A Composite Cathode Material with Dual Active Substances for All-Solid-State Batteries and Its Application

Abstract

The present invention belongs to the technical field of battery materials, and provides a dual-active material composite cathode material for all-solid-state batteries and its application. The active materials of the composite cathode material for all-solid-state batteries of the present invention include a rigid cathode material and a plastic cathode material, and the mass ratio of the rigid cathode material to the plastic cathode material is 50-80:20-50, and the mass fraction of the active materials in the composite cathode material is ≥95%. The composite cathode material for all-solid-state batteries of the present invention contains dual active materials of a rigid cathode material and a plastic cathode material. The plastic cathode material can not only provide ion channels, but also provide energy through redox reactions, improving the energy density of all-solid-state batteries; compared with traditional single-active material composite cathode materials, the mass energy density and volume energy density of the dual-active material all-solid-state battery composite cathode material of the present invention are increased by more than 30% and 15% respectively.

Description

Technical Field

[0001] The present invention relates to the technical field of battery materials, and particularly relates to a dual-active material composite cathode material for all-solid-state batteries and its application. Background Art

[0002] Currently, the energy density of traditional liquid lithium-ion batteries has approached the theoretical limit. For example, the energy density of lithium iron phosphate batteries has reached 140 Wh / kg (BYD), and the energy density of ternary lithium batteries has reached 265 Wh / kg (CATL). In order to break through the energy density bottleneck, all-solid-state lithium batteries using inorganic solid electrolytes to replace organic electrolytes have emerged. The theoretical energy density is as high as 500 Wh / kg, but the current energy density of all-solid-state lithium batteries is about 360 Wh / kg. To reach the theoretical value of 500 Wh / kg of energy density, a series of technical problems completely different from traditional liquid lithium batteries need to be solved.

[0003] In all-solid-state lithium batteries, plastic solid electrolytes act as ion transport channels. Since oxide cathodes are rigid and have low ionic conductivity, it is necessary to first mix the plastic solid electrolytes acting as ion transport channels with active materials, binders, and conductive agents in a certain proportion and then cold-press them to form a composite cathode. In order to achieve efficient ion transport, the plastic solid electrolyte in the composite cathode of all-solid-state lithium batteries needs to reach a certain volume fraction. Since the density of most plastic solid electrolytes is higher than that of liquid electrolytes, when filling the pores with the same volume fraction in the composite cathode, the mass fraction of the plastic solid electrolyte in the composite cathode of all-solid-state lithium batteries needs to be higher, which means that the content of active materials will be lower. Currently, in order to ensure a good ion conductive network in the composite cathode of all-solid-state lithium batteries, the content of the plastic solid electrolyte needs to be greater than 20 wt%. Therefore, the content of active materials in the composite cathode of all-solid-state lithium batteries based on rigid oxide cathodes is only 70 wt%, and it is difficult to exceed 85 wt%.

[0004] The solid-liquid physical contact of traditional liquid lithium-ion batteries can ensure that the content of active materials in the composite cathode is as high as 95 wt%. It is estimated that for composite cathode materials based on rigid oxide cathodes, for every 10 wt% increase in the content of active materials, the energy density of the battery increases by about 14.6%. Therefore, while ensuring good solid-solid physical contact, increasing the content of active materials in the composite cathode from 70 wt% to 95 wt% is the key to further improving the energy density of all-solid-state lithium batteries. Summary of the Invention

[0005] The purpose of the present invention is to provide a dual-active material composite cathode material for all-solid-state batteries and its application in view of the deficiencies of the prior art.

[0006] To achieve the above-mentioned invention purpose, the present invention provides the following technical solutions:

[0007] The present invention provides a composite cathode material with dual active substances for all-solid-state batteries. The active substances of the composite cathode material include a rigid cathode material and a plastic cathode material. The mass ratio of the rigid cathode material to the plastic cathode material is 50-80:20-50, and the mass fraction of the active substances in the composite cathode material is ≥95%.

[0008] Preferably, the rigid cathode material is a ternary oxide cathode material, a binary halide cathode material or a binary sulfide cathode material, and the plastic cathode material is a ternary halide cathode material.

[0009] Preferably, the chemical general formula of the ternary oxide cathode material is A x M y O z and / or A x' M y' (N a O b ) z' , wherein A independently includes Li or Na, M independently includes one or more of Ti, V, Cr, Mn, Fe, Co, Ni and Cu, N includes one or more of P, S and W, 0≤x≤2, 1≤y≤2, 1≤z≤4, 0≤x'≤3, 0≤y'≤1, 0≤a≤1, 0≤b≤1, 1≤z'≤4.

[0010] Preferably, the chemical general formula of the binary halide cathode material is M'X c , wherein M' includes one or more of Mg, Al, Si, P, Ca, Ti, V, Cr, Mn, Fe, Co, Ni, Cu, Zn, Ga, Zr and Nb, X includes one or more of F, Cl, Br and I, and 2≤c≤6.

[0011] Preferably, the chemical general formula of the binary sulfide cathode material is M" c' S d , wherein M" includes one or more of Ti, V, Mn, Fe, Co, Ni, Mo and Sn, 1≤c'≤4, 1≤d≤6.

[0012] Preferably, the chemical general formula of the ternary halide cathode material is A' m D n B e , wherein A' includes Li or Na, D includes one or more of Ti, V, Cr, Mn, Fe, Co, Ni and Cu, B includes one or more of F, Cl, Br, I, O and S, 1≤m≤4, 0.1≤n≤1, 3≤e≤8.

[0013] Preferably, the composite cathode material further comprises a binder and a conductive agent.

[0014] The present invention also provides an application of the dual-active material composite cathode material for all-solid-state batteries in all-solid-state batteries.

[0015] Advantages of the present invention:

[0016] The dual-active material composite cathode material for all-solid-state batteries of the present invention contains dual-active materials of a rigid cathode material and a plastic cathode material. The plastic cathode material therein can not only provide ion channels but also provide energy through redox reactions. When applied to all-solid-state batteries, the charge-discharge curve has characteristic charge-discharge platforms of the two active materials, which can improve the energy density of all-solid-state batteries. Compared with the traditional single-active material composite cathode material composed of an oxide cathode and a plastic electrolyte, the mass energy density and volume energy density of the dual-active material all-solid-state battery composite cathode material of the present invention are increased by more than 30% and 15% respectively. Description of the Drawings

[0017] Figure 1 For LiCoO of Example 1 2 +Li 3 TiCl 6 Scanning electron microscope image of the dual-active material all-solid-state battery composite cathode material.

[0018] Figure 2 For LiCoO of Example 1 2 +Li 3 TiCl 6 First-cycle charge-discharge curve of the dual-active material all-solid-state battery composite cathode material in an all-solid-state lithium battery.

[0019] Figure 3 For LiNi of Example 2 0.5 Mn 0.3 Co 0.2 O 2 +Li 3 TiCl 6 First-cycle charge-discharge curve of the dual-active material all-solid-state battery composite cathode material in an all-solid-state lithium battery.

[0020] Figure 4 For LiNi of Example 3 0.6 Mn 0.3 Co 0.1 O 2 +Li 3 TiCl 6 First-cycle charge-discharge curve of the dual-active material all-solid-state battery composite cathode material in an all-solid-state lithium battery.

[0021] Figure 5For the LiNi of Example 4 0.88 Mn 0.03 Co 0.09 O 2 +Li 3 TiCl 6 First charge-discharge curve of the composite cathode material for a dual-active-material all-solid-state battery in an all-solid-state lithium battery.

[0022] Figure 6 For the LiFePO of Example 5 4 +Li 3 TiCl 6 First charge-discharge curve of the composite cathode material for a dual-active-material all-solid-state battery in an all-solid-state lithium battery.

[0023] Figure 7 For the LiMn of Example 6 2 O 4 +Li 3 TiCl 6 First charge-discharge curve of the composite cathode material for a dual-active-material all-solid-state battery in an all-solid-state lithium battery.

[0024] Figure 8 For the Li of Example 7 2 MnO 3 ·LiNi 1 / 3 Co 1 / 3 Mn 1 / 3 O 2 +Li 3 TiCl 6 First charge-discharge curve of the composite cathode material for a dual-active-material all-solid-state battery in an all-solid-state lithium battery.

[0025] Figure 9 For the FeCl of Example 8 3 +Li 3 TiCl 6 First charge-discharge curve of the composite cathode material for a dual-active-material all-solid-state battery in an all-solid-state lithium battery.

[0026] Figure 10 For the VCl of Example 9 3 +Li 3 TiCl 6 First charge-discharge curve of the composite cathode material for a dual-active-material all-solid-state battery in an all-solid-state lithium battery.

[0027] Figure 11 For the TiS of Example 10 2 +Li 3 TiCl 6 First charge-discharge curve of the composite cathode material for a dual-active-material all-solid-state battery in an all-solid-state lithium battery. Detailed implementation mode

[0028] The present invention provides a composite cathode material for all-solid-state batteries with dual active substances. The active substances of the composite cathode material include a rigid cathode material and a plastic cathode material. The mass ratio of the rigid cathode material to the plastic cathode material is preferably 50-80:20-50, more preferably 50-70:25-45, and still more preferably 55-65:27-35; the mass fraction of the active substances in the composite cathode material is preferably ≥95%, more preferably ≥97%.

[0029] In the present invention, the rigid cathode material is preferably a ternary oxide cathode material, a binary halide cathode material or a binary sulfide cathode material, and the plastic cathode material is preferably a ternary halide cathode material.

[0030] In the present invention, the chemical general formula of the ternary oxide cathode material is preferably A x M y O z and / or A x' M y' (N a O b ) z' , wherein, A preferably independently includes Li or Na, M preferably independently includes one or more of Ti, V, Cr, Mn, Fe, Co, Ni and Cu, and N preferably includes one or more of P, S and W; the value of x is preferably 0≤x≤2, more preferably 0.5≤x≤1; the value of y is preferably 1≤y≤2, more preferably 1≤y≤1.5; the value of z is preferably 1≤z≤4, more preferably 2≤z≤4; the value of x' is preferably 0≤x'≤3, more preferably 1≤x'≤2; the value of y' is preferably 0≤y'≤1, more preferably 0.5≤y'≤1; the value of a is preferably 0≤a≤1, more preferably 0.25≤a≤0.5; the value of b is preferably 0≤b≤1, more preferably 0.5≤b≤1; the value of z' is preferably 1≤z'≤4, more preferably 2≤z'≤4.

[0031] In the ternary oxide cathode material of the present invention, when M includes several of Ti, V, Cr, Mn, Fe, Co, Ni and Cu, the value of y is preferably the sum of the values of all elements of M.

[0032] In the present invention, the chemical general formula of the binary halide cathode material is preferably M'X c, wherein M' preferably comprises one or more of Mg, Al, Si, P, Ca, Ti, V, Cr, Mn, Fe, Co, Ni, Cu, Zn, Ga, Zr and Nb, and X preferably comprises one or more of F, Cl, Br and I; the value of c is preferably 2 ≤ c ≤ 6, more preferably 3 ≤ c ≤ 5.

[0033] In the present invention, the chemical general formula of the binary sulfide cathode material is preferably M" c' S d , wherein M" preferably comprises one or more of Ti, V, Mn, Fe, Co, Ni, Mo and Sn; the value of c' is preferably 1 ≤ c' ≤ 4, more preferably 1 ≤ c' ≤ 2; the value of d is preferably 1 ≤ d ≤ 6, more preferably 2 ≤ d ≤ 4.

[0034] In the present invention, the chemical general formula of the ternary halide cathode material is preferably A' m D n B e , wherein A' preferably comprises Li or Na, D preferably comprises one or more of Ti, V, Cr, Mn, Fe, Co, Ni and Cu, and B preferably comprises one or more of F, Cl, Br, I, O and S; the value of m is preferably 1 ≤ m ≤ 4, more preferably 2 ≤ m ≤ 3; the value of n is preferably 0.1 ≤ n ≤ 1, more preferably 0.5 ≤ n ≤ 1; the value of e is preferably 3 ≤ e ≤ 8, more preferably 4 ≤ e ≤ 6.

[0035] In the present invention, the composite cathode material preferably further comprises a binder and a conductive agent.

[0036] The present invention also provides an application of the all-solid-state battery dual-active material composite cathode material in an all-solid-state battery.

[0037] The technical solutions provided by the present invention are described in detail below with reference to the embodiments, but they should not be construed as limiting the protection scope of the present invention.

[0038] Example 1

[0039] The dual active materials in the composite cathode material are LiCoO with a mass ratio of 70:27 2 and Li 3 TiCl 6 , and the mass fraction of the dual active materials in the composite cathode material is 97%, and the mass ratio of the binder polyvinylidene fluoride to the conductive agent carbon black is 1:3.

[0040] The composite cathode material of this example is denoted as LiCoO 2 +Li 3 TiCl 6 composite cathode material.

[0041] Example 2

[0042] The dual active materials in the composite cathode material are LiNi with a mass ratio of 70:27 0.5 Mn 0.3 Co 0.2 O 2 and Li 3 TiCl 6 , and the mass fraction of the dual active materials in the composite cathode material is 97%. The mass ratio of the binder polyvinylidene fluoride to the conductive agent carbon black is 1:3.

[0043] The composite cathode material of this example is denoted as LiNi 0.5 Mn 0.3 Co 0.2 O 2 +Li 3 TiCl 6 composite cathode material.

[0044] Example 3

[0045] The dual active materials in the composite cathode material are LiNi with a mass ratio of 70:27 0.6 Mn 0.3 Co 0.1 O 2 and Li 3 TiCl 6 , and the mass fraction of the dual active materials in the composite cathode material is 97%. The mass ratio of the binder polyvinylidene fluoride to the conductive agent carbon black is 1:3.

[0046] The composite cathode material of this example is denoted as LiNi 0.6 Mn 0.3 Co 0.1 O 2 +Li 3 TiCl 6 composite cathode material.

[0047] Example 4

[0048] The dual active materials in the composite cathode material are LiNi with a mass ratio of 70:27 0.88 Mn 0.03 Co 0.09 O 2 and Li 3 TiCl 6 , and the mass fraction of the dual active materials in the composite cathode material is 97%. The mass ratio of the binder polyvinylidene fluoride to the conductive agent carbon black is 1:3.

[0049] The composite cathode material of this example is denoted as LiNi 0.88 Mn0.03 Co 0.09 O 2 +Li 3 TiCl 6 Composite positive electrode material.

[0050] Example 5

[0051] The dual active materials in the composite positive electrode material are LiFePO with a mass ratio of 70:25 4 and Li 3 TiCl 6 , and the mass fraction of the dual active materials in the composite positive electrode material is 95%, and the mass ratio of the binder polyvinylidene fluoride to the conductive agent carbon black is 1:3.

[0052] The composite positive electrode material of this example is denoted as LiFePO 4 +Li 3 TiCl 6 Composite positive electrode material.

[0053] Example 6

[0054] The dual active materials in the composite positive electrode material are LiMn with a mass ratio of 70:25 2 O 4 and Li 3 TiCl 6 , and the mass fraction of the dual active materials in the composite positive electrode material is 95%, and the mass ratio of the binder polyvinylidene fluoride to the conductive agent carbon black is 1:3.

[0055] The composite positive electrode material of this example is denoted as LiMn 2 O 4 +Li 3 TiCl 6 Composite positive electrode material.

[0056] Example 7

[0057] The dual active materials in the composite positive electrode material are Li 2 MnO 3 ·LiNi 1 / 3 Co 1 / 3 Mn 1 / 3 O 2 and Li 3 TiCl 6 , and the mass fraction of the dual active materials in the composite positive electrode material is 95%, and the mass ratio of the binder polyvinylidene fluoride to the conductive agent carbon black is 1:3. In the dual active materials, Li 2 MnO 3 in LiNi 1 / 3 Co 1 / 3 Mn 1 / 3 O2 The phase content in it is 50%.

[0058] The composite cathode material of this embodiment is denoted as Li 2 MnO 3 ·LiNi 1 / 3 Co 1 / 3 Mn 1 / 3 O 2 +Li 3 TiCl 6 composite cathode material.

[0059] Example 8

[0060] The dual active substances in the composite cathode material are FeCl with a mass ratio of 50:45 3 and Li 3 TiCl 6 , and the mass fraction of the dual active substances in the composite cathode material is 95%. The mass ratio of the binder polyvinylidene fluoride to the conductive agent carbon black is 1:3.

[0061] The composite cathode material of this embodiment is denoted as FeCl 3 +Li 3 TiCl 6 composite cathode material.

[0062] Example 9

[0063] The dual active substances in the composite cathode material are VCl with a mass ratio of 50:45 3 and Li 3 TiCl 6 , and the mass fraction of the dual active substances in the composite cathode material is 95%. The mass ratio of the binder polyvinylidene fluoride to the conductive agent carbon black is 1:3.

[0064] The composite cathode material of this embodiment is denoted as VCl 3 +Li 3 TiCl 6 composite cathode material.

[0065] Example 10

[0066] The dual active substances in the composite cathode material are TiS with a mass ratio of 50:45 2 and Li 3 TiCl 6 , and the mass fraction of the dual active substances in the composite cathode material is 95%. The mass ratio of the binder polyvinylidene fluoride to the conductive agent carbon black is 1:3.

[0067] The composite cathode material of this embodiment is denoted as TiS 2 +Li 3 TiCl 6Composite positive electrode material.

[0068] The composite positive electrode materials of Examples 1 to 10 were respectively made into composite positive electrode sheets with an average thickness of 40 μm by a dry film-forming technique (rolling temperature: 100 °C). A Li-In alloy was used as the negative electrode, and Li 2 ZrCl 6 and Li 6 PS 5 Cl were used as the solid electrolyte to assemble a all-solid-state lithium battery.

[0069] The first charge-discharge curves of the all-solid-state batteries assembled from Examples 1 to 10 were measured at 25 °C and 0.1C, as Figures 2 to 11 shown.

[0070] It can be seen from Figure 2 that the first-cycle Coulombic efficiency of the all-solid-state lithium battery assembled with the LiCoO 2 +Li 3 TiCl 6 composite positive electrode material was 110.7%, and the discharge specific capacity was 212 mAh / g, which was 51.4% higher than that of the all-solid-state lithium battery assembled with the single LiCoO 2 composite positive electrode material (140 mAh / g), and 11.6% higher than that of the all-solid-state lithium battery assembled with the single Li 3 TiCl 6 composite positive electrode material (when 2 Li + were deintercalated / inserted, 190 mAh / g).

[0071] It can be seen from Figure 3 that the first-cycle Coulombic efficiency of the all-solid-state lithium battery assembled with the LiNi 0.5 Mn 0.3 Co 0.2 O 2 +Li 3 TiCl 6 composite positive electrode material was 122.2%, and the discharge specific capacity was 284 mAh / g, which was 67.1% higher than that of the all-solid-state lithium battery assembled with the single LiNi 0.5 Mn 0.3 Co 0.2 O 2 composite positive electrode material (170 mAh / g), and 49.5% higher than that of the all-solid-state lithium battery assembled with the single Li 3 TiCl 6 composite positive electrode material (when 2 Li + were deintercalated / inserted, 190 mAh / g).

[0072] It can be seen from Figure 4 that LiNi 0.6 Mn0.3 Co 0.1 O 2 + Li 3 TiCl 6 The initial Coulombic efficiency of the all - solid - state lithium battery assembled with the composite cathode material is 109.4%, and the discharge specific capacity is 266 mAh / g, which is higher than that of the single LiNi 0.6 Mn 0.3 Co 0.1 O 2 The discharge specific capacity of the all - solid - state lithium battery assembled with the composite cathode material (180 mAh / g) is increased by 47.8% compared with that of the single Li 3 TiCl 6 The discharge specific capacity of the all - solid - state lithium battery assembled with the composite cathode material (when 2 Li are de - intercalated / inserted, 190 mAh / g) is increased by 40%. +

[0073] It can be seen from Figure 5 that for LiNi 0.88 Mn 0.03 Co 0.09 O 2 + Li 3 TiCl 6 The initial Coulombic efficiency of the all - solid - state lithium battery assembled with the composite cathode material is 104.3%, and the discharge specific capacity is 306 mAh / g, which is higher than that of the single LiNi 0.88 Mn 0.03 Co 0.09 O 2 The discharge specific capacity of the all - solid - state lithium battery assembled with the composite cathode material (200 mAh / g) is increased by 53% compared with that of the single Li 3 TiCl 6 The discharge specific capacity of the all - solid - state lithium battery assembled with the composite cathode material (when 2 Li are de - intercalated / inserted, 190 mAh / g) is increased by 61%. +

[0074] It can be seen from Figure 6 that for LiFePO 4 + Li 3 TiCl 6 The initial Coulombic efficiency of the all - solid - state lithium battery assembled with the composite cathode material is 94.6%, and the discharge specific capacity is 212 mAh / g, which is higher than that of the single LiFePO 4 The discharge specific capacity of the all - solid - state lithium battery assembled with the composite cathode material (140 mAh / g) is increased by 55% compared with that of the single Li 3 TiCl 6 The discharge specific capacity of the all - solid - state lithium battery assembled with the composite cathode material (when 1 Li is de - intercalated / inserted, 95 mAh / g) is increased by 123.2%. +

[0075] It can be seen from Figure 7 that the first-cycle Coulombic efficiency of the all-solid-state lithium battery assembled with the LiMn 2 O 4 +Li 3 TiCl 6 composite cathode material is 91%, and the discharge specific capacity is 136.5 mAh / g, which is 24.1% higher than that of the all-solid-state lithium battery assembled with a single LiMn 2 O 4 composite cathode material (110 mAh / g), and 43.7% higher than that of the all-solid-state lithium battery assembled with a single Li 3 TiCl 6 composite cathode material (when one Li + is deintercalated, 95 mAh / g).

[0076] It can be seen from Figure 8 that the first-cycle Coulombic efficiency of the all-solid-state lithium battery assembled with the Li 2 MnO 3 ·LiNi 1 / 3 Co 1 / 3 Mn 1 / 3 O 2 +Li 3 TiCl 6 composite cathode material is 81.6%, and the discharge specific capacity is 253 mAh / g, which is 15% higher than that of the all-solid-state lithium battery assembled with a single Li 2 MnO 3 ·LiNi 1 / 3 Co 1 / 3 Mn 1 / 3 O 2 composite cathode material (220 mAh / g), and 166.3% higher than that of the all-solid-state lithium battery assembled with a single Li 3 TiCl 6 composite cathode material (when one Li + is deintercalated, 95 mAh / g).

[0077] It can be seen from Figure 9 that the first-cycle Coulombic efficiency of the all-solid-state lithium battery assembled with the FeCl 3 +Li 3 TiCl 6 composite cathode material is 115.8%, and the discharge specific capacity is 162.9 mAh / g, which is 35.8% higher than that of the all-solid-state lithium battery assembled with a single FeCl 3 composite cathode material (120 mAh / g), and higher than that of the all-solid-state lithium battery assembled with a single Li 3 TiCl 6The discharge specific capacity of the all-solid-state lithium battery assembled with the composite cathode material (when 1 Li is deintercalated / inserted + , 95 mAh / g) is increased by 71.5%.

[0078] As can be seen from Figure 10 , VCl 3 +Li 3 TiCl 6 The first-cycle Coulombic efficiency of the all-solid-state lithium battery assembled with the composite cathode material is 107.6%, and the discharge specific capacity is 167.3 mAh / g, which is 28.7% higher than that of the all-solid-state lithium battery assembled with the single VCl 3 composite cathode material (130 mAh / g), and 76.1% higher than that of the all-solid-state lithium battery assembled with the single Li 3 TiCl 6 composite cathode material (when 1 Li is deintercalated / inserted + , 95 mAh / g).

[0079] As can be seen from Figure 11 , TiS 2 +Li 3 TiCl 6 The first-cycle Coulombic efficiency of the all-solid-state lithium battery assembled with the composite cathode material is 115.8%, and the discharge specific capacity is 310.5 mAh / g, which is 55.3% higher than that of the all-solid-state lithium battery assembled with the single TiS 2 composite cathode material (200 mAh / g), and 63.4% higher than that of the all-solid-state lithium battery assembled with the single Li 3 TiCl 6 composite cathode material (when 2 Li are deintercalated / inserted + , 190 mAh / g).

[0080] The above are only the preferred embodiments of the present invention. It should be noted that for those of ordinary skill in the art, without departing from the principle of the present invention, several improvements and modifications can be made, and these improvements and modifications should also be regarded as the protection scope of the present invention.

Claims

1. A dual-active material composite positive electrode material for an all-solid-state battery, characterized in that: The composite positive electrode material is composed of an active substance, a binder and a conductive agent, wherein the active substance of the composite positive electrode material is composed of a rigid positive electrode material and a plastic positive electrode material, wherein the mass ratio of the rigid positive electrode material to the plastic positive electrode material is 50-80:20-50, and the mass fraction of the active substance in the composite positive electrode material is ≥95%; The rigid positive electrode material is a ternary oxide positive electrode material, a binary halide positive electrode material or a binary sulfide positive electrode material, and the plastic positive electrode material is a ternary halide positive electrode material; The chemical formula of the ternary halide positive electrode material is A' m D n B e , wherein A' is Li or Na, D is one of Ti, V, Cr, Mn, Fe, Co, Ni and Cu, B is one of F, Cl, Br, I, O and S, 1≤m≤4, 0.1≤n≤1, 3≤e≤8.

2. The all-solid-state battery dual-active material composite positive electrode material according to claim 1, characterized in that: The chemical formula of the ternary oxide positive electrode material is A x M y O z and / or A x' M y' (N a O b ) z' , wherein A is independently Li or Na, M is independently one or more of Ti, V, Cr, Mn, Fe, Co, Ni and Cu, N is one or more of P, S and W, 0≤x≤2, 1≤y≤2, 1≤z≤4, 0≤x'≤3, 0≤y'≤1, 0≤a≤1, 0≤b≤1, 1≤z'≤4.

3. The all-solid-state battery dual-active material composite positive electrode material according to claim 2, characterized in that: The chemical formula of the binary halide positive electrode material is M'X c , wherein M' is one of Mg, Al, Si, P, Ca, Ti, V, Cr, Mn, Fe, Co, Ni, Cu, Zn, Ga, Zr and Nb, X is one of F, Cl, Br and I, and 2≤c≤6.

4. The all-solid-state battery dual-active material composite positive electrode material according to claim 3, characterized in that: The chemical formula of the binary sulfide positive electrode material is M" c' S d , wherein M" is one of Ti, V, Mn, Fe, Co, Ni, Mo and Sn, 1≤c'≤4, 1≤d≤6.

5. Application of the dual-active material composite positive electrode material for all-solid-state batteries according to any one of claims 1 to 4 in all-solid-state batteries.

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