Solid-state electrolyte composite and lithium battery

Abstract

This invention discloses a solid electrolyte composite material and a lithium battery. The solid electrolyte composite material includes a lithium-containing solid electrolyte material, a stabilizer, and an active additive; the lithium-containing solid electrolyte material is one or more of a sulfide solid electrolyte material, a halide electrolyte material, and a NASICON phase oxide electrolyte material; the stabilizer is a polymer; and the active additive is a non-metallic halide. When applied to a lithium-ion battery, this solid electrolyte composite material forms a highly stable protective film with low electronic conductivity and high ionic conductivity on the surface of the electrode material, thereby protecting the negative electrode material and improving the charge-discharge cycle performance and safety performance of the lithium metal battery.

Description

Technical Field

[0001] This invention relates to the field of lithium (ion) battery technology, and in particular to a solid electrolyte composite additive material for lithium (ion) batteries that improves cycle performance and safety performance. Background Technology

[0002] Lithium-ion batteries have seen rapid development in electronic devices and power supplies due to their high energy density, high operating voltage, and long cycle life. However, most commercially available lithium-ion batteries currently use flammable and leak-prone organic electrolytes, leading to serious safety hazards. In contrast, replacing organic electrolytes with solid electrolyte layers can effectively solve the safety problems of lithium-ion batteries. Simultaneously, the use of high-energy-density electrodes such as lithium metal can effectively improve the energy density of the battery system, thereby enabling the development of high-energy-density power batteries. However, due to the strong reducing properties of negative electrode materials such as lithium metal, currently developed solid electrolyte materials, such as sulfide electrolytes, oxide electrolytes, and halide electrolytes, generally suffer from instability with lithium, severely limiting their application.

[0003] When solid-state electrolyte materials are directly exposed to strongly reducing anodes such as lithium metal or to lithium alloy intermediates formed during electrochemical cycling, severe chemical reactions occur at the interface between the electrolyte material and the anode material, resulting in a surface passivation film that hinders electron / ion conduction. This leads to a continuous deterioration in the battery's cycle life and safety performance. To overcome this problem, researchers typically pre-fabricate a protective film on the surface of electrode particles such as lithium metal. This protective film mitigates the chemical reaction between the electrolyte and the high-energy-density anode, thus achieving long-cycle all-solid-state lithium (ion) batteries. Compared to liquid batteries, research on additives in solid-state electrolytes for solid-state batteries is much less extensive. Summary of the Invention

[0004] The present invention aims to at least partially solve one of the technical problems in the prior art, or at least provide a commercial alternative.

[0005] This invention provides a solid electrolyte composite material that can form a protective film with low electronic conductivity and high ionic conductivity with extremely high stability on the surface of electrode material, thereby protecting the electrode material and improving the charge-discharge cycle performance and safety performance of lithium-ion batteries.

[0006] A solid electrolyte composite material includes a lithium-containing solid electrolyte material, a stabilizer, and an active additive; the lithium-containing solid electrolyte material is one or more of sulfide solid electrolyte materials, halide electrolyte materials, and NASICON phase oxide electrolyte materials; the stabilizer is a polymer, including one or more of polyethylene terephthalate (PET), polyvinylidene fluoride (PVDF), polytetrafluoroethylene (PTFE), polyethylene oxide (PEO), styrene-butadiene rubber latex adhesive (SBR), and their derivatives; the active additive is a non-metallic halide, including at least one of POX3, PSX3, PNX2, and their mixtures, composites, or compounds; wherein X is one or more of F, Cl, Br, and I.

[0007] Specifically, the sulfide solid electrolyte material includes: silver-germanium sulfide ore Li6PS5Cl and its derivatives; lithium-germanium-phosphorus-sulfur phase Li... 10 MP2S 12 and its derivatives, M = one or more of Si, Ge, Sn, Zn, Al; lithium-phosphorus-sulfur phase Li3PS4 phase or Li7P3S 11 Phases and their derivatives; Li4SiS4 phase and its derivatives.

[0008] According to embodiments of the present invention, when the solid electrolyte composite material is silver-sulfur germanium ore Li6PS5Cl and its derivatives, or lithium-phosphorus-sulfur phase Li3PS4 phase or Li7P3S 11 When processing phases and their derivatives, the stabilizer may not be added, that is, the amount of stabilizer added may be 0.

[0009] In some preferred embodiments, the silver-steresulfurite Li6PS5Cl and its derivatives comprise: Li6PS5Cl, and a stoichiometric amount of Li. 6-x PS 5-x X 1+x 0≤x≤0.7, where X is one or more of F, Cl, Br, and I; and oxygen-doped Li 6- x PS 5-x-y X 1+x O y , 0≤x≤0.7, 0≤y≤1, X is one or more of F, Cl, Br, I.

[0010] In some preferred embodiments, the lithium-germanium-phosphorus-sulfur phase Li 10 MP2S 12 Its derivatives include: Li 10 MP2S 12M = one or more of Si, Ge, Sn, Sb, Zn, and Al; lithium germanium phosphorus sulfur phase with partial stoichiometry, halogen-doped lithium germanium phosphorus sulfur phase and oxygen-doped lithium germanium phosphorus sulfur phase.

[0011] In some preferred embodiments, the lithium phosphorus-sulfur phase is a Li3PS4 phase or a Li7P3S phase. 11 Phases, including: Li3PS4; Li7P3S 11 ; Stoichiometric lithium-phosphorus-sulfur phase; Halogen-doped lithium-phosphorus-sulfur phase; Metal element M-doped lithium-phosphorus-sulfur phase, M = Al, Mg, Si, Sn, Sb; Oxygen-doped lithium-phosphorus-sulfur phase.

[0012] Specifically, the halide electrolyte material is Li a MX b M = one or more of Al, In, Ga, Y, Sc, La-series rare earth elements, Nb, Ta, Zr, Hf, and Fe, X is one or more of F, Cl, Br, and I, 0.5≤a≤4, 3≤b≤8.

[0013] Specifically, the NASICON phase oxide electrolyte material is Li7La3Zr2O 12 Or Li 1+x Al x Ti 2-x (PO4)3 (x = 0 to 0.4) and its derivatives.

[0014] In some preferred embodiments, the NASICON phase oxide electrolyte material Li7La3Zr2O 12 Or Li 1+ x Al x Ti 2-x (PO4)3 and its derivatives include: Li7La3Zr2O 12 Li 1+x Al x Ti 2-x (PO4)3, (x = 0–0.4); halogen-doped or Ti, Hf, Ce, Si-doped Li7La3Zr2O 12 Li 1+x Al x Ti 2-x (PO4)3 phase material, (x = 0 to 0.4).

[0015] In some embodiments, the lithium-containing solid electrolyte material is selected from Li3PS4, Li 5.5 PS 4.5 Cl 1.5One or more of Li3OCl, Li3OBr, Li3SCl, Li3N, Li5NCl2, Li5NBr2, and Li8PNCl2.

[0016] In some embodiments, the solid electrolyte composite material is composed of or made from the lithium-containing solid electrolyte material, stabilizers, and active additives.

[0017] In some embodiments, the mass ratio of the lithium-containing solid electrolyte material, stabilizer, and additive in the solid electrolyte composite material is n:m:l; wherein 65 < n < 99; 0 ≤ m < 25; 0.1 < l < 10; optionally, 70 ≤ n ≤ 94; 0 ≤ m ≤ 25; 5 ≤ l ≤ 10, for example 94:1:5, 95:0:5, 70:25:5, 85:5:10.

[0018] All components of the solid electrolyte composite material of this invention can be commercially available or prepared according to existing literature methods.

[0019] The present invention also provides a method for preparing the above-mentioned solid electrolyte composite material, comprising: taking each component, mixing, and grinding. Alternatively, it can be prepared using conventional methods in the art.

[0020] The present invention also provides the application of the above-mentioned solid electrolyte composite material in solid-state batteries as any one of solid electrolyte, solid electrolyte stabilizer, positive and / or negative electrode ion conduction additive, and electrode-electrolyte interface modifier.

[0021] The present invention also provides a lithium battery, comprising:

[0022] The above-mentioned solid electrolyte composite material;

[0023] positive electrode;

[0024] Negative electrode; and

[0025] An electrolyte, which is inserted between the positive electrode and the negative electrode, includes sulfide solid electrolytes, oxide solid electrolytes, halide electrolytes, nitride electrolytes, polymer electrolytes, organic electrolytes, or combinations thereof.

[0026] Specifically, the lithium battery is a lithium-ion battery, including all-solid-state batteries, semi-solid-state batteries, and liquid batteries.

[0027] The solid electrolyte composite material described in this invention can improve the cycle performance and safety performance of lithium (ion) batteries.

[0028] The solid electrolyte composite material of the present invention regulates and optimizes the composition, composite structure and morphology of the solid electrolyte composite additive material by using different composite methods. By utilizing the composite additive material, a layer of low electronic conductivity and high ionic conductivity with high stability is formed on the surface of lithium and its alloy anode materials during battery resting, formation or cycling, thereby realizing a highly stable solid lithium metal battery with long cycle life.

[0029] The solid electrolyte composite material described in this invention can improve the commercial application value of lithium-ion batteries, including all-solid-state secondary batteries, specifically by improving the interface stability of lithium (ion) batteries, reducing the surface impedance of electrode materials, and inhibiting lithium dendrite growth. Attached Figure Description

[0030] Figure 1 The performance curves of lithium symmetric batteries obtained by using the solid electrolyte composite material prepared in Example 1 as the electrolyte of an all-solid-state battery are shown.

[0031] Figure 2 The composition of the lithium sheet surface was analyzed after 100 hours of lithium symmetric battery cycling, using the solid electrolyte composite material prepared in Example 1 as the electrolyte for an all-solid-state battery.

[0032] Figure 3 The performance curves of lithium symmetric batteries obtained by using the solid electrolyte composite material prepared in Example 2 as the electrolyte of an all-solid-state battery are shown.

[0033] Figure 4 The composition of the lithium sheet surface was analyzed after 100 hours of lithium symmetric battery cycling, using the solid electrolyte composite material prepared in Example 1 as the electrolyte for an all-solid-state battery.

[0034] Figure 5 The first cycle curve of a Li-Si battery obtained by using the solid electrolyte composite material prepared in Example 1 as a silicon anode additive and an electrolyte for an all-solid-state battery is shown.

[0035] Figure 6 The image shows the performance curves of a lithium symmetric battery using Li3PS4, the solid electrolyte material obtained in Comparative Example 1, as the electrolyte.

[0036] Figure 7 The image shows the performance curves of a lithium symmetric battery using Li3PS4, the solid electrolyte material obtained in Comparative Example 2, as the electrolyte.

[0037] The attached image includes a Chinese-English translation.

[0038] English Chinese Position Location Synchrotron X-ray Synchrotron X-ray Binding energy Binding energy Intensity strength Bulk Particle body Surface surface Capacity capacity Voltage Voltage Cycle number Number of cycles Molar Fraction of PS species mole fraction of PS molecules Reaction energy per reaction atom The reaction energy of each reacting atom Detailed Implementation

[0039] The present invention will now be described through specific embodiments. Unless otherwise specified, all technical means used in this invention are methods well known to those skilled in the art. Furthermore, the embodiments should be understood as illustrative, not limiting, of the scope of the invention; the essence and scope of the invention are defined only by the claims. For those skilled in the art, various changes or modifications to the material composition and dosage in these embodiments without departing from the essence and scope of the invention also fall within the protection scope of this invention.

[0040] Except for the method of ball milling used in the Li3YCl6 synthesis described in the reference (Advanced Materials 2018, 30, 1803075), all other raw materials and reagents used in this invention are commercially available.

[0041] Example 1

[0042] A solid electrolyte composite material is composed of lithium-containing solid electrolyte material Li3PS4, stabilizer SBR and additive PNCl2, wherein the mass ratio of the lithium-containing solid electrolyte material, stabilizer and additive is 94:1:5.

[0043] The preparation method of the solid electrolyte composite material in this embodiment:

[0044] Weigh 0.94 g of Li3PS4 sulfide solid electrolyte material (commercially purchased), 0.01 g of SBR, and 0.05 g of PNCl2 material in a glove box. Grind them in a mortar for 10 minutes, then place them in a 50 ml agate ball mill jar with agate balls of various sizes at a ball-to-material ratio of 25:1. Vacuum seal the ball mill jar in the glove box, then transfer it to a ball mill and mill at 250 rpm for 1 hour to obtain the solid electrolyte composite material.

[0045] Example 2

[0046] A solid electrolyte composite material, comprising lithium-containing solid electrolyte material Li 5.5 PS 4.5 Cl 1.5 The lithium-containing solid electrolyte material is composed of PNCl2 and POCl3 in a 1:1 ratio, and the mass ratio of the PNCl2 and POCl3 to the additives is 95:5.

[0047] The preparation method of the solid electrolyte composite material in this embodiment:

[0048] Similar to Example 1, except that the lithium-containing solid electrolyte material was replaced with commercially available Li-340 with an ionic conductivity of 7 mS / cm. 5.5 PS 4.5 Cl 1.5The material, without polymer stabilizers, uses PNCl2 and POCl3 in a 1:1 mass ratio as additives. The compounding process is performed directly in a glove box, without ball milling. Specifically, 0.95 grams of commercially available lithium-containing solid electrolyte material Li was weighed in the glove box. 5.5 PS 4.5 Cl 1.5 0.025 g of PNCl2 material and 0.025 g of POCl3 material (note: POCl3 is liquid) are placed in a mortar and ground for 10 minutes to obtain a solid electrolyte composite material.

[0049] Example 3

[0050] A solid electrolyte composite material, comprising lithium-containing solid electrolyte material Li7La3Zr2O 12 The preparation method of the lithium-containing solid electrolyte material, in which the stabilizer PEO and additive are composed of PNCl2, and the mass ratio of the stabilizer and additive is 70:25:5, is as follows:

[0051] Weigh 0.70 grams of commercially available lithium-containing solid electrolyte material Li7La3Zr2O into the glove box. 12 0.25 g of PEO and 0.05 g of PNCl2 were ground in a mortar for 10 minutes, then placed in a 50 ml zirconia grinding jar with zirconia balls of various sizes added at a ball-to-material ratio of 25:1. The grinding jar was vacuum-sealed in a glove box, then transferred to a ball mill and milled at 500 rpm for 5 hours to obtain the solid electrolyte composite material described in Example 3.

[0052] The samples were characterized using scanning electron microscopy, transmission electron microscopy, and XPS. Subsequently, the application of this solid-state electrolyte composite material in all-solid-state batteries was validated.

[0053] Example 4

[0054] A solid electrolyte composite material, comprising a lithium-containing solid electrolyte material Li3YCl6, a stabilizer PVDF, and additives PNCl2, POCl3, and PSCl3 in a 1:1:1 ratio, wherein the mass ratio of the lithium-containing solid electrolyte material, stabilizer, and additives is 85:5:10, is described in the preparation method below.

[0055] Weigh 0.85 g of lithium-containing solid electrolyte material Li3YCl6, 0.5 g of PVDF, 0.033 g of PNCl2, 0.033 g of POCl3, and 0.033 g of PSCl3 into a glove box and grind them in a mortar for 10 minutes. Then, place them in a 50 ml zirconia grinding jar and add zirconia balls of various sizes at a ball-to-material ratio of 25:1. Vacuum seal the grinding jar in the glove box, then transfer it to a ball mill and grind it at 250 rpm for 5 hours to obtain the solid electrolyte composite material.

[0056] The samples were characterized using scanning electron microscopy, transmission electron microscopy, and XPS. Subsequently, the application of this solid-state electrolyte composite material in all-solid-state batteries was validated.

[0057] Application Example 1

[0058] The solid electrolyte composite material prepared in Example 1 was used as a solid electrolyte for the application of solid lithium (ion) full batteries.

[0059] The specific operation is as follows: 150 mg of the solid electrolyte composite material prepared in Example 1 was weighed into a glove box and placed in the inner liner of the mold battery. After being flattened, the electrolyte sheet was pressed under a pressure of 350 MPa. Subsequently, unmodified lithium sheets were added to both ends of the electrolyte sheet for lithium symmetric battery testing. Constant current charge-discharge testing was conducted with a current of 1 mA cm⁻¹. -2 The time is 1 hour.

[0060] Figure 1 The performance curves of lithium symmetric batteries obtained by using the solid electrolyte composite material prepared in Example 1 as the electrolyte of an all-solid-state battery are shown. Figure 1 The solid electrolyte composite material prepared in Example 1 is shown to be stable for lithium as a solid electrolyte, and no short circuit was observed after 3000 hours of cycling in a lithium symmetric battery.

[0061] Figure 2 The composition of the lithium sheet surface was analyzed after 100 hours of lithium symmetric battery cycling, using the solid electrolyte composite material prepared in Example 1 as the electrolyte for an all-solid-state battery. Figure 2 The lithium foil surface is rich in PNCl. - Cl - Li + Components.

[0062] Application Example 2

[0063] The solid electrolyte composite material prepared in Example 1 was used as a solid electrolyte additive for the application of solid lithium (ion) full batteries.

[0064] The specific procedure is as follows: 20 mg of the solid electrolyte composite material prepared in Example 1 and 80 mg of commercially available Li were weighed into a glove box. 10 GeP2S 12 The mixture was ground and mixed in a mortar. The resulting material was placed in the inner liner of a molded battery, leveled, and then pressed into electrolyte sheets under a pressure of 350 MPa. Unmodified lithium sheets were then added to both ends of the electrolyte sheets for lithium-ion symmetric battery testing. Constant current charge-discharge testing was conducted at a current of 1 mA cm⁻¹. -2 The time is 1 hour.

[0065] The results show that the battery has a long cycle stability of >1000 hours.

[0066] Application Example 3

[0067] The solid electrolyte composite material prepared in Example 2 was used as a solid electrolyte for the application of solid lithium (ion) full batteries.

[0068] The specific operation is as follows: 150 mg of the solid electrolyte composite material prepared in Example 2 was weighed into a glove box and placed in the inner liner of the mold battery. After being flattened, the electrolyte sheet was pressed under a pressure of 350 MPa. Subsequently, unmodified lithium sheets were added to both ends of the electrolyte sheet for lithium symmetric battery testing. Constant current charge-discharge testing was conducted with a current of 1 mA cm⁻¹. -2 The time is 1 hour.

[0069] Figure 3 The performance curves of lithium symmetric batteries obtained by using the solid electrolyte composite material prepared in Example 2 as the electrolyte of an all-solid-state battery are shown. Figure 3 The solid electrolyte composite material prepared in Example 2 is shown to be stable for lithium as a solid electrolyte, and no short circuit was observed after 1000 hours of cycling in a lithium symmetric battery.

[0070] Figure 4 The composition of the lithium sheet surface was analyzed after 100 hours of lithium symmetric battery cycling, using the solid electrolyte composite material prepared in Example 1 as the electrolyte for an all-solid-state battery. Figure 4 The lithium foil surface is rich in PNCl. - O - Cl - Li + Components.

[0071] Application Example 4

[0072] The solid electrolyte composite material prepared in Example 1 was used as a negative electrode additive in an all-solid-state lithium-silicon battery.

[0073] The specific operation is as follows: Weigh 30 mg of the solid electrolyte composite material prepared in Example 1 in a glove box, mix it with 70 mg of pure silicon anode, and grind and mix it in a mortar. The resulting material is silicon anode powder with additives. All-solid-state Li-Si battery assembly: Weigh 70 mg of commercially available Li₂ with an ionic conductivity of 7 mS / cm. 5.5 PS 4.5 Cl 1.5 The material, used as the electrolyte, was placed inside the mold battery liner. After being spread out, the electrolyte sheet was pressed under a pressure of 150 MPa. Subsequently, silicon anode powder with additives was added to one end of the electrolyte sheet, spread evenly, and pressed under a pressure of 350 MPa. Then, a lithium metal sheet was added to the other end. After compaction under a pressure of 25 MPa, the liner was transferred to the mold battery for sealing and electrochemical performance testing.

[0074] The results are as follows Figure 5 As shown, the obtained Li-Si battery exhibits good reversible cycling. Both the lithium metal and silicon electrodes can achieve good electrochemical cycling reactions under the solid electrolyte composite material prepared in Example 1, and no short circuit phenomenon was observed.

[0075] Application Example 5

[0076] The solid electrolyte composite material prepared in Example 2 was used as a negative electrode additive in solid-state lithium (ion) full batteries.

[0077] The specific operation is as follows: Weigh 30 mg of the solid electrolyte composite material prepared in Example 2 in a glove box and mix it with a 70 mg graphite anode. Grind and mix the mixture in a mortar. The resulting material is the graphite anode powder with additives. Then weigh 70 mg of commercially available lithium cobalt oxide and 30 mg of commercially available Li3InCl6 electrolyte material, grind and mix them in a mortar until homogeneous, and record this as lithium cobalt oxide cathode powder. All-solid-state battery assembly: Weigh 70 mg of commercially available Li3InCl6 electrolyte material with an ionic conductivity of 7 mS / cm. 5.5 PS 4.5 Cl 1.5 The material, used as the electrolyte, was placed in the inner liner of a molded battery. After being spread out, the electrolyte sheet was pressed under a pressure of 150 MPa. Subsequently, graphite anode powder with additives was added to one end of the electrolyte sheet and spread evenly, while lithium cobalt oxide cathode powder was added to the other end and spread evenly as well. Then, the all-solid-state battery was pressed under a pressure of 350 MPa. After compaction, the inner liner was transferred to the molded battery for sealing and electrochemical performance testing.

[0078] The results show that the electrolyte composite material prepared in Example 2 can achieve good cycling performance.

[0079] Comparative Example 1

[0080] Only lithium-containing solid electrolyte material Li3PS4 was used as the electrolyte (this material is the same as the lithium-containing solid electrolyte material used in Example 1, without the addition of stabilizers and additives). Performance testing and comparison were conducted using methods similar to those used in Example 1. Figure 6 The image shows the performance curves of a lithium-symmetric battery using Li3PS4, the solid electrolyte material obtained in Comparative Example 1, as the electrolyte. Figure 1 The comparison revealed that Li3PS4, a solid electrolyte material that has not been combined with stabilizers and additives, exhibits a significant short circuit when used as an electrolyte in a lithium symmetric battery after 100 hours of cycling.

[0081] Comparative Example 2

[0082] Only lithium-containing solid electrolyte material Li is used 5.5 PS 4.5 Cl 1.5 As the electrolyte (this material is the same as the lithium-containing solid electrolyte material used in Example 2, without the addition of stabilizers and additives), performance tests and comparisons were performed using a method similar to that used in Application Example 3. Figure 7 The image shows the performance curves of a lithium-symmetric battery using Li3PS4, the solid electrolyte material obtained in Comparative Example 2, as the electrolyte. Figure 3 Comparative analysis revealed that the solid electrolyte material Li, which was not composited with stabilizers and additives, showed superior performance. 5.5 PS 4.5 Cl 1.5 As an electrolyte, it exhibits significant short-circuiting phenomena after 100 hours of cycling in a lithium-symmetric battery.

[0083] The results show that, compared with solid electrolyte materials without stabilizers and additives, the solid electrolyte composite material provided by this invention has the characteristics of improving the cycle performance and safety performance of lithium-ion batteries, and can effectively alleviate problems such as short circuits in electrodes including metallic lithium in the use of all-solid-state batteries.

[0084] Although the present invention has been described in detail above with general descriptions, specific embodiments, and experiments, modifications or improvements can be made to it, which will be obvious to those skilled in the art. Therefore, all such modifications or improvements made without departing from the spirit of the present invention fall within the scope of protection claimed by the present invention.

Claims

1. A solid electrolyte composite material, characterized in that, The invention comprises a lithium-containing solid electrolyte material, a stabilizer, and an active additive; the lithium-containing solid electrolyte material is one or more of sulfide solid electrolyte materials, halide electrolyte materials, and NASICON phase oxide electrolyte materials; the stabilizer is a polymer, including one or more of polyethylene terephthalate (PET), polyvinylidene fluoride (PVDF), polytetrafluoroethylene (PTFE), polyethylene oxide (PEO), styrene-butadiene rubber latex adhesive (SBR), and their derivatives; the active additive is a non-metallic halide, including at least one of POX3, PSX3, PNX2, and their mixtures, composites, or compounds; wherein X is one or more of F, Cl, Br, and I.

2. The solid electrolyte composite material according to claim 1, characterized in that, The sulfide solid electrolyte material includes: silver sulfide germanium ore Li6PS5Cl and its derivatives; lithium germanium phosphorus sulfide phase Li... 10 MP2S 12 and its derivatives, M = one or more of Si, Ge, Sn, Zn, Al; lithium-phosphorus-sulfur phase Li3PS4 phase or Li7P3S 11 Phases and their derivatives; Li4SiS4 phases and their derivatives; and / or, The halide electrolyte material is Li a MX b M = one or more of Al, In, Ga, Y, Sc, La-series rare earth elements, Nb, Ta, Zr, Hf, and Fe; X is one or more of F, Cl, Br, and I; 0.5 ≤ a ≤ 4, 3 ≤ b ≤ 8; and / or, The NASICON phase oxide electrolyte material is Li7La3Zr2O 12 Or Li 1+x Al x Ti 2-x (PO4)3 and its derivatives.

3. The solid electrolyte composite material according to claim 2, characterized in that, The silver sulfide germanium ore Li6PS5Cl and its derivatives comprise: Li6PS5Cl, and Li in a stoichiometric ratio. 6-x PS 5-x X 1+x 0≤x≤0.7, where X is one or more of F, Cl, Br, and I; and oxygen-doped Li 6-x PS 5-x-y X 1+x O y , 0≤x≤0.7, 0≤y≤1, X is one or more of F, Cl, Br, I; The lithium-germanium-phosphosulfur phase Li 10 MP2S 12 Its derivatives include: Li 10 MP2S 12 M = one or more of Si, Ge, Sn, Sb, Zn, and Al; lithium germanium phosphorus-sulfur phase with partial stoichiometry, halogen-doped lithium germanium phosphorus-sulfur phase and oxygen-doped lithium germanium phosphorus-sulfur phase; The lithium phosphorus sulfide phase is either Li3PS4 or Li7P3S. 11 Phases, including: Li3PS4; Li7P3S 11 ; Stoichiometric lithium-phosphorus-sulfur phase; Halogen-doped lithium-phosphorus-sulfur phase; Metal element M-doped lithium-phosphorus-sulfur phase, M = Al, Mg, Si, Sn, Sb; Oxygen-doped lithium-phosphorus-sulfur phase; The NASICON phase oxide electrolyte material Li7La3Zr2O 12 Or Li 1+x Al x Ti 2-x (PO4)3 and its derivatives include: Li7La3Zr2O 12 Li 1+x Al x Ti 2-x (PO4)3, (x = 0–0.4); halogen-doped or Ti, Hf, Ce, Si-doped Li7La3Zr2O 12 Li 1+x Al x Ti 2-x (PO4)3 phase material, (x = 0 to 0.4).

4. The solid electrolyte composite material according to claim 1, characterized in that, The lithium-containing solid electrolyte material is selected from Li3PS4, Li 5.5 PS 4.5 Cl 1.5 One or more of Li3OCl, Li3OBr, Li3SCl, Li3N, Li5NCl2, Li5NBr2, and Li8PNCl2.

5. The solid electrolyte composite material according to any one of claims 1-4, characterized in that, The mass ratio of the lithium-containing solid electrolyte material, stabilizer, and additives in the solid electrolyte composite material is n:m:l; wherein, 65 < n < 99; 0 ≤ m < 25; 0.1 < l < 10.

6. The solid electrolyte composite material according to claim 5, characterized in that, 70≤n≤94;0≤m≤25;5≤l≤10; 7. The solid electrolyte composite material according to any one of claims 1-4, characterized in that, The mass ratio of the lithium-containing solid electrolyte material, stabilizer, and additives in the solid electrolyte composite material is 94:1:5, 95:0:5, 70:25:5, or 85:5:

10.

8. The solid electrolyte composite material according to any one of claims 1-5, characterized in that, include: Take each component, mix them, and grind them.

9. The solid electrolyte composite material according to any one of claims 1-5 is used in solid-state batteries as a solid electrolyte, a solid electrolyte stabilizer, a positive and / or negative electrode ion conduction additive, or an electrode-electrolyte interface modifier.

10. A lithium battery, characterized in that, include: The solid electrolyte composite material according to any one of claims 1-5; positive electrode; negative electrode; as well as An electrolyte, which is inserted between the positive electrode and the negative electrode, and includes sulfide solid electrolytes, oxide solid electrolytes, halide electrolytes, nitride electrolytes, polymer electrolytes, organic electrolytes, or combinations thereof; Optionally, the lithium battery is a lithium-ion battery, including all-solid-state batteries, semi-solid-state batteries, and liquid batteries.

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