a "viscoelastic" physical property, no longer the rigid solid state of traditional inorganic electrolytes. This softening characteristic allows the electrolyte to conform to the microstructure of the electrode surface like a flexible medium when in contact with the electrode, filling the electrode pores and surface defects to form a continuous, gapless interfacial contact, rather than the "point-to-point" rigid contact of traditional solid-state batteries, thus eliminating the high impedance problem caused by insufficient contact at its source.

[0009] (2) Structural support and dynamic regulation of inorganic halide modifiers: Inorganic halide modifiers form a stable microstructure framework in the system, change the chemical environment and coordination relationship of lithium ions and anions, and can change the transport dynamics of lithium ions and enhance the migration mechanism of ions in solid electrolytes.

[0010] (3) Dynamic interactions between components: Through specific preparation processes, lithium salt, low-melting-point halide, and inorganic halide modifier form a defect-rich amorphous / nanocrystalline composite structure at the atomic scale, with dynamic chemical bonding and ion exchange between components. When microcracks are generated in the electrolyte due to mechanical stress or electrode volume changes, the components at the crack interface can re-achieve interface fusion through ion migration and chemical bond reconstruction, thus completing the "self-healing" of the microcracks. Furthermore, the synergistic effect of the ternary components forms a multidimensional ion transport channel. The lithium salt provides a sufficient source of lithium ions, the softening state of the low-melting-point halide reduces the resistance to lithium ion migration, and the crystal defects and active sites of the inorganic halide modifier provide additional migration paths for lithium ions.

[0011] In some embodiments, the softening point of the low-melting-point halide is 25-60 °C. In some embodiments, the molar ratio of the lithium salt to the sum of the low-melting-point halide and the inorganic halide modifier is (1-5):1; such as (1.5-4):1, 1:1, 2:1, 3:1, 4:1, 5:1, etc.

[0012] In some embodiments, the molar ratio of the low-melting-point halide to the inorganic halide modifier is (0.1-4):1; such as (0.5-1.6):1, 0.5:1, 1:1, 1.5:1, 2.0:1, 2.5:1, 3.0:1, 3.5:1, etc.

[0013] In some embodiments, the lithium salt includes at least one of lithium carbonate, lithium oxide, lithium hydroxide, lithium chloride, lithium iodide, lithium bromide, lithium fluoride, lithium nitrate, lithium sulfate, lithium acetate, lithium tert-butoxy, lithium tantalate, lithium titanate, lithium niobate, lithium cobalt oxide, lithium nitride, lithium manganese oxide, lithium iron phosphate, lithium borohydride, lithium hexafluorophosphate, lithium bis(fluorosulfonyl)imide, lithium bis(trifluoromethanesulfonyl)imide, lithium difluorooxalate borate, lithium tetrafluoroborate, lithium hexafluoroarsenate, lithium perchlorate, lithium trifluoromethanesulfonate, and lithium dioxalate borate.

[0014] In some embodiments, the low-melting-point halide includes at least one of gallium trifluoride, indium fluoride, and aluminum oxychloride.

[0015] In some embodiments, the inorganic halide modifier includes at least one of aluminum trifluoride, chromium trifluoride, iridium trichloride, ruthenium trichloride, titanium tetrafluoride, germanium tetrafluoride, titanium tetrachloride, tin tetrachloride, zirconium tetrachloride, zirconium tetrafluoride, titanium tetrabromide, tantalum pentachloride, niobium pentachloride, niobium pentafluoride, molybdenum pentachloride, antimony pentafluoride, vanadium pentafluoride, antimony pentachloride, vanadium pentachloride, molybdenum hexafluoride, and tantalum hexafluoride.

[0016] The present invention also provides a method for preparing the electrolyte, which can be carried out by traditional solid-phase method, hydrothermal method, liquid-phase method, wet chemical method, ball milling / high-energy ball milling method.

[0017] In some embodiments, the method for preparing the electrolyte includes the following steps: The electrolyte is prepared by high-energy ball milling of lithium salt, low-melting-point halide, and inorganic halide modifier.

[0018] In some embodiments, the high-energy ball mill operates at a speed of 500-800 rpm, such as 550 rpm, 600 rpm, 650 rpm, 700 rpm, 750 rpm, etc.; and the milling time is 10-70 h, such as 30-60 h, 40 h, 45 h, 50 h, 55 h, etc.

[0019] In some embodiments, the high-energy ball milling process includes zirconia beads; the diameter of the ball milling beads is 0.5-10 mm; such as 2-8 mm, 3 mm, 4 mm, 5 mm, 6 mm, 7 mm, etc.

[0020] In some embodiments, the ball-to-material mass ratio in the high-energy ball mill is (20-50):1; such as 30:1, 40:1, etc.

[0021] The present invention also provides a solid-state battery, including the electrolyte described above.

[0022] In some embodiments, the solid-state battery includes a positive electrode layer, an electrolyte layer, and a negative electrode layer; the positive electrode layer and / or the electrolyte layer includes the electrolyte.

[0023] In some embodiments, the positive electrode layer includes a positive electrode active material, the electrolyte, and a conductive agent.

[0024] In some embodiments, the mass ratio of the positive electrode active material, the electrolyte, and the conductive agent is (60-80):(20-40):(1-5); such as 70:30:3.

[0025] In some embodiments, the positive electrode active material includes at least one of layered oxide materials, polyanionic materials, or spinel structure materials.

[0026] In some embodiments, the layered oxide material includes at least one of lithium cobalt oxide, lithium nickel cobalt manganese oxide (NCM), lithium nickel cobalt aluminum oxide, lithium nickel oxide, lithium manganese oxide, lithium titanate, etc.

[0027] In some embodiments, N+C+M=1 and Li / N+C+M=1 in the NCM, preferably N / C / M=1 / 1 / 1, 8 / 1 / 1, 6 / 2 / 2, 5 / 3 / 2, or 7 / 2 / 1.

[0028] In some embodiments, the polyanionic material includes at least one of lithium iron phosphate, lithium manganese iron phosphate, lithium manganese phosphate, and lithium vanadium phosphate.

[0029] In some embodiments, the spinel structural material includes at least one of lithium manganese oxide, lithium nickel manganese oxide, etc.

[0030] In some embodiments, the conductive agent includes at least one of natural graphite, artificial graphite, conductive carbon black (such as Ketjen black, Super-P, acetylene black), carbon nanotubes, and carbon nanofibers (such as vapor-grown carbon fiber (VGCF)).

[0031] In some embodiments, the negative electrode layer comprises a negative electrode material.

[0032] In some embodiments, the negative electrode material includes at least one of Li, Li-In alloy, Si, graphite, and silicon-carbon composite materials.

[0033] The present invention also provides a method for assembling the solid-state battery, comprising the following steps: stacking a positive electrode layer, an electrolyte layer, and a negative electrode layer in sequence, applying pressure to press them together, and then encapsulating them in a battery casing to obtain the solid-state battery.

[0034] In some embodiments, the applied pressure includes applying a pressure below 3.0 MPa; such as 0.1-3.0 MPa, 0.1-2.8 MPa, 0.2-2.5 MPa, 0.3-2.4 MPa, etc.

[0035] The present invention also provides an electrical device, including the aforementioned solid-state battery.

[0036] In some embodiments, the electrical equipment includes power equipment (such as electric vehicles, electric cars), electronic devices (such as mobile phones, tablets, laptops, digital cameras, etc.), wearable devices (such as watches, bracelets, VR glasses, etc.), energy storage power stations, etc.

[0037] The beneficial effects of this invention are: The electrolyte of this invention has the characteristics of adaptive interface contact, self-healing repair and low impedance ion transport, which can ensure the stable operation of the all-solid-state battery under low pressure conditions.

[0038] The electrolyte of the present invention has a low melting point and high ionic conductivity. Its low solid melting point gives it a certain degree of fluidity or viscoelasticity at room temperature. This allows the electrolyte to achieve long-term, close, and adaptive contact with the electrodes (especially high-capacity negative electrodes) with only extremely low external stacking pressure when used as an electrolyte material in all-solid-state batteries. This enables the construction of low-pressure all-solid-state batteries with high interface stability, high rate performance, and excellent safety.

[0039] The electrolyte of this invention has dynamic reversible characteristics. During battery cycling, it can adapt to changes in electrode volume and maintain tight interfacial contact. When microcracks or damage occur inside, the electrolyte can achieve "adaptive" bonding of the interface and "self-healing" of the microcracks through its own fluidity, which significantly improves the long-term cycle life and reliability of all-solid-state batteries under low-pressure conditions. Attached Figure Description

[0040] Figure 1 The electrolyte Li2Ga in Example 1 0.5 Al 0.5 Electrochemical impedance spectroscopy curve of F3Cl2 at room temperature.

[0041] Figure 2 The electrolyte LiGa in Example 2 0.7 Zr 0.3 F 2.1 Cl 2.2Electrochemical impedance spectroscopy test curve at room temperature.

[0042] Figure 3 The electrolyte Li in Example 3 1.4 Ga 0.2 Ta 0.8 F 0.6 Cl 5.4 The first charge-discharge specific capacity when running at room temperature and 0.3~1.0 MPa.

[0043] Figure 4 The electrolyte Li in Example 7 0.7 Ga 0.2 Ta 0.8 O 1.4 F 0.6 Electrochemical impedance spectroscopy curve of Cl4 at room temperature.

[0044] Figure 5 The electrolyte LiGa in Example 6 0.2 Nb 0.8 F 0.6 The first charge-discharge specific capacity of Cl5 at room temperature and 0.5~0.8 MPa.

[0045] Figure 6 The electrolyte Li in Example 24 1.4 Ga 0.2 Zr 0.8 F 3.8 Cl 1.4 The first charge-discharge specific capacity when running at room temperature and 0.8~1.7 MPa.

[0046] Figure 7 The electrolyte Li in Example 26 1.4 Ga 0.2 Ti 0.8 F 0.6 Cl 4.6 The first charge-discharge specific capacity when operating at room temperature and 0.7~1.7 MPa.

[0047] Figure 8 The specific capacity of the electrolyte Li2GaF3Cl2 in Comparative Example 1 during the first charge-discharge cycle at room temperature and 8.0~10.0 MPa is given.

[0048] Figure 9 The specific capacity of the electrolyte Li2AlF3Cl2 in Comparative Example 2 during the first charge-discharge cycle at room temperature and 40.0~50.0 MPa is given. Detailed Implementation

[0049] The present invention will be further described in detail below through specific embodiments. Unless otherwise specified, the raw materials, reagents, or apparatus used in the embodiments and comparative examples are all available from conventional commercial sources or can be obtained by existing technical methods. Unless otherwise specified, the test or experimental methods are conventional methods in the art.

[0050] The testing methods for the performance of each solid-state battery in the following examples and comparative examples are as follows: The electrochemical impedance spectroscopy (EIS) method was as follows: 120 mg of electrolyte was weighed and placed in a mold containing a stainless steel sheet with a diameter of 1 cm. A pressure of 2 MPa was applied and maintained for 1 minute. Then, another stainless steel sheet with a diameter of 1 cm was placed on top of the pressed electrolyte, so that stainless steel sheets were attached to both sides as blocking electrodes. A pressure of 2 MPa was then applied and maintained for 1 minute. Finally, the mixture was transferred to a battery mold for subsequent EIS testing. The EIS testing mode was constant potential EIS, and the EIS testing frequency was set to 0.1 Hz–10 Hz. 6 The conductivity (Hz) is calculated using the formula σ = L / SR (where L is the electrolyte tablet thickness, S is the electrolyte tablet area, and R is obtained from the Nyquist plot obtained from EIS testing). After the test, the electrolyte tablet thickness L is measured using a digital micrometer, and S = πD 2 / 4, the conductivity σ can be obtained by using the conductivity formula σ=L / SR.

[0051] First charge / discharge specific capacity: Set the test mode to constant current mode, set the activation rate to 0.05 C, the activation voltage range to 2.8 V-4.3 V, set the post-activation rate to 0.5 C, the voltage range to 2 V-4.3 V, and the nominal capacity to 200 mAh / g. Then input the active material mass to start the battery charge / discharge test.

[0052] Example 1 This embodiment prepares an electrolyte and its solid-state battery, and the specific process is as follows: 1. Preparation of electrolyte: In an argon glove box with both water and oxygen content less than 0.01 ppm, using an electronic balance with an accuracy of 0.0001 g, weigh 0.2229 g of lithium chloride, 0.1666 g of gallium trifluoride, and 0.1104 g of aluminum trifluoride, respectively. Place the weighed drug powder in an agate mortar and perform preliminary manual grinding for 15 min. During the grinding process, use an alternating method of "circular grinding + cross grinding" until the mixture is a uniform grayish-white powder with no visible particle agglomeration, thus obtaining a preliminary mixed drug powder. Next, weigh 20 g of zirconia grinding beads with a particle size of 5 mm. First, place the zirconia grinding beads in a high-energy grinding jar, then add the pre-mixed drug powder, close the grinding jar tightly and seal it, and place the high-energy grinding jar in a high-energy ball mill. Set the ball mill parameters to 700 rpm and 20 h. During the ball milling process, pause for 5 minutes every 10 minutes, and then reverse the direction. After the ball milling is completed, open the grinding jar in the glove box and use an agate scraper to collect the electrolyte powder on the jar wall and the surface of the grinding beads, thus obtaining the electrolyte.

[0053] 2. Preparation of battery cathode material: NCM811 was selected as the cathode active material with a purity ≥99.5%, and dried in an oven at 120 ℃ for 12 h for later use. In an argon glove box with water and oxygen contents both less than 0.01 ppm, using an electronic balance with an accuracy of 0.0001 g, 0.3500 g of NCM811, 0.1500 g of the prepared electrolyte, and 0.0150 g of conductive agent VGCF were weighed. First, the weighed cathode active material and electrolyte powder were placed in an agate mortar and preliminarily hand-ground. During the grinding process, an alternating method of "circular grinding + cross grinding" was used for 60 min. Then, the conductive agent VGCF was added to the agate mortar, and the same grinding method was used for 10 min until the mixture was a uniform black powder with no visible particle agglomeration, thus obtaining the final cathode material.

[0054] 3. Preparation of battery anode material: Select lithium sheet with a thickness of 0.06 mm (purity ≥99.99%) and indium sheet with a thickness of 0.1 mm (purity ≥99.99%), cut them into 10 mm diameter discs in a glove box using a punching machine, and stack them together as the battery composite anode (Li-In alloy anode).

[0055] 4. Solid-state battery assembly: In an argon glove box with water and oxygen contents both less than 0.01 ppm, using an electronic balance with an accuracy of 0.0001 g, 0.1000 g of the prepared electrolyte and 0.0100 g of the prepared battery positive electrode material were weighed. Using a solid-state battery mold with a diameter of 1 cm, the prepared negative electrode, electrolyte and positive electrode were stacked tightly in sequence in the mold to prepare an all-solid-state battery.

[0056] Figure 1 The electrolyte Li2Ga in Example 1 0.5 Al 0.5 Electrochemical impedance spectroscopy (EIS) curves of F3Cl2 at room temperature were obtained. The graph shows a continuous pattern transitioning from a single, smooth, compressed semicircle to a near 45° oblique line. The intercept in the high-frequency region is almost zero on the real axis of the complex impedance, indicating a low overall impedance value without multi-circle separation or abnormal impedance fluctuations. These results demonstrate that the electrolyte exhibits extremely low bulk ion transport resistance and interfacial contact resistance under room temperature conditions without high-pressure compaction. Calculations show that its room-temperature ionic conductivity can reach 8.2 × 10⁻⁶. -3 S / cm, at 10 -3 ~10 -2 The conductivity is on the order of S / cm, far exceeding the room temperature ionic conductivity of traditional inorganic solid electrolytes and polymer-inorganic composite electrolytes. At the same time, the single smooth spectral characteristics also confirm that the ternary components were uniformly mixed at the atomic scale through high-energy ball milling, forming a dense amorphous structure without obvious phase separation, which provides a material basis for the interface adaptive contact and self-healing mechanism.

[0057] Example 2 This embodiment prepares an electrolyte and its solid-state battery, and the specific process is as follows: 1. Preparation of electrolyte: In an argon glove box with both water and oxygen content less than 0.01 ppm, using an electronic balance with an accuracy of 0.0001 g, weigh 0.1821 g of lithium chloride, 0.2177 g of gallium trifluoride, and 0.1001 g of zirconium tetrachloride, respectively. Place the weighed drug powder in an agate mortar and perform preliminary manual grinding for 15 min. During the grinding process, use an alternating method of "circular grinding + cross grinding" until the mixture is a uniform grayish-white powder with no visible particle agglomeration, thus obtaining a preliminary mixed drug powder. Next, weigh 20 g of zirconia grinding beads with a particle size of 5 mm. First, place the zirconia grinding beads in a high-energy grinding jar, then add the pre-mixed drug powder, close the grinding jar tightly and seal it, and place the high-energy grinding jar in a high-energy ball mill. Set the ball mill parameters to 700 rpm and 20 h. During the ball milling process, pause for 5 minutes every 10 minutes, and then reverse the direction. After the ball milling is completed, open the grinding jar in the glove box and use an agate scraper to collect the electrolyte powder on the jar wall and the surface of the grinding beads, thus obtaining the electrolyte.

[0058] 2. Preparation of battery cathode material: NCM811 was selected as the cathode active material with a purity ≥99.5%, and dried in an oven at 120 ℃ for 12 h for later use. In an argon glove box with water and oxygen contents both less than 0.01 ppm, using an electronic balance with an accuracy of 0.0001 g, 0.3500 g of NCM811, 0.1500 g of the prepared electrolyte, and 0.0150 g of conductive agent VGCF were weighed. First, the weighed cathode active material and electrolyte powder were placed in an agate mortar and preliminarily hand-ground. During the grinding process, an alternating method of "circular grinding + cross grinding" was used for 60 min. Then, the conductive agent VGCF was added to the agate mortar, and the same grinding method was used for 10 min until the mixture was a uniform black powder with no visible particle agglomeration, thus obtaining the final cathode material.

[0059] 3. Preparation of battery anode material: Select lithium sheet with a thickness of 0.06 mm (purity ≥99.99%) and indium sheet with a thickness of 0.1 mm (purity ≥99.99%), cut them into 10 mm diameter discs in a glove box using a punching machine, and stack them together as the battery composite anode (Li-In alloy anode).

[0060] 4. Solid-state battery assembly: In an argon glove box with both water and oxygen content less than 0.01 ppm, using an electronic balance with an accuracy of 0.0001 g, 0.1000 g of the prepared electrolyte and 0.0100 g of the prepared battery positive electrode material were weighed. Using a solid-state battery mold with a diameter of 1 cm, the prepared negative electrode, electrolyte, and positive electrode were stacked tightly in sequence in the mold to prepare an all-solid-state battery.

[0061] Figure 2 The electrolyte LiGa in Example 2 0.7 Zr 0.3 F 2.1 Cl 2.2 Electrochemical impedance spectroscopy (EIS) curves at room temperature were obtained. The curves show a small, smooth, compressed semicircle in the high-frequency region, followed by a smooth transition to a nearly 45° oblique line in the mid-to-low-frequency region. The intercept between the high-frequency region and the real axis of the complex impedance is extremely small, and the overall impedance change is continuous without multi-circle separation or abnormal fluctuations. These results indicate that the electrolyte maintains low bulk ion transport resistance and interfacial contact impedance under room temperature conditions without high-pressure compaction. Calculations show that its room-temperature ionic conductivity can reach 6.5 × 10⁻⁶. -3 S / cm, at 10 -3 ~10 -2 The S / cm scale meets the ion transport requirements for high-rate operation of all-solid-state batteries.

[0062] Example 3 This embodiment prepares an electrolyte and its solid-state battery, and the specific process is as follows: 1. Preparation of electrolyte: In an argon glove box with both water and oxygen content less than 0.01 ppm, using an electronic balance with an accuracy of 0.0001 g, weigh 0.2015 g of lithium chloride, 0.1892 g of gallium trifluoride, and 0.1093 g of tantalum pentachloride. Place the weighed drug powder in an agate mortar and perform preliminary manual grinding for 15 min. During the grinding process, use an alternating method of "circular grinding + cross grinding" until the mixture is a uniform grayish-white powder with no visible particle agglomeration, thus obtaining a preliminary mixed drug powder. Next, weigh 20 g of zirconia grinding beads with a particle size of 5 mm. First, place the zirconia grinding beads in a high-energy grinding jar, then add the pre-mixed drug powder, close the grinding jar tightly and seal it, and place the high-energy grinding jar in a high-energy ball mill. Set the ball mill parameters to 700 rpm and 20 h. During the ball milling process, pause for 5 minutes every 10 minutes, and then reverse the direction. After the ball milling is completed, open the grinding jar in the glove box and use an agate scraper to collect the electrolyte powder on the jar wall and the surface of the grinding beads, thus obtaining the electrolyte.

[0063] 2. Preparation of battery cathode material: NCM811 was selected as the cathode active material with a purity ≥99.5%, and dried in an oven at 120 ℃ for 12 h for later use. In an argon glove box with water and oxygen contents both less than 0.01 ppm, using an electronic balance with an accuracy of 0.0001 g, 0.3500 g of NCM811, 0.1500 g of the prepared electrolyte, and 0.0150 g of conductive agent VGCF were weighed. First, the weighed cathode active material and electrolyte powder were placed in an agate mortar and preliminarily hand-ground. During the grinding process, an alternating method of "circular grinding + cross grinding" was used for 60 min. Then, the conductive agent VGCF was added to the agate mortar, and the same grinding method was used for 10 min until the mixture was a uniform black powder with no visible particle agglomeration, thus obtaining the final cathode material.

[0064] 3. Preparation of battery anode material: Select lithium sheet with a thickness of 0.06 mm (purity ≥99.9%) and indium sheet with a thickness of 0.1 mm (purity ≥99.9%), cut them into 10 mm diameter discs in a glove box using a punching machine, and stack them together as the battery composite anode (Li-In alloy anode).

[0065] 4. Solid-state battery assembly: In an argon glove box with water and oxygen contents both less than 0.01 ppm, using an electronic balance with an accuracy of 0.0001 g, 0.1000 g of the prepared electrolyte and 0.0100 g of the prepared battery positive electrode material were weighed. Using a solid-state battery mold with a diameter of 1 cm, the prepared negative electrode, electrolyte and positive electrode were stacked tightly in sequence in the mold to prepare an all-solid-state battery.

[0066] Figure 3 The electrolyte Li in Example 3 1.4 Ga 0.2 Ta 0.8 F 0.6 Cl 5.4 The first-cycle charge-discharge specific capacity was measured at room temperature and 0.3–1.0 MPa. The first-cycle charge-discharge specific capacity curve shows that the battery achieved stable charge-discharge under low-pressure, room-temperature conditions of 0.3–1.0 MPa. The charging curve steadily increased from approximately 2.9 V to 3.68 V, while the discharging curve gradually decreased from 3.68 V to 2.18 V. The charge-discharge plateau was clear without significant voltage drops or fluctuations. The first-cycle discharge specific capacity reached approximately 178 mAh / g, indicating good matching between charging and discharging specific capacities, and the first-cycle coulombic efficiency was at a high level. These results demonstrate that the present invention, using TaCl5 as the modified halide electrolyte, can provide efficient ion transport and stable interfacial contact for all-solid-state batteries under low-pressure conditions without high-pressure compaction.

[0067] Example 4-29 The preparation processes of all-solid-state batteries in Examples 4-29 and Examples 1-3 are identical except for the raw materials used in preparing the electrolyte. For details of the raw materials used in preparing the electrolyte in Examples 1-29 and Comparative Examples 1-2, please refer to Table 1. The operating pressure of the prepared solid-state batteries was tested. The results are shown in Table 1.

[0068] Table 1

[0069] Figure 4 The electrolyte Li in Example 7 0.7 Ga 0.2 Ta 0.8 O 1.4 F 0.6Electrochemical impedance spectroscopy (EIS) curves of Cl4 at room temperature were obtained. The curves show a clear compressed semicircle in the high-frequency region, followed by a smooth transition to a nearly 45° sloping line in the mid-to-low frequency region. The intercept between the high-frequency region and the real axis of the complex impedance is small, and the overall impedance change is continuous without multi-circle separation or abnormal fluctuations. These results indicate that the electrolyte maintains low bulk ion transport resistance and interfacial contact impedance even under room temperature conditions without high-pressure compaction. Calculations show that its room-temperature ionic conductivity can reach 8.5 × 10⁻⁶. -3 S / cm, at 10 -3 ~10 -2 The S / cm scale meets the ion transport requirements for high-rate operation of all-solid-state batteries; at the same time, the single continuous spectral characteristics confirm that Li2O, GaF3 and TaCl5 were uniformly mixed at the atomic scale through high-energy ball milling, forming a compact amorphous composite structure without obvious phase separation.

[0070] Figure 5 The electrolyte LiGa in Example 6 0.2 Nb 0.8 F 0.6 The first-cycle charge-discharge specific capacity of NbCl5 at room temperature and 0.5–0.8 MPa was measured. The first-cycle charge-discharge specific capacity curve shows that the battery achieved stable charge-discharge under low-pressure, room-temperature conditions of 0.5–0.8 MPa. The charging curve steadily increased from approximately 2.9 V to 3.68 V, while the discharging curve gradually decreased from 3.68 V to 2.18 V. The charge-discharge plateau was clear without significant voltage drops or fluctuations. The first-cycle discharge specific capacity reached approximately 143 mAh / g, indicating good matching between charging and discharging specific capacities, and the first-cycle coulombic efficiency was at a high level. These results demonstrate that this invention, using NbCl5 as a modified halide electrolyte, can provide efficient ion transport and stable interfacial contact for all-solid-state batteries under low-pressure conditions without high-pressure compaction.

[0071] Figure 6 The electrolyte Li in Example 24 1.4 Ga 0.2 Zr 0.8 F 3.8 Cl 1.4The first-cycle charge-discharge specific capacity was measured at room temperature and within a pressure range of 0.8–1.7 MPa. The first-cycle charge-discharge specific capacity curve shows that the battery achieved stable charge-discharge under low-pressure, room-temperature conditions of 0.8–1.7 MPa. The charging curve steadily increased from approximately 2.9 V to 3.68 V, while the discharging curve gradually decreased from 3.68 V to 2.18 V. The charge-discharge plateau was clear without significant voltage drops or fluctuations. The first-cycle discharge specific capacity reached approximately 180 mAh / g, indicating good matching between the charging and discharging specific capacities, and the first-cycle coulombic efficiency was at a high level. These results demonstrate that the present invention, using ZrF4 as a modified halide electrolyte, can provide efficient ion transport and stable interfacial contact for all-solid-state batteries under low-pressure conditions without high-pressure compaction.

[0072] Figure 7 The electrolyte Li in Example 26 1.4 Ga 0.2 Ti 0.8 F 0.6 Cl 4.6 The first-cycle charge-discharge specific capacity was measured at room temperature and 0.7–1.7 MPa. The first-cycle charge-discharge specific capacity curve shows that the battery achieved stable charge-discharge under low-pressure, room-temperature conditions of 0.7–1.7 MPa. The charging curve steadily increased from approximately 2.9 V to 3.68 V, while the discharging curve gradually decreased from 3.68 V to 2.18 V. The charge-discharge plateau was clear without significant voltage drops or fluctuations. The first-cycle discharge specific capacity reached approximately 180 mAh / g, indicating good matching between charging and discharging specific capacities, and the first-cycle coulombic efficiency was at a high level. These results demonstrate that the present invention, using TiCl4 as a modified halide electrolyte, can provide efficient ion transport and stable interfacial contact for all-solid-state batteries under low-pressure conditions without high-pressure compaction.

[0073] Comparative Example 1 This comparative example demonstrates the preparation of an all-solid-state battery, and the specific process is as follows: 1. Preparation of electrolyte materials: In an argon glove box with water and oxygen contents both less than 0.01 ppm, using an electronic balance with an accuracy of 0.0001 g, weigh 0.2004 g of lithium chloride and 0.2995 g of gallium trifluoride, respectively. Without inorganic halide modifiers, place the weighed drug powders in an agate mortar and perform preliminary manual grinding for 15 min. During the grinding process, use an alternating method of "circular grinding + cross grinding" until the mixture is a uniform grayish-white powder with no visible particle agglomeration, thus obtaining a preliminary mixed drug powder. Next, weigh 20 g of zirconia grinding beads with a particle size of 5 mm. First, place the zirconia grinding beads in a high-energy grinding jar, then add the pre-mixed drug powder, close the grinding jar tightly and seal it, and place the high-energy grinding jar in a high-energy ball mill. Set the ball mill parameters to 700 rpm and 20 h. During the ball milling process, pause for 5 minutes every 10 minutes, and then reverse the direction. After the ball milling is completed, open the grinding jar in the glove box and use an agate scraper to collect the electrolyte powder on the jar wall and the surface of the grinding beads, thus obtaining the electrolyte.

[0074] 2. Preparation of battery cathode material: NCM811 was selected as the cathode active material with a purity ≥99.5%, and dried in an oven at 120 ℃ for 12 h for later use. In an argon glove box with water and oxygen contents both less than 0.01 ppm, using an electronic balance with an accuracy of 0.0001 g, 0.3500 g of NCM811, 0.1500 g of the prepared electrolyte, and 0.0150 g of conductive agent VGCF were weighed. First, the weighed cathode active material and electrolyte powder were placed in an agate mortar and preliminarily hand-ground. During the grinding process, an alternating method of "circular grinding + cross grinding" was used for 60 min. Then, the conductive agent VGCF was added to the agate mortar, and the same grinding method was used for 10 min until the mixture was a uniform black powder with no visible particle agglomeration, thus obtaining the final cathode material.

[0075] 3. Preparation of battery anode material: Select lithium sheet with a thickness of 0.06 mm (purity ≥99.99%) and indium sheet with a thickness of 0.1 mm (purity ≥99.99%), cut them into 10 mm diameter discs in a glove box using a punching machine, and stack them together as the battery composite anode (Li-In alloy anode).

[0076] 4. Solid-state battery assembly: In an argon glove box with both water and oxygen content less than 0.01 ppm, using an electronic balance with an accuracy of 0.0001 g, 0.1000 g of the prepared electrolyte and 0.0100 g of the prepared battery positive electrode material were weighed. Using a solid-state battery mold with a diameter of 1 cm, the prepared negative electrode, electrolyte, and positive electrode were stacked tightly in sequence in the mold to prepare an all-solid-state battery.

[0077] Figure 8 The first charge-discharge specific capacity of the electrolyte Li2GaF3Cl2 in Comparative Example 1 is measured at room temperature and 8.0–10.0 MPa. This comparative example, lacking an inorganic halide modifier and relying solely on a combination of lithium salt and low-melting-point halide, suffers from two major drawbacks: First, the absence of a microstructural framework means the low-melting-point halide softens and becomes excessively fluid, resulting in insufficient electrolyte mechanical strength. This prevents the electrolyte from maintaining tight interfacial contact under low pressure, requiring a high pressure above 8.0 MPa to avoid interfacial delamination, far exceeding the ≤3 MPa operating pressure of the embodiments of this invention. Second, the ion transport channel is singular, lacking active sites and defect pathways provided by the modified halide, resulting in a room-temperature ionic conductivity of only 2.1 × 10⁻⁶. -4 S / cm, much lower than 8.2 × 10 in Example 1. -3 The S / cm ratio resulted in a first-cycle discharge specific capacity of only 86 mAh / g and a significant reduction in coulombic efficiency, fully demonstrating the key role of inorganic halide modifiers in improving electrolyte performance.

[0078] Comparative Example 2 This comparative example demonstrates the preparation of an all-solid-state battery, and the specific process is as follows: 1. Preparation of electrolyte materials: In an argon glove box with water and oxygen content both less than 0.01 ppm, using an electronic balance with an accuracy of 0.0001 g, weigh 0.2512 g of lithium chloride and 0.2487 g of aluminum trifluoride, respectively, ensuring no low-melting-point halides. Place the weighed drug powder in an agate mortar and perform preliminary manual grinding for 15 min. During the grinding process, use an alternating method of "circular grinding + cross grinding" until the mixture is a uniform grayish-white powder with no visible particle agglomeration, thus obtaining a preliminary mixed drug powder. Next, weigh 20 g of zirconia grinding beads with a particle size of 5 mm. First, place the zirconia grinding beads in a high-energy grinding jar, then add the pre-mixed drug powder, close the grinding jar tightly and seal it, and place the high-energy grinding jar in a high-energy ball mill. Set the ball mill parameters to 700 rpm and 20 h. During the ball milling process, pause for 5 minutes every 10 minutes, and then reverse the direction. After the ball milling is completed, open the grinding jar in the glove box and use an agate scraper to collect the electrolyte powder on the jar wall and the surface of the grinding beads, thus obtaining the electrolyte.

[0079] 2. Preparation of battery cathode material: NCM811 was selected as the cathode active material with a purity ≥99.5%, and dried in an oven at 120 ℃ for 12 h for later use. In an argon glove box with water and oxygen contents both less than 0.01 ppm, using an electronic balance with an accuracy of 0.0001 g, 0.3500 g of NCM811, 0.1500 g of the prepared electrolyte, and 0.0150 g of conductive agent VGCF were weighed. First, the weighed cathode active material and electrolyte powder were placed in an agate mortar and preliminarily hand-ground. During the grinding process, an alternating method of "circular grinding + cross grinding" was used for 60 min. Then, the conductive agent VGCF was added to the agate mortar, and the same grinding method was used for 10 min until the mixture was a uniform black powder with no visible particle agglomeration, thus obtaining the final cathode material.

[0080] 3. Preparation of battery anode material: Select lithium sheet with a thickness of 0.06 mm (purity ≥99.99%) and indium sheet with a thickness of 0.1 mm (purity ≥99.99%), cut them into 10 mm diameter discs in a glove box using a punching machine, and stack them together as the battery composite anode (Li-In alloy anode).

[0081] 4. Solid-state battery assembly: In an argon glove box with both water and oxygen content less than 0.01 ppm, using an electronic balance with an accuracy of 0.0001 g, 0.1000 g of the prepared electrolyte and 0.0100 g of the prepared battery positive electrode material were weighed. Using a solid-state battery mold with a diameter of 1 cm, the prepared negative electrode, electrolyte, and positive electrode were stacked tightly in sequence in the mold to prepare an all-solid-state battery.

[0082] Figure 9 The first-cycle charge-discharge specific capacity of the electrolyte Li2AlF3Cl2 in Comparative Example 2 is shown in the figure at room temperature and 40.0~50.0 MPa. This comparative example, lacking low-melting-point halides and relying solely on a combination of lithium salt and inorganic halide modifiers, loses its interfacial adaptability. The electrolyte is in a rigid solid state, unable to adapt to changes in electrode surface morphology and volume. The solid-solid interface is a typical "point-to-point" contact with numerous voids, requiring a high voltage of over 40 MPa to barely maintain the ion conduction pathway, far exceeding the low-pressure requirements of this embodiment. As shown in the figure, the first-cycle discharge specific capacity is only 62 mAh / g, with low coulombic efficiency. Furthermore, the capacity rapidly decays during cycling due to interfacial peeling, fully demonstrating the indispensability of low-melting-point halides for achieving stable operation under low pressure.

[0083] Example 30 This embodiment prepares an electrolyte and its solid-state battery, and the specific process is as follows: 1. Preparation of electrolyte materials: In an argon glove box with water and oxygen contents both less than 0.01 ppm, using an electronic balance with an accuracy of 0.0001 g, weigh 0.0402 g of lithium oxide, 0.1011 g of lithium chloride, 0.1687 g of aluminum oxychloride, and 0.1378 g of tantalum pentachloride, respectively. Place the weighed drug powders in an agate mortar and perform preliminary manual grinding for 15 min. During the grinding process, use an alternating method of "circular grinding + cross grinding" until the mixture is a uniform grayish-white powder with no visible particle agglomeration, thus obtaining a preliminary mixed drug powder. Next, weigh 20 g of zirconia grinding beads with a particle size of 5 mm. First, place the zirconia grinding beads in a high-energy grinding jar, then add the pre-mixed drug powder, close the grinding jar tightly and seal it, and place the high-energy grinding jar in a high-energy ball mill. Set the ball mill parameters to 700 rpm and 20 h. During the ball milling process, pause for 5 minutes every 10 minutes, and then reverse the direction. After the ball milling is completed, open the grinding jar in the glove box and use an agate scraper to collect the electrolyte powder on the jar wall and the surface of the grinding beads, thus obtaining the electrolyte.

[0084] 2. Preparation of battery cathode material: NCM811 was selected as the cathode active material with a purity ≥99.5%, and dried in an oven at 120 ℃ for 12 h for later use. In an argon glove box with water and oxygen contents both less than 0.01 ppm, using an electronic balance with an accuracy of 0.0001 g, 0.3500 g of NCM811, 0.1500 g of the prepared electrolyte, and 0.0150 g of conductive agent VGCF were weighed. First, the weighed cathode active material and electrolyte powder were placed in an agate mortar and preliminarily hand-ground. During the grinding process, an alternating method of "circular grinding + cross grinding" was used for 60 min. Then, the conductive agent VGCF was added to the agate mortar, and the same grinding method was used for 10 min until the mixture was a uniform black powder with no visible particle agglomeration, thus obtaining the final cathode material.

[0085] 3. Preparation of battery anode material: Select lithium sheet with a thickness of 0.06 mm (purity ≥99.99%) and indium sheet with a thickness of 0.1 mm (purity ≥99.99%), cut them into 10 mm diameter discs in a glove box using a punching machine, and stack them together as the battery composite anode (Li-In alloy anode).

[0086] 4. Solid-state battery assembly: In an argon glove box with both water and oxygen content less than 0.01 ppm, using an electronic balance with an accuracy of 0.0001 g, 0.1000 g of the prepared electrolyte and 0.0100 g of the prepared battery positive electrode material were weighed. Using a solid-state battery mold with a diameter of 1 cm, the prepared negative electrode, electrolyte, and positive electrode were stacked tightly in sequence in the mold to prepare an all-solid-state battery.

[0087] Examples 31-43 The preparation processes of the all-solid-state batteries in Examples 31-43 and Example 30 are identical except for the raw materials used in preparing the electrolyte. For details of the raw materials used in preparing the electrolyte in Examples 30-43, please refer to Table 2. The operating pressure of the prepared solid-state batteries was also tested. The results are shown in Table 2.

[0088] Table 2

[0089] Example 44 This embodiment prepares an electrolyte and its solid-state battery, and the specific process is as follows: 1. Preparation of electrolyte materials: In an argon glove box with both water and oxygen content less than 0.01 ppm, using an electronic balance with an accuracy of 0.0001 g, weigh 0.1011 g of lithium chloride, 0.2440 g of lithium hexafluorophosphate, 0.2840 g of lithium bis(trifluoromethanesulfonyl)imide, 0.1732 g of aluminum oxychloride, and 0.1328 g of zirconium tetrachloride. Place the weighed drug powders in an agate mortar and perform preliminary manual grinding for 15 min. During the grinding process, use an alternating method of "circular grinding + cross grinding" until the mixture is a uniform grayish-white powder with no visible particle agglomeration, thus obtaining a preliminary mixed drug powder. Next, weigh 20 g of zirconia grinding beads with a particle size of 5 mm. First, place the zirconia grinding beads in a high-energy grinding jar, then add the pre-mixed drug powder, close the grinding jar tightly and seal it, and place the high-energy grinding jar in a high-energy ball mill. Set the ball mill parameters to 700 rpm and 20 h. During the ball milling process, pause for 5 minutes every 10 minutes, and then reverse the direction. After the ball milling is completed, open the grinding jar in the glove box and use an agate scraper to collect the electrolyte powder on the jar wall and the surface of the grinding beads, thus obtaining the electrolyte.

[0090] 2. Preparation of battery cathode material: NCM811 was selected as the cathode active material with a purity ≥99.5%, and dried in an oven at 120 ℃ for 12 h for later use. In an argon glove box with water and oxygen contents both less than 0.01 ppm, using an electronic balance with an accuracy of 0.0001 g, 0.3500 g of NCM811, 0.1500 g of the prepared electrolyte, and 0.0150 g of conductive agent VGCF were weighed. First, the weighed cathode active material and electrolyte powder were placed in an agate mortar and preliminarily hand-ground. During the grinding process, an alternating method of "circular grinding + cross grinding" was used for 60 min. Then, the conductive agent VGCF was added to the agate mortar, and the same grinding method was used for 10 min until the mixture was a uniform black powder with no visible particle agglomeration, thus obtaining the final cathode material.

[0091] 3. Preparation of battery anode material: Select lithium sheet with a thickness of 0.06 mm (purity ≥99.99%) and indium sheet with a thickness of 0.1 mm (purity ≥99.99%), cut them into 10 mm diameter discs in a glove box using a punching machine, and stack them together as the battery composite anode (Li-In alloy anode).

[0092] 4. Solid-state battery assembly: In an argon glove box with both water and oxygen content less than 0.01 ppm, using an electronic balance with an accuracy of 0.0001 g, 0.1000 g of the prepared electrolyte and 0.0100 g of the prepared battery positive electrode material were weighed. Using a solid-state battery mold with a diameter of 1 cm, the prepared negative electrode, electrolyte, and positive electrode were stacked tightly in sequence in the mold to prepare an all-solid-state battery.

[0093] Examples 45-58 The preparation processes of the all-solid-state batteries in Examples 45-58 and Example 44 are identical except for the raw materials used in preparing the electrolyte. For details of the raw materials used in preparing the electrolyte in Examples 44-58, please refer to Table 3. The operating pressure of the prepared solid-state batteries was also tested. The results are shown in Table 3.

[0094] Table 3

[0095] The above embodiments are preferred embodiments of the present invention, but the embodiments of the present invention are not limited to the above embodiments. Any changes, modifications, substitutions, combinations, or simplifications made without departing from the spirit and principle of the present invention shall be considered equivalent substitutions and shall be included within the protection scope of the present invention.

Claims

1. An electrolyte, characterized in that: It includes lithium salts, low-melting-point halides, and inorganic halide modifiers; the softening point of the low-melting-point halides is 20-70℃.

2. The electrolyte according to claim 1, characterized in that: The molar ratio of the lithium salt to the sum of the low-melting-point halide and inorganic halide modifier is (1-5):1; and / or, the molar ratio of the low-melting-point halide and inorganic halide modifier is (0.1-4):

1.

3. The electrolyte according to claim 1, characterized in that: The lithium salt includes at least one of lithium carbonate, lithium oxide, lithium hydroxide, lithium chloride, lithium iodide, lithium bromide, lithium fluoride, lithium nitrate, lithium sulfate, lithium acetate, lithium tert-butoxy, lithium tantalate, lithium titanate, lithium niobate, lithium cobalt oxide, lithium nitride, lithium manganese oxide, lithium iron phosphate, lithium borohydride, lithium hexafluorophosphate, lithium bis(fluorosulfonyl)imide, lithium bis(trifluoromethanesulfonyl)imide, lithium difluorooxalate borate, lithium tetrafluoroborate, lithium hexafluoroarsenate, lithium perchlorate, lithium trifluoromethanesulfonate, and lithium di(oxalate borate).

4. The electrolyte according to claim 1, characterized in that: The low-melting-point halide includes at least one of gallium trifluoride, indium fluoride, and aluminum oxychloride.

5. The electrolyte according to claim 1, characterized in that: The inorganic halide modifier includes at least one of aluminum trifluoride, chromium trifluoride, iridium trichloride, ruthenium trichloride, titanium tetrafluoride, germanium tetrafluoride, titanium tetrachloride, tin tetrachloride, zirconium tetrachloride, zirconium tetrafluoride, titanium tetrabromide, tantalum pentachloride, niobium pentachloride, niobium pentafluoride, molybdenum pentachloride, antimony pentafluoride, vanadium pentafluoride, antimony pentachloride, vanadium pentachloride, molybdenum hexafluoride, and tantalum hexafluoride.

6. A method for preparing the electrolyte according to any one of claims 1-5, characterized in that: Includes the following steps: The electrolyte is prepared by high-energy ball milling of lithium salt, low-melting-point halide, and inorganic halide modifier.

7. A solid-state battery, characterized in that: Includes the electrolyte as described in any one of claims 1-5.

8. The solid-state battery according to claim 7, characterized in that: The solid-state battery includes a positive electrode layer, an electrolyte layer, and a negative electrode layer; the positive electrode layer and / or the electrolyte layer includes an electrolyte.

9. A method for assembling a solid-state battery according to claim 7 or 8, characterized in that: Includes the following steps: The positive electrode layer, electrolyte layer, and negative electrode layer are stacked sequentially, pressed under pressure, and then encapsulated in a battery casing to obtain the solid-state battery.

10. The method for assembling a solid-state battery according to claim 9, characterized in that: The applied pressure includes applying a pressure of less than 3.0 MPa.

11. An electrical appliance, characterized in that: Includes the solid-state battery as described in claim 7 or 8.

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