RuOx quantum dot / Prussian blue analogue heterojunction material and preparation method and application thereof
By preparing RuOx quantum dot/Prussian blue analog heterojunction materials, the problem of instability of Prussian blue analog cathode materials at high potentials was solved, realizing a proton energy storage device with high energy density and long cycle stability, which has important scientific significance and application prospects.
Patent Information
- Application Number
- CN202511158185.3
- Authority / Receiving Office
- CN · China
- Patent Type
- Applications(China)
- Current Assignee / Owner
- Filing Date
- 2025-08-19
- Publication Date
- 2025-11-11
AI Technical Summary
In existing proton energy storage devices, Prussian blue analog cathode materials are easily oxidized and unstable at high potentials, and the introduction of multi-metal centers can destroy the framework stability, resulting in poor electronic structure and limiting their cycle stability and conductivity.
RuOx quantum dots were prepared by hydrothermal method and formed heterojunctions with vanadium hexacyanoferrite materials to construct RuOx quantum dot/Prussian blue analog heterojunction materials. The heterostructure was used to adjust the d-electron configuration, thereby enhancing the conductivity and cycling stability.
A proton energy storage device with high energy density and long cycling stability was achieved. The RuOx quantum dot/Prussian blue analog heterojunction material has a specific capacity of 162 mAh g–1 at a current density of 1 mA g–1, an assembled device energy density of 53 Wh kg–1, and a capacity retention of 86% after 10,000 cycles.
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Figure CN120933071A_ABST
Abstract
Description
Technical Field
[0001] This invention belongs to the field of proton energy storage cathode material technology, specifically a RuO x Quantum dot / Prussian blue analog heterojunction materials, their preparation methods, and applications. Background Technology
[0002] Against the backdrop of global carbon neutrality and energy transition, electrochemical energy storage technology is experiencing rapid development. Currently, technologies based on non-metallic charge carriers (such as H₂) are being rapidly developed. + NH4 + F − Cl − Advanced energy storage devices, particularly proton (H) batteries, have distinguished themselves due to their cost-effectiveness, safety, and environmental friendliness. + Protons, as the smallest and lightest charge carriers in nature, possess unique advantages such as light weight, inherent sustainability, environmental friendliness, and low cost. Through rapid Faraday reactions in electrode materials and surface ion adsorption / desorption, proton energy storage devices offer a new approach to solving the energy crisis. They combine the high energy density of batteries with the rapid charge-discharge capabilities of capacitors, achieving superior electrochemical performance (e.g., charging in seconds and 10,000 cycles) such as MXene and WO3. Research on proton energy storage is not only a scientific exploration to break through the physical limits of existing energy storage technologies but also a necessary path to promote the energy transition towards a green, efficient, and inclusive direction.
[0003] Among the various electrode materials used for proton energy storage, research has mainly focused on materials such as MoO. x V x O y On the anode material. However, the development of high-performance devices also depends on high-quality cathode materials. In proton-rich electrolytes, most cathode materials are prone to severe oxidation reactions at high potentials, leading to structural instability.
[0004] Prussian blue analogues (PBAs) have emerged as a promising class of cathode materials. Their unique open-frame structure provides an efficient channel for rapid proton insertion / extraction. However, single-metal-centered PBAs (e.g., FeFe-PBA) have a finite electronic structure. d Electron localization leads to low intrinsic specific capacity and conductivity, as well as poor cycling stability and rate performance, thus limiting interfacial reaction kinetics. Furthermore, directly introducing multimetal centers disrupts framework stability, and d electrons struggle to form beneficial couplings, resulting in the failure of multimetal synergy. Summary of the Invention
[0005] To address the shortcomings of the prior art, the purpose of this invention is to provide a RuO xQuantum dot / Prussian blue analogue heterojunction materials, their preparation methods, and applications. This invention prepares RuO2 via a hydrothermal method. x Quantum dots, then RuO2 is obtained through in-situ co-precipitation technology. x Quantum dots are doped into vanadium hexacyanoferrite (VHCF) materials to obtain RuO. x Quantum dot / Prussian blue analogue heterojunction materials. The RuO of this invention... x Quantum dot / Prussian blue analogue heterojunction materials induce heterostructure-based... d - p Orbital hybridization to modulate transition metals in PBAs d The electronic configuration overcomes the technical defect of low specific capacity in vanadium hexacyanoferrite materials, while also addressing the issues of unsatisfactory conductivity and cycle stability in vanadium hexacyanoferrite. Furthermore, it utilizes RuO... x Quantum dot / Prussian blue analogue heterojunction material is used as the cathode material. Proton energy storage devices assembled with molybdenum oxide / MXene anode have high energy density and long cycle stability.
[0006] To solve the above-mentioned technical problems, the present invention adopts the following technical solution: A RuO x The preparation method of quantum dot / Prussian blue analogue materials includes the following steps: Soluble ruthenium salts are mixed in water and then subjected to hydrothermal treatment. The soluble ruthenium salts hydrolyze and oxidize in the high-temperature water to form ultra-small RuO₂. x Quantum dots, yielding RuO x Quantum dot solution.
[0007] Vanadium pentoxide powder was added to hydrochloric acid solution and mixed thoroughly to form a yellow suspension. Glycerol was then added dropwise, and the mixture was heated and stirred to initiate a redox reaction, resulting in a clear blue solution. This solution contained high-valence vanadium (V2O2). 5+ ) Restored to a lower valence state (such as V) 4+ or V 3 + At the same time, a soluble vanadium complex is formed, which provides an active precursor for the subsequent synthesis of vanadium hexacyanoferrate, namely the vanadium precursor solution.
[0008] The vanadium precursor solution was diluted with deionized water, and after stirring, a clear blue solution was formed. Then, it was reacted with RuO₂. x Quantum dot solutions were mixed to obtain a black mixture. Potassium ferricyanide solution was then added dropwise to the mixture, followed by heating and aging to promote co-precipitation and crystallization. This allowed the vanadium precursor to fully react with potassium ferricyanide, forming vanadium hexacyanoferrate crystals, which were then processed using RuO2. xThe interfacial interactions between quantum dots and vanadium hexacyanoferrate (such as coordination bonds and electrostatic attraction) construct a stable heterojunction structure. After centrifugation, washing, and vacuum drying overnight, the black powder was collected to obtain RuO. x Quantum dot / Prussian blue analog heterojunction materials.
[0009] Preferably, the Prussian blue analogue is selected from V-based Prussian blue containing multiple active sites.
[0010] Preferably, the volume fraction of the hydrochloric acid solution is 21%~31%, and the molar ratio of vanadium pentoxide, hydrochloric acid and glycerol is 2~3:4~5:1~2.
[0011] Preferably, the conditions for the redox reaction are: heating and stirring at 60℃~80℃ for 1h~2h.
[0012] Preferably, the hydrothermal treatment conditions are: hydrothermal treatment at 100℃~150℃ for 10h~15h.
[0013] Preferably, the synthesis of RuO x When aging quantum dot / Prussian blue analogue heterostructure materials, the heating aging conditions are: heating at 60℃~80℃ for 9h~15h. Excessive temperature can cause the Prussian blue analogue structure to collapse, reducing RuO₂ levels. x Cyclic stability of quantum dot / Prussian blue analogue heterojunction materials; Too low a temperature is unfavorable for the growth of Prussian blue analogues. Too short a time, and the Prussian blue analogues do not have enough time to nucleate and grow; too long a time, and the Prussian blue analogues tend to aggregate, leading to low utilization of active sites.
[0014] Preferably, in order to construct a stable and high-capacity RuO x Quantum dot / Prussian blue analogue heterojunction materials, vanadium precursor in vanadium precursor solution, RuO x RuO in quantum dot solution x The molar ratio of quantum dots to potassium ferricyanide is 0.5~1.5:1~1.2:1~2, RuO x Too many quantum dots result in low capacity, RuO x Too few quantum dots result in poor conductivity and cycling stability.
[0015] Preferably, the concentration of the vanadium precursor in the precursor solution is 3.6 mol / L to 5.6 mmol / L; RuO x In quantum dot solution, RuO x The concentration of quantum dots was 3.6 mol / L to 5.6 mmol / L; the concentration of potassium ferricyanide in the potassium ferricyanide solution was 3.6 mol / L to 5.6 mmol / L.
[0016] Preferably, RuO xThe quantum dot / Prussian blue analog heterojunction material was subjected to three alternating centrifugal washes with ethanol and three alternating centrifugations with deionized water in order to remove excess organic matter, acid and metal ion salts.
[0017] This invention also protects RuO prepared by the above-described preparation method. x Quantum dot / Prussian blue analog heterojunction materials.
[0018] This invention also protects RuO x Application of quantum dot / Prussian blue analog heterojunction materials in the preparation of proton energy storage cathode materials.
[0019] Compared with the prior art, the beneficial effects of the present invention are: 1. This invention provides RuO x Quantum dot / Prussian blue analogue heterojunction materials are prepared according to the following steps: soluble ruthenium salt is dissolved in water and then subjected to hydrothermal treatment to obtain RuO. x Quantum dot solution; by mixing vanadium pentoxide into hydrochloric acid solution, then adding glycerol and carrying out a redox reaction, a vanadium precursor solution is obtained; RuO x Quantum dot solution and vanadium precursor solution are mixed, then potassium ferricyanide solution is added, and the mixture is heated for aging to achieve RuO2. x The anchoring of quantum dots on a Prussian blue analogue framework structure yields RuO x Quantum dot / Prussian blue analog heterojunction materials.
[0020] Compared to existing technologies, which mostly employ multi-metal constructions of Prussian blue analogues, resulting in poor capacity and low cycling stability, this invention addresses the issue of RuO₂. x Structural design of quantum dot / Prussian blue analogue heterojunction materials was carried out, firstly by obtaining RuO2 using a hydrothermal method. x Quantum dot structure, RuO x The quantum dot structure design provides spatial conditions for anchoring on Prussian blue analogues, shortening the ion diffusion path and facilitating efficient ion diffusion; then, RuO is added during the in-situ co-precipitation of the Prussian blue analogue. x Quantum dots provide high specific capacity with multiple reactivity. Additionally, RuO2 prepared using the method of this invention... x Quantum dot / Prussian blue analogue heterojunction materials have a heterojunction structure. The construction of this heterojunction structure provides multiple reactive sites, facilitating multiple redox reactions, contributing pseudocapacitance, and enhancing RuO₂. x The electrochemical activity of quantum dot / Prussian blue analogue heterojunction materials; the heterojunction interface effect also provides charge transfer channels, promotes electron transport, and the heterojunction interface effectively enhances the RuO2 content. xThe study of electrochemical reaction kinetics of quantum dot / Prussian blue analog heterojunction materials, and thus research on proton energy storage that meets the requirements of high energy density and long cycle stability, has important scientific significance and application prospects, and will further promote the development of the proton energy storage field.
[0021] 2. The RuO of the present invention x Quantum dot / Prussian blue analogue heterojunction materials possess multiple reactive active sites and rapid electrochemical reaction kinetics in proton energy storage cathode research, achieving high performance at 1 mA g⁻¹. –1 At current density, RuO x The specific capacity of the quantum dot / Prussian blue analog heterojunction material reached 162 mAh g. –1 RuO x Quantum dot (RuO) x Using QDs / Prussian blue analogue (VHCF) heterojunction material as the cathode material, a proton energy storage device assembled with molybdenum oxide / MXene anode exhibits high energy density (53Wh / kg). –1 It also exhibits excellent long-cycle stability (86.1% retention after 10,000 cycles).
[0022] 3. In this invention, because RuO x Quantum dots formed a heterojunction with VHCF, rather than RuO x The introduction of quantum dots into the VHCF framework enables RuO x Quantum dot / Prussian blue analogue heterojunction materials ensure that PBAs can utilize multi-metal synergy without compromising structural stability. Attached Figure Description
[0023] Figure 1 This is a SEM image of the VHCF material prepared in Comparative Example 2 of this invention.
[0024] Figure 2 The RuO prepared as Comparative Example 1 of this invention x TEM image of QDs material.
[0025] Figure 3 RuO prepared in Example 1 of this invention x SEM image of QDs / VHCF heterojunction material.
[0026] Figure 4 RuO is the embodiment of the present invention. x QDs / VHCF heterojunction material, Comparative Example 1 RuO x CV curves of QDs material and VHCF material of Comparative Example 2 at 5 mV / s.
[0027] Figure 5RuO is the embodiment of the present invention. x CV curves of QDs / VHCF heterojunction materials at different scan rates.
[0028] Figure 6 RuO is the embodiment of the present invention. x GCD curves of QDs / VHCF heterojunction materials at different scan rates.
[0029] Figure 7 RuO is the embodiment of the present invention. x EIS impedance diagrams of QDs / VHCF heterojunction materials at different scan rates.
[0030] Figure 8 To adopt the RuO of Embodiment 1 of the present invention x MoO3 / MXene / / RuO3 assembled from QDs / VHCF heterojunction materials x Schematic diagram of the QDs / VHCF proton energy storage device.
[0031] Figure 9 RuO is the embodiment of the present invention. x MoO3 / MXene / / RuO3 assembled from QDs / VHCF heterojunction materials x Cyclic stability diagram of QDs / VHCF proton energy storage device. Detailed Implementation
[0032] The specific embodiments of the present invention are described in detail below, but it should be understood that the scope of protection of the present invention is not limited to the specific embodiments. All other embodiments obtained by those skilled in the art based on the embodiments of the present invention without inventive effort are within the scope of protection of the present invention. Unless otherwise specified, the experimental methods described in the embodiments of the present invention are conventional methods.
[0033] Considering the technical problems of low specific capacity of existing V-based Prussian blue analogues, as well as the technical defects of poor cycling stability and rate performance of Prussian blue analogues, this invention uses RuO x QDs and VHCF were combined to obtain RuO x QDs / VHCF heterojunction materials. Induced by heterostructure. d - p Orbital hybridization to modulate transition metals in PBAs d Electronic configuration, thereby achieving high-performance proton storage. RuO₂ is prepared by in-situ co-precipitation. x QDs were fixed onto the cyano group (C≡N) of VHCF, thereby constructing a robust RuO group. xThe QDs / VHCF heterostructure synergistically enhances capacity, stability, and conductivity. Ruthenium 4 d orbital with C≡N 2 p Between the tracks d - p Orbital hybridization induces a π-feedback effect, facilitating electron transfer from the Ru to the PBAs framework and providing a pathway for ternary transition metals. d The regulation of electrons provides a highly efficient "electronic highway." This invention relates to Prussian blue analogues. d The manipulation of electrons provides a fundamental understanding and proposes a general heterostructure design strategy for advanced proton storage devices.
[0034] The technical solution of the present invention will be explained and illustrated below using embodiments, as detailed below: In this embodiment of the invention, RuO is first prepared. x QDs material and VHCF material, then RuO x QDs materials are combined with VHCF materials to prepare RuO x QDs / VHCF heterojunction material, namely RuO of the present invention x Quantum dot / Prussian blue analogue materials.
[0035] Example 1 A RuO x The preparation method of QDs / VHCF heterojunction material includes the following steps: S1. Ruthenium chloride (62.5 mg, 0.3 mmol) and 30 mL of deionized water were mixed and stirred at room temperature for 1 h. The mixture was then transferred to a 50 mL stainless steel autoclave lined with polytetrafluoroethylene and kept at 110°C for 11 h to obtain RuO. x Aqueous solutions of QDs, i.e., RuO x Quantum dot solution.
[0036] S2. Dilute 50 mL of 32% hydrochloric acid to 75 mL, add 4 g of vanadium pentoxide powder to form a yellow suspension, then add 700 µL of glycerol dropwise, and stir continuously at 60°C for 1 h to form a clear blue solution, thus obtaining the vanadium precursor solution.
[0037] S3. Take 469 µL of vanadium precursor solution and dilute it to 50 mL with deionized water. A clear blue solution is formed under stirring. Then add 30 mL of RuO2. x Aqueous solutions of QDs were stirred to form a black mixture. Then, 50 mL of a 3.6 mol / L K3Fe(CN)6 solution was added dropwise to the mixture. At this point, the vanadium precursor and RuO2 in the vanadium precursor solution... x RuO in quantum dot solutionx The quantum dots and potassium ferricyanide were mixed in a molar ratio of 1:1:1 and stirred at 60°C for 9 hours. The mixture was then centrifuged, washed, and vacuum dried overnight to collect the black powder, yielding RuO. x QDs / VHCF heterojunction material.
[0038] Example 2 A RuO x The preparation method of QDs / VHCF heterojunction material includes the following steps: S1. Ruthenium chloride (62.5 mg, 0.3 mmol) and 30 mL of deionized water were mixed and stirred at room temperature for 1 h. Then, the mixture was transferred to a 50 mL stainless steel autoclave lined with polytetrafluoroethylene and kept at 100°C for 15 h to obtain RuO. x Aqueous solutions of QDs, i.e., RuO x Quantum dot solution.
[0039] S2. Dilute 50 mL of 32% hydrochloric acid to 75 mL, add 4 g of vanadium pentoxide powder to form a yellow suspension, then add 700 µL of glycerol dropwise, and stir continuously at 80°C for 1.5 h to form a clear blue solution, thus obtaining the vanadium precursor solution.
[0040] S3. Take 234 µL of vanadium precursor solution and dilute it to 50 mL with deionized water. A clear blue solution is formed under stirring. Then add 30 mL of RuO2. x Aqueous solutions of QDs were stirred to form a black mixture. Then, 100 mL of a 3.6 mmol / L K3Fe(CN)6 solution was added dropwise to the mixture. At this point, the vanadium precursor and RuO2 in the vanadium precursor solution... x RuO in quantum dot solution x Quantum dots and potassium ferricyanide were mixed in a molar ratio of 0.5:1:2 and stirred at 80°C for 12 hours. The mixture was then centrifuged, washed, and vacuum dried overnight to collect the black powder, yielding RuO. x QDs / VHCF heterojunction material.
[0041] Example 3 A RuO x The preparation method of QDs / VHCF heterojunction material includes the following steps: S1. Ruthenium chloride (62.5 mg, 0.3 mmol) and 30 mL of deionized water were mixed and stirred at room temperature for 1 h. The mixture was then transferred to a 50 mL stainless steel autoclave lined with polytetrafluoroethylene and kept at 150°C for 10 h to obtain RuO. x Aqueous solutions of QDs, i.e., RuO x Quantum dot solution.
[0042] S2. Dilute 50 mL of 32% hydrochloric acid to 75 mL, add 4 g of vanadium pentoxide powder to form a yellow suspension, then add 700 µL of glycerol dropwise, and stir continuously at 70°C for 2 h to form a clear blue solution, thus obtaining the vanadium precursor solution.
[0043] S3. Take 703 µL of vanadium precursor solution and dilute it to 50 mL with deionized water. A clear blue solution is formed under stirring. Then add 30 mL of RuO2. x Aqueous solutions of QDs were stirred to form a black mixture. Then, 75 mL of a 3.6 mmol / L K3Fe(CN)6 solution was added dropwise to the mixture. At this point, the vanadium precursor and RuO2 in the vanadium precursor solution... x RuO in quantum dot solution x The molar ratio of quantum dots to potassium ferricyanide was 1.5:1:1.5. The mixture was stirred at 70°C for 15 hours, and then collected as a black powder by centrifugation, washing, and vacuum drying overnight to obtain RuO. x QDs / VHCF heterojunction material.
[0044] Comparative Example 1 A RuO x The preparation method of QDs materials includes the following steps: Ruthenium chloride (62.5 mg, 0.3 mmol) was mixed with 30 mL of deionized water and stirred at room temperature for 1 h. The mixture was then transferred to a 50 mL stainless steel autoclave lined with polytetrafluoroethylene and maintained at 110°C for 11 h to obtain RuO. x The aqueous solution of QDs was then centrifuged, washed, and vacuum dried overnight to collect a black powder, yielding RuO. x QDs materials.
[0045] Comparative Example 2 A method for preparing VHCF material includes the following steps: S1. Dilute 50 mL of 32% hydrochloric acid to 75 mL, add 4 g of vanadium pentoxide powder to form a yellow suspension, then add 700 µL of glycerol dropwise, and stir continuously at 60°C for 1 h to form a clear blue solution, thus obtaining the vanadium precursor solution.
[0046] S2. Take 469µL of vanadium precursor solution and dilute it with deionized water to 50mL. Under stirring, a clear blue solution is formed. Then, 50mL of 3.6mol / L K3Fe(CN)6 solution is added dropwise to the blue solution. Stir at 60℃ for 9h. Finally, collect the green powder by centrifugation, washing and vacuum drying overnight to obtain VHCF material.
[0047] Examples 1 to 3 of this invention all yielded RuO with high energy density and excellent cycling performance. x QDs / VHCF heterojunction materials, the following example uses RuO2 from Example 1. x Taking QDs / VHCF heterojunction materials as an example, the specific research methods and results are shown below: Figure 1 The image shows a SEM image of the VHCF material prepared in Comparative Example 2 of this invention. As can be seen from the image, the average particle size of the VHCF material is 30 nm.
[0048] Figure 2 The RuO prepared as Comparative Example 1 of this invention x TEM images of QDs materials show that RuO x The QDs material is uniformly dispersed with an average size of approximately 1.6 nm.
[0049] Figure 3 RuO prepared in Example 1 of this invention x SEM images of QDs / VHCF heterojunction materials show that RuO x The Q material is uniformly and densely anchored on the VHCF material.
[0050] This invention uses Chenhua CHI660 to test RuO x The behavior of QDs / VHCF heterojunction materials in proton energy storage. The proton energy storage cathode material was tested using an aqueous electrolyzer, with a platinum sheet as the counter electrode, an Ag / AgCl electrode as the reference electrode, and a 3 mol / L H2SO4 solution as the electrolyte, forming a three-electrode system for testing.
[0051] Figure 4 To use RuO from Example 1 respectively x QDs / VHCF heterojunction material, Comparative Example 1 RuO x QDs material and VHCF material of Comparative Example 2 at 5 mVs −1 The CV curve at the scan rate showed RuO x QDs / VHCF heterojunction materials possess abundant redox active sites, enabling them to provide high specific capacity as proton storage cathode materials. (1 mAg) –1 At current density, RuO x The specific capacity of the QDs / VHCF heterojunction material reached 162 mAh g. –1 The specific capacity is far superior to that of VHCF materials (114 mAh g). –1 ) and RuO x The specific capacity of QDs material (116 mAh g) –1 ).
[0052] Figure 5 RuO, as in Example 1 x The CV curves of the QDs / VHCF heterojunction material at different scan rates show that RuO x QDs / VHCF heterojunction materials exhibit rapid electrochemical reaction kinetics, RuO x The heterostructure between QDs and VHCF materials can promote charge transfer and enhance RuO x Electrochemical reaction kinetics of QDs / VHCF heterojunction materials.
[0053] Figure 6 RuO, as in Example 1 x The GCD curves of the QDs / VHCF heterojunction material at different current densities show that the GCD curves are symmetrical triangles, even at 40 A g. −1 Even at high current densities, it can still achieve 127mAh g. −1 The impressive capacity indicates that it has an ultrafast proton insertion / extraction rate and excellent rate performance.
[0054] Figure 7 RuO, as in Example 1 x QDs / VHCF heterojunction material, Comparative Example 1 RuO x The EIS impedance diagrams of the QDs material and the VHCF material in Comparative Example 2 show that VHCF-RuO x QDs heterojunction materials have the lowest internal resistance, and the highest slope and lowest internal resistance in the low-frequency region.
[0055] Figure 8 To adopt RuO of Example 1 x QDs / VHCF heterojunction material assembled with MoO3 / MXene anode MoO3 / MXene / / RuO x A schematic diagram of the QDs / VHCF proton energy storage device, and the assembly method is as follows: using RuO x Using QDs / VHCF heterojunction material as the positive electrode, MoO3 / MXene as the negative electrode, a glass ultrafine fiber filtration membrane (Whatman, GF / D) as the separator, and 3 mol / L H2SO4 solution as the electrolyte, MoO3 / MXene / / RuO3 was assembled. x QDs / VHCF proton energy storage devices.
[0056] Figure 9 For MoO3 / MXene / / RuO x Cyclic stability plot of QDs / VHCF proton energy storage device, MoO3 / MXene / / RuO xQDs / VHCF proton energy storage devices can achieve an energy density of 53Wh / kg. –1 The figure also shows that MoO3 / MXene / / RuO x QDs / VHCF proton energy storage devices exhibit excellent long-term cycling stability, retaining 86% capacity after 10,000 cycles.
[0057] In summary, the RuO of the present invention x QDs / VHCF heterojunction materials exhibit a distinct three-dimensional and zero-dimensional composite structure, which facilitates efficient ion diffusion. Simultaneously, the heterojunction interface provides a convenient transport channel for charge transfer, ensuring the stability of RuO₂. x Fast electrochemical reaction kinetics of QDs / VHCF heterojunction materials for proton storage. RuO x The multiple reactive sites and high electrochemical activity of QDs / VHCF heterojunction materials enable them to exhibit high specific capacity in proton storage. At 1 mA g –1 At current density, RuO x The specific capacity of QDs / VHCF reached 162mAh g. –1 RuO x QDs / VHCF heterojunction material is used as the positive electrode material, and MoO3 / MXene is assembled with MoO3 / MXene / / RuO as the negative electrode. x QDs / VHCF proton energy storage devices have high energy density (53Wh / kg). –1 With its excellent long-term cycling stability (86% retention rate after 10,000 cycles), proton energy storage devices have a very broad prospect in promoting the energy transition towards a green, efficient and inclusive direction.
[0058] Obviously, those skilled in the art can make various modifications and variations to this invention without departing from its spirit and scope. Therefore, if these modifications and variations fall within the scope of the claims and their equivalents, this invention also intends to include these modifications and variations. The above-described embodiments are merely preferred embodiments for fully illustrating the invention, and their scope of protection is not limited thereto. Equivalent substitutions or modifications made by those skilled in the art based on this invention are all within the scope of protection of this invention, which is defined by the claims.
Claims
1. A RuO x The method for preparing quantum dot / Prussian blue analog heterojunction materials is characterized by, Includes the following steps: Soluble ruthenium salts are mixed in water, and then subjected to hydrothermal treatment. The soluble ruthenium salts are hydrolyzed and oxidized to obtain RuO. x Quantum dot solution; Vanadium pentoxide and hydrochloric acid solution were mixed, and then glycerol was added dropwise to carry out a redox reaction. The vanadium in vanadium pentoxide was reduced from a high oxidation state to a low oxidation state by hydrochloric acid and glycerol to obtain a vanadium precursor solution. Vanadium precursor solution, RuO x A quantum dot solution and a potassium ferricyanide solution are mixed and heated for aging, causing the vanadium precursor to react with potassium ferricyanide to form vanadium hexacyanoferrate crystals, RuO. x Quantum dots interact with vanadium hexacyanoferrite crystals at the interface to form heterojunctions, yielding RuO₂. x Quantum dot / Prussian blue analog heterojunction materials.
2. A RuO according to claim 1 x The method for preparing quantum dot / Prussian blue analog heterojunction materials is characterized by, The hydrothermal treatment conditions are: hydrothermal treatment at 100℃~150℃ for 10h~15h.
3. A RuO according to claim 1 x The method for preparing quantum dot / Prussian blue analog heterojunction materials is characterized by, The volume fraction of the hydrochloric acid solution is 21%~31%.
4. A RuO according to claim 3 x The method for preparing quantum dot / Prussian blue analog heterojunction materials is characterized by, The molar ratio of vanadium pentoxide, hydrochloric acid and glycerol is 2~3:4~5:1~2.
5. A RuO according to claim 1 x The method for preparing quantum dot / Prussian blue analog heterojunction materials is characterized by, The conditions for the redox reaction are: heating and stirring at 60℃~80℃ for 1h~2h.
6. A RuO according to claim 1 x The method for preparing quantum dot / Prussian blue analog heterojunction materials is characterized by, Vanadium precursor in vanadium precursor solution, RuO x RuO in quantum dot solution x The molar ratio of quantum dots to potassium ferricyanide is 0.5~1.5:1~1.2:1~2.
7. A RuO according to claim 1 x The method for preparing quantum dot / Prussian blue analog heterojunction materials is characterized by, The conditions for heat aging are: heating at 60℃~80℃ for 9h~15h.
8. A RuO according to claim 1 x The method for preparing quantum dot / Prussian blue analog heterojunction materials is characterized by, In the vanadium precursor solution, the concentration of the vanadium precursor ranged from 3.6 mol / L to 5.6 mmol / L; RuO x In quantum dot solution, RuO x The concentration of quantum dots was 3.6 mol / L to 5.6 mmol / L; the concentration of potassium ferricyanide in the potassium ferricyanide solution was 3.6 mol / L to 5.6 mmol / L.
9. A RuO prepared by the method according to any one of claims 1-8 x Quantum dot / Prussian blue analog heterojunction materials.
10. A RuO as described in claim 9 x Application of quantum dot / Prussian blue analog heterojunction materials in the preparation of proton energy storage cathode materials.