Solid-state battery electrode and application thereof

Abstract

The invention relates to a solid-state battery electrode and application thereof. The solid-state battery electrode comprises an electrode layer; the material of the electrode layer comprises an active material and a thermal strain regulation and control material; the thermal strain regulation and control material is distributed among particles of the active material, the linear thermal expansion coefficient alpha of the thermal strain regulation and control material is in a range of-20.0 * 10 <-6 > K <-1 > < = alpha < 0 * 10 <-6 > K <-1 > within a temperature range of-100 DEG C to 100 DEG C, and the thermal strain regulation and control material expands in volume along with temperature reduction and shrinks in volume along with temperature rise; the sum of the mass of the active material and the thermal strain regulation and control material accounts for 80%-100% of the mass of the electrode layer, and the mass ratio of the active material to the thermal strain regulation and control material is 100: (0.1-20).

Description

Technical Field

[0001] The present invention relates to the technical field of electrochemical energy storage, and in particular to a solid-state battery electrode and applications thereof. Background Art

[0002] In recent years, with the development of electric vehicles, electric ships, and electric aircraft, the demand for lithium-ion batteries has also increased. Batteries with high specific energy, long life, low cost, and safety are urgently needed. Solid-state batteries, due to the introduction of solid-state electrolytes, can significantly improve battery safety performance and are compatible with higher energy density positive and negative electrode materials (such as metallic lithium anodes), thereby increasing the overall energy density of the battery.

[0003] Solid electrolyte materials can be divided into oxides, sulfides, halides and polymers according to their components. Among them, oxide solid electrolyte materials include Li 1.5 Al 0.5 Ge 1.5 (PO4)3 and Li 1.3 Al 0.3 Ti 1.7 (PO4)3, Li7La3Zr2O with garnet structure 12 and the perovskite structure of Li5La3Ti2O 12 Oxides have the highest thermal stability and mechanical strength, and have good room temperature ionic conductivity and electrochemical stability, but they are too rigid, have poor processing performance, and are difficult to prepare on a large scale and at low cost; sulfides have the highest room temperature ionic conductivity and can be divided into glass phase (such as Li2S-P2S5), silver germanium sulfide such as Li6PS5X (X=Cl, Br, I), Li 10 GeP2S 12 And thio-LISICON structure electrolyte. The most representative one is Li-ion battery reported by Professor Kanno's research group at Tokyo Institute of Technology in Japan. 10 GeP2S 12 (LGPS) and Li 9.54 Si 1.74 P 1.44 S 11.7 C l0.3(LSPSC) materials, among which LGPS has a room temperature ionic conductivity of up to 12mS / cm, which exceeds that of commercial electrolytes, while LSPSC has a room temperature ionic conductivity of 25mS / cm, which is the solid electrolyte with the highest ionic conductivity at present. However, sulfides have a narrow electrochemical window, are unstable in air, easily produce harmful hydrogen sulfide gas, and are relatively expensive; polymer solid electrolytes can be divided into polyethylene oxide (PEO), polyacrylonitrile (PAN), polysiloxane, etc. according to the matrix. Their room temperature ionic conductivity is relatively low, but due to their high flexibility, they are easy to produce and prepare on a large scale, and are basically compatible with existing battery production processes. The discovery of these lithium ion conductor materials has promoted the rapid development of all-solid-state lithium batteries, but the all-solid-state lithium batteries reported so far have not yet shown satisfactory electrochemical performance. The main problem they have is the interface problem between solids.

[0004] At the particle scale, all-solid-state batteries have a variety of solid-solid contact interfaces, most of which are point contacts, including metal lithium-electrolyte, electrolyte particle-electrolyte particle, cathode particle-electrolyte particle, conductive additive-cathode particle, cathode current collector-cathode particle, cathode cracks, etc. Among them, the solid-solid contact problem between the electrode and the solid electrolyte in all-solid-state batteries is particularly prominent.

[0005] For composite electrodes, the accompanying lithium ion intercalation and deintercalation, or phase transition, of the electrode materials during charge and discharge inevitably causes volume changes and generates internal stress within the limited internal battery space, leading to an increase in the interfacial gaps mentioned above. During charging, the delithiation of the positive electrode material increases the Coulomb repulsion between layers along the c-axis of the positive electrode material's microscopic crystal structure, resulting in macroscopic structural expansion. For the negative electrode material, the volume change is even more significant. For example, during charging, the volume expansion rate of graphite negative electrodes is around 10%, while that of silicon negative electrodes is as high as 320%. Lithium metal negative electrodes, ignoring the substrate, experience an infinite volume change. Therefore, the volume expansion of both positive and negative electrode materials during charging can generate significant stress within the battery, impacting its cycle stability and lifespan. In particular, the significant volume expansion of the negative electrode during charging can excessively compress the electrode sheet, blocking lithium ion migration channels, hindering ion transport, and deteriorating battery performance. In addition, the repeated volume expansion and contraction during multiple cycles will also lead to a continuous decrease in the contact area between the active material and the electrolyte, causing a gradual increase in internal resistance and an exponential decay of the battery capacity.

[0006] In addition, the ionic conductivity and ion migration number of polymer solid electrolytes are low, and the ionic conductivity becomes even lower as the temperature decreases, making them unusable in low-temperature solid-state batteries. Inorganic solid electrolyte materials (oxides, sulfides, halides, etc.) have high ionic conductivity, but because they are rigid materials with very poor elasticity, they expand and contract with temperature. At low temperatures, inorganic solid electrolyte materials exhibit the characteristic of shrinking in volume, resulting in gaps between the solid electrolytes, causing the area of ​​ion transmission channels to decrease and the internal resistance of the battery to increase. When the temperature is below -20°C, the solid particles shrink rapidly due to the cold, causing the physical gaps to increase sharply, resulting in a short circuit in ion transmission, resulting in the inability of ions to conduct, causing the low-temperature solid-state battery to fail and become unusable; in high-temperature environments, the inorganic solid electrolyte material exhibits the characteristic of volume expansion, and the internal pressure of the battery increases. In extreme cases, the stress between the particles is too large and may cause them to break.

[0007] In summary, the huge volume changes caused by the electrochemical cycle process of the electrode material lead to large stresses inside the battery. In addition, the volume changes caused by thermal expansion and contraction between the particles inside the electrode material, between the particles inside the solid electrolyte material, and between the electrode and the solid electrolyte in high and low temperature environments cause gaps between the particles and lead to interface contact problems. These have seriously restricted the application of solid-state batteries. In particular, the increase in internal resistance caused by the interface expansion and contraction effect of the electrode particle level at low temperatures is an important factor leading to the deterioration of the low-temperature performance of solid-state batteries. Therefore, there is an urgent need to improve the electrode materials and pole pieces of solid-state batteries to solve the serious interface problems between the electrode and the electrolyte. Summary of the Invention

[0008] The purpose of the present invention is to provide a solid-state battery electrode and its application to address the problems and technical defects of the existing technology, such as increased internal pressure of the battery, solid-solid interface and battery failure caused by volume changes of solid-state battery electrode particles. By introducing thermal strain control materials into the electrode structure, it is possible to effectively improve the interface contact problems between the solid-state battery electrode active material and the solid electrolyte, and between the active material materials, effectively alleviate the accumulation of solid-solid interface stress, and compensate for the internal stress of the battery caused by the volume change of the positive electrode active material particles due to temperature through the volume contraction of the thermal strain control materials at high temperatures and the volume expansion at low temperatures, thereby improving the interface contact stability and ion transmission efficiency, thereby significantly improving the cycle stability and high and low temperature performance of the solid-state battery.

[0009] To achieve the above objectives, in a first aspect, the present invention provides a solid-state battery electrode, comprising an electrode layer;

[0010] The material of the electrode layer includes: an active material and a thermal strain regulating material; the thermal strain regulating material is distributed between the particles of the active material, and within the temperature range of -100°C to 100°C, the linear thermal expansion coefficient α of the thermal strain regulating material is -20.0×10 -6 K -1 ≤α<0×10 -6 K -1 The volume expands as the temperature decreases and contracts as the temperature increases.

[0011] The sum of the mass of the active material and the thermal strain regulating material accounts for 80%-100% of the mass of the electrode layer, and the mass ratio of the active material to the thermal strain regulating material is 100:0.1-20.

[0012] Preferably, within the temperature range of -60°C to 100°C, the linear thermal expansion coefficient α of the thermal strain regulating material is -5.0×10 -6 K -1 ≤α≤-0.1×10 -6 K -1 within the scope of

[0013] In the temperature range of -100°C to 0°C, the particle size of the active material is 2nm-23μm, and the particle size of the thermal strain regulating material is 25nm-18μm;

[0014] In the temperature range of greater than 0°C to 30°C, the particle size of the active material is in the range of 10nm-25μm, and the particle size of the thermal strain regulating material is in the range of 20nm-15μm;

[0015] In the temperature range of greater than 30° C. to 100° C., the particle size of the active material is 30 nm-27 μm, and the particle size of the thermal strain regulating material is 16 nm-12 μm.

[0016] Preferably, the thermal strain regulating material includes: one or more of anisotropic materials, isotropic materials or organic framework materials; preferably, the thermal strain regulating material includes: anisotropic materials and / or isotropic materials containing alkali metal elements.

[0017] Further preferably, the anisotropic materials include: PbTiO3, BaTiO3, BiNi 1-x Fe xO3 (0≤x≤1), PMN ferroelectric ceramics, PMN ferroelectric ceramics doped with titanium dioxide, PZN ferroelectric ceramics, PZN ferroelectric ceramics doped with titanium dioxide, NbOPO4, AlPO4, FePO4 doped with any one or more of Li, Mg or Zn, one or more of nanostructured or porous SiO2, LiB(CN)2, NaB(CN)2, Zn(CN)2, Cd(CN)2, nanosized ZrO2, nanosized HfO2, nanosized Cu2O, and nanosized Ag2O;

[0018] The isotropic materials include: Mg2Al4Si5O doped with transition metal elements or rare earth elements 12 , Mg2Al2Si5O doped with transition metal elements or rare earth elements 18 , CaTi4P6O doped with transition metal elements or rare earth elements 24 , Sc2(WO4)3, KZr2(PO4)3, NaZr2(PO4)3, Li2ZrF6, LiFeP2O7, LiZr2(PO4)3, porous ZrP2O7 ceramics, porous Zr(P 1-x V x )2O7 ceramics (0<x<1), porous ZrV2O7 ceramics, ZrW2O8 ceramics, HfW2O8 ceramics, porous CuFeS2, Lu2Fe doped with Co or Al 17 , Y2Fe doped with Co or Al 17 , LaFe doped with any one or more of Al, Ga or rare earth elements 10.5 Co 1.0 Si 1.5 , one or more of rare earth-doped Mn3AN (A = Zn, Ga or Cu);

[0019] The organic framework material includes one or more of: a zwitterion-modified metal organic framework material, a nanostructured cellulose framework zeolite imidazole ester framework material, a cross-linked or highly oriented acrylonitrile polymer PAN network support framework material, and a vinyl functionalized metal organic framework material.

[0020] Preferably, the solid-state battery electrode further comprises: a composite material layer; the composite material layer is located on the surface of the electrode layer and is one or more layers, and the composite material layer comprises: one or more of active material, solid electrolyte material, and thermal strain control material; and / or,

[0021] The solid-state battery electrode also includes: a solid electrolyte membrane layer, which is one layer or multiple layers; wherein, when the solid-state battery electrode does not include the composite material layer, the solid electrolyte membrane layer is located above the electrode layer; when the solid-state battery electrode includes the composite material layer, the solid electrolyte membrane layer is located above the composite material layer and is located on one side or both sides of the composite material layer.

[0022] Preferably, the solid electrolyte membrane layer further includes no more than 50 wt % of a thermal strain regulating material.

[0023] Preferably, the solid electrolyte material includes: one or more of a polymer electrolyte material, an inorganic solid electrolyte material or an organic-inorganic composite solid electrolyte material;

[0024] The inorganic solid electrolyte material includes one or more of an oxide solid electrolyte, a sulfide solid electrolyte, and a halide solid electrolyte.

[0025] Preferably, the solid electrolyte material in the solid electrolyte membrane layer is the same as the solid electrolyte material in the composite material layer.

[0026] Preferably, the solid-state battery electrode is a positive electrode and / or a negative electrode;

[0027] The active material of the positive electrode includes one or more of lithium iron phosphate, lithium cobalt oxide, lithium manganese oxide, lithium nickel cobalt manganese oxide, lithium nickel cobalt aluminum oxide, lithium rich layered oxide, lithium nickel manganese oxide, lithium titanate, graphite fluoride, MnO2, FeS2, FeF3, S, H2O, CO2, and O2;

[0028] The active material of the negative electrode includes: one or more of carbon-based negative electrode materials, silicon-based negative electrode materials, lithium-based negative electrode materials, tin-based negative electrode materials and other types of negative electrode materials;

[0029] The carbon-based negative electrode material includes one or more of natural graphite, artificial graphite, high-phase pyrolytic graphite, graphitized carbon fiber, graphitized mesophase carbon microspheres, hard carbon, soft carbon, carbon nanotubes, graphene and composite materials thereof;

[0030] The silicon-based negative electrode material includes: silicon material, silicon oxide material, silicon-carbon composite material;

[0031] The lithium-based negative electrode material includes: metallic lithium, lithium alloy material, and composite metallic lithium material;

[0032] The tin-based negative electrode material includes: tin-based material, tin oxide material;

[0033] The other types of negative electrode materials include lithium titanium oxide materials Li4Ti5O 12, transition metal sulfide material MoS2.

[0034] In a second aspect, an embodiment of the present invention provides a solid-state battery, comprising the solid-state battery electrode described in the first aspect above;

[0035] The solid-state battery includes one or more of an in-situ solid-state battery, a semi-solid-state battery, a hybrid solid-liquid battery, or a fully solid-state battery.

[0036] The solid-state battery electrode provided by the embodiment of the present invention has an electrode layer material comprising an active material and a thermal strain regulating material; the thermal strain regulating material is distributed between particles of the active material, and within a temperature range of -100°C to 100°C, the linear thermal expansion coefficient α of the thermal strain regulating material is within -20.0×10 -6 K -1 ≤α<0×10 -6 K -1 The volume of the active material in a solid-state battery electrode can be effectively suppressed by introducing thermal strain control materials into the electrode to reduce the volume change caused by temperature changes.

[0037] On the one hand, when a solid-state battery is exposed to low temperatures, the size of the active material particles shrinks, and the gaps between the active material particles and between the active material particles and the solid electrolyte of the solid-state battery increase. The interface shrinkage effect at the electrode particle level at low temperatures increases the internal resistance of the battery. The thermal strain control material introduced into the electrode of the present invention expands in volume at low temperatures, which can play a "spatial compensation" role, effectively reducing the gap problem caused by the volume shrinkage of materials such as the electrode active material, thereby effectively ensuring the solid-solid interface contact problem between the electrode active material particles and between the active material particles and the solid electrolyte particles. When the temperature decreases, the electrode material shrinks in volume, and the negative thermal expansion material expands in the opposite direction. The particle size changes of the two are linked and adapted, thus ensuring solid-solid contact at the solid-state battery particle level. Therefore, when the solid-state battery electrode proposed by the present invention is used in a low-temperature environment, especially below -20°C, the linked adaptive change in the particle size of the thermal strain control material can effectively improve the solid-solid contact problem caused by the volume shrinkage of the active material, thereby effectively preventing battery failure caused by physical gaps between particles.

[0038] On the other hand, when the solid-state battery is in a high-temperature environment, the active material particles expand due to heat, which causes the gaps between the active material particles and between the active material particles and the solid electrolyte to become smaller. In extreme cases, the particles are squeezed and crushed due to excessive stress. The thermal strain control material introduced in the electrode of the present invention shrinks in volume at high temperatures, and the volume expansion of the electrode active material and the volume contraction of the thermal strain control material can achieve a linkage adaptation of the particle size changes of the two. Therefore, the thermal strain control material can play a "reverse support" role for the volume expansion of the electrode active material, providing sufficient deformation space for the active material particles. Therefore, when the solid-state battery electrode proposed by the present invention is used in a high-temperature environment, the volume contraction of the thermal strain control material can effectively alleviate the interfacial stress and inter-particle extrusion caused by the expansion of the active material, maintain good interfacial contact, suppress the increase in internal resistance, and improve cycle stability and rate performance.

[0039] Furthermore, during the charging process, the solid-state battery needs to convert the external input electrical energy into energy to drive the redox reaction of the positive and negative active materials. This process is accompanied by violent chemical reactions and continuous release of heat, which causes the internal temperature of the battery to rise significantly. As the temperature rises, thermal expansion occurs generally in the particles of the positive and negative active materials, especially the volume expansion of the negative electrode material in the charging state is more significant. In view of this characteristic, the present invention introduces a thermal strain regulating material into the electrode layer to cause its volume to shrink during the temperature rise, and provides sufficient buffer space for the volume expansion of the electrode active material through the linkage adaptation mechanism of the reverse change of particle size. The thermal strain linkage mechanism of the thermal strain regulating material realizes that the temperature rise during the charging process causes the volume expansion of the active material to be coupled with the volume change of the thermal strain regulating material, which can effectively alleviate the problems of inter-particle interface destruction and internal resistance increase caused by the expansion of the active material, thereby improving the charge and discharge stability and safety of the solid-state battery. BRIEF DESCRIPTION OF THE DRAWINGS

[0040] Figure 1 This is a charge-discharge and cycle performance curve of the soft-pack solid-state battery of Example 1;

[0041] Figure 2 This is a charge-discharge and cycle performance curve of the soft-pack solid-state battery of Example 2;

[0042] Figure 3 This is a charge-discharge and cycle performance curve of the soft-pack solid-state battery of Example 3;

[0043] Figure 4 This is a charge-discharge and cycle performance curve of the soft-pack solid-state battery of Example 4;

[0044] Figure 5 This is a charge-discharge and cycle performance curve of the soft-pack solid-state battery of Example 5;

[0045] Figure 6 This is a charge-discharge and cycle performance curve of the button-type solid-state battery of Example 6;

[0046] Figure 7 This is a charge-discharge and cycle performance curve of the soft-pack solid-state battery of Example 7;

[0047] Figure 8 This is a charge-discharge and cycle performance curve of the soft-pack solid-state battery of Example 8;

[0048] Figure 9 This is a charge-discharge and cycle performance curve of the soft-pack solid-state battery of Comparative Example 1;

[0049] Figure 10 This is a charge-discharge and cycle performance curve of the button-type solid-state battery of Comparative Example 2;

[0050] Figure 11 2 is a cycle-specific capacity diagram of Example 6 and Comparative Example 2. DETAILED DESCRIPTION

[0051] The technical solution of the present invention is further described in detail below through the accompanying drawings and embodiments.

[0052] An embodiment of the present invention provides a solid-state battery electrode, comprising an electrode layer. The electrode layer is made of active material and thermal strain control material.

[0053] The thermal strain-modulating material in this invention refers to a material that undergoes predictable and controllable volume changes (including expansion or contraction) during temperature changes. The thermal strain-modulating material in this invention exhibits negative thermal expansion, meaning it contracts when the temperature rises and expands when the temperature drops.

[0054] The thermal strain regulating material is distributed between the particles of the active material, and in the temperature range of -100℃ to 100℃, the linear thermal expansion coefficient α of the thermal strain regulating material is -20.0×10 -6 K -1 ≤α<0×10 -6 K -1 In addition, the volume expands as the temperature decreases and contracts as the temperature increases. Preferably, in the temperature range of -60°C to 100°C, the linear thermal expansion coefficient α of the thermal strain regulating material is -5.0×10 -6 K -1 ≤α≤-0.1×10 -6 K -1 within the range.

[0055] Specifically, the linear thermal expansion coefficient α of the thermal strain control material in the temperature range of -100°C to 100°C can be any value within the above range, such as -20.0×10 -6 K -1 、-18.0×10 -6 K -1 、-16.0×10 -6 K -1 、-15.0×10 -6 K -1 、-13.0×10 -6 K -1 、-12.0×10 -6 K -1 、-10.0×10 -6 K -1 , -9.0×10 -6 K -1 , -8.0×10 -6 K -1 , -7.0×10 -6 K -1 , -6.0×10 -6 K -1 , -5.0×10 -6 K -1 , -4.0×10 -6 K -1 、-3.0×10 -6 K -1 , -2.0×10 -6 K -1 , -1.0×10 - 6 K -1 , -0.5×10 -6 K -1 , -0.4×10 -6 K -1 、-0.3×10 -6 K -1 、-0.2×10 -6 K -1 、-0.1×10 -6 K -1 、-0.08×10 -6 K -1 , -0.05×10 -6 K -1 , -0.04×10 -6 K -1 、-0.03×10 -6 K -1 , -0.02×10 -6 K -1 , -0.01×10-6 K -1 , -0.005×10 -6 K -1 The thermal expansion coefficient of the thermal strain control material of the present invention increases as the temperature decreases and decreases as the temperature increases within the temperature range of -100°C to 100°C, but does not necessarily follow the above rule outside the temperature range of -100°C to 100°C.

[0056] The linear thermal expansion coefficient, α, refers to the change in length per unit length of a material within a certain temperature range for each 1°C (or 1 Kelvin) increase in temperature. The mathematical expression is α = (1 / L0)·(dL / dT); α is the linear thermal expansion coefficient (measured in K-1 or °C-1), L0 is the initial length of the material, dL is the slight change in length, dT is the slight change in temperature, and dL / dT is the rate of change in length per unit temperature change. If α > 0, the material expands with increasing temperature; if α < 0, the material contracts with increasing temperature.

[0057] The thermal strain control material in this application is a material with a linear thermal expansion coefficient α less than 0. It should be noted that while the linear expansion coefficient of the thermal strain control material described in this invention is negative, this does not preclude the possibility that the crystalline material may have a positive coefficient in some direction. For example, when the temperature rises, the material's crystal structure contracts along the c-axis, which can simultaneously appear to contract along the a-axis, but can also appear to expand along the a-axis.

[0058] The active material in the present invention is a conventional material having a linear thermal expansion coefficient α>0.

[0059] Therefore, in different regions from low temperature, room temperature to high temperature, the active material and the thermal strain regulation material in the present invention exhibit different expansion characteristics, which are specifically manifested as follows: when the temperature gradually changes from the low temperature zone to the room temperature zone and the high temperature zone, the particle size of the active material continues to increase, but the particle size of the thermal strain regulation material continues to decrease, that is, in the low temperature zone, the active material exhibits a relatively smallest particle size, and the thermal strain regulation material exhibits a relatively largest particle size; in the high temperature zone, the active material exhibits a relatively largest particle size, and the thermal strain regulation material exhibits a relatively smallest particle size.

[0060] In the present invention, unless otherwise specified, the numerical value corresponding to the particle size refers to the median particle size D50. The median particle size D50 is the particle size at which the particles of the material are ranked at 50% by number. The particle size D50 can be measured using instruments and conventional methods known in the art. For example, the particle size D50 can be measured using a Mastersizer 3000 laser particle size analyzer manufactured by Malvern Instruments Ltd. in the United Kingdom.

[0061] As temperature changes, the particle sizes of the active material and the thermal strain control material of the present invention change in opposite directions and adapt in a coordinated manner. To achieve this coordinated adaptation, the present invention considers the control and optimization requirements for the particle sizes of the active material and the thermal strain control material at different temperature ranges, as detailed below.

[0062] In the temperature range of -100°C to 0°C, the particle size of the active material is 2nm-23μm; it can be any value within the above numerical range, such as 2nm, 4nm, 6nm, 8nm, 10nm, 20nm, 30nm, 50nm, 60nm, 80nm, 100nm, 200nm, 300nm, 400nm, 450nm, 500nm, 520nm, 530nm, 550nm, 580nm, 600nm, 700nm, 800nm, 900nm, 1μm, 2μm, 3μm, 5μm, 7μm, 8μm, 10μm, 12μm, 15μm, 18μm, 20μm, 21μm, 23μm, but is not limited to these. The particle size of the thermal strain regulating material is 25nm-18μm; it can be any value within the above numerical range, such as 25nm, 50nm, 60nm, 80nm, 100nm, 120nm, 140nm, 160nm, 180nm, 200nm, 300nm, 500nm, 600nm, 700nm, 800nm, 900nm, 1μm, 2μm, 3μm, 5μm, 7μm, 8μm, 10μm, 12μm, 15μm, 18μm, but not limited to this.

[0063] In the temperature range of greater than 0°C to 30°C, the particle size range of the active material is 10nm-25μm; it can be any value within the above numerical range, such as 10nm, 20nm, 30nm, 50nm, 60nm, 80nm, 100nm, 200nm, 300nm, 400nm, 450nm, 500nm, 520nm, 530nm, 550nm, 580nm, 600nm, 700nm, 800nm, 900nm, 1μm, 2μm, 3μm, 5μm, 7μm, 8μm, 10μm, 12μm, 15μm, 18μm, 20μm, 21μm, 23μm, 24μm, 25μm, but is not limited to these. The particle size of the thermal strain regulating material is 20nm-15μm; it can be any value within the above numerical range, such as 20nm, 25nm, 50nm, 60nm, 80nm, 100nm, 120nm, 140nm, 160nm, 180nm, 200nm, 300nm, 500nm, 600nm, 700nm, 800nm, 900nm, 1μm, 2μm, 3μm, 5μm, 7μm, 8μm, 10μm, 12μm, 15μm, but not limited to this.

[0064] In the temperature range of greater than 30°C to 100°C, the particle size of the active material is 30nm-27μm; it can be any value within the above numerical range, such as 30nm, 50nm, 60nm, 80nm, 100nm, 200nm, 300nm, 400nm, 450nm, 500nm, 550nm, 580nm, 600nm, 700nm, 800nm, 900nm, 1μm, 2μm, 3μm, 5μm, 7μm, 8μm, 10μm, 12μm, 15μm, 18μm, 20μm, 21μm, 23μm, 24μm, 25μm, 26μm, 27μm, but is not limited to these. The particle size of the thermal strain regulating material is 16nm-12μm; it can be any value within the above numerical range, such as 16nm, 18nm, 20nm, 25nm, 50nm, 60nm, 80nm, 100nm, 120nm, 140nm, 160nm, 180nm, 200nm, 300nm, 500nm, 600nm, 700nm, 800nm, 900nm, 1μm, 2μm, 3μm, 5μm, 7μm, 8μm, 10μm, 12μm, but not limited to this.

[0065] The sum of the mass of the active material and the thermal strain control material accounts for 80%-100% of the mass of the electrode layer, and can be any value within the above range, such as 80%, 82%, 85%, 90%, 92%, 95%, 96%, 98%, or 100%. The mass ratio of the active material to the thermal strain control material is 100:0.1-20, and can be any value within the above range, such as 100:0.1, 100:0.2, 100:0.3, 100:0.4, 100:0.5, 100:0.6, 100:0.7, 100:0.8, 100:0.9, 100:1, 100:5, 100:6, 100:8, 100:10, 100:12, 100:15, 100:18, 100:19, and 100:20. When within the above percentage range, combined with the thermal expansion coefficient, particle size and other parameters of the active material and the thermal strain regulation material, the thermal strain regulation material can achieve synergistic linkage with the volume change of the active material, providing sufficient space to accommodate the volume expansion and volume contraction of the active material, thereby effectively improving problems such as solid-solid contact and internal stress of the battery.

[0066] In the specific implementation of the present invention, the optional thermal strain control materials include: one or more of anisotropic materials, isotropic materials or organic framework materials; preferably include: anisotropic materials and / or isotropic materials containing alkali metal elements.

[0067] Anisotropic materials are materials whose physical or chemical properties, in whole or in part, vary depending on the direction. In this context, they specifically refer to thermally strain-modulating materials whose expansion / contraction properties vary completely or partially in all directions when the temperature changes.

[0068] Isotropic materials are materials whose physical and chemical properties do not vary depending on the direction. This means that the material's performance values ​​measured in different directions are exactly the same, also known as homogeneity. In this context, this refers specifically to thermally strain-modulating materials that exhibit the same expansion / contraction properties in all directions when subjected to temperature changes.

[0069] The anisotropic materials may specifically include: PbTiO3, BaTiO3, BiNi 1-x Fe xO3 (0≤x≤1), PMN ferroelectric ceramics, PMN ferroelectric ceramics doped with titanium dioxide, PZN ferroelectric ceramics, PZN ferroelectric ceramics doped with titanium dioxide, NbOPO4, AlPO4, FePO4 doped with any one or more of Li, Mg or Zn, one or more of nanostructured or porous SiO2, LiB(CN)2, NaB(CN)2, Zn(CN)2, Cd(CN)2, nanosized ZrO2, nanosized HfO2, nanosized Cu2O, and nanosized Ag2O.

[0070] The isotropic materials may specifically include: Mg2Al4Si5O doped with transition metal elements or rare earth elements 12 , Mg2Al2Si5O doped with transition metal elements or rare earth elements 18 , CaTi4P6O doped with transition metal elements or rare earth elements 24 , Sc2(WO4)3, KZr2(PO4)3, NaZr2(PO4)3, Li2ZrF6, LiFeP2O7, LiZr2(PO4)3, porous ZrP2O7 ceramics, porous Zr(P 1-x V x )2O7 ceramics (0<x<1), porous ZrV2O7 ceramics, ZrW2O8 ceramics, HfW2O8 ceramics, porous CuFeS2, Lu2Fe doped with Co or Al 17 , Y2Fe doped with Co or Al 17 , LaFe doped with any one or more of Al, Ga or rare earth elements 10.5 Co 1.0 Si 1.5 , one or more of rare earth-doped Mn3AN (A=Zn, Ga or Cu).

[0071] The organic framework material may specifically include: one or more of: a zwitterion-modified metal organic framework material, a nanostructured cellulose framework zeolite imidazolate framework material, a cross-linked or highly oriented acrylonitrile polymer PAN network support framework material, and a vinyl functionalized metal organic framework material.

[0072] The present invention can effectively improve or even offset the volume changes of solid-state battery electrodes in high and low temperature environments and during charging by limiting the thermal expansion coefficient of the thermal strain regulation material, the particle size of the active material and the thermal strain regulation material at different ambient temperatures of low temperature, room temperature and high temperature, and the mass ratio of the thermal strain regulation material in the electrode layer, effectively solve the problems of solid-solid contact and internal stress of the solid-state battery, and ensure the use requirements of the solid-state battery from ultra-low temperature to ultra-high temperature.

[0073] The solid-state battery electrode of the present invention may further include conductive agents, binders and other additives known or commonly used in various battery electrodes. The present invention has no special restrictions on this and will not elaborate on this.

[0074] In addition, the solid-state battery electrode of the present invention may further include: a composite material layer and / or a solid electrolyte membrane layer.

[0075] The composite material layer, located on the surface of the electrode layer, comprises one or more layers. The composite material layer includes one or more of an active material, a solid electrolyte material, and a thermal strain control material. The active material and thermal strain control material in the composite material layer can be the same or different from those in the electrode layer. Using the same materials can yield better performance.

[0076] Preferably, the composite material layer includes at least a thermal strain regulating material. When the composite material layer includes a thermal strain regulating material, an interface layer having a thermal strain regulating material is constructed between the electrode of the solid-state battery and the solid electrolyte of the solid-state battery. When the solid-state battery is in different environments such as high temperature and low temperature, the presence of the thermal strain regulating material in the interface layer can effectively suppress the change in the distance between the electrode and the solid electrolyte due to temperature changes. That is, when the solid-state battery is at a low temperature, the distance between the electrode and the solid electrolyte increases due to their respective contraction when cooled. In addition to the synergistic regulation of the thermal strain regulating material in the electrode layer, the volume expansion of the thermal strain regulating material in the composite material layer can further ensure that the composite material layer, the electrode and the solid electrolyte continue to maintain good solid-solid contact; when the solid-state battery is at a high temperature, the distance between the electrode and the solid electrolyte becomes smaller due to thermal expansion. In addition to the synergistic regulation of the thermal strain regulating material in the electrode layer, the volume contraction of the thermal strain regulating material in the composite material layer can further prevent battery failure caused by excessive stress between the components. Therefore, the present invention introduces a composite material layer containing a thermal strain regulating material on the surface of the electrode layer of the electrode, thereby constructing a bridge conductive layer with adaptive volume change between the electrode layer and the solid electrolyte membrane, which can form a good contact interface regardless of high or low temperature, thereby effectively ensuring the solid-solid interface contact problem between the electrode and the solid electrolyte, and ensuring the effective operation of various battery components.

[0077] More preferably, the composite material layer includes an active material, a solid electrolyte material, and a thermal strain control material. The mass ratio of the combined active material and solid electrolyte material to the thermal strain control material is 100:0.1-20. The combined mass of the active material, solid electrolyte material, and thermal strain control material accounts for 80%-100% of the composite material layer. The specific ranges for the active material, solid electrolyte material, and thermal strain control material are the same as those described above for the various materials in the electrode layer and are not further elaborated.

[0078] The solid electrolyte membrane layer is one or more layers. When a solid-state battery electrode does not include a composite material layer but includes a solid electrolyte membrane layer, the solid electrolyte membrane layer is located above the electrode layer. When a solid-state battery electrode includes both a composite material layer and a solid electrolyte membrane layer, the solid electrolyte membrane layer is located above the composite material layer and may be located on one or both sides of the composite material layer.

[0079] Preferably, the solid electrolyte membrane layer further includes a thermal strain control material not exceeding 50 wt% of the mass of the solid electrolyte membrane layer. The amount not exceeding 50 wt% of the mass of the solid electrolyte membrane layer can be any value within the above range, including but not limited to 0.2 wt%, 0.3 wt%, 0.5 wt%, 0.8 wt%, 1 wt%, 5 wt%, 8 wt%, 10 wt%, 12 wt%, 15 wt%, 18 wt%, 20 wt%, 30 wt%, 40 wt%, and 50 wt%. The inclusion of the thermal strain control material in the solid electrolyte membrane layer can effectively offset the change in the gap between the solid electrolyte particles due to changes in ambient temperature, ensure the channel for ion transmission, and effectively prevent the increase in the internal resistance of the battery.

[0080] The solid electrolyte material in the solid electrolyte membrane layer and the solid electrolyte material in the composite material layer may include: one or more of polymer electrolyte materials, inorganic solid electrolyte materials or organic-inorganic composite solid electrolyte materials; among which, the inorganic solid electrolyte material includes: one or more of oxide solid electrolytes, sulfide solid electrolytes, and halide solid electrolytes.

[0081] The specific selection of the solid electrolyte material in the solid electrolyte membrane layer and the solid electrolyte material in the composite material layer can be the same or different. Preferably, when the solid electrolyte material in the composite material layer and the solid electrolyte material in the solid electrolyte membrane layer are the same type, lithium ion transmission is particularly smooth and rapid, which can significantly improve the lithium ion transmission efficiency and help improve ionic conductivity. The solid electrolyte membrane layer forms a fast ion conduction layer between the electrode and the solid electrolyte in the solid-state battery of the present invention.

[0082] The solid-state battery electrode proposed in the present invention can specifically be a positive electrode or a negative electrode.

[0083] When it is a positive electrode, the active material may include: one or more of lithium iron phosphate, lithium cobalt oxide, lithium manganese oxide, lithium nickel cobalt manganese oxide, lithium nickel cobalt aluminum oxide, lithium-rich layered oxide, lithium nickel manganese oxide, lithium titanate, graphite fluoride, MnO2, FeS2, FeF3, S, H2O, CO2, and O2.

[0084] In the case of a negative electrode, the active material may include one or more of: a carbon-based negative electrode material, a silicon-based negative electrode material, a lithium-based negative electrode material, a tin-based negative electrode material, and other types of negative electrode materials.

[0085] Among them, the carbon-based negative electrode materials include: one or more of natural graphite, artificial graphite, high-phase pyrolytic graphite, graphitized carbon fiber, graphitized mesophase carbon microspheres, hard carbon, soft carbon, carbon nanotubes, graphene and their composite materials;

[0086] Silicon-based negative electrode materials include: silicon materials, silicon oxide materials, and silicon-carbon composite materials;

[0087] Lithium-based negative electrode materials include: metallic lithium, lithium alloy materials, and composite metallic lithium materials;

[0088] Tin-based negative electrode materials include: tin-based materials, tin oxide materials;

[0089] Other types of negative electrode materials, including lithium titanium oxide materials Li4Ti5O 12 , transition metal sulfide material MoS2.

[0090] The selection of positive or negative electrode active materials can be based on the specific types and forms of the various positive or negative electrode materials listed above, and can be selected and optimized by those skilled in the art using conventional techniques from existing published literature or commonly used positive or negative electrode materials in the industry. No further specific limitations are provided herein. The selection of such electrode active materials is a conventional technique within the skill of those skilled in the art and should not be considered a technical contribution requiring creative effort.

[0091] The solid-state battery electrode proposed in the embodiment of the present invention can be applied to solid-state batteries. Applicable solid-state batteries include: one or more of in-situ solid-state batteries, semi-solid-state batteries, hybrid solid-liquid batteries or all-solid-state batteries. The solid-state battery obtained by the present invention can be used at different temperatures such as high and low temperatures or under different charging and discharging conditions because the electrodes contain thermal strain regulation materials, and has excellent environmental adaptability. The solid-state battery of the present invention is preferably applicable in a wide temperature range of -60°C to 100°C, and has excellent high and low temperature electrochemical properties, especially the low-temperature capacity performance, low-temperature cycle and low-temperature rate performance are greatly improved.

[0092] The solid-state battery of the present invention has high energy density, structural stability and excellent cycle performance. It can be applied to lithium batteries, lithium battery packs or lithium battery modules, and is widely used in consumer electronics, electric vehicles, large-scale energy storage and other fields. It also has good application prospects in large-scale energy storage systems.

[0093] To make the objectives, technical solutions, and advantages of the present invention more apparent, the present invention will be further described in detail below with reference to the accompanying drawings. It is apparent that the embodiments described are only some, not all, of the present invention. All other embodiments derived by persons of ordinary skill in the art based on the embodiments of the present invention without creative effort are intended to fall within the scope of protection of the present invention.

[0094] The reagents and materials used in the following examples and comparative examples, including raw materials, solid electrolytes, lithium salts, additives, initiators, solvents, and other reagents, as well as positive and negative electrode materials, were all commercially available. Where specific experimental procedures or conditions are not specified in the examples, the procedures or conditions were followed according to conventional experimental procedures or conditions in the art.

[0095] Example 1

[0096] (1) Using laboratory-synthesized lithium-rich manganese-based materials as positive electrode active materials.

[0097] The synthesis method is as follows: Ni 0.12 Co 0.12 Mn 0.76 The CO3 precursor (purchased from Zhongwei New Materials Co., Ltd.) and Li2CO3 (purchased from Inochem Co., Ltd.) were mechanically mixed in a mass ratio of 1:1.4, and the mixture was heated to 500°C at a rate of 5°C / min in a nitrogen atmosphere in a reactor, and then reacted at 500°C for 5 hours in an oxygen atmosphere; then the mixture was heated to 850°C at a rate of 5°C / min in a nitrogen atmosphere, kept at 850°C for 12 hours, then cooled to 500°C, and annealed at 500°C for 5 hours to obtain the product lithium-rich manganese-based material (Li 1.14 Ni 0.13 Co 0.13 Mn 0.54 O2).

[0098] (2) Using commercial lithium-carbon composite materials as negative electrode active materials.

[0099] The particle size distribution of the lithium-carbon composite material particles is 1 μm to 12 μm. The lithium-carbon composite material is stored and handled in a dry atmosphere or an inert atmosphere throughout. The carbon material in the lithium-carbon composite material is porous carbon, and the pores include micropores, mesopores, or a combination of multiple pores. The porosity range is optional between 5% and 80%. The lithium-carbon composite material Li-C used in this example has a porosity of 50%.

[0100] (3) Selection of thermal strain control materials.

[0101] Li2ZrF6 is used as the thermal strain control material, and its average linear expansion coefficient at -100℃-0℃ is about -3.5×10 -6 / K to -2.0×10 -6 / K, the average linear expansion coefficient at 0℃-30℃ is about -4.0×10 -6 / K to -3.0×10 -6 / K, the average linear expansion coefficient at 30℃-100℃ is about -5.0×10 -6 / K to -6.0×10 -6 / K.

[0102] (4) Prepare soft-pack batteries, and the preparation process is as follows.

[0103] Step 1. Preparation of positive electrode for soft pack battery:

[0104] A premixed powder of 95 wt% positive electrode active material LRM, 3 wt% polytetrafluoroethylene (PTFE), and 2 wt% conductive carbon black was rolled into a film at 150°C, and then rolled and laminated at 170°C to produce a positive electrode sheet. The positive electrode active material accounts for 95% of the total mass of the positive electrode sheet, excluding the current collector, and its surface loading is 25 mg / cm 2 .

[0105] Step 2. Preparation of negative electrode for soft pack battery:

[0106] The lithium-carbon composite material Li-C of 93wt%, PTFE of 2wt%, and Li2ZrF6 of 5wt% was pre-mixed and rolled into a film at 150°C, and then rolled and coated at 170°C. Among them, the mass of the negative electrode sheet excluding the current collector is 98% of the total mass of the negative electrode active material and the thermal strain control material, and the surface loading of the active material is 4mg / cm 2 .

[0107] Step 3. Prepare solid electrolyte membrane interface layers on the surfaces of the positive electrode and negative electrode respectively:

[0108] The inorganic solid electrolyte LATP (chemical formula: Li 1.3 Al 0.3 Ti 1.7(PO4)3) particles, methyl methacrylate monomer / ethylene oxide monomer (the mass ratio in this example is 1:1, and the optional mass ratio range in the specific implementation is between 1:3-3:1) and lithium bis(trifluoromethanesulfonyl)imide are compounded in a mass ratio of 2:6:2, dispersed in dimethyl carbonate (DMC) to form a slurry with a solid content of 20wt%, and extruded and coated on the surfaces of the positive electrode sheet and the negative electrode sheet respectively. After heat drying, a composite solid electrolyte thin film interface layer with a thickness of about 6μm is formed on the surfaces of the positive electrode sheet and the negative electrode sheet respectively.

[0109] Step 4. Soft pack battery assembly:

[0110] The positive electrode sheet and the negative electrode sheet, each carrying a solid electrolyte film interface layer, are cut into 73mm×60mm and 75mm×62mm sheets respectively by a die-cutting machine, matched with an ion conductor membrane with a width of 78mm, and composite multi-layered. Then, through welding, packaging and hot pressing, a soft-pack battery containing battery cell 1-1 is obtained.

[0111] Step 5. Electrochemical performance test:

[0112] The soft pack battery containing the battery cell 1-1 was heated at 0.5 mA / cm at 25°C. 2 The current density is charged to 4.8V, and then discharged to 2V for charge and discharge electrochemical cycle. The charge and discharge and cycle performance curves are shown in Figure 2. Figure 1 The electrochemical performance test data are recorded in Table 3.

[0113] Example 2

[0114] (1) Using laboratory-synthesized lithium-rich manganese-based materials as positive electrode active materials.

[0115] The specific method is the same as that of Example 1.

[0116] (2) Using commercial lithium-carbon composite materials as negative electrode active materials.

[0117] The specific method is the same as that of Example 1.

[0118] (3) Selection of thermal strain control materials.

[0119] LiFeP2O7 is used as the thermal strain control material, and its average linear expansion coefficient at -100℃-0℃ is about -0.5×10 -6 / K to -1.0×10 -6 / K, the average linear expansion coefficient at 0℃-30℃ is about -1.0×10 -6 / K to -2.0×10 -6 / K, and the average linear expansion coefficient at 30℃-100℃ is about -2.0×10 -6 / K to -4.0×10-6 / K.

[0120] (4) Prepare soft-pack batteries, and the preparation process is as follows.

[0121] Step 1. Preparation of positive electrode sheet of soft-pack battery: same as Example 1.

[0122] Step 2. Preparation of negative electrode for soft pack battery:

[0123] The lithium-carbon composite material Li-C of 96.5wt%, PTFE of 3wt%, and LiFeP2O7 of 0.5wt% was pre-mixed and rolled into a film at 150°C, and then rolled and coated at 170°C. Among them, the mass of the negative electrode sheet excluding the current collector is 97% of the total mass of the negative electrode active material and the thermal strain control material, and the surface loading of the active material is 4mg / cm 2 .

[0124] Step 3. Prepare solid electrolyte membrane interface layers on the surfaces of the positive electrode sheet and the negative electrode sheet respectively: same as in Example 1.

[0125] Step 4. Soft-pack battery assembly: As in Example 1, a soft-pack battery containing battery cell 1-2 is obtained.

[0126] Step 5. Electrochemical performance test: The test method is the same as in Example 1, and the charge-discharge and cycle performance curves are as follows: Figure 2 The electrochemical performance test data are recorded in Table 3.

[0127] Example 3

[0128] (1) Using laboratory-synthesized lithium-rich manganese-based materials as positive electrode active materials.

[0129] The specific method is the same as that of Example 1.

[0130] (2) Using commercial lithium-carbon composite materials as negative electrode active materials.

[0131] The specific method is the same as that of Example 1.

[0132] (3) Selection of thermal strain control materials.

[0133] Same as Example 1.

[0134] (4) Prepare soft-pack batteries, and the preparation process is as follows.

[0135] Step 1. Preparation of positive electrode sheet of soft-pack battery: same as Example 1.

[0136] Step 2. Preparation of negative electrode for soft pack battery:

[0137] The lithium-carbon composite material Li-C (82 wt%), PTFE (3 wt%), and Li2ZrF6 (15 wt%) were pre-mixed and rolled into a film at 150 ° C. After calendering, the film was coated at 170 ° C. Among them, the mass of the negative electrode sheet excluding the current collector is 97% of the total mass of the negative electrode active material and the thermal strain control material. The surface loading of the active material is 4 mg / cm 2 .

[0138] Step 3. Prepare solid electrolyte membrane interface layers on the surfaces of the positive electrode sheet and the negative electrode sheet respectively: same as in Example 1.

[0139] Step 4. Soft-pack battery assembly: As in Example 1, a soft-pack battery containing battery cells 1-3 is obtained.

[0140] Step 5. Electrochemical performance test: The test method is the same as in Example 1, and the charge-discharge and cycle performance curves are as follows: Figure 3 The electrochemical performance test data are recorded in Table 3.

[0141] Example 4

[0142] (1) Using laboratory-synthesized lithium-rich manganese-based materials as positive electrode active materials.

[0143] The specific method is the same as that of Example 1.

[0144] (2) Using commercial lithium-carbon composite materials as negative electrode active materials.

[0145] The specific method is the same as that of Example 1.

[0146] (3) Selection of thermal strain control materials.

[0147] Same as Example 1.

[0148] (4) Prepare soft-pack batteries, and the preparation process is as follows.

[0149] Step 1. Preparation of positive electrode sheet of soft-pack battery: same as Example 1.

[0150] Step 2. Preparation of negative electrode for soft pack battery:

[0151] Take 0.15g carboxymethyl cellulose (CMC, purity 92%) and dissolve it in 20ml deionized water, stir to form a uniform solution, add 9g silicon carbon negative electrode, 0.13g conductive carbon black (SP), 0.02g carbon nanotubes (CNT), 0.42g styrene butadiene rubber (SBR) suspension with a mass fraction of 50% and 0.5g Li2ZrF6 in sequence, and then stir for 8 hours to prepare the electrode slurry. The electrode slurry is coated on copper foil and dried at 60°C to obtain the negative electrode sheet. The negative electrode active material accounts for 90% and the surface loading is 4mg / cm 2The thermal strain regulating material Cu2O (particle size 30nm) was further magnetron sputtered to a thickness of 2μm on the surface of the negative electrode sheet, and the composite electrode layer of the active material and the thermal strain regulating material was obtained by roller pressing.

[0152] Step 3. Prepare solid electrolyte membrane interface layers on the surfaces of the positive electrode sheet and the negative electrode sheet respectively: same as in Example 1.

[0153] Step 4. Soft-pack battery assembly: As in Example 1, a soft-pack battery containing battery cells 1-4 is obtained.

[0154] Step 5. Electrochemical performance test: The test method is the same as in Example 1, and the charge-discharge and cycle performance curves are as follows: Figure 4 The electrochemical performance test data are recorded in Table 3.

[0155] Example 5

[0156] (1) Using laboratory-synthesized lithium-rich manganese-based materials as positive electrode active materials.

[0157] The specific method is the same as that of Example 1.

[0158] (2) Using commercial lithium-carbon composite materials as negative electrode active materials.

[0159] The specific method is the same as that of Example 1.

[0160] (3) Selection of thermal strain control materials.

[0161] Same as Example 1.

[0162] (4) Prepare soft-pack batteries, and the preparation process is as follows.

[0163] Step 1. Preparation of positive electrode sheet of soft-pack battery: same as Example 1.

[0164] Step 2. Preparation of negative electrode for soft pack battery:

[0165] Take 0.15g carboxymethyl cellulose (CMC, purity 92%) and dissolve it in 20ml deionized water, stir to form a uniform solution, add 9g silicon carbon negative electrode, 0.13g conductive carbon black (SP), 0.02g carbon nanotubes (CNT), 0.42g styrene butadiene rubber (SBR) suspension with a mass fraction of 50% and 0.5g Li2ZrF6 in sequence, and then stir for 8 hours to prepare the electrode slurry. The electrode slurry is coated on copper foil and dried at 60°C to obtain the negative electrode sheet. The negative electrode active material accounts for 90% and the surface loading is 4mg / cm 2. Further, a 2μm thick thermal strain control material ZrO2 (particle size 35nm) was magnetron sputtered on the surface of the negative electrode sheet. Then, the inorganic solid electrolyte LATP (chemical formula: LiAlTi(PO4)3) particles, methyl methacrylate monomer / ethylene oxide monomer (mass ratio 1:1 in this example) and lithium bis(trifluoromethanesulfonyl imide) were compounded in a mass ratio of 2:6:2 and dispersed in dimethyl carbonate (DMC) to form a slurry with a solid content of 20wt%. The slurry was extrusion-coated on the surface and thermally dried to form a composite solid electrolyte thin film interface layer with a thickness of about 2μm. After the composite solid electrolyte thin film interface layer was solidified, a 2μm thick thermal strain control material ZrO2 was magnetron sputtered on it. After roller pressing, a composite electrode layer of active material, thermal strain control material and solid electrolyte was obtained.

[0166] Step 3. Prepare the solid electrolyte membrane interface layer on the surface of the positive electrode:

[0167] Inorganic solid electrolyte LATP (chemical formula: LiAlTi(PO4)3) particles, methyl methacrylate monomer / ethylene oxide monomer (mass ratio of 1:1 in this example) and lithium bis(trifluoromethanesulfonyl)imide are compounded in a mass ratio of 2:6:2, dispersed in dimethyl carbonate (DMC) to form a slurry with a solid content of 20wt%, extruded and coated on the surface of the positive electrode sheet, and after heat drying, a composite solid electrolyte thin film interface layer with a thickness of about 6μm is formed on the surface of the positive electrode sheet.

[0168] Step 4. Soft-pack battery assembly: As in Example 1, obtain a soft-pack battery containing battery cells 1-5.

[0169] Step 5. Electrochemical performance test: The test method is the same as in Example 1, and the charge-discharge and cycle performance curves are as follows: Figure 5 The electrochemical performance test data are recorded in Table 3.

[0170] Example 6

[0171] (1) Using laboratory-synthesized lithium-rich manganese-based materials as positive electrode active materials.

[0172] The specific method is the same as that of Example 1.

[0173] (2) Using commercial lithium-carbon composite materials as negative electrode active materials.

[0174] The specific method is the same as that of Example 1.

[0175] (3) Selection of thermal strain control materials.

[0176] Same as Example 1.

[0177] (4) Prepare button batteries. The preparation process is as follows.

[0178] Step 1. Preparation of button cell positive electrode:

[0179] A premixed powder of 95 wt% positive electrode active material LRM, 3 wt% polytetrafluoroethylene (PTFE), and 2 wt% conductive carbon black was rolled into a film at 150°C, and then rolled and laminated at 170°C to produce a positive electrode sheet. The positive electrode active material accounts for 95% of the total mass of the positive electrode sheet, excluding the current collector, and its surface loading is 25 mg / cm 2 .

[0180] Step 2. Preparation of button cell negative electrode:

[0181] The lithium-carbon composite material Li-C of 93wt%, PTFE of 2wt%, and Li2ZrF6 of 5wt% was pre-mixed and rolled into a film at 150°C, and then rolled and coated at 170°C. Among them, the mass of the negative electrode sheet excluding the current collector accounts for 93% of the total mass, and the surface loading of the active material is 4mg / cm 2 .

[0182] Step 3. Prepare solid electrolyte membrane interface layers on the surfaces of the positive electrode and negative electrode respectively:

[0183] Inorganic solid electrolyte LATP (chemical formula: LiAlTi(PO4)3) particles, methyl methacrylate monomer / ethylene oxide monomer (mass ratio of 1:1 in this example) and lithium bis(trifluoromethanesulfonyl)imide are compounded in a mass ratio of 2:6:2, dispersed in dimethyl carbonate (DMC) to form a slurry with a solid content of 20wt%, and extruded and coated on the surfaces of the positive electrode and the negative electrode respectively. After thermal drying, a composite solid electrolyte thin film interface layer with a thickness of about 6μm is formed on the surfaces of the positive electrode and the negative electrode respectively.

[0184] Step 4. Button battery assembly:

[0185] The positive electrode sheet and the negative electrode sheet respectively carrying the solid electrolyte film interface layer were cut into discs with a diameter of 12 mm and 14 mm by a cutting machine, and assembled and sealed with the solid electrolyte membrane interface layer to obtain button batteries containing battery cells 1-6.

[0186] Step 5. Electrochemical performance test of button cell:

[0187] The button cell containing battery cells 1-6 was charged to 4.8V at a rate of 0.1C at room temperature, and then discharged to 2V at a rate of 0.1C at -40°C for charge and discharge electrochemical cycles. The charge and discharge and cycle performance curves are shown in Figure 2. Figure 6 The electrochemical performance test data are recorded in Table 3.

[0188] Example 7

[0189] (1) Commercial lithium cobalt oxide material LCO (LiCoO2) is used as the positive electrode active material.

[0190] (2) Using commercial lithium-carbon composite materials as negative electrode active materials.

[0191] The specific method is the same as that of Example 1.

[0192] (3) Selection of thermal strain control materials.

[0193] Same as Example 1.

[0194] (4) Prepare soft-pack batteries, and the preparation process is as follows.

[0195] Step 1. Preparation of positive electrode for soft pack battery:

[0196] A premixed powder of 95 wt% of the positive electrode active material LCO, 3 wt% of polytetrafluoroethylene (PTFE), and 2 wt% of conductive carbon black was rolled into a film at 150°C, and then rolled and laminated at 170°C to prepare the positive electrode sheet. The positive electrode active material accounts for 95% of the total mass of the positive electrode sheet excluding the current collector, and its surface loading is 25 mg / cm 2 .

[0197] Step 2. Preparation of negative electrode for soft pack battery:

[0198] 96wt% lithium-carbon composite material Li-C, 2wt% PTFE, and 2wt% Li2ZrF6 were pre-mixed and rolled into a film at 150°C, and then rolled and coated at 170°C. Among them, the mass of the negative electrode sheet excluding the current collector accounts for 96% of the total mass, and the surface loading of the active material is 4mg / cm 2 .

[0199] Step 3. Prepare solid electrolyte membrane interface layers on the surfaces of the positive electrode and negative electrode respectively:

[0200] Inorganic solid electrolyte LATP (chemical formula: LiAlTi(PO4)3) particles, methyl methacrylate monomer / ethylene oxide monomer (mass ratio of 1:1 in this example) and lithium bis(trifluoromethanesulfonyl)imide are compounded in a mass ratio of 2:6:2, dispersed in dimethyl carbonate (DMC) to form a slurry with a solid content of 20wt%, and extruded and coated on the surfaces of the positive electrode and the negative electrode respectively. After thermal drying, a composite solid electrolyte thin film interface layer with a thickness of about 6μm is formed on the surfaces of the positive electrode and the negative electrode respectively.

[0201] Step 4. Soft-pack battery assembly: As in Example 1, obtain a soft-pack battery containing battery cells 1-7.

[0202] Step 5. Electrochemical performance test:

[0203] The soft pack battery containing battery cells 1-7 was heated at 80°C at 0.5 mA / cm 2 The current density is charged to 4.55V, and then discharged to 3V for charge and discharge electrochemical cycle. The charge and discharge and cycle performance curves are as follows Figure 7 The electrochemical performance test data are recorded in Table 3.

[0204] Example 8

[0205] (1) Commercial lithium cobalt oxide material LCO (LiCoO2) is used as the positive electrode active material.

[0206] (2) Using commercial lithium-carbon composite materials as negative electrode active materials.

[0207] The specific method is the same as that of Example 1.

[0208] (3) Selection of thermal strain control materials.

[0209] Same as Example 1.

[0210] (4) Prepare soft-pack batteries, and the preparation process is as follows.

[0211] Step 1. Preparation of positive electrode for soft pack battery:

[0212] A premixed powder of 95 wt% of the positive electrode active material LCO, 3 wt% of polytetrafluoroethylene (PTFE), and 2 wt% of conductive carbon black was rolled into a film at 150°C, and then rolled and laminated at 170°C to prepare the positive electrode sheet. The positive electrode active material accounts for 95% of the total mass of the positive electrode sheet excluding the current collector, and its surface loading is 25 mg / cm 2 .

[0213] Step 2. Preparation of negative electrode for soft pack battery:

[0214] The lithium-carbon composite material Li-C of 93wt%, PTFE of 2wt%, and Li2ZrF6 of 5wt% was pre-mixed and rolled into a film at 150°C, and then rolled and coated at 170°C. Among them, the mass of the negative electrode sheet excluding the current collector accounts for 93% of the total mass, and the surface loading of the active material is 4mg / cm 2 .

[0215] Step 3. Prepare solid electrolyte membrane interface layers on the surfaces of the positive electrode and negative electrode respectively:

[0216] Inorganic solid electrolyte LATP (chemical formula: LiAlTi(PO4)3) particles, methyl methacrylate monomer / ethylene oxide monomer (mass ratio of 1:1 in this example) and lithium bis(trifluoromethanesulfonyl)imide are compounded in a mass ratio of 2:6:2, dispersed in dimethyl carbonate (DMC) to form a slurry with a solid content of 20wt%, and extruded and coated on the surfaces of the positive electrode and the negative electrode respectively. After thermal drying, a composite solid electrolyte thin film interface layer with a thickness of about 6μm is formed on the surfaces of the positive electrode and the negative electrode respectively.

[0217] Step 4. Soft-pack battery assembly: As in Example 1, a soft-pack battery containing battery cells 1-8 is obtained.

[0218] Step 5. Electrochemical performance test: The soft pack battery containing battery cells 1-8 was subjected to an electrochemical test at 45°C and 0.5 mA / cm 2 The current density is charged to 4.55V, and then discharged to 3V for charge and discharge electrochemical cycle. The charge and discharge and cycle performance curves are shown in Figure 2. Figure 8 The electrochemical performance test data are recorded in Table 3.

[0219] Example 9

[0220] (1) Using laboratory-synthesized lithium-rich manganese-based materials as positive electrode active materials.

[0221] The specific method is the same as that of Example 1.

[0222] (2) Using commercial lithium-carbon composite materials as negative electrode active materials.

[0223] The specific method is the same as that of Example 1.

[0224] (3) Selection of thermal strain control materials.

[0225] Same as Example 1.

[0226] (4) Prepare soft-pack batteries, and the preparation process is as follows.

[0227] Step 1. Preparation of positive electrode sheet of soft-pack battery: same as Example 1.

[0228] Step 2. Preparation of negative electrode sheet for soft-pack battery: same as in Example 1.

[0229] Step 3. Prepare solid electrolyte membrane interface layers on the surfaces of the positive electrode and negative electrode respectively:

[0230] Inorganic solid electrolyte LATP (chemical formula: LiAlTi(PO4)3) particles, methyl methacrylate monomer / ethylene oxide monomer (in this case, the mass ratio of the two is 1:1) and lithium bis(trifluoromethanesulfonyl)imide and Li2ZrF6 are compounded in a mass ratio of 1:6:2:1, dispersed in dimethyl carbonate (DMC) to form a slurry with a solid content of 20wt%, and extruded and coated on the surfaces of the positive electrode and the negative electrode respectively. After heat drying, a composite solid electrolyte thin film interface layer with a thickness of about 6μm is formed on the surfaces of the positive electrode and the negative electrode respectively.

[0231] Step 4. Soft-pack battery assembly: As in Example 1, a soft-pack battery containing battery cells 1-9 is obtained.

[0232] Step 5. Electrochemical performance test: The test method is the same as in Example 1, and the charge-discharge and cycle performance curves are as follows: Figure 9 The electrochemical performance test data are recorded in Table 3.

[0233] Comparative Example 1

[0234] (1) Using laboratory-synthesized lithium-rich manganese-based materials as positive electrode active materials.

[0235] The specific method is the same as that of Example 1.

[0236] (2) Using commercial lithium-carbon composite materials as negative electrode active materials.

[0237] The specific method is the same as that of Example 1.

[0238] (3) Prepare soft-pack batteries, the preparation process is as follows.

[0239] Step 1. Preparation of positive electrode sheet of soft-pack battery: same as Example 1.

[0240] Step 2. Preparation of negative electrode for soft pack battery:

[0241] The 98wt% lithium-carbon composite material Li-C and 2wt% PTFE were pre-mixed and rolled into a film at 150°C, and then rolled and coated at 170°C. Among them, the mass of the negative electrode sheet excluding the current collector is 98% of the total mass of the negative electrode active material and thermal strain control material, and the surface loading of the active material is 4mg / cm 2 .

[0242] Step 3. Prepare solid electrolyte membrane interface layers on the surfaces of the positive electrode sheet and the negative electrode sheet respectively: same as in Example 1.

[0243] Step 4. Soft-pack battery assembly: As in Example 1, a soft-pack battery containing battery cell D1-1 is obtained.

[0244] Step 5. Electrochemical performance test:

[0245] The soft pack battery containing the battery cell D1-1 was heated at 0.5 mA / cm at 25 °C. 2 The current density is charged to 4.8V, and then discharged to 2V for charge and discharge electrochemical cycle. The charge and discharge and cycle performance curves are shown in Figure 2. Figure 9 The electrochemical performance test data are recorded in Table 3.

[0246] Comparative Example 2

[0247] (1) Using laboratory-synthesized lithium-rich manganese-based materials as positive electrode active materials.

[0248] The specific method is the same as that of Example 1.

[0249] (2) Using commercial lithium-carbon composite materials as negative electrode active materials.

[0250] The specific method is the same as that of Example 1.

[0251] (3) Prepare button batteries. The preparation process is as follows.

[0252] Step 1. Preparation of positive electrode sheet of soft-pack battery: same as Example 6.

[0253] Step 2. Preparation of button cell negative electrode:

[0254] The 98wt% lithium-carbon composite material Li-C and 2wt% PTFE were pre-mixed and rolled into a film at 150°C, and then rolled and coated at 170°C. Among them, the mass of the negative electrode sheet excluding the current collector is 98% of the total mass of the negative electrode active material and thermal strain control material, and the surface loading of the active material is 4mg / cm 2 .

[0255] Step 3. Prepare solid electrolyte membrane interface layers on the surfaces of the positive electrode sheet and the negative electrode sheet respectively: same as Example 6.

[0256] Step 4. Button battery assembly: As in Example 6, a button battery containing battery cell D1-2 is obtained.

[0257] Step 5. Electrochemical performance test: The method is the same as that in Example 6. The charge-discharge and cycle performance curves are as follows: Figure 10 The electrochemical performance test data are recorded in Table 3.

[0258] The morphology and physicochemical properties of the materials used in the above examples and comparative examples were characterized as follows:

[0259] 1. Morphology characterization:

[0260] The average particle size of each material at different temperatures was tested by a high and low temperature hot stage polarizing microscope, as shown in Table 1:

[0261]

[0262]

[0263] Table 1

[0264] 2. Characterization of physical and chemical properties:

[0265] The impedance test of the batteries assembled in each embodiment and comparative example was performed using a 1 kHz high frequency test on an Autolab electrochemical workstation, as shown in Table 2:

[0266]

[0267] Table 2

[0268] As can be seen from Table 2, the impedance of the soft-pack batteries of Examples 1-5, 7-9 of the present invention and Comparative Example 1 after the first cycle is lower than 0.04Ω, and the impedance of the button batteries of Example 6 and Comparative Example 2 is higher than 6Ω. It can be seen that whether the thermal strain regulating material is added to the electrode active material has little effect on the impedance of the battery after the first cycle; after 20 cycles, the impedance of the soft-pack batteries of Examples 1-5, 7-9 is lower than 0.1Ω, but the impedance of the soft-pack battery of Comparative Example 1 is as high as 0.468Ω, which is more than 4 times the impedance of the battery of the embodiment of the present invention. The button battery of Example 6 of the present invention is about 10.7Ω, and the button battery of Comparative Example 2 reaches 35.8Ω, which is more than 3 times the impedance of the battery of the embodiment of the present invention. This shows that after a relatively small number of cycles, the battery impedance of the comparative example has increased significantly due to the absence of thermal strain regulating material in the electrode material, but the electrode material of the present invention contains thermal strain regulating material, which can effectively prevent the increase of battery impedance; and after 50 cycles, the impedance of the soft-pack batteries of Examples 1-5 and 7-9 are all lower than 0.15Ω, but the impedance of the soft-pack battery of Comparative Example 1 is about 1.0Ω, which is about 6 times the impedance of the battery of the embodiment of the present invention, the button battery of Example 6 of the present invention is about 13Ω, and the button battery of Comparative Example 2 reaches 70Ω, which is much higher than the embodiments of the present invention. This shows that after a long number of cycles, the electrode material of the present invention can still effectively suppress the increase in battery impedance due to the presence of the thermal strain regulating material. After 100 cycles, the impedance of the soft-pack batteries of Examples 1-5, 7-9 is up to 0.304Ω, but the impedance of the soft-pack battery of Comparative Example 1 is 2.554Ω, which is about 8 to 23 times the impedance of the battery of the embodiment of the present invention. The button battery of Example 6 of the present invention is 19.626Ω, and the button battery of Comparative Example 2 reaches 128.479Ω, which is much higher than the embodiment of the present invention. This shows that after long cycles, the electrode material of the present invention with the thermal strain regulating material can significantly suppress the increase in battery impedance.

[0269] The electrochemical test results of each embodiment and comparative example are recorded in Table 3.

[0270]

[0271]

[0272] Table 3

[0273] In Examples 1-3, using a lithium-rich manganese-based material as the positive electrode, after mixing the negative electrode lithium-carbon Li-C active material with the thermal strain control material, the soft-pack batteries assembled in Examples 1-2 had a capacity retention rate of more than 70% after 100 cycles at room temperature 25°C, and greater than 60% in Example 3. In Comparative Example 1, the negative electrode lithium-carbon Li-C active material did not contain the thermal strain control material, and the assembled soft-pack battery had a capacity retention rate of only about 38% after 100 cycles at room temperature 25°C. This shows that by mixing the thermal strain control material in the negative electrode at an appropriate mass percentage, it is possible to effectively cope with the change in the negative electrode volume during charge and discharge, and have excellent long-cycle capacity retention.

[0274] As shown in Example 4, the negative electrode sheet obtained by mixing the silicon negative electrode active material with the thermal strain control material Li2ZrF6 has a thin layer of the thermal strain control material Cu2O on its surface, and the capacity retention rate after 100 cycles at room temperature of 25°C is as high as over 70%. As shown in Example 5, by simultaneously carrying a composite material layer containing the thermal strain control material above and below the solid electrolyte membrane layer, the capacity retention rate after 100 cycles at room temperature of 25°C is as high as over 80%. This shows that by mixing the thermal strain control material in an appropriate proportion into the silicon negative electrode, it can effectively cope with the drastic volume changes during charge and discharge, and endow the battery with excellent cycle stability.

[0275] Compared with Example 1, after the button cell is assembled in Example 6, the battery is charged and discharged for 100 cycles at -40°C, and its capacity retention rate is as high as 93% or more. This shows that after the thermal strain regulating material is added to the lithium-carbon Li-C active material, the battery has very excellent low-temperature long-cycle performance. After the button cell is assembled in Comparative Example 2, the battery is charged and discharged for 100 cycles at -40°C, and it cannot be cycled for 100 cycles. The battery fails due to the low temperature. The cycle-specific capacity diagram of Example 6 and Comparative Example 2 is shown in the figure below. Figure 11 shown.

[0276] Compared with Example 1, the capacity retention rate of the battery assembled in Example 7 is as high as over 98% after 100 cycles of charge and discharge at 80°C. This shows that after adding thermal strain regulation material to lithium carbon Li-C active material, the battery assembled with lithium cobalt oxide positive electrode material can have very excellent long cycle performance at a high temperature of 80°C.

[0277] Compared with Example 1, the positive electrode material of the battery assembled in Example 8 is lithium cobalt oxide (LCO). After the battery was subjected to 100 charge-discharge cycles at 45°C, its capacity retention rate was as high as over 99%. This shows that after adding the thermal strain control material to the lithium-carbon Li-C active material, the battery assembled with the lithium cobalt oxide positive electrode material has very excellent long-term cycle performance at a high temperature of 45°C.

[0278] Compared with Example 1, in Example 9, a thermal strain regulating material is added to the solid electrolyte membrane layer. After the soft-pack battery is charged and discharged for 100 cycles at 25°C, its capacity retention rate is as high as more than 85%. This shows that after the thermal strain regulating material is added to the solid electrolyte at the same time, the battery can obtain better cycle performance.

[0279] The present invention utilizes the volume contraction of thermal strain control materials during heating and the volume expansion characteristics during cooling to provide structural "reverse support" or "spatial compensation" for the thermal expansion or contraction of electrode active materials caused by temperature changes. This control mechanism can effectively alleviate the thermally induced stress on the interface between the electrode and the solid electrolyte during charging and discharging, and reduce the risk of interface cracking, debonding or increased contact resistance. At the same time, the thermal strain control material does not affect the migration channel of lithium ions, while ensuring ionic conductivity, it improves the interface stability and capacity retention rate in the electrochemical cycle. Experiments have shown that solid-state batteries using the solid-state battery electrodes proposed in the embodiments of the present invention can exhibit lower interface impedance growth rates and better cycle life under high and low temperature and long cycle conditions, with significant performance improvement.

[0280] The specific implementation methods described above further illustrate the objectives, technical solutions and beneficial effects of the present invention in detail. It should be understood that the above description is only a specific implementation method of the present invention and is not intended to limit the scope of protection of the present invention. Any modifications, equivalent substitutions, improvements, etc. made within the spirit and principles of the present invention should be included in the scope of protection of the present invention.

Claims

1. A solid-state battery electrode, characterized in that: The solid-state battery electrode includes an electrode layer; The material of the electrode layer includes: an active material and a thermal strain regulating material; the thermal strain regulating material is distributed between the particles of the active material, and within the temperature range of -100°C to 100°C, the linear thermal expansion coefficient α of the thermal strain regulating material is -20.0×10 -6 K -1 ≤α<0×10 -6 K -1 The volume expands as the temperature decreases and contracts as the temperature increases. The sum of the mass of the active material and the thermal strain regulating material accounts for 80%-100% of the mass of the electrode layer, and the mass ratio of the active material to the thermal strain regulating material is 100:0.1-20.

2. The solid-state battery electrode according to claim 1, characterized in that In the temperature range of -60°C to 100°C, the linear thermal expansion coefficient α of the thermal strain regulating material is -5.0×10 -6 K -1 ≤α≤-0.1×10 -6 K -1 within the scope of In the temperature range of -100°C to 0°C, the particle size of the active material is 2nm-23μm, and the particle size of the thermal strain regulating material is 25nm-18μm; In the temperature range of greater than 0°C to 30°C, the particle size of the active material is in the range of 10nm-25μm, and the particle size of the thermal strain regulating material is in the range of 20nm-15μm; In the temperature range of greater than 30° C. to 100° C., the particle size of the active material is 30 nm-27 μm, and the particle size of the thermal strain regulating material is 16 nm-12 μm.

3. The solid-state battery electrode according to claim 1, characterized in that The thermal strain regulating material includes: one or more of anisotropic materials, isotropic materials or organic framework materials; preferably, the thermal strain regulating material includes: anisotropic materials and / or isotropic materials containing alkali metal elements.

4. The solid-state battery electrode according to claim 3, characterized in that The anisotropic materials include: PbTiO3, BaTiO3, BiNi 1-x Fe x O3 (0≤x≤1), PMN ferroelectric ceramics, PMN ferroelectric ceramics doped with titanium dioxide, PZN ferroelectric ceramics, PZN ferroelectric ceramics doped with titanium dioxide, NbOPO4, AlPO4, FePO4 doped with any one or more of Li, Mg or Zn, one or more of nanostructured or porous SiO2, Li B(CN)2, NaB(CN)2, Zn(CN)2, Cd(CN)2, nanosized ZrO2, nanosized HfO2, nanosized Cu2O, and nanosized Ag2O; The isotropic materials include: Mg2Al4Si5O doped with transition metal elements or rare earth elements 12 , Mg2Al2Si5O doped with transition metal elements or rare earth elements 18 , CaTi4P6O doped with transition metal elements or rare earth elements 24 , Sc2(WO4)3, KZr2(PO4)3, NaZr2(PO4)3, Li2ZrF6, LiFeP2O7, Li Zr2(PO4)3, porous ZrP2O7 ceramics, porous Zr(P 1-x V x )2O7 ceramics (0<x<1), porous ZrV2O7 ceramics, ZrW2O8 ceramics, HfW2O8 ceramics, porous CuFeS2, Lu2Fe doped with Co or Al 17 , Y2Fe doped with Co or Al 17 , LaFe doped with any one or more of Al, Ga or rare earth elements 10.5 Co 1.0 Si 1.5 , one or more of rare earth-doped Mn3AN (A = Zn, Ga or Cu); The organic framework material includes one or more of: a zwitterion-modified metal organic framework material, a nanostructured cellulose framework zeolite imidazole ester framework material, a cross-linked or highly oriented acrylonitrile polymer PAN network support framework material, and a vinyl functionalized metal organic framework material.

5. The solid-state battery electrode according to claim 1, characterized in that The solid-state battery electrode further comprises: a composite material layer; the composite material layer is located on the surface of the electrode layer and is one or more layers, and the composite material layer comprises: one or more of active material, solid electrolyte material, and thermal strain control material; and / or, The solid-state battery electrode also includes: a solid electrolyte membrane layer, which is one layer or multiple layers; wherein, when the solid-state battery electrode does not include the composite material layer, the solid electrolyte membrane layer is located above the electrode layer; when the solid-state battery electrode includes the composite material layer, the solid electrolyte membrane layer is located above the composite material layer and is located on one side or both sides of the composite material layer.

6. The solid-state battery electrode according to claim 5, characterized in that The solid electrolyte membrane layer also includes no more than 50 wt % of a thermal strain regulating material.

7. The solid-state battery electrode according to claim 5, characterized in that The solid electrolyte material includes: one or more of a polymer electrolyte material, an inorganic solid electrolyte material or an organic-inorganic composite solid electrolyte material; The inorganic solid electrolyte material includes one or more of an oxide solid electrolyte, a sulfide solid electrolyte, and a halide solid electrolyte.

8. The solid-state battery electrode according to claim 7, characterized in that The solid electrolyte material in the solid electrolyte membrane layer is the same as the solid electrolyte material in the composite material layer.

9. The solid-state battery electrode according to claim 1, characterized in that The solid-state battery electrode is a positive electrode and / or a negative electrode; The active material of the positive electrode includes one or more of lithium iron phosphate, lithium cobalt oxide, lithium manganese oxide, lithium nickel cobalt manganese oxide, lithium nickel cobalt aluminum oxide, lithium rich layered oxide, lithium nickel manganese oxide, lithium titanate, graphite fluoride, MnO2, FeS2, FeF3, S, H2O, CO2, and O2; The active material of the negative electrode includes: one or more of carbon-based negative electrode materials, silicon-based negative electrode materials, lithium-based negative electrode materials, tin-based negative electrode materials and other types of negative electrode materials; The carbon-based negative electrode material includes one or more of natural graphite, artificial graphite, high-phase pyrolytic graphite, graphitized carbon fiber, graphitized mesophase carbon microspheres, hard carbon, soft carbon, carbon nanotubes, graphene and composite materials thereof; The silicon-based negative electrode material includes: silicon material, silicon oxide material, silicon-carbon composite material; The lithium-based negative electrode material includes: metallic lithium, lithium alloy material, and composite metallic lithium material; The tin-based negative electrode material includes: tin-based material, tin oxide material; The other types of negative electrode materials include lithium titanium oxide materials Li4Ti5O 12 , transition metal sulfide material MoS2.

10. A solid-state battery, characterized in that: The solid-state battery comprises the solid-state battery electrode according to any one of claims 1 to 9 above; The solid-state battery includes one or more of an in-situ solid-state battery, a semi-solid-state battery, a hybrid solid-liquid battery, or a fully solid-state battery.

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