Preparation method and application of high-voltage organic positive electrode composite material for all-solid-state battery

Abstract

The invention discloses a preparation method and application of a high-voltage organic positive electrode composite material for an all-solid-state battery. The organic positive electrode material is a 2, 3, 5, 6-site substitute of 1, 4-benzoquinone or a 3, 4, 5, 6-site substitute of 1, 2-benzoquinone, and is used as a solid solvent to be compounded with a solid electrolyte to form a solid solution structure. The solid electrolyte is a chloride solid electrolyte, the chemical composition general formula of the chloride solid electrolyte is LixMClx + y, and M is one or a combination of more elements selected from In, Y, Sc, Zr, Hf, Al, Nb and Ta. The relative proportion of M ions in the benzoquinone substitute and the chloride electrolyte is accurately regulated and controlled through a mechanochemical method, so that the composite solid solution structure of the organic positive electrode and the solid electrolyte is optimized. The all-solid-state organic battery prepared by the method has high working voltage and excellent cycling stability. The invention provides a new technical path for the application of the organic positive electrode material in the field of all-solid-state batteries, and has important practical value and industrialization prospect.

Description

Technical Field

[0001] The present invention relates to the technical field of lithium - ion batteries, and more particularly, to a high - voltage organic cathode composite material for all - solid - state batteries, a preparation method thereof, and an application thereof. Background Art

[0002] The development history of lithium - ion battery cathode materials can be traced back to the 1970s when researchers began to explore lithium - intercalation compounds as energy storage materials. In 1980, the Goodenough team first proposed lithium cobalt oxide (LiCoO2) as a cathode material, which was commercialized by Sony in 1991, marking the beginning of the lithium - ion battery era (Mater. Res. Bull., 1980, 15, 783 - 789). Lithium cobalt oxide became the first choice for early portable electronic devices due to its high voltage and high energy density. However, problems such as high cost, scarce cobalt resources, and poor thermal stability gradually emerged. To address these challenges, in the late 1990s, lithium iron phosphate (LiFePO4) was first synthesized (J. Electrochem. Soc., 1997, 144, 1188). Lithium iron phosphate has been widely used in the field of power batteries due to its excellent thermal stability and long cycle life. Entering the 21st century, with the rapid development of electric vehicles and energy storage systems, researchers turned their attention to high - energy - density nickel - cobalt - manganese ternary materials (LiNi x Mn y Co 1-x-y O2) and nickel - cobalt - aluminum ternary materials (LiNi 0.8 Co 0.15 Al 0.05 O2). By adjusting the ratio of nickel, cobalt, manganese, or aluminum, these materials achieve a balance between energy density and cost and have become the mainstream cathode materials for current power batteries. However, traditional inorganic cathode materials still face many challenges (Chem. Mater., 2010, 22, 587–603): First, key metal resources such as cobalt and nickel are scarce and their prices fluctuate greatly, resulting in high costs. Second, the production and recycling processes of these materials pose a great pressure on the environment.

[0003] Organic electrode materials have received extensive research attention due to their structural diversity, cost-effectiveness, and environmental sustainability, with the expectation of breaking through the technical bottlenecks of existing lithium-ion batteries through a sustainable, low-cost, and designable material system (Nat. Rev. Chem., 2020, 4, 127–142). In the past few decades, organic cathode materials have been widely explored in the field of electrochemical energy storage and are mainly divided into two categories: p-type (dual-ion mechanism) and n-type (rocking chair mechanism). P-type organic cathode materials, such as conductive polymers like polyaniline and polythiophene, are known for their redox chemistry involving lone-pair electrons and high average working voltages. However, p-type organic cathode materials face practical challenges, including significant structural distortions caused by the insertion / extraction of large-radius anions, the need for customized electrolytes in dual-ion batteries, and limited redox activity. On the other hand, typical n-type organic materials, such as quinone derivatives with carbonyl redox chemistry, exhibit excellent reversibility and structural stability, making them strong candidates for practical applications. Nevertheless, n-type organic cathode materials still face long-term challenges, including lower working voltages (mostly < 3 V) compared to transition metal oxides (such as LiCoO2, LiNi x Mn y Co 1-x-y O2, etc.), and poor cycle stability due to severe dissolution in liquid electrolytes. In the past few decades, researchers have made a great deal of efforts to address these challenges. Typical strategies for increasing the working voltage include introducing electron-withdrawing functional groups, achieving charge delocalization using sacrificial metals, designing mesoscopic structures, or exploring new redox chemistries beyond the typical enol-carbonyl paradigm. At the same time, efforts to alleviate the dissolution of n-type organic cathode materials in liquid electrolytes have mainly focused on polymerization, expanding the conjugated region, and synthesizing organic salts. However, these strategies are often difficult to balance, resulting in challenges in simultaneously achieving high working voltages and long-term cycle stability in all-solid-state batteries.

[0004] In summary, the present invention provides a simple preparation method for a high-voltage organic cathode composite material for all-solid-state batteries, and demonstrates that the organic active molecules in this composite material have a high average working potential and excellent cycle performance, meeting the needs of more diverse solid-state batteries and having important research significance. Summary of the Invention

[0005] Aiming at the deficiencies of the existing technology, the purpose of the present invention is to provide a preparation method for a high-voltage organic cathode composite material for all-solid-state batteries. This method can enable n-type organic materials to have a relatively high working voltage in all-solid-state batteries, and the working potential for lithium metal can reach up to 3.6 V (room temperature). At the same time, the all-solid-state lithium-ion battery prepared by this method has excellent cycle performance, high charge-discharge specific capacity, etc., and is expected to broaden the application fields of all-solid-state lithium-ion batteries.

[0006] To achieve the above object, the present invention discloses the following technical content: A high-voltage organic cathode composite material for an all-solid-state battery prepared by a mechanochemical method, the general formula of its composition is: Li x MCl x+y (60 wt.%) | C 6+u N u O2Cl 4-u-z F z (20 wt.%) | Conductive additive (20 wt.%) 0 ≤ x ≤ 3; 3 ≤ y ≤ 5 0 ≤ u ≤ 4; 0 ≤ z ≤ 4 Wherein the chloride solid electrolyte contains elements Li, M, Cl, where M is one or more elements selected from In, Y, Sc, Zr, Hf, Al, Nb, Ta; the organic cathode material C 6+u N u O2Cl 4-u-z F z Is a 2,3,5,6-substituted product of 1,4-benzoquinone or a 3,4,5,6-substituted product of 1,2-benzoquinone; the high-voltage organic cathode composite material for an all-solid-state battery has an amorphous or mixed-phase characteristic composed of an amorphous and a crystalline phase, wherein the crystal structure of the crystalline phase belongs to C2 / m, Pnma, Space group. The working potential of the organic active material in the high-voltage organic cathode composite material for an all-solid-state battery with respect to lithium metal is 3.3 - 3.6 V.

[0007] The preparation method of the high-voltage organic cathode composite material for an all-solid-state battery according to the present invention includes the following steps: Mix the organic cathode material, the conductive additive, and the chloride solid electrolyte in a mass ratio of 2:2:6, and prepare the cathode composite material by a mechanochemical synthesis method under an inert gas or vacuum condition; the ball milling speed is 350 rpm, and the ball milling time is 4 hours; wherein: The organic cathode material is a 2,3,5,6-substituted product of 1,4-benzoquinone or a 3,4,5,6-substituted product of 1,2-benzoquinone, specifically including but not limited to 2,3,5,6-tetrachloro-1,4-benzoquinone, 2,3-dichloro-5,6-dicyano-1,4-benzoquinone, 2,3,5,6-tetrafluoro-1,4-benzoquinone, and 3,4,5,6-tetrachloro-1,2-benzoquinone; the chloride solid electrolyte precursor is selected from one or a combination of indium chloride (InCl3), yttrium chloride (YCl3), scandium chloride (ScCl3), zirconium chloride (ZrCl4), hafnium chloride (HfCl4), aluminum chloride (AlCl3), and niobium chloride (NbCl5); among them, the combination methods of the precursors include but are not limited to: indium chloride (InCl3) and zirconium chloride (ZrCl4) are mixed in a molar ratio of 1:1, or indium chloride (InCl3), aluminum chloride (AlCl3), and niobium chloride (NbCl5) are mixed in a molar ratio of 1:1:1.

[0008] The present invention further discloses the application of the high-voltage organic cathode composite material of the all-solid-state battery in meeting more diverse all-solid-state battery requirements, effectively suppressing interfacial side reactions, and improving the battery cycle life and safety. Experimental results show that the all-solid-state organic battery prepared by this method exhibits a high working voltage (working potential against lithium metal ≥ 3.5 V) and excellent cycle stability (capacity retention rate ≥ 70% after 3500 cycles at 1C rate) in electrochemical performance tests. A more detailed description of the present invention is as follows: The first embodiment: A class of high-voltage organic cathode composite materials for all-solid-state batteries, the general formula of its composition is: Li x MCl x+y (60 wt.%) | C 6+u N u O2Cl 4-u-z F z (20 wt.%) | Conductive additive (20 wt.%) 0 ≤ x ≤ 3; 3 ≤ y ≤ 5 0 ≤ u ≤ 4; 0 ≤ z ≤ 4 The high-voltage organic composite material for all-solid-state batteries described above has an amorphous or mixed-phase characteristic composed of amorphous and crystalline phases, and the crystal structure of the crystalline phase belongs to C2 / m, Pnma, Space group (Bruker AXS D8Advance).

[0009] The high-voltage organic composite material for all-solid-state batteries described above is prepared from an organic cathode material, a conductive additive, and a chloride solid electrolyte: Preferably, the organic cathode material is 3,4,5,6-tetrachloro-1,2-benzoquinone, 2,3,5,6-tetrachloro-1,4-benzoquinone, 2,3-dichloro-5,6-dicyano-1,4-benzoquinone; Preferably, the chloride solid electrolyte precursor is aluminum chloride (AlCl3), niobium chloride (NbCl5), scandium chloride (ScCl3), zirconium chloride (ZrCl4); The preparation method of the high-voltage organic composite material for all-solid-state batteries as described above includes the following steps: Put the mixture of the organic cathode material, the conductive additive, and the chloride solid electrolyte into a ball milling jar, where the mass fraction ratio of the organic cathode material, the conductive additive, and the chloride solid electrolyte is 2:2:6. Using devices such as a planetary ball mill, the raw material powders collide with each other in the ball milling jar to undergo a mechanochemical reaction to generate the target product. The raw material powders in the ball milling jar can be in a vacuum or protected by an inert gas (such as nitrogen, argon, helium, etc.).

[0010] Preferably, the ball milling speed is 350 rpm; Preferably, the ball milling time is 4 h; The phase structure of the high-voltage organic composite material for all-solid-state batteries obtained in the first embodiment should be amorphous or a mixed phase composed of amorphous and crystalline phases.

[0011] There is no limitation on the shape of the high-voltage organic composite material for all-solid-state batteries obtained in the first embodiment, such as granular, layered, needle-like, etc.

[0012] There is no limitation on the size of the high-voltage organic composite material for all-solid-state batteries obtained in the first embodiment. The preferred particle size is above 0.1 µm and below 10 µm. Embodiment

[0013] A lithium-ion battery includes the positive electrode, the negative electrode, and a solid electrolyte layer located between the positive electrode and the negative electrode, and is characterized in that at least the positive electrode, the negative electrode, and the solid electrolyte layer contain the high-voltage organic composite material for all-solid-state batteries described above.

[0014] The positive electrode includes organic compound particles, conductive additive particles, and chloride particles.

[0015] The negative electrode includes negative electrode active material particles.

[0016] The solid electrolyte layer is between the positive electrode and the negative electrode.

[0017] The negative electrode active material refers to a material that can absorb and release metal ions, such as metal materials, carbon materials, nitrogen materials, etc. The metal material can be a single metal or an alloy.

[0018] Preferably, the negative electrode active material is a Li-In alloy with a lithium metal mass fraction of 0-4 wt%. To ensure the electrochemical cycle stability, chemical stability, and ionic conductivity, at least one of the positive electrode, negative electrode, and the solid electrolyte layer of the above lithium-ion battery may contain one or more additional electrolyte materials. There are no requirements for this additional electrolyte material, and it can be an oxide solid electrolyte, a sulfide solid electrolyte, a chloride solid electrolyte, a polymer electrolyte, etc.

[0019] Oxide solid electrolytes refer to oxygen-containing solid electrolytes, such as NASICON type, LISICON type, garnet type, perovskite type, Li3PO4 or its N-substituted body.

[0020] Sulfide solid electrolytes refer to sulfur-containing solid electrolytes, such as Li2S-P2S5, Li2S-GeS2, Li6PS5Cl, Li 10 GeP2S 12 etc.

[0021] Chloride solid electrolytes refer to solid electrolytes containing chloride anions and may also contain other anions, such as Li3InCl6, Li3YCl6, or Li3ScCl6, etc.

[0022] Preferably, the solid electrolyte layers located between the positive electrode and the negative electrode are Li3InCl6 (positive electrode side) and Li6PS5Cl (negative electrode side), respectively.

[0023] The high-voltage organic composite material for all-solid-state batteries provided by the present invention has the following positive effects: (1) The high-voltage organic positive electrode composite material can significantly increase the working potential of the active organic molecules against lithium metal, thereby achieving a high working voltage.

[0024] (2) The high-voltage organic positive electrode composite material has excellent mechanical properties, can effectively adapt to the mechanical stress in the all-solid-state battery system, and ensure the structural stability of the material.

[0025] (3) The high-voltage organic positive electrode composite material exhibits high interfacial electrochemical stability, can effectively inhibit interfacial side reactions, and improve the cycle life and safety of the battery.

[0026] (4) The high-voltage organic positive electrode composite material is applicable to lithium-ion secondary batteries at room temperature, has excellent cycle performance, high charge-discharge specific capacity, and high safety, meeting the actual application requirements. Description of the Drawings

[0027] Figure 1 is the Li obtained in Examples 1-3 of the present invention2.34 In 0.78 Zr 0.22 Cl 5.56 (60 wt.%) | 3,4,5,6 - tetrachloro - 1,2 - benzoquinone (o - C6O2Cl4) (20 wt.%) | conductive additive (20 wt.%), Li 1.77 In 0.59 Zr 0.41 Cl 5.18 (60 wt.%) | o - C6O2Cl4 (20 wt.%) | conductive additive (20 wt.%), Li 0.84 In 0.28 Zr 0.72 Cl 4.56 (60 wt.%) | o - C6O2Cl4 (20 wt.%) | conductive additive (20 wt.%), Li 0.84 In 0.28 Zr 0.72 Cl 4.56 (60 wt.%) | 3,4,5,6 - tetrachloro - 1,4 - benzoquinone (p - C6O2Cl4) (20 wt.%) | conductive additive (20 wt.%), Li 0.84 In 0.28 Zr 0.72 Cl 4.56 (60 wt.%) | 2,3 - dichloro - 5,6 - dicyano - 1,4 - benzoquinone (C8N2O2Cl2) (20 wt.%) | conductive additive (20 wt.%) X - ray diffraction phase analysis diagram of high - voltage organic composite material; Figure 2 is Li obtained in Example 1 of the present invention 2.34 In 0.78 Zr 0.22 Cl 5.56 (60 wt.%) | o - C6O2Cl4 (20wt.%) | conductive additive (20 wt.%), Li 1.77 In 0.59 Zr 0.41 Cl 5.18 (60 wt.%) | o - C6O2Cl4 (20 wt.%) | conductive additive (20 wt.%) and Li 0.84 In 0.28 Zr 0.72 Cl 4.56 (60 wt.%) | o - C6O2Cl4 (20 wt.%) | conductive additive (20wt.%) charge - discharge curve of high - voltage organic composite material; Figure 3It is the charge-discharge curve of the high-voltage organic composite material of Li2ZrCl6 (60 wt.%) | p-C6O2Cl4 (20 wt.%) | conductive additive (20 wt.%) obtained in Example 2 of the present invention; Figure 4 It is the charge-discharge curve of the high-voltage organic composite material of Li2ZrCl6 (60 wt.%) | C8N2O2Cl2 (20 wt.%) | conductive additive (20 wt.%) obtained in Example 3 of the present invention; Figure 5 It is Li obtained in Example 4 of the present invention 1.89 In 0.63 Al 0.37 Cl 5.26 (60 wt.%) | o-C6O2Cl4 (20wt.%) | charge-discharge curve of the high-voltage organic composite material of conductive additive (20 wt.%); Figure 6 It is Li obtained in Example 5 of the present invention 1.89 In 0.63 Sc 0.37 Cl 5.26 (60 wt.%) | o-C6O2Cl4 (20wt.%) | charge-discharge curve of the high-voltage organic composite material of conductive additive (20 wt.%); Figure 7 It is Li obtained in Example 6 of the present invention 1.56 In 0.64 Nb 0.24 Al 0.12 Cl 5.28 (60 wt.%) | o-C6O2Cl4 (20wt.%) | charge-discharge curve of the high-voltage organic composite material of conductive additive (20 wt.%); Figure 8 It is Li obtained in Comparative Example 1 of the present invention 2.34 In 0.78 Zr 0.22 Cl 5.56 (60 wt.%) | C6O2H4 (20 wt.%) | charge-discharge curve of the organic composite material of conductive additive (20 wt.%); Figure 9 It is the charge-discharge curve of the organic composite material of Li6PS5Cl (60 wt.%) | o-C6O2Cl4 (20 wt.%) | conductive additive (20 wt.%) obtained in Comparative Example 2 of the present invention.

[0028] Figure 10 It is the long cycle performance graph of the all-solid-state lithium-ion battery obtained in Application Example 1 of the present invention. Detailed implementation manners

[0029] The following examples are used to illustrate the present invention, but not to limit the scope of the present invention. For those without specific technical or conditions indicated in the examples, the techniques or conditions described in the literature in the art are followed, or the product specifications are followed. For those raw materials, reagents or instruments without the manufacturer indicated, they are all conventional products that can be obtained through regular channels of merchants.

[0030] Example 1

[0031] The present invention provides a series of high-voltage organic composite materials for all-solid-state batteries, and their components are Li x MCl x+y (x = 2.34, 1.77, 0.84, y = 3.22, 3.41, 3.72) (60 wt.%) | 3,4,5,6-tetrachloro-1,2-benzoquinone (o-C6O2Cl4) (20 wt.%) | conductive additive (20 wt.%). The specific preparation method is as follows: Take commercially available 3,4,5,6-tetrachloro-1,2-benzoquinone (o-C6O2Cl4), conductive additive, Li3InCl6 solid electrolyte, and ZrCl4, and uniformly mix them in a glove box protected by argon according to different feeding ratios. Among them, the mass ratio of o-C6O2Cl4, conductive additive, Li3InCl6 plus ZrCl4 is maintained at 2:2:6, and the molar ratio of o-C6O2Cl4 to ZrCl4 is 1:2, 1:1, 1:0.5 respectively, corresponding to the cases of M = In, Zr in Li x MCl x+y with x = 2.34, 1.77, 0.84, y = 3.22, 3.41, 3.72. And o-C6O2Cl4 corresponds to the case of u = 0, z = 0 for C 6+u N u O2Cl 4-u-z F z Take 0.2 g of the mixed powder and put it into a 50 mL ball milling jar, and correspondingly put 40 g of ball milling beads into the ball milling jar. After sealing the ball milling jar, ball mill it at a speed of 350 rpm for 4 h. Subsequently, transfer the ball milling jar to the glove box and scrape the powder in the jar to obtain the high-voltage organic composite material.

[0032] For the obtained Li 2.34 In 0.78 Zr 0.22 Cl 5.56 (60 wt.%) | o-C6O2Cl4 (20 wt.%) | conductive additive (20 wt.%), Li 1.77 In 0.59Zr 0.41 Cl 5.18 (60 wt.%) | o-C6O2Cl4 (20 wt.%) | conductive additive (20 wt.%) and Li 0.84 In 0.28 Zr 0.72 Cl 4.56 (60 wt.%) | o-C6O2Cl4 (20 wt.%) | conductive additive (20 wt.%) composite materials were subjected to X-ray diffraction phase analysis (XRD), and the results are as Figure 1 shown. The analysis results show that the crystalline phase composition of the obtained composite materials has the C2 / m space group.

[0033] Using Li3InCl6 powder as the solid electrolyte layer close to the positive electrode, Li6PS5Cl as the solid electrolyte layer close to the negative electrode, Li-In alloy as the negative electrode, and the obtained high-voltage organic composite material, the components of which are Li x MCl x+y (x = 2.34, 1.77, 0.84, y = 3.22, 3.41, 3.72) (60 wt.%) | o-C6O2Cl4 (20 wt.%) | conductive additive (20 wt.%), as the counter electrode, a solid-state battery was assembled using a die cell in a glove box under an argon atmosphere. The solid-state battery was subjected to electrochemical charge-discharge tests at room temperature, and the charge-discharge cut-off voltage was 2.50 - 4.20 V (vs. Li + / Li), and the charge-discharge current density was 0.1C (1C = 218 mA g -1 , o-C6O2Cl4). The charge-discharge curves are as Figure 2 shown. Among the three high-voltage organic composite materials, the average working potential and discharge capacity of the organic active substances are summarized in Table 1.

[0034] Table 1 <![CDATA[Li 3(1-x) In 1-x Zr x Cl 6-2x in which the value of x]]> <![CDATA[Average working potential (V vs. Li + / Li)]]> <![CDATA[Discharge capacity (mAh g -1 )]]> 0.22 3.31 197 0.41 3.42 206 0.72 3.45 209 Example

[0035]

[0036] The present invention provides a high-voltage organic composite material for all-solid-state batteries, the components of which are Li2ZrCl6 (60 wt.%) | 3,4,5,6-tetrachloro-1,4-benzoquinone (p-C6O2Cl4) (20 wt.%) | conductive additive (20 wt.%).

[0037] Except that the raw materials are changed to 3,4,5,6-tetrachloro-1,4-benzoquinone (p-C6O2Cl4), conductive additive, and lithium zirconium chloride (Li2ZrCl6) solid electrolyte, and the charge and discharge cut-off voltage is 2.40 - 4.20 V (vs. Li + / Li), other procedural steps are the same as those in Example 1, corresponding to M = Zr, x = 2, y = 4 in the composition representation Li x MCl x+y in Claim 2; and the case of u = 0, z = 0 for C 6+u N u O2Cl 4-u-z F z . In the obtained high-voltage organic composite material, the crystalline phase component has space group ( Figure 1 ), the average working voltage of the organic active material is 3.01 V (vs. Li + / Li), and the charge and discharge curve is as Figure 3 shown.

[0038] Example 3

[0039] The present invention provides a high-voltage organic composite material for all-solid-state batteries, and its components are Li2ZrCl6 (60 wt.%) | 2,3-dichloro-5,6-dicyano-1,4-benzoquinone (C8N2O2Cl2) (20 wt.%) | conductive additive (20 wt.%).

[0040] Except that the raw materials are changed to 2,3-dichloro-5,6-dicyano-1,4-benzoquinone (C8N2O2Cl2), conductive additive, and lithium zirconium chloride (Li2ZrCl6) solid electrolyte, and the charge and discharge cut-off voltage is 2.60 - 4.30 V (vs. Li + / Li), other procedural steps are the same as those in Example 1, corresponding to M = Zr, x = 2, y = 4 in the composition representation Li x MCl x+y in Claim 2; and the case of u = 2, z = 0 for C 6+u N u O2Cl 4-u- z z F. In the obtained high-voltage organic composite material, the crystalline phase component has space group ( Figure 1 ), the average working voltage of the organic active material is 3.43 V (vs. Li + / Li), and the charge and discharge curve is as Figure 4 shown.

[0041] Example 4

[0042] The present invention provides a high-voltage organic composite material for all-solid-state batteries, and its components are Li 1.89 In 0.63 Al 0.37 Cl 5.26 (60 wt.%) | 3,4,5,6-tetrachloro-1,2-benzoquinone (o-C6O2Cl4) (20 wt.%) | conductive additive (20 wt.%).

[0043] Except that the raw materials are changed to 3,4,5,6-tetrachloro-1,2-benzoquinone (o-C6O2Cl4), conductive additive, and Li 1.89 In 0.63 Al 0.37 Cl 5.26 solid electrolyte, where the molar ratio of o-C6O2Cl4 to AlCl3 is 1:1, and the charge-discharge cut-off voltage is 2.80 - 4.10 V (vs. Li + / Li), other process steps are the same as those in Example 1, corresponding to the case where M = Al, x = 1.89, y = 3.37 in the composition representation of Li x MCl x+y in claim 2; C 6+u N u O2Cl 4-u-z F z is u = 0, z = 0. In the obtained high-voltage organic composite material, the average working voltage of the organic active material is 3.47 V (vs. Li + / Li), and the charge-discharge curve is as Figure 5 shown.

[0044] Example 5

[0045] The present invention provides a high-voltage organic composite material for all-solid-state batteries, and its components are Li 1.89 In 0.63 Sc 0.37 Cl 5.26 (60 wt.%) | 3,4,5,6-tetrachloro-1,2-benzoquinone (o-C6O2Cl4) (20 wt.%) | conductive additive (20 wt.%).

[0046] Except that the raw materials are changed to 3,4,5,6-tetrachloro-1,2-benzoquinone (o-C6O2Cl4), conductive additive, and Li 1.89 In 0.63 Sc 0.37 Cl5.26 A solid electrolyte, where the molar ratio of o-C6O2Cl4 to ScCl3 is other than 1:1, and the other process steps are the same as in Example 1, corresponding to the composition of Li in Claim 2 x MCl x+y where M = Sc, x = 1.89, y = 3.37; C 6+ u N u O2Cl 4-u-z F z in the case of u = 0 and z = 0. In the obtained high-voltage organic composite material, the average working voltage of the organic active material is 3.34 V (vs. Li + / Li), and the charge-discharge curve is as Figure 6 shown.

[0047] Example 6

[0048] The present invention provides a high-voltage organic composite material for all-solid-state batteries, and its components are Li 1.56 In 0.64 Nb 0.24 Al 0.12 Cl 5.28 (60 wt.%) | 3,4,5,6-tetrachloro-1,2-benzoquinone (o-C6O2Cl4) (20 wt.%) | conductive additive (20 wt.%).

[0049] Except that the raw materials are changed to 3,4,5,6-tetrachloro-1,2-benzoquinone (o-C6O2Cl4), conductive additive, and Li 1.56 In 0.64 Nb 0.24 Al 0.12 Cl 5.28 A solid electrolyte, where the molar ratio of o-C6O2Cl4 to NbCl5 and AlCl3 is 1:1:0.3, and the charge-discharge cut-off voltage is 2.90 - 4.30 V (vs. Li + / Li), and the other process steps are the same as in Example 1, corresponding to the case of Li x MCl x+y where M = Nb, Al, x = 1.56, y = 3.72; C 6+u N u O2Cl 4-u-z F z in the case of u = 0 and z = 0. In the obtained high-voltage organic composite material, the average working voltage of the organic active material is 3.60 V (vs. Li + / Li), and the charge-discharge curve is as Figure 7 shown.

[0050] Comparative Example 1

[0051] Using the same procedure steps as in Example 1, the raw materials were changed to 1,4-benzoquinone (C6O2H4), a conductive additive, and a Li2ZrCl6 solid electrolyte to obtain an organic composite material. Among them, the mass ratio of C6O2H4, the conductive additive, and Li2ZrCl6 was maintained at 2:2:6, and the molar ratio of C6O2H4 to ZrCl4 was 1:1. The test methods for Comparative Example 1 and the solid-state battery were the same as those in the above Examples 1-6, except for the different organic cathode materials. The charge-discharge curves are as Figure 8 shown.

[0052] Comparative Example 2

[0053] Using the same procedure steps as in Example 1, the raw materials were changed to 3,4,5,6-tetrachloro-1,2-benzoquinone (o-C6O2Cl4), a conductive additive, and a Li6PS5Cl solid electrolyte to obtain an organic composite material. Among them, the mass ratio of o-C6O2Cl4, the conductive additive, and Li6PS5Cl was maintained at 2:2:6. The test methods for Comparative Example 2 and the solid-state battery were the same as those in the above Examples 1-6, except for the different solid electrolyte materials. The charge-discharge curves are as Figure 9 shown.

[0054] Using the high-voltage organic composite material obtained in Example 6 as the positive electrode, Li3InCl6 as the solid electrolyte layer close to the positive electrode, Li6PS5Cl as the solid electrolyte layer close to the negative electrode, and Li-In alloy as the negative electrode, a solid-state battery was assembled using a die battery in a glove box under an argon atmosphere. Electrochemical charge-discharge tests were performed on the solid-state battery at room temperature, and the charge-discharge cut-off voltage was 2.90 - 4.30 V (vs. Li + / Li), and the charge-discharge current density was 1C (1C = 218 mA g -1 , o-C6O2Cl4). Figure 10 This is the long-cycle performance of this all-solid-state lithium-ion battery at room temperature. It can be seen that the high-voltage organic composite material involved in the present invention can be applied to all-solid-state batteries at room temperature, providing a feasible option for broadening the applicable materials of all-solid-state batteries.

[0055] Finally, it should be noted that the above embodiments are only used to illustrate the technical solutions of the present invention, rather than to limit it; although the present invention has been described in detail with reference to the foregoing embodiments, those of ordinary skill in the art should understand that they can still modify the technical solutions described in the foregoing embodiments, or perform equivalent replacements on some or all of the technical features; and these modifications or replacements do not make the essence of the corresponding technical solutions deviate from the scope of the technical solutions of the embodiments of the present invention.

Claims

1. A preparation method of a high-voltage organic cathode composite material for all-solid-state batteries, characterized in that: Mix an organic cathode material, a conductive additive, and a chloride solid electrolyte in a mass ratio of 2:2:6, and prepare the cathode composite material by mechanochemical synthesis under an inert gas or vacuum condition; the ball milling speed is 350 rpm and the ball milling time is 4 hours; wherein: The organic cathode material is a 2,3,5,6-substituted product of 1,4-benzoquinone or a 3,4,5,6-substituted product of 1,2-benzoquinone, specifically including but not limited to 2,3,5,6-tetrachloro-1,4-benzoquinone, 2,3-dichloro-5,6-dicyano-1,4-benzoquinone, 2,3,5,6-tetrafluoro-1,4-benzoquinone, and 3,4,5,6-tetrachloro-1,2-benzoquinone; the chloride solid electrolyte precursor is selected from one or a combination of indium chloride (InCl3), yttrium chloride (YCl3), scandium chloride (ScCl3), zirconium chloride (ZrCl4), hafnium chloride (HfCl4), aluminum chloride (AlCl3), and niobium chloride (NbCl5); wherein, the combination mode of the precursors includes but is not limited to: indium chloride (InCl3) and zirconium chloride (ZrCl4) are mixed in a molar ratio of 1:1, or indium chloride (InCl3), aluminum chloride (AlCl3), and niobium chloride (NbCl5) are mixed in a molar ratio of 1:1:

1.

2. The preparation method according to claim 1, characterized in that: The high-voltage organic cathode composite material for all-solid-state batteries prepared by mechanochemical synthesis has a general composition formula of: Li x MCl x+y (60 wt.%)|C 6+u N u O2Cl 4-u-z F z (20 wt.%)|Conductive additive (20 wt.%) 0≤x≤3; 3≤y≤5 0≤u≤4; 0≤z≤4 Wherein the chloride solid electrolyte contains elements Li, M, and Cl, where M is one or more elements selected from In, Y, Sc, Zr, Hf, Al, Nb, and Ta; the organic cathode material C 6+u N u O2Cl 4-u-z F z is a 2,3,5,6-substituted product of 1,4-benzoquinone or a 3,4,5,6-substituted product of 1,2-benzoquinone; The working potential of the organic active material in the all-solid-state battery to lithium metal of the high-voltage organic cathode composite material is 3.3-3.6 V.

3. The high-voltage organic cathode composite material for all-solid-state batteries according to claim 1, characterized in that: The high-voltage organic cathode composite material has an amorphous or mixed-phase characteristic composed of amorphous and crystalline phases, and the crystal structure of the crystalline phase belongs to C2 / m, Pnma, Pm1 space group.

4. A lithium-ion battery, characterized in that: The lithium-ion battery includes a cathode, an anode, and a solid electrolyte layer located between the cathode and the anode, wherein at least one of the cathode, the anode, and the solid electrolyte layer contains the high-voltage organic cathode composite material for all-solid-state batteries according to any one of claims 1-3.

5. Application of the high-voltage organic cathode composite material for all-solid-state batteries prepared by the method of claim 1 in meeting the more diverse requirements of solid-state batteries.

6. Application of the high-voltage organic cathode composite material for all-solid-state batteries prepared by the method of claim 1 in effectively suppressing interfacial side reactions and improving the cycle life and safety of the battery.

Images