Ultrafast response solid-state micro energy storage module for high-power application

Abstract

The invention provides a high-power application-oriented ultrafast response solid-state micro energy storage module, which comprises an ultrafast response solid-state micro energy storage module main body, the ultrafast response solid-state micro energy storage module main body comprises a solid-state positive electrode unit, a solid-state negative electrode unit, a three-dimensional porous nano-structure electrode substrate, a pulse response type interface modification layer and an embedded micro-channel heat dissipation structure which are arranged in a stacked manner. According to the ultrafast response solid-state micro energy storage module for the high-power application provided by the invention, the collaborative improvement of ultrafast response and high-power output is realized, and the power-energy density tradeoff limitation of a traditional device is broken through; the cycling stability is obviously improved, and the long-term service requirements under extreme working conditions of wide temperature range, high rate and the like are met; the collaborative design of the gradient channel and the asymmetric electrode optimizes ion transmission dynamics and electric field distribution uniformity; the multifunctional interface modification layer and the three-dimensional interpenetrating heat dissipation network synchronously solve the problems of interface failure and thermal runaway.

Description

Technical Field

[0001] The present invention relates to the field of solid-state micro energy storage technology, and in particular to an ultrafast response solid-state micro energy storage module for high-power applications. Background Art

[0002] Solid-state micro-energy storage refers to a micro-energy storage system that uses solid electrode materials and solid electrolytes. Compared with traditional liquid lithium batteries, solid-state micro-energy storage systems have higher safety and energy density while avoiding the risks of liquid electrolyte leakage and fire. Existing solid-state energy storage devices face multiple technical bottlenecks in high-power scenarios:

[0003] 1. Limited ion transport: The interface impedance of traditional solid electrolytes is high, and the lithium ion migration rate cannot meet the instantaneous high current requirements;

[0004] 2. Inadequate thermal management: External heat dissipation design results in redundant volume and is difficult to match the thermal distribution characteristics of microscale devices;

[0005] 3. Single electrode structure: Symmetrical electrode configuration easily leads to local electric field concentration, accelerating interfacial side reactions and capacity decay;

[0006] 4. Dynamic response hysteresis: Rigid interface materials cannot adapt to volume deformation under high magnification, resulting in interface contact failure.

[0007] To this end, an ultrafast response solid-state micro energy storage module for high power applications is proposed. Summary of the Invention

[0008] The present invention aims to solve the problems raised in the background technology and provides an ultrafast response solid-state micro energy storage module for high-power applications.

[0009] The specific technical solutions are as follows:

[0010] An ultrafast response solid-state micro energy storage module for high-power applications, comprising:

[0011] The ultra-fast response solid-state micro energy storage module body includes:

[0012] The stacked solid-state positive electrode unit and the solid-state negative electrode unit are isolated by a composite solid electrolyte layer to achieve ion conduction;

[0013] The three-dimensional porous nanostructured electrode matrix is ​​conformally coated on the surface of the positive and negative electrode units, and its pore network and gradient ion transmission channels form a continuous through-hole structure;

[0014] The gradient ion transmission channel is embedded in the three-dimensional porous matrix along the thickness direction of the electrode, and the channel diameter decreases exponentially from the positive electrode to the negative electrode;

[0015] The pulse-responsive interface modification layer is covered on both sides of the composite solid electrolyte layer in a sandwich structure, and its metal-organic framework material forms a chemical bond connection with the positive and negative electrode surfaces;

[0016] The embedded microchannel heat dissipation structure adopts the form of a three-dimensional interpenetrating network distributed inside the positive and negative electrode units. Its tree-like fractal flow channels form a conformal thermal interface with the electrode active material.

[0017] The asymmetric electrode topology is designed by matching the curvature of the positive electrode fractal structure with the negative electrode honeycomb structure to form a spatially staggered electric field distribution.

[0018] As a preferred embodiment of the present invention, the composite solid electrolyte layer is composed of the following components:

[0019] Lithium lanthanum zirconium matrix material with a grain size of 20-50 nm and 0.5-2 wt.% graphene quantum dots doped at the grain boundaries;

[0020] In situ grown lithium phosphorus sulfur nitrogen interfacial layer with a thickness of 5-10 nm and a molar ratio of Li3PO4 to Li2S of 3:1;

[0021] Gradient lithium ion concentration distribution, surface Li + The concentration is 1.2-1.5 mol / L, and the internal concentration is 0.8-1.0 mol / L;

[0022] The surface roughness of the electrolyte layer is Ra<10nm, and the contact surface with the electrode presents a periodic corrugated structure.

[0023] As a preferred embodiment of the present invention, the method for constructing the three-dimensional porous nanostructured electrode matrix includes:

[0024] Using femtosecond laser direct writing technology to etch a three-dimensional graphene skeleton with a porosity of more than 50% on the surface of the metal foil;

[0025] MoS2 nanosheet arrays were grown vertically on the skeleton surface by electrochemical deposition, with an interlayer spacing of 0.6-1.2 nm.

[0026] Atomic layer deposition is used to coat the nanosheet surface with 3-5 layers of niobium oxide interface layer, with a single layer thickness of 0.3-0.5nm;

[0027] Argon plasma treatment forms carboxyl functional groups on the surface of carbon fibers.

[0028] As a preferred embodiment of the present invention, the gradient ion transport channel satisfies:

[0029] The surface area channel diameter is 20-50nm, the aspect ratio is 5:1-10:1, and the inner wall is modified with a lithium fluoride coating;

[0030] The channel diameter in the middle transition region is 10-20 nm, with a spiral topology and a spiral angle of 30°-45°;

[0031] The channel diameter in the bottom region is 5-10 nm, and the angle between the channel axis and the normal of the electrode surface is <5°;

[0032] The conductivity of lithium ions filled in the channel is >10 -3 S / cm solid polymer electrolyte.

[0033] As a preferred embodiment of the present invention, the pulse-responsive interface modification layer comprises:

[0034] ZIF-8 type MOFs material with a pore size of 1.2-1.6 nm and loaded with lithiated polyvinylpyrrolidone;

[0035] In situ polymerized polyethylene oxide electrolyte with a molecular weight of 600 kDa and EO / Li + =15:1;

[0036] Lithium lanthanum titanium oxide nanowire reinforcement phase, with a diameter of 10-20nm, a length of 1-3μm, and radial arrangement;

[0037] The pyrolytic carbon coating is formed by chemical vapor deposition at 600-800°C.

[0038] As a preferred solution of the present invention, the embedded microchannel heat dissipation structure includes:

[0039] Bionic tree-like fractal flow channel network, primary flow channel width 200-500 μm, fractal iteration number 3-5 times;

[0040] The phase change energy storage material fills the chamber, which contains an octadecane / graphene composite phase change material;

[0041] The graphene aerogel insulation layer is wrapped around the outside of the flow channel;

[0042] The MEMS temperature sensor array is embedded inside the electrode with a spacing of 1-2 mm.

[0043] As a preferred embodiment of the present invention, the asymmetric electrode topology satisfies:

[0044] The positive fractal dimension is 1.6-1.8, and the fractal iteration depth is 4-6 layers;

[0045] The pore size of the negative electrode honeycomb structure is 50-200 μm, and the wall thickness to pore size ratio is 1:8-1:12;

[0046] The curvature radius of the positive electrode surface is 100-200nm, and the curvature radius of the negative electrode surface is 300-500nm;

[0047] A serrated interlocking structure is provided at the electrode contact interface.

[0048] As a preferred embodiment of the present invention, under the test conditions of 25°C:

[0049] Response time ≤ 3ms;

[0050] Energy density ≥180Wh / kg;

[0051] Power density ≥ 20kW / kg;

[0052] Cycle life ≥80,000 times.

[0053] As a preferred embodiment of the present invention, the method for preparing the ultrafast response solid-state micro energy storage module for high-power applications comprises the following steps:

[0054] Femtosecond laser direct writing is used to construct a three-dimensional electrode skeleton;

[0055] The interface is modified by alternating atomic layer deposition and electrochemical deposition;

[0056] The gradient channel is self-assembled under a 0.5-1T magnetic field, and the magnetic field direction forms a 45° angle with the electrode thickness direction;

[0057] All-solid-state packaging is achieved using plasma activated bonding.

[0058] As a preferred embodiment of the present invention, the ultrafast response solid-state micro energy storage module for high-power applications is used for:

[0059] Pulse power system: Peak current ≥500A / cm 2 , pulse width 1-10ms;

[0060] Transient energy device: charge and discharge efficiency ≥ 95%;

[0061] Extreme environment equipment: operating temperature range -40℃~150℃;

[0062] Miniaturized energy supply unit: module volume ≤ 1cm 3 , weight ≤2g.

[0063] The present invention has the following beneficial effects:

[0064] The ultrafast response solid-state micro energy storage module for high-power applications provided by the present invention achieves a synergistic improvement in ultrafast response and high power output, breaking through the power-energy density trade-off limitations of traditional devices; significantly improves cycle stability and adapts to long-term service requirements under extreme working conditions such as wide temperature range and high rate; the coordinated design of gradient channels and asymmetric electrodes optimizes ion transport dynamics and electric field distribution uniformity; the multifunctional interface modification layer and the three-dimensional interpenetrating heat dissipation network simultaneously solve the problems of interface failure and thermal runaway; the miniaturization and high reliability design meet the needs of military, aerospace and other fields for instantaneous high power and adaptation to extreme environments; the modular architecture provides a scalable energy storage solution for the next generation of high-energy equipment; material modification (such as MOFs dynamic interface), structural design (such as fractal-honeycomb electrodes) and process innovation (such as magnetic field-assisted self-assembly) form a technical closed loop to achieve performance optimization from the nanoscale to the system level. BRIEF DESCRIPTION OF THE DRAWINGS

[0065] Figure 1 A schematic structural diagram of an ultrafast response solid-state micro energy storage module for high-power applications provided by an embodiment of the present invention;

[0066] Figure 2 A schematic cross-sectional view of an ultrafast response solid-state micro energy storage module for high-power applications provided by an embodiment of the present invention.

[0067] In the attached figure:

[0068] 1. Ultrafast response solid-state micro energy storage module body; 101. Solid-state positive electrode unit; 102. Solid-state negative electrode unit; 103. Composite solid electrolyte layer; 104. Three-dimensional porous nanostructured electrode matrix; 105. Pulse-responsive interface modification layer. DETAILED DESCRIPTION

[0069] The technical solution of the present invention will be further described below with reference to the accompanying drawings and through specific implementation methods.

[0070] Among them, the drawings are only used for illustrative purposes and represent only schematic diagrams rather than actual pictures, and should not be understood as limiting this patent; in order to better illustrate the embodiments of the present invention, some parts of the drawings may be omitted, enlarged or reduced, and do not represent the size of the actual product; for those skilled in the art, it is understandable that some well-known structures and their descriptions in the drawings may be omitted.

[0071] The same or similar numbers in the drawings of the embodiments of the present invention correspond to the same or similar parts; in the description of the present invention, it should be understood that if the terms "upper", "lower", "left", "right", "inside", "outside" and the like indicate an orientation or position relationship based on the orientation or position relationship shown in the drawings, it is only for the convenience of describing the present invention and simplifying the description, and does not indicate or imply that the device or element referred to must have a specific orientation, be constructed and operate in a specific orientation. Therefore, the terms describing the position relationship in the drawings are only used for illustrative purposes and cannot be understood as limiting this patent. For ordinary technicians in this field, the specific meanings of the above terms can be understood according to specific circumstances.

[0072] In the description of the present invention, unless otherwise expressly specified or limited, when the term "connection" or the like appears to indicate a connection relationship between components, such term should be understood in a broad sense. For example, it can be a fixed connection, a detachable connection, or an integral connection; it can be a mechanical connection or an electrical connection; it can be a direct connection or an indirect connection through an intermediate medium; it can be internal communication between two components or an interaction between two components. For those skilled in the art, the specific meanings of the above terms in the present invention can be understood in specific circumstances.

[0073] Example

[0074] The ultrafast response solid-state micro energy storage module provided in this embodiment is oriented to high power applications, such as Figure 1-Figure 2 As shown, it includes an ultrafast response solid-state micro energy storage module body 1, which includes: a stacked solid-state positive electrode unit 101, a solid-state negative electrode unit 102, a three-dimensional porous nanostructured electrode matrix 104, a pulse-responsive interface modification layer 105, and an embedded microchannel heat dissipation structure, wherein:

[0075] The stacked solid-state positive electrode unit 101 and the solid-state negative electrode unit 102 are isolated and ion-conducted by the composite solid electrolyte layer 103;

[0076] The three-dimensional porous nanostructured electrode matrix 104 is conformally coated on the surface of the positive and negative electrode units, and its pore network (porosity>50%) forms a continuous through-structure with the gradient ion transmission channel;

[0077] Gradient ion transport channels are embedded in a three-dimensional porous matrix along the thickness of the electrode, with the channel diameter decreasing exponentially from the positive electrode to the negative electrode (20-50 nm on the surface → 5-10 nm on the bottom);

[0078] The pulse-responsive interface modification layer 105 is covered on both sides of the composite solid electrolyte layer 103 in a sandwich structure, and its metal organic framework material (MOFs) forms a chemical bond connection with the positive and negative electrode surfaces;

[0079] The embedded microchannel heat dissipation structure adopts the form of a three-dimensional interpenetrating network distributed inside the positive and negative electrode units. Its tree-like fractal flow channels form a conformal thermal interface with the electrode active material.

[0080] The asymmetric electrode topology configuration forms a spatially staggered electric field distribution through the curvature matching design of the positive electrode fractal structure and the negative electrode honeycomb structure (curvature radius ratio 3:1-5:1).

[0081] The ultra-fast response solid-state micro energy storage module for high-power applications that adopts the above technical solution achieves efficient ion transmission and electron isolation through the structural design of stacked solid-state electrodes and composite electrolytes, thereby improving the overall energy density and power output efficiency; the continuous connection between the three-dimensional porous matrix and the gradient channel optimizes the ion diffusion path, significantly shortens the charge transfer time, and enhances the rapid response capability; the asymmetric electrode topology and curvature matching design improve the uniformity of the electric field distribution, reduce the interfacial polarization effect, and improve the electrochemical stability; the conformal integration of the embedded microchannel and the electrode realizes efficient thermal management and avoids performance degradation caused by local overheating.

[0082] The composite solid electrolyte layer 103 is composed of the following components:

[0083] Lithium lanthanum zirconium oxide (LLZO) matrix material with a grain size of 20-50 nm and 0.5-2 wt.% graphene quantum dots doped at the grain boundaries;

[0084] An in situ grown lithium phosphorus sulfur nitrogen (LiPON) interfacial layer with a thickness of 5-10 nm and a molar ratio of Li3PO4 to Li2S of 3:1;

[0085] Gradient lithium ion concentration distribution, surface Li + The concentration is 1.2-1.5 mol / L, and the internal concentration is 0.8-1.0 mol / L;

[0086] The surface roughness of the electrolyte layer is Ra<10nm, and the contact surface with the electrode presents a periodic corrugated structure (wavelength 200-500nm).

[0087] The above technical solution combines the nanocrystalline LLZO matrix with graphene quantum dot doping to enhance the mechanical strength and ionic conductivity of the electrolyte and inhibit dendrite growth; the gradient lithium ion concentration distribution cooperates with the surface corrugated structure to reduce the interface impedance and improve the ion migration kinetics; the in-situ growth of the LiPON interface layer forms a stable electrode / electrolyte interface, reducing side reactions and capacity attenuation.

[0088] The method for constructing the three-dimensional porous nanostructured electrode substrate 104 includes:

[0089] A femtosecond laser direct writing technique (wavelength 1030nm, pulse energy 2-5mJ) was used to etch a three-dimensional graphene skeleton with a porosity of >50% on the surface of the metal foil.

[0090] Molybdenum disulfide (MoS2) nanosheet arrays were grown vertically on the skeleton surface by electrochemical deposition, with an interlayer spacing of 0.6-1.2nm;

[0091] Atomic layer deposition (ALD) is used to coat the nanosheets with 3-5 layers of niobium oxide (Nb2O5) interfacial layer, with a single layer thickness of 0.3-0.5 nm.

[0092] The carbon fibers were treated with argon plasma (power 50-100 W, time 10-30 s) to form carboxyl functional groups on the surface.

[0093] Using the above technical solution, the three-dimensional graphene skeleton constructed by femtosecond laser direct writing provides a highly conductive network and abundant active sites, enhancing the current-carrying capacity of the electrode; the vertically grown MoS2 nanosheet array and the niobium oxide coating layer work synergistically to improve the specific capacity and cycle stability of the electrode; the surface functionalization by plasma treatment improves the wettability of the electrode material and the electrolyte, promoting interfacial charge transfer.

[0094] Among them, the gradient ion transmission channel satisfies:

[0095] The surface area channel diameter is 20-50nm, the aspect ratio is 5:1-10:1, and the inner wall is modified with a lithium fluoride (LiF) coating (thickness 2-5nm);

[0096] The channel diameter in the middle transition region is 10-20 nm, with a spiral topology and a spiral angle of 30°-45°;

[0097] The channel diameter in the bottom region is 5-10 nm, and the angle between the channel axis and the normal of the electrode surface is <5°;

[0098] The conductivity of lithium ions filled in the channel is >10 -3 S / cm solid polymer electrolyte.

[0099] Using the above technical solution, the exponentially decreasing design of the gradient channel is combined with the spiral topology to achieve dynamic regulation of the ion transmission rate to adapt to the rate requirements of different charging and discharging stages; the lithium fluoride coating on the inner wall of the channel and the solid polymer electrolyte filling synergistically inhibit side reactions and enhance the selective transmission of lithium ions; the small angle design between the channel axis and the electrode normal reduces the tortuosity of the ion transmission path and reduces energy loss.

[0100] Wherein, the pulse response type interface modification layer 105 comprises:

[0101] ZIF-8 type MOFs material with a pore size of 1.2-1.6 nm and loaded with lithiated polyvinylpyrrolidone (Li-PVP);

[0102] In situ polymerized polyethylene oxide (PEO) electrolyte with a molecular weight of 600 kDa and EO / Li + =15:1;

[0103] Lithium lanthanum titanate (LLTO) nanowire reinforcement phase, 10-20 nm in diameter and 1-3 μm in length, arranged radially;

[0104] The pyrolytic carbon coating (thickness 2-5 nm) was formed by chemical vapor deposition (CVD) at 600-800 °C.

[0105] Using the above technical solution, the composite structure of IF-8 type MOFs and Li-PVP gives the interface dynamic response characteristics, balancing the ion flux and interface stability at high rates; the radial LLTO nanowire reinforcement phase and the pyrolytic carbon coating layer improve the mechanical strength of the interface and inhibit interface failure caused by volume expansion; the in-situ polymerization of PEO electrolyte forms a continuous ion path, reducing the interface contact resistance and improving the interface compatibility.

[0106] Among them, the embedded microchannel heat dissipation structure includes:

[0107] Bionic tree-like fractal flow channel network, primary flow channel width 200-500 μm, fractal iteration number 3-5 times;

[0108] The phase change energy storage material fills the cavity, which contains octadecane / graphene composite phase change material (melting point 55±2°C);

[0109] A graphene aerogel insulation layer (thermal conductivity <0.03W / m·K) is wrapped around the outside of the flow channel;

[0110] The MEMS temperature sensor array (accuracy ±0.1°C) is embedded inside the electrode with a spacing of 1-2 mm.

[0111] Using the above technical solution, the bionic tree-like fractal flow channel network optimizes the heat dissipation path and improves the uniformity of heat dissipation efficiency through a multi-level branching design; the synergistic effect of phase change material and graphene aerogel realizes rapid absorption and directional isolation of thermal energy, enhancing temperature control capabilities; the embedded layout of the MEMS sensor array realizes real-time monitoring and precise control of the internal temperature of the module.

[0112] Among them, the asymmetric electrode topology satisfies:

[0113] The positive fractal dimension is 1.6-1.8, and the fractal iteration depth is 4-6 layers;

[0114] The pore size of the negative electrode honeycomb structure is 50-200 μm, and the wall thickness to pore size ratio is 1:8-1:12;

[0115] The curvature radius of the positive electrode surface is 100-200nm, and the curvature radius of the negative electrode surface is 300-500nm;

[0116] A serrated interlocking structure (tooth height 10-20 μm, tooth pitch 50-100 μm) is provided at the electrode contact interface.

[0117] By adopting the above technical solution, the fractal dimension and iteration depth are matched to expand the effective reaction area of ​​the electrode and optimize the charge distribution density; the pore size and wall thickness ratio of the honeycomb structure are designed to balance the mechanical strength and ion diffusion efficiency to avoid structural collapse; the serrated interlocking structure enhances the mechanical bonding force of the electrode interface and suppresses the structural stratification problem during the cycle.

[0118] Among them, the ultra-fast response solid-state micro energy storage module for high-power applications, under 25°C test conditions:

[0119] Response time ≤3ms (0-90% rated power);

[0120] Energy density ≥180Wh / kg (1C discharge rate);

[0121] Power density ≥ 20kW / kg (10C pulse discharge);

[0122] Cycle life ≥ 80,000 times (capacity retention rate > 80%, test temperature -20 ~ 60 ° C).

[0123] Using the above technical solution, the ultra-fast response time meets the instantaneous high power demand and is suitable for pulse discharge scenarios; the synergistic improvement of high energy and power density breaks through the performance bottleneck of traditional energy storage devices; the long cycle life under a wide temperature range reflects the stability and reliability of the module in extreme environments.

[0124] The method for preparing the ultrafast response solid-state micro energy storage module for high-power applications includes the following steps:

[0125] Femtosecond laser direct writing (scanning speed 100-200 mm / s) was used to construct the three-dimensional electrode skeleton;

[0126] By atomic layer deposition (100-200 cycles) and electrochemical deposition (current density 2-5mA / cm 2 ) alternatingly modify the interface;

[0127] The gradient channel is self-assembled under a 0.5-1T magnetic field, and the magnetic field direction forms a 45° angle with the electrode thickness direction;

[0128] Plasma activated bonding (power 200-300W, pressure 5-10MPa) is used to achieve full solid-state packaging.

[0129] Using the above technical solution, the alternating process of femtosecond laser direct writing and atomic layer deposition achieves nanometer-level precision structural control, ensuring the integrity of the electrode / electrolyte interface; magnetic field-assisted self-assembly technology realizes the orderly arrangement of gradient channels, improving preparation efficiency and structural consistency; plasma activated bonding process avoids the damage to the nanostructure caused by high-temperature sintering and maintains the intrinsic properties of the material.

[0130] Among them, this ultra-fast response solid-state micro energy storage module for high-power applications is used for:

[0131] Pulse power system: Peak current ≥500A / cm 2 , pulse width 1-10ms;

[0132] Transient energy device: charge and discharge efficiency ≥ 95% (100C rate);

[0133] Extreme environment equipment: operating temperature range -40℃~150℃;

[0134] Miniaturized energy supply unit: module volume ≤ 1cm 3 , weight ≤2g.

[0135] By adopting the above technical solutions, the high pulse current carrying capacity meets the demand for instantaneous high power in the military and industrial fields; the wide operating temperature range expands the application potential of the module in special scenarios such as aerospace and polar exploration; the miniaturized design breaks through the volume limitations of traditional energy storage systems and provides solutions for portable high-energy equipment.

[0136] In summary, the ultrafast response solid-state micro energy storage module for high-power applications provided in this embodiment has the following advantages:

[0137] The ultrafast response solid-state micro energy storage module for high-power applications provided by the present invention achieves a synergistic improvement in ultrafast response and high power output, breaking through the power-energy density trade-off limitations of traditional devices; significantly improves cycle stability and adapts to long-term service requirements under extreme working conditions such as wide temperature range and high rate; the coordinated design of gradient channels and asymmetric electrodes optimizes ion transport dynamics and electric field distribution uniformity; the multifunctional interface modification layer and the three-dimensional interpenetrating heat dissipation network simultaneously solve the problems of interface failure and thermal runaway; the miniaturization and high reliability design meet the needs of military, aerospace and other fields for instantaneous high power and adaptation to extreme environments; the modular architecture provides a scalable energy storage solution for the next generation of high-energy equipment; material modification (such as MOFs dynamic interface), structural design (such as fractal-honeycomb electrodes) and process innovation (such as magnetic field-assisted self-assembly) form a technical closed loop to achieve performance optimization from the nanoscale to the system level.

[0138] Working Principle Process

[0139] 1.Structural collaborative design:

[0140] The main ion transport channel is formed by stacking solid-state electrodes and gradient electrolytes, while the three-dimensional porous matrix is ​​used to expand the reaction interface;

[0141] Asymmetric electrode topology optimizes electric field distribution, combined with pulse-responsive interface to dynamically regulate ion flux;

[0142] Embedded microfluidics are conformally integrated with the energy storage unit to achieve directional conduction and real-time regulation of thermal energy.

[0143] 2. Dynamic working process:

[0144] Charging stage: Lithium ions diffuse rapidly from the positive electrode through the gradient channel, the MOFs interface layer adaptively regulates the ion flux, and the fractal electrode configuration balances the charge distribution;

[0145] Discharge stage: When high power is output, the spiral channel accelerates ion transmission, and the microchannel synchronously starts phase change to absorb heat and suppress temperature rise;

[0146] Cyclic process: The zigzag interlocking structure and the chemically bonded interface jointly suppress volume deformation and maintain structural integrity.

[0147] The above are only preferred embodiments of the present invention and do not limit the implementation mode and protection scope of the present invention. For those skilled in the art, it should be aware that all solutions obtained by equivalent substitutions and obvious changes made using the description and illustrations of the present invention should be included in the protection scope of the present invention.

Claims

1. An ultrafast response solid-state micro energy storage module for high-power applications, comprising an ultrafast response solid-state micro energy storage module body (1), characterized in that: The ultrafast response solid-state micro energy storage module body (1) comprises: A solid-state positive electrode unit (101) and a solid-state negative electrode unit (102) are stacked and isolated by ion conduction via a composite solid electrolyte layer (103); The three-dimensional porous nanostructured electrode substrate (104) is conformally coated on the surface of the positive and negative electrode units, and its pore network and the gradient ion transmission channel form a continuous through-hole structure; The gradient ion transmission channel is embedded in the three-dimensional porous matrix along the thickness direction of the electrode, and the channel diameter decreases exponentially from the positive electrode to the negative electrode; The pulse-responsive interface modification layer (105) is covered on both sides of the composite solid electrolyte layer (103) in a sandwich structure, and its metal organic framework material forms a chemical bond connection with the positive and negative electrode surfaces; The embedded microchannel heat dissipation structure adopts the form of a three-dimensional interpenetrating network distributed inside the positive and negative electrode units. Its tree-like fractal flow channels form a conformal thermal interface with the electrode active material. The asymmetric electrode topology is designed by matching the curvature of the positive electrode fractal structure with the negative electrode honeycomb structure to form a spatially staggered electric field distribution.

2. The ultrafast response solid-state micro energy storage module for high-power applications according to claim 1, characterized in that: The composite solid electrolyte layer (103) is composed of the following components: Lithium lanthanum zirconium matrix material with a grain size of 20-50 nm and 0.5-2 wt.% graphene quantum dots doped at the grain boundaries; In situ grown lithium phosphorus sulfur nitrogen interfacial layer with a thickness of 5-10 nm and a molar ratio of Li3PO4 to Li2S of 3:1; Gradient lithium ion concentration distribution, surface Li + The concentration is 1.2-1.5 mol / L, and the internal concentration is 0.8-1.0 mol / L; The surface roughness of the electrolyte layer is Ra<10nm, and the contact surface with the electrode presents a periodic corrugated structure.

3. The ultrafast response solid-state micro energy storage module for high-power applications according to claim 1, characterized in that: The method for constructing the three-dimensional porous nanostructured electrode matrix (104) comprises: Using femtosecond laser direct writing technology to etch a three-dimensional graphene skeleton with a porosity of more than 50% on the surface of the metal foil; MoS2 nanosheet arrays were grown vertically on the skeleton surface by electrochemical deposition, with an interlayer spacing of 0.6-1.2 nm. Atomic layer deposition is used to coat the nanosheet surface with 3-5 layers of niobium oxide interface layer, with a single layer thickness of 0.3-0.5nm; Argon plasma treatment forms carboxyl functional groups on the surface of carbon fibers.

4. The ultrafast response solid-state micro energy storage module for high-power applications according to claim 1, characterized in that: The gradient ion transmission channel satisfies: The surface area channel diameter is 20-50nm, the aspect ratio is 5:1-10:1, and the inner wall is modified with a lithium fluoride coating; The channel diameter in the middle transition region is 10-20 nm, with a spiral topology and a spiral angle of 30°-45°; The channel diameter in the bottom region is 5-10 nm, and the angle between the channel axis and the normal of the electrode surface is <5°; The conductivity of lithium ions filled in the channel is >10 -3 S / cm solid polymer electrolyte.

5. The ultrafast response solid-state micro energy storage module for high-power applications according to claim 1, characterized in that: The pulse-responsive interface modification layer (105) comprises: ZIF-8 type MOFs material with a pore size of 1.2-1.6 nm and loaded with lithiated polyvinylpyrrolidone; In situ polymerized polyethylene oxide electrolyte with a molecular weight of 600 kDa and EO / Li + =15:1; Lithium lanthanum titanium oxide nanowire reinforcement phase, with a diameter of 10-20nm, a length of 1-3μm, and radial arrangement; The pyrolytic carbon coating is formed by chemical vapor deposition at 600-800°C.

6. The ultrafast response solid-state micro energy storage module for high-power applications according to claim 1, characterized in that: The embedded microchannel heat dissipation structure comprises: Bionic tree-like fractal flow channel network, primary flow channel width 200-500 μm, fractal iteration number 3-5 times; The phase change energy storage material fills the chamber, which contains an octadecane / graphene composite phase change material; The graphene aerogel insulation layer is wrapped around the outside of the flow channel; The MEMS temperature sensor array is embedded inside the electrode with a spacing of 1-2 mm.

7. The ultrafast response solid-state micro energy storage module for high-power applications according to claim 1, characterized in that: The asymmetric electrode topology satisfies: The positive fractal dimension is 1.6-1.8, and the fractal iteration depth is 4-6 layers; The pore size of the negative electrode honeycomb structure is 50-200 μm, and the wall thickness to pore size ratio is 1:8-1:12; The curvature radius of the positive electrode surface is 100-200nm, and the curvature radius of the negative electrode surface is 300-500nm; A serrated interlocking structure is provided at the electrode contact interface.

8. The ultrafast response solid-state micro energy storage module for high-power applications according to claim 1, characterized in that: Under 25℃ test conditions: Response time ≤ 3ms; Energy density ≥180Wh / kg; Power density ≥ 20kW / kg; Cycle life ≥80,000 times.

9. The ultrafast response solid-state micro energy storage module for high-power applications according to claim 1, characterized in that: The preparation method of the ultrafast response solid-state micro energy storage module for high-power applications comprises the following steps: Femtosecond laser direct writing is used to construct a three-dimensional electrode skeleton; The interface is modified by alternating atomic layer deposition and electrochemical deposition; The gradient channel is self-assembled under a 0.5-1T magnetic field, and the magnetic field direction forms a 45° angle with the electrode thickness direction; All-solid-state packaging is achieved using plasma activated bonding.

10. The ultrafast response solid-state micro energy storage module for high-power applications according to claim 1, characterized in that: This ultrafast response solid-state micro energy storage module for high-power applications is used for: Pulse power system: Peak current ≥500A / cm 2 , pulse width 1-10ms; Transient energy device: charge and discharge efficiency ≥ 95%; Extreme environment equipment: operating temperature range -40℃~150℃; Miniaturized energy supply unit: module volume ≤ 1cm 3 , weight ≤2g.

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