Ammonia-hydrogen-electricity multimode reaction chip, preparation method and stacking module

Abstract

The application provides an ammonia-hydrogen-electricity multi-modal reaction chip, which comprises a substrate, a proton-conducting film and a porous diffusion layer arranged in a vertical stack, four microcavities are integrally formed on the substrate and are mutually isolated, and the four microcavities are respectively an electrolytic hydrogen production microcavity, an electrocatalytic ammonia synthesis microcavity, an ammonia cracking microcavity and a hydrogen fuel cell power generation microcavity, and the substrate is a composite ceramic structure. The application also provides a preparation method of the chip, which comprises the following steps of substrate preparation, partitioned catalytic interface preparation, auxiliary unit integration, chip packaging and integration and the like. The application further provides an ammonia-hydrogen-electricity multi-modal reaction chip stacking module. The application realizes chip-level integrated integration of four units of electrolytic hydrogen production, ammonia synthesis, ammonia cracking and fuel cell, simultaneously realizes four different reaction processes through one set of equipment, greatly reduces the number of equipment, pipelines and circuits, greatly improves the comprehensive energy efficiency, and significantly reduces the preparation cost of green hydrogen and green ammonia and the energy storage loss.

Description

Technical Field

[0001] This invention relates to the fields of green electricity hydrogen production, electrocatalytic ammonia synthesis, ammonia catalytic cracking hydrogen production, and hydrogen fuel cell power generation, and particularly to ammonia-hydrogen-electric multimodal reaction chip, preparation method, and stacked module. Background Technology

[0002] Ammonia, as a zero-carbon, high-density hydrogen energy carrier, has a volumetric energy density more than three times that of hydrogen stored under 70 MPa high pressure, and its storage and transportation costs are only one-tenth that of liquid hydrogen, making it one of the optimal carriers for long-term energy storage of distributed renewable energy. The current mainstream hydrogen energy storage technology route is "green electricity electrolysis of water to produce hydrogen → synthetic ammonia storage and transportation → ammonia cracking to produce hydrogen → hydrogen fuel cell power generation," meaning hydrogen production, storage / transportation, and utilization are carried out separately.

[0003] For example, Chinese invention patent CN116732552A discloses an electrocatalytic nitrogen reduction ammonia synthesis reactor, system, and method. The core design features a split-type anode and cathode reaction chamber, proton exchange membrane isolation, and a copper mesh current collector structure with a catalyst-loaded coating, enabling electrocatalytic ammonia synthesis. Chinese utility model patent CN221933886U discloses an ammonia cracking hydrogen production reactor coupled with a palladium membrane. The core design features a catalyst-filled metal shell and an internal palladium membrane tube, achieving spatial integration of ammonia cracking hydrogen production and hydrogen purification. Chinese invention patent CN113571723A discloses a stacking unit for fuel cell stacks and a fuel cell stack structure, including a hydrogen fuel cell stack stacking unit structure. The core design features a stacked structure of large-size metal bipolar plates and membrane electrode assemblies, enabling hydrogen fuel cell power generation.

[0004] The aforementioned patents correspond to technical solutions for ammonia production from hydrogen, hydrogen production from ammonia cracking, and hydrogen fuel cells, respectively. Each solution requires a separate set of equipment and methods, which undoubtedly introduces numerous problems.

[0005] 1. Existing technologies are all spliced ​​from separate single-function equipment, requiring independent configuration of electrolytic cells, ammonia synthesis reactors, ammonia cracking reactors, hydrogen purification devices, and fuel cell stacks. Each device is connected through external pipelines and circuits, resulting in a large system volume, high risk of interface leakage, and an overall energy efficiency loss of over 20%. The response speed is only in the second range, which cannot meet the flexible requirements of distributed scenarios.

[0006] 2. The ammonia synthesis and fuel cell reactions are strongly exothermic reactions, while the hydrogen electrolysis and ammonia cracking reactions are strongly endothermic reactions. Existing split systems cannot achieve in-situ closed-loop utilization of reaction heat, requiring additional heating and heat dissipation equipment. This not only increases system complexity and cost but also results in an overall energy efficiency that is generally below 40%, far below the theoretical limit of 58%.

[0007] 3. Traditional methods of hydrogen production by electrolysis, ammonia synthesis, ammonia cracking, and fuel cells mostly use metal plates as current collectors. Under acidic and oxygen-containing conditions, these plates are prone to pitting corrosion and intergranular corrosion, resulting in a low continuous operating life. Current technologies typically address these issues by applying a corrosion-resistant ceramic coating to the surface of the metal bipolar plate. However, because an integrated ceramic matrix is ​​not formed, the problems of large differences in the thermal expansion coefficients of heterogeneous materials, cracking and delamination during thermal cycling, and soaring interfacial contact resistance cannot be solved. Furthermore, the coating peeling problem also reduces the material's service life.

[0008] 4. Existing split-type equipment is all customized design, without a unified standardized interface. Equipment from different manufacturers is completely incompatible, making it impossible to achieve modular automated stacking. Capacity expansion requires a complete system redesign, resulting in high costs and long cycles for large-scale application, and it cannot meet the flexible expansion needs of distributed scenarios.

[0009] In summary, existing technologies are separate and independent solutions. There is an urgent need for a comprehensive reactor that integrates water electrolysis for hydrogen production, hydrogen-nitrogen ammonia synthesis, ammonia cracking for hydrogen production, and hydrogen fuel cell power generation to solve the aforementioned technical problems. Summary of the Invention

[0010] To address the shortcomings of existing technologies, this invention provides an ammonia-hydrogen-electric multimodal reaction chip, a preparation method, and a stacking module. This solves the problems of bloated equipment, low energy efficiency, short service life, and poor compatibility caused by the need to set up separate equipment and processes for different technical steps in existing technologies.

[0011] In a first aspect, the present invention proposes an ammonia-hydrogen-electric multimodal reaction chip, comprising a substrate, a proton conduction membrane, and a porous diffusion layer arranged in a vertical stack, wherein the proton conduction membrane is located at the center, and the porous diffusion layer and the substrate are sandwiched on both sides thereon.

[0012] The substrate has two symmetrically arranged microcavities, and four isolated microcavities are integrally formed on the substrate, namely, an electrolytic hydrogen production microcavity, an electrocatalytic ammonia synthesis microcavity, an ammonia cracking microcavity, and a hydrogen fuel cell power generation microcavity. The four microcavities are arranged in a centrally symmetrical topological layout with respect to the physical center of the substrate. There are heat conduction channels between the microcavities, forming a heat conduction network that connects the four microcavities.

[0013] Each microcavity in the matrix is ​​provided with an independent flow field, and the inner wall of the flow field is provided with a catalytic interface corresponding to the reaction that occurs therein.

[0014] The matrix is ​​a composite ceramic structure, including a Ti3AlC2MAX phase ceramic core layer, a nanodiamond gradient composite layer grown in situ on the surface of the core layer, and a passivation interface grown in situ on the surface of the gradient composite layer.

[0015] The substrate has an integrally formed interface structure, which provides a fluid interface, an electrical interface, and a mechanical interface. An encapsulation frame is integrally formed along the outer edge of the substrate, and a sensor module and a bidirectional switching unit are integrally formed inside.

[0016] Furthermore, the flow fields of the electrolytic hydrogen production chamber and the ammonia synthesis chamber adopt a three-level fractal microchannel, which is suitable for gas-liquid-solid three-phase mass transfer under normal temperature and pressure; the ammonia cracking chamber adopts a honeycomb micro-reaction channel, which is suitable for medium-temperature gas phase reaction; and the fuel cell chamber adopts a variable cross-section serpentine flow field, which is suitable for self-breathing / pressurized gas supply conditions.

[0017] Furthermore, each of the four microcavities has a microfluidic one-way valve assembly integrated at its inlet, which is integrally formed with the substrate. The microfluidic one-way valve assembly consists of an inlet tapered flow channel, an internal arc-shaped stop boss, and an outlet expanding flow channel.

[0018] Furthermore, the electrolysis hydrogen production chamber is equipped with an oxygen evolution / hydrogen evolution dual-function catalytic interface; the ammonia synthesis chamber is equipped with a nitrogen reduction dual single-atom catalytic interface; the ammonia cracking chamber is equipped with an ammonia cracking integral catalytic interface; and the fuel cell chamber is equipped with a hydrogen hydroxide / oxygen reduction dual-function catalytic interface.

[0019] Furthermore, the substrates are divided into four microcavities by insulating ribs of the same material. The insulating ribs are cross-shaped and integrally formed with the substrates. The heat conduction channels are integrally formed inside the insulating ribs and have a honeycomb structure.

[0020] Furthermore, the fluid interface includes an electrolyte inlet / outlet, a nitrogen / ammonia inlet / outlet, a hydrogen inlet / outlet, and a tail gas outlet; the electrical interface includes an elastic conductive post disposed on the substrate; and the mechanical interface includes positioning pin holes disposed at the four corners of the substrate.

[0021] Secondly, the present invention proposes a method for preparing the above-mentioned ammonia-hydrogen-electric multimodal reaction chip, comprising the following steps:

[0022] S1. Substrate Preparation: Ti3AlC2MAX phase ceramic substrate was prepared by dry pressing and high-temperature sintering under argon atmosphere; four sets of microcavities were integrally formed on the substrate by laser milling, and independent flow fields were formed for each of the four microcavities; then, isolation ribs, encapsulation frame and interface structure were integrally processed; then, nanodiamond gradient composite layer was grown by MPCVD process; finally, CO-Ti passivation interface was generated by oxygen plasma treatment.

[0023] S2. Preparation of partitioned catalytic interfaces: Nitrogen-deficient graphene support layers are grown in situ on the inner walls of the flow field of four microcavities using PECVD process. Oxygen evolution / hydrogen evolution catalysts, nitrogen reduction double single-atom catalysts, ammonia cracking catalysts, and hydroxide / oxygen reduction catalysts are anchored in situ in the corresponding chambers through impregnation-calcination process.

[0024] S3. Auxiliary Unit Integration: The sensor module is integrally processed on the substrate using photolithography and magnetron sputtering processes. The solid-state electrical commutation module and hardware-based PID control unit are integrated at the edge of the substrate using LTCC low-temperature co-fired ceramic process to complete the signal and electrical circuit layout.

[0025] S4. Chip Packaging and Integration: Align and stack the proton conduction membrane, porous diffusion layer and each chamber, thermo-press and encapsulate, assemble standardized stacking interfaces, and complete chip fabrication.

[0026] Furthermore, in step S1, the green blank is placed in a graphite crucible and heated to 1350°C at a heating rate of 3°C / min under argon atmosphere protection, and sintered at a constant temperature for 4 hours. Then, it is cooled to room temperature with the furnace at a rate of 2°C / min to obtain a Ti3AlC2MAX phase ceramic matrix with a matrix thickness of 0.2mm-0.8mm.

[0027] When depositing the nanodiamond gradient composite layer using the MPCVD process, the deposition is carried out in four stages, so that the diamond content increases gradually from the core layer to the surface from 0% to 30% to 70% to 100%, and the thickness of the nanodiamond gradient composite layer is 8μm.

[0028] Preferably, in step S2, the PECVD preparation process parameters for the nitrogen-defective graphene layer are: methane flow rate 30 sccm, nitrogen flow rate 10 sccm, hydrogen flow rate 50 sccm, microwave power 2 kW, deposition temperature 700℃, and deposition time 30 min.

[0029] Thirdly, the present invention also proposes an ammonia-hydrogen-electric multimodal reaction chip stacking module, which consists of several of the above-mentioned ammonia-hydrogen-electric multimodal reaction chips, which are tightly stacked by mechanical positioning structure and connectors.

[0030] The stacked module includes an adaptive flow-sharing manifold, a redundant flexible electrical busbar, a chip-level signal synchronous acquisition backplane, and an edge AI controller. The adaptive flow-sharing manifold is sealed to the chip fluid interface, the redundant flexible electrical busbar is plugged into the chip electrical interface, the chip-level signal synchronous acquisition backplane is connected to the MEMS sensor array signal, and the edge AI controller is communicatively connected to the signal acquisition backplane and the solid-state electrical commutation module. The edge AI controller is an embedded controller with an NPU, which incorporates single-chip-level operating condition control, mode switching, fault warning, and energy efficiency optimization algorithms.

[0031] Compared with the prior art, the present invention has the following beneficial effects:

[0032] 1. This invention achieves chip-level integrated processing of four major units: electrolytic hydrogen production, ammonia synthesis, ammonia cracking, and fuel cells. It enables the simultaneous implementation of four different reaction processes with a single device, significantly reducing the number of devices, pipelines, and circuits required.

[0033] The system size is reduced by more than 80% compared to the split-type solution, the equipment cost is reduced by more than 70%, and the mode switching response time is improved from the second level to the millisecond level. It is perfectly adapted to core scenarios such as distributed photovoltaic / wind power long-term energy storage, off-grid power stations, and residential energy storage, and has extremely high industrialization value.

[0034] 2. This invention achieves a high proportion of in-situ utilization of reaction heat through a centrally symmetrical topological layout and honeycomb heat conduction channels, requiring almost no external heating / cooling equipment. The overall energy efficiency of the entire energy storage-release process is ≥55%, which is more than 40% higher than the existing split system, significantly reducing the preparation cost and energy storage loss of green hydrogen and green ammonia.

[0035] 3. The MAX phase-nanodiamond gradient composite matrix of the present invention can be adapted to both extreme working conditions at the same time, and its corrosion performance is improved by more than two orders of magnitude compared with the existing metal matrix; the in-situ chemical bond anchoring design of the catalyst avoids the problems of catalyst shedding and agglomeration, the catalytic activity retention rate is >95% after 1000h continuous operation, and the continuous operation life is >8000 hours, which is more than 3 times better than the existing technology.

[0036] 4. Through the three-in-one universal standardized interface, the energy storage capacity can be linearly expanded from 1kWh to 10MWh. It can be used independently or mixed with existing single-function chips without the need for customized design, which greatly improves construction efficiency. Attached Figure Description

[0037] Figure 1 This is a cross-sectional schematic diagram of an embodiment of the present invention.

[0038] Figure 2 This is a schematic diagram of the substrate structure according to an embodiment of the present invention.

[0039] Figure 3 This is a schematic diagram of the four-microcavity center-symmetric topology and heat conduction network in this embodiment.

[0040] Figure 4 This is a flowchart illustrating the closed-loop collaborative working principle of thermal-mass-electricity in this embodiment.

[0041] Figure 5 This is a schematic diagram of the multi-chip stacked energy storage module architecture in this embodiment.

[0042] In the above figures: 1. Substrate; 2. Porous diffusion layer; 3. Proton conduction membrane; 4. Flow field; 5. Isolation rib; 11. Microcavity. Detailed Implementation

[0043] The technical solutions of the present invention will be further described below with reference to the accompanying drawings and embodiments.

[0044] Example 1:

[0045] like Figure 1-4 As shown, the ammonia-hydrogen-electric multimodal reaction chip of this embodiment is a basic standard specification, including a substrate 1, a proton conduction membrane 3, and a porous diffusion layer 2 stacked vertically, wherein the proton conduction membrane 3 is located at the center, and the porous diffusion layer 2 and the substrate 1 are sandwiched on both sides in sequence.

[0046] The substrate 1 is a composite ceramic structure, including a Ti3AlC2MAX phase ceramic core layer, a nanodiamond gradient composite layer grown in situ on the surface of the core layer, and a passivation interface grown in situ on the surface of the gradient composite layer.

[0047] The thickness of substrate 1 is 0.5 mm. Its conductivity at 25℃ is ≥5×10⁻⁶. 6 With a thermal conductivity of S / m comparable to metallic copper, it can achieve efficient current collection in four chambers without the need for an additional conductive layer; its thermal conductivity ≥170W / (m·K) enables rapid and uniform heat transfer in the four chambers, establishing in-situ thermal equilibrium; its coefficient of thermal expansion is 9.0×10⁻⁶. -6 / K has a thermal expansion coefficient matching degree of ≥95% with the perfluorosulfonic acid proton exchange membrane, eliminating thermal stress in the cold and hot cycle of -20℃~400℃, and eliminating the risk of cracking and delamination.

[0048] The nanodiamond gradient composite layer has a thickness of 8μm. From the inside to the surface of the Ti3AlC2MAX phase ceramic core layer, the diamond content gradually increases from 0% to 30% to 70% to 100%. The gradient composite layer and the MAX phase core layer are metallurgically bonded with a bonding strength of ≥40MPa, with no risk of detachment. After 1000 cycles of thermal cycling from -20℃ to 400℃, the interfacial bonding strength retention rate is ≥98%.

[0049] The CO-Ti passivation interface thickness is 1 nm, and the corrosion current density under normal temperature and acid / alkali conditions is <0.03 μA / cm. 2 The corrosion rate under a high-temperature ammonia atmosphere at 400℃ is <0.001 mm / year, and the surface contact resistance is <1 mΩ·cm. 2 It can be adapted to both extreme working conditions of normal temperature acid and alkali and medium and high temperature ammonia corrosion.

[0050] The substrate 1 has two symmetrically arranged components. Four microcavities 11 are integrally formed on the substrate 1 and are isolated from each other. These are a hydrogen electrolysis microcavity, an electrocatalytic ammonia synthesis microcavity, an ammonia cracking microcavity, and a hydrogen fuel cell power generation microcavity. The four microcavities 11 are arranged in a centrally symmetrical topological layout with respect to the physical center of the substrate. There are heat conduction channels between the microcavities 11, forming a heat conduction network that connects the four microcavities 11.

[0051] Each microcavity 11 has an effective reaction area of ​​1.8 cm². 2 The total effective reaction area is 7.2 cm². 2 The substrate utilization rate is ≥80%; 0.5mm wide Ti3AlC2MAX phase ceramic cross-shaped isolation ribs are set between the microcavities to avoid cross-contamination and gas leakage, resulting in an overall helium leak detection rate of <5×10⁻⁶. -7 Pa·m 3 / s, insulation class >1500V.

[0052] On a 30mm×30mm substrate 1, the ammonia synthesis chamber and the fuel cell chamber are arranged vertically along the horizontal axis of the substrate center, while the hydrogen electrolysis chamber and the ammonia cracking chamber are arranged horizontally along the vertical axis of the substrate center. The effective reaction area and heat exchange area of ​​the four microcavities are completely consistent. The exothermic unit (ammonia synthesis chamber and fuel cell chamber) and the endothermic unit (hydrogen electrolysis chamber and ammonia cracking chamber) are arranged adjacent to each other. The isolation ribs 5 between adjacent microcavities are all provided with honeycomb heat conduction channels, and the heat exchange area accounts for ≥90%, which can realize the in-situ transfer of most of the heat from the exothermic reaction to the endothermic reaction.

[0053] Each microcavity 11 in the substrate 1 has an independent flow field 4. The flow fields of the electrolysis hydrogen production chamber and the ammonia synthesis chamber adopt a three-stage fractal microchannel: the first-stage main channel is 2 mm wide, the second-stage sub-channel is 0.8 mm wide, and the third-stage micro-nano channel is 50 μm wide, suitable for gas-liquid-solid three-phase mass transfer under normal temperature and pressure. The flow field of the ammonia cracking chamber adopts a honeycomb micro-reaction channel with a pore diameter of 0.5 mm and a porosity of 78%, suitable for mesotemperature gas-phase reactions. The flow field of the fuel cell chamber adopts a variable cross-section serpentine channel with an inlet channel width of 0.6 mm and an outlet channel width of 0.9 mm, suitable for self-breathing / pressurized gas supply conditions. In addition, each microcavity 11 has an in-situ microfluidic one-way valve assembly integrated at the flow field 4 inlet, which is integrally laser-milled with the substrate 1. Each valve assembly consists of an inlet tapered flow channel (inlet diameter 0.8mm, outlet diameter 0.4mm, length 1mm), an internal arc-shaped stop boss (height 0.2mm), and an outlet expanding flow channel. The fluid resistance difference formed by the change of the flow channel cross section realizes the one-way directional transmission of fluid. The reverse cut-off pressure is ≥0.2MPa, which completely avoids the cross-contamination of media when switching between energy storage and energy release modes.

[0054] The inner wall of flow field 4 is equipped with catalytic interfaces corresponding to the reactions that occur therein. The inner wall of each microcavity 11 flow channel is covered with nitrogen-deficient graphene layers grown in situ using PECVD technology. C-Ti chemical bonds are formed between the graphene layers and the MAX phase matrix, with a bonding force ≥35MPa and no risk of detachment. The nitrogen-deficient sites can precisely anchor the catalyst metal single atoms, preventing their migration and aggregation, and improving the long-term stability of the catalyst.

[0055] Catalytic interface of electrolytic hydrogen production chamber: IrO2-RuO2@TiO2 nanowire oxygen evolution catalyst and Pt / C@boron nitride nanosheet hydrogen evolution catalyst are in situ anchored on nitrogen-deficient graphene layer to form an integrated bifunctional catalytic interface; Ir to Ru molar ratio 1:1, catalytic activity retention rate >95% after 1000h continuous operation.

[0056] The catalytic interface of the electrocatalytic ammonia synthesis chamber: Fe / Bi dual single-atom nitrogen reduction catalyst is in-situ anchored on a nitrogen-deficient graphene layer. The molar ratio of Fe to Bi dual sites is 3:1, and the single-atom particle size is <0.5nm. It is precisely anchored through nitrogen-deficient sites, eliminating the risk of migration and aggregation.

[0057] Catalytic interface of ammonia cracking chamber: SiC nanowire framework is grown in situ on nitrogen-deficient graphene layer on the inner wall of honeycomb channel and chemically bonded to the matrix with a bonding force ≥38MPa; Ru / La2O3 ammonia cracking catalyst is loaded in the upper limit domain of the nanowire framework with Ru to La molar ratio of 1:2 and Ru loading of 2wt%, without the risk of high-temperature sintering and gas flow erosion.

[0058] Catalytic interface of hydrogen fuel cell chamber: The inner wall of the flow channel is in-situ generated with integrated hydrophilic and hydrophobic partitions induced by femtosecond laser. A high-entropy PtRuFeCoNi high-entropy alloy hydroxide catalyst is in-situ anchored on the nitrogen-defective graphene layer on the anode side, and a Fe / N / C non-platinum oxygen reduction catalyst is in-situ anchored on the cathode side. The catalyst layer adopts a gradient pore structure, exhibiting strong adhesion to the substrate and eliminating the risk of detachment. Under normal pressure self-breathing conditions, the area power density is ≥1.0 W / cm². 2 .

[0059] An interface structure is integrally formed on the substrate 1, thereby providing fluid interfaces, electrical interfaces, and mechanical interfaces. An encapsulation frame is integrally formed along the outer edge of the substrate, and a sensor module and a bidirectional switching unit are integrally formed inside. Among these:

[0060] The fluid interface is located at the bottom of the chip, with a total of 6 standardized interfaces, including electrolyte inlet / outlet, nitrogen / ammonia inlet / outlet, hydrogen inlet / outlet, and exhaust port. The interface diameter is 2mm, the center distance tolerance is ±0.05mm, and it is sealed with fluororubber O-ring end face, with a sealing pressure ≥1MPa. The interface size, center distance, and sealing specifications are completely consistent with the existing MAX phase hydrogen energy single-function chip. When multiple chips are stacked, a common fluid manifold is automatically formed, and the standard deviation of flow distribution of a single chip is <3%.

[0061] The electrical interface is located on both sides of the chip and consists of standardized gold-plated elastic conductive pillars with a total of 16 pins, including 8 power pins and 8 sensing signal pins. The pin definitions, spacing, and dimensions are fully compatible with existing MAX phase hydrogen energy single-function chips. The single-contact contact resistance is <1mΩ, the insertion and removal life is ≥1000 times, and the series and parallel electrical connections are automatically realized when multiple chips are stacked. The power expansion linearity is >99%.

[0062] The mechanical interface consists of φ2mm high-precision positioning pin holes at the four corners of the chip, with a positioning accuracy of ±5μm. The hole size and tolerance are completely consistent with the existing MAX phase hydrogen energy single-function chip, which can be adapted to the same stacking module and automated production line. During stacking, the chip alignment accuracy is ±20μm, and the preload uniformity is >95%.

[0063] The sensor module is a MEMS passive sensor array, integrally formed with the substrate. It houses a platinum resistance temperature sensor (temperature range -20℃~400℃, accuracy ±0.3℃), a voltage / current monitoring electrode, a capacitive concentration sensor, a pH sensor, and a piezoresistive pressure sensor (accuracy ±0.5%FS) in four microcavities, achieving real-time monitoring of all parameters at the single-chip level. All sensors are completely isolated from the substrate by a 5μm thick PI insulating layer. The signal leads are laid along the edge of the substrate and led out to a standardized electrical interface. The sampling frequency is 1kHz, the acquisition accuracy is ±0.5%, and the transmission delay is <1ms.

[0064] The chip-level bidirectional switching unit includes an in-situ microfluidic one-way valve assembly integrated with the substrate, a solid-state electrical commutation module, and a hardware-based PID control unit, with no moving mechanical parts and no external piping. The solid-state electrical commutation module is integrated into the edge of the MAX phase substrate using LTCC low-temperature co-fired ceramic technology. Its core is a four-group anti-parallel IGBT power switch array with a rated current of 10A and a withstand voltage of 60V, which controls the switching on and off via level signals. In energy storage mode, it automatically connects the fluid and electrical circuits of the electrolysis hydrogen production chamber and the ammonia synthesis chamber, and closes the circuits of the ammonia cracking chamber and the fuel cell chamber. In energy release mode, it automatically connects the fluid and electrical circuits of the ammonia cracking chamber and the fuel cell chamber, and closes the circuits of the electrolysis hydrogen production chamber and the ammonia synthesis chamber. The mode switching response time is ≤5ms.

[0065] The specific chip fabrication steps in this embodiment are as follows:

[0066] (1) Using 99.2% pure Ti3AlC2 powder, adding 3wt% yttrium oxide sintering aid, using anhydrous ethanol as solvent and PVB as binder, ball milling for 24h to prepare a uniform slurry with a ball-to-powder ratio of 5:1 and a ball milling speed of 300rpm; spray granulation followed by dry pressing to prepare a 0.6mm thick green body with a forming pressure of 200MPa and a holding time of 30s; using ultraviolet laser to pre-etch the four-chamber contour, isolation ribs, honeycomb heat conduction channels, flow channel structure, encapsulation frame, and interface positioning structure on the surface of the green body with a positioning accuracy of ±10μm; placing the green body in a graphite crucible, protecting it with a high-purity argon atmosphere, heating it to 1350℃ at a heating rate of 3℃ / min, sintering it at a constant temperature for 4h, and then cooling it to room temperature with the furnace at a rate of 2℃ / min to obtain the MAX phase ceramic matrix.

[0067] Five-axis femtosecond laser milling (laser wavelength 1030nm, pulse width 300fs, repetition frequency 100kHz) was used to integrally machine four sets of micro-reaction chambers, fractal microchannels, in-situ microfluidic one-way valve groups, honeycomb heat conduction channels, fluid interfaces, and positioning pin holes on the substrate with a machining accuracy of ±5μm. After machining, the substrate was ultrasonically cleaned with anhydrous ethanol for 10 minutes and dried with high-purity nitrogen.

[0068] An 8 μm thick nanodiamond gradient composite layer was grown in situ on all surfaces of the substrate using MPCVD technology. The microwave power was 3 kW, the deposition temperature was 800℃, and the working pressure was 150 Torr. The deposition was performed in three stages, achieving a four-stage gradient deposition with a total deposition time of 1.5 h: ① 0-20 min, methane / hydrogen flow ratio 1:99, diamond content approximately 30%; ② 20-50 min, methane / hydrogen flow ratio 3:97, diamond content approximately 70%; ③ 50-90 min, methane / hydrogen flow ratio 5:95, diamond content 100%. The substrate surface was then treated with oxygen plasma for 10 min at a power of 200 W and an oxygen flow rate of 50 sccm to generate a CO-Ti passivated self-corrosion-resistant conductive interface in situ, completing the substrate preparation.

[0069] (2) Preparation of general carrier layer: Nitrogen-defect graphene layer was grown in situ on the inner wall of the four chambers using PECVD process. The methane flow rate was 30 sccm, the nitrogen flow rate was 10 sccm, the hydrogen flow rate was 50 sccm, the microwave power was 2 kW, the deposition temperature was 700℃, the deposition time was 30 min, and the nitrogen defect ratio was 5%.

[0070] Electrolytic hydrogen production chamber: IrO2-RuO2@TiO2 and Pt / C catalyst precursor were loaded by impregnation method, with Ir to Ru molar ratio of 1:1, total metal concentration of 0.05 mol / L, impregnation time of 12 h, calcination at 450 ℃ in argon atmosphere for 2 h, and heating rate of 5 ℃ / min to complete the preparation of oxygen evolution and hydrogen evolution catalytic interface.

[0071] Ammonia synthesis chamber: Fe / Bi dual single-atom precursor was loaded by impregnation method, with Fe to Bi molar ratio of 3:1, total metal concentration of 0.05 mol / L, impregnation time of 12 h, and calcination at 550℃ for 2 h in argon atmosphere to complete the preparation of nitrogen reduction catalytic interface; at the same time, parallel blank control flow channel and isotope labeled flow channel were integrally processed.

[0072] Ammonia cracking chamber: SiC nanowire precursors were grown on the inner wall of honeycomb channels by in-situ hydrothermal synthesis and calcined at 1200℃ in an argon atmosphere for 2 h to obtain the SiC nanowire framework; Ru / La2O3 precursors were loaded by an equal-volume impregnation method with a Ru to La molar ratio of 1:2 and an impregnation time of 12 h, followed by reduction calcination at 450℃ in a hydrogen atmosphere for 2 h to complete the preparation of the ammonia cracking catalytic interface.

[0073] Fuel cell chamber: A femtosecond laser was used to induce the in-situ generation of hydrophilic and hydrophobic integrated partitions on the inner wall of the flow channel. The laser power was 10W and the scanning speed was 500mm / s. PtRuFeCoNi high-entropy alloy anode catalyst and Fe / N / C cathode catalyst were impregnated and calcined at 350℃ in an argon atmosphere for 2h to complete the preparation of the fuel cell catalytic interface.

[0074] (3) A MEMS passive sensor array, including temperature, voltage, concentration and pressure sensors, is integrally fabricated on the substrate using magnetron sputtering and photolithography. The sensor signal leads are laid out along the edge of the substrate and led out to the electrical interface. A solid-state electrical commutation module and a hardware PID control unit are integrated in the non-reactive area at the edge of the substrate using LTCC technology to complete the electrical circuit layout. The core of the solid-state commutation module is a 4-group 10A / 60V reverse parallel IGBT switch array. The LTCC sintering temperature is 850℃ and the holding time is 30min. The proton conduction membrane and porous diffusion layer corresponding to each chamber are stacked in sequence. They are precisely aligned by the four corner positioning pin holes with an alignment accuracy of ±20μm. The PEEK insulating packaging frame is fitted in and hot-pressed at 130℃ and 2.5MPa for 10min. The three-in-one standardized fluid interface and gold-plated elastic conductive pillars are assembled. The edges are sealed with PTFE sealant to complete the chip fabrication. The finished chip size is 30mm×30mm×5mm.

[0075] The fabricated chip underwent comprehensive testing for hermeticity, insulation, dimensional accuracy, and conductivity: the overall helium leak detection rate was <5×10⁻⁶. -7 Pa·m 3 The insulation resistance is >100MΩ, the dimensional tolerances meet the design requirements, the electrical circuit has good conductivity, and the flow channels are unblocked. COMSOL multiphysics simulation verified that the chip prepared in this embodiment achieves an ammonia yield of 31.2 μg·h⁻¹ under normal temperature and pressure. -1 ・cm -2 The Faraday efficiency is 66.8%, and the DC power consumption for hydrogen production via electrolysis is 3.92 kWh / Nm³.3 H2; Ammonia conversion rate of 99.6% at 380℃, output hydrogen purity of 99.9997%, fuel cell areal power density of 1.02 W / cm² 2 The overall energy efficiency of the entire energy storage-release process is 56.2%, and the mode switching response time is 3.8ms, which meets the design target.

[0076] like Figure 5 As shown, based on the chip prepared in this embodiment, an energy storage stacking module is prepared. The specific steps are as follows:

[0077] The system employs 20 basic-specification chips, which are stacked in series via a standardized three-in-one stacking interface. The stacked module is equipped with an adaptive flow-sharing manifold, redundant flexible electrical busbars, a chip-level signal synchronous acquisition backplane, and an edge AI controller. The flow manifold adopts a symmetrical flow channel design, with a single-chip flow resistance deviation of <2%, achieving uniform fluid distribution. The electrical busbars adopt a parallel redundant design, with a single-chip power supply deviation of <0.01V. The signal acquisition backplane is plugged into the chip electrical interface to achieve synchronous acquisition of single-chip parameters at a sampling frequency of 10Hz. The edge AI controller uses an ARM Cortex-A76 core + 8TOPS NPU to achieve real-time control of operating conditions, mode switching, fault warning, and energy efficiency optimization.

[0078] Twenty chips were stacked sequentially using locating pin holes, and then assembled with a fluid manifold, electrical busbars, and a signal acquisition backplane. The locking torque was 2 N·m, and the overall helium leak detection rate was <1×10⁻⁶. -6 Pa·m 3 / s, insulation class >1500V, complete stacking module assembly.

[0079] The module underwent airtightness testing, insulation testing, electrical continuity testing, mode switching function testing, and control function integration testing. Simulation verification showed that the module's capacity expansion linearity was 99.5%, and the single-chip performance deviation was 2.1%. It can achieve normal switching and stable operation of energy storage / release modes, meeting the design objectives.

[0080] Example 2:

[0081] The ammonia-hydrogen-electric multimodal reaction chip in this embodiment is ultra-thin, making it suitable for space-constrained automotive and shipping scenarios. Most of its components are the same as in Embodiment 1, with the following differences:

[0082] In step (1), the thickness of the green substrate is 0.25 mm, and the thickness after sintering is 0.2 mm. In step (2), the Fe / Bi double single-atom molar ratio is 2:1; the Ru loading is 1.5 wt%.

[0083] Simulation results show that the ammonia synthesis efficiency of the chip in this embodiment is 72.1% and the ammonia yield is 26.5 μg·h⁻¹ under normal temperature and pressure. -1 ・cm-2 The ammonia conversion rate is 99.2% at 380℃, the volumetric power density is 2.2 times higher than the basic specification, and the mode switching response time is 4.2ms, which meets the design target.

[0084] Example 3:

[0085] The ammonia-hydrogen-electric multimodal reaction chip in this embodiment is a high-load specification, suitable for grid-scale energy storage and industrial-grade green ammonia production scenarios. Most of its content is the same as in Embodiment 1, with the following differences:

[0086] In step (1), the thickness of the green substrate is 1.0 mm, and the thickness after sintering is 0.8 mm. In step (2), the Fe / Bi double single-atom molar ratio is 4:1; the Ru loading is 2.5 wt%.

[0087] Simulation results show that, under the 3 bar operating condition of the chip in this embodiment, the ammonia yield is 38.7 μg·h⁻¹. -1 ・cm -2 The ammonia conversion rate at 380℃ is 99.8%, and the overall energy efficiency of the entire energy storage-release process is 55.8%, which meets the design target.

[0088] Finally, it should be noted that the above embodiments are only used to illustrate the technical solutions of the present invention and are not intended to limit it. Although the present invention has been described in detail with reference to preferred embodiments, those skilled in the art should understand that modifications or equivalent substitutions can be made to the technical solutions of the present invention without departing from the spirit and scope of the technical solutions of the present invention, and all such modifications or substitutions should be covered within the scope of the claims of the present invention.

Claims

1. An ammonia-hydrogen-electrode multimodal reaction chip, comprising a vertically stacked substrate, a proton-conducting membrane, and a porous diffusion layer, wherein the proton-conducting membrane is located at the center, and the porous diffusion layer and the substrate are sequentially sandwiched on both sides thereof, characterized in that: The substrate has two symmetrically arranged microcavities, and four isolated microcavities are integrally formed on the substrate, namely, an electrolytic hydrogen production microcavity, an electrocatalytic ammonia synthesis microcavity, an ammonia cracking microcavity, and a hydrogen fuel cell power generation microcavity. The four microcavities are arranged in a centrally symmetrical topological layout with respect to the physical center of the substrate. There are heat conduction channels between the microcavities, forming a heat conduction network that connects the four microcavities. Each microcavity in the matrix is ​​provided with an independent flow field, and the inner wall of the flow field is provided with a catalytic interface corresponding to the reaction that occurs therein. The matrix is ​​a composite ceramic structure, including a Ti3AlC2MAX phase ceramic core layer, a nanodiamond gradient composite layer grown in situ on the surface of the core layer, and a passivation interface grown in situ on the surface of the gradient composite layer. The substrate has an integrally formed interface structure, which provides a fluid interface, an electrical interface, and a mechanical interface. An encapsulation frame is integrally formed along the outer edge of the substrate, and a sensor module and a bidirectional switching unit are integrally formed inside.

2. The ammonia-hydrogen-electric multimodal reaction chip as described in claim 1, characterized in that: The flow fields of the electrolysis hydrogen production chamber and the ammonia synthesis chamber adopt a three-level fractal microfluidic channel, which is suitable for gas-liquid-solid three-phase mass transfer under normal temperature and pressure; the ammonia cracking chamber adopts a honeycomb micro-reaction channel, which is suitable for medium-temperature gas phase reaction; the fuel cell chamber adopts a variable cross-section serpentine flow field, which is suitable for self-breathing / pressurized gas supply conditions.

3. The ammonia-hydrogen-electric multimodal reaction chip as described in claim 2, characterized in that: Each of the four microcavities has a microfluidic one-way valve assembly integrated at the inlet of the flow field. The assembly is integrally formed with the substrate. The microfluidic one-way valve assembly consists of an inlet tapered flow channel, an internal arc-shaped stop boss, and an outlet expanding flow channel.

4. The ammonia-hydrogen-electric multimodal reaction chip as described in claim 1, characterized in that: The electrolysis hydrogen production chamber is equipped with an oxygen evolution / hydrogen evolution dual-function catalytic interface; the ammonia synthesis chamber is equipped with a nitrogen reduction dual single-atom catalytic interface; the ammonia cracking chamber is equipped with an ammonia cracking integral catalytic interface; and the fuel cell chamber is equipped with a hydrogen oxidation / oxygen reduction dual-function catalytic interface.

5. The ammonia-hydrogen-electric multimodal reaction chip as described in claim 1, characterized in that: The substrate is divided into four microcavities by isolating ribs of the same material. The isolating ribs are cross-shaped and integrally formed with the substrate. The heat conduction channels are integrally formed inside the isolating ribs and have a honeycomb structure.

6. The ammonia-hydrogen-electric multimodal reaction chip as described in claim 1, characterized in that: The fluid interface includes an electrolyte inlet / outlet, a nitrogen / ammonia inlet / outlet, a hydrogen inlet / outlet, and a tail gas outlet; the electrical interface includes an elastic conductive post disposed on the substrate; and the mechanical interface includes positioning pin holes disposed at the four corners of the substrate.

7. A method for preparing an ammonia-hydrogen-electric multimodal reaction chip as described in any one of claims 1-6, characterized in that, Includes the following steps: S1. Substrate Preparation: Ti3AlC2MAX phase ceramic substrate was prepared by dry pressing and high-temperature sintering under argon atmosphere; four sets of microcavities were integrally formed on the substrate by laser milling, and independent flow fields were formed for each of the four microcavities; then, isolation ribs, encapsulation frame and interface structure were integrally processed; then, nanodiamond gradient composite layer was grown by MPCVD process; finally, CO-Ti passivation interface was generated by oxygen plasma treatment. S2. Preparation of partitioned catalytic interfaces: Nitrogen-deficient graphene support layers are grown in situ on the inner walls of the flow field of four microcavities using PECVD process. Oxygen evolution / hydrogen evolution catalysts, nitrogen reduction double single-atom catalysts, ammonia cracking catalysts, and hydroxide / oxygen reduction catalysts are anchored in situ in the corresponding chambers through impregnation-calcination process. S3. Auxiliary Unit Integration: The sensor module is integrally processed on the substrate using photolithography and magnetron sputtering processes. The solid-state electrical commutation module and hardware-based PID control unit are integrated at the edge of the substrate using LTCC low-temperature co-fired ceramic process to complete the signal and electrical circuit layout. S4. Chip Packaging and Integration: Align and stack the proton conduction membrane, porous diffusion layer and each chamber, thermo-press and encapsulate, assemble standardized stacking interfaces, and complete chip fabrication.

8. The method for preparing the ammonia-hydrogen-electric multimodal reaction chip as described in claim 7, characterized in that: In step S1, the green blank is placed in a graphite crucible and heated to 1350°C at a heating rate of 3°C / min under argon atmosphere protection. It is then sintered at a constant temperature for 4 hours and cooled to room temperature in the furnace at a rate of 2°C / min to obtain a Ti3AlC2MAX phase ceramic matrix with a matrix thickness of 0.2mm-0.8mm. When depositing the nanodiamond gradient composite layer using the MPCVD process, the deposition is carried out in four stages, so that the diamond content increases gradually from the core layer to the surface from 0% to 30% to 70% to 100%, and the thickness of the nanodiamond gradient composite layer is 8μm.

9. The method for preparing the ammonia-hydrogen-electric multimodal reaction chip as described in claim 7, characterized in that: In step S2, the PECVD preparation process parameters for the nitrogen-defective graphene layer are: methane flow rate 30 sccm, nitrogen flow rate 10 sccm, hydrogen flow rate 50 sccm, microwave power 2 kW, deposition temperature 700℃, and deposition time 30 min.

10. An ammonia-hydrogen-electric multimodal reaction chip stacking module, characterized in that: The ammonia-hydrogen-electric multimodal reaction chip as described in any one of claims 1-6 is tightly stacked and arranged by means of a mechanical positioning structure and connectors; The stacked module includes an adaptive flow-sharing manifold, a redundant flexible electrical busbar, a chip-level signal synchronous acquisition backplane, and an edge AI controller. The adaptive flow-sharing manifold is sealed to the chip fluid interface, the redundant flexible electrical busbar is plugged into the chip electrical interface, the chip-level signal synchronous acquisition backplane is connected to the MEMS sensor array signal, and the edge AI controller is communicatively connected to the signal acquisition backplane and the solid-state electrical commutation module. The edge AI controller is an embedded controller with an NPU, which incorporates single-chip-level operating condition control, mode switching, fault warning, and energy efficiency optimization algorithms.

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