Pi-conjugated composite organic negative electrode material for hydrogen ion battery
By designing π-conjugated composite organic anode materials, the problems of low specific capacity and poor cycle stability of organic materials in hydrogen ion batteries were solved, achieving high specific capacity and long cycle life performance of hydrogen ion batteries.
Patent Information
- Application Number
- CN202511016543.7
- Authority / Receiving Office
- CN · China
- Patent Type
- Applications(China)
- Current Assignee / Owner
- Filing Date
- 2025-07-23
- Publication Date
- 2025-10-28
AI Technical Summary
Existing organic materials used as anode materials for hydrogen ion batteries suffer from limited specific capacity, low operating voltage, and poor cycle stability, hindering their further development in the battery field.
By employing π-conjugated composite organic anode materials, a stable framework with an extended conjugated system and abundant active sites is constructed through the controlled condensation reaction of thionine and organic ketone compounds. This forms a highly conjugated aromatic framework and a continuous electron delocalization network of imine bonds, ensuring rapid electron transport. Furthermore, the cross-linked chemical bond network prevents the electrolyte penetration of active materials.
It significantly improves the high specific capacity and efficient charge transport capability of hydrogen ion batteries. The material maintains structural integrity during long-term cycling, and the battery can stably cycle for more than 6,000 times at high current density. The proton storage specific capacity reaches 163.4 mAh g-1, which is far higher than that of existing materials.
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Figure CN120854554A_ABST
Abstract
Description
Technical Field
[0001] This invention relates to the field of electrode materials technology for ion batteries, and specifically to a π-conjugated composite organic anode material for hydrogen ion batteries. Background Technology
[0002] With increasing prominence of environmental and energy issues, the development of large-scale energy storage devices is crucial for converting renewable energy into stable electricity. Aqueous rechargeable batteries, especially aqueous lithium-ion batteries (ALIBs), have attracted significant attention due to their inherent safety, non-toxicity, and cost-effectiveness. However, the finite and scarce nature of lithium resources, coupled with continuously rising costs, poses a significant challenge to the large-scale deployment of ALIBs for grid-scale applications. Therefore, researchers have begun exploring alternative charge carriers, such as sodium hydroxide (Na₂O₃). + K + Zn 2+ and Mg 2+ Used in water-based rechargeable batteries. Non-metallic ions, including hydrated hydrogen ions (H3O). + ) and NH4 + It has also been studied because of its abundance, but its larger ionic radius and lower charge radius ratio often result in performance that is not as good as lithium-based systems.
[0003] In recent years, hydrogen ions (H+) + Due to the small size and lightweight nature of the proton carrier, this type of battery is a highly promising candidate. Utilizing the Grotthuss mechanism, this type of battery achieves proton conduction in an aqueous electrolyte, exhibiting excellent rate performance, although inorganic materials such as MnO2, V2O5, Prussian blue analogues (PBAs), MoO3, and titanium-based oxides have been shown to possess H3O in acidic electrolytes. + Storage capacity, but its practical application is affected by structural instability and H... + Solubility and toxicity issues hinder the insertion / extraction process.
[0004] Organic materials, as sustainable alternatives, offer advantages such as structural tunability, environmental compatibility, and abundant resources. Recent studies have shown that organic compounds such as pyridine-4,5,9,10-tetraone (PTO), 3,4,9,10-perylenetetracarboxylic dianhydride (PTCDA), pyrrolizine (ALO), and polyimides (PIs) exhibit advantages in reversible H3O. + It has potential in storage; however, existing organic H... + Although the host materials (such as quinones, conjugated polymers) have limited specific capacity (<150mAh g), -1 Problems such as low operating voltage (<0.8V) and poor cycle stability due to molecular dissolution (capacity retention rate <70% after 500 cycles) hinder the further development of organic materials in the battery field. Summary of the Invention
[0005] In view of this, the purpose of this invention is to propose a π-conjugated composite organic anode material for hydrogen ion batteries, so as to solve the problems of small specific capacity and poor cycle performance of traditional organic materials when applied to ion batteries.
[0006] To achieve the above objectives, this invention provides a π-conjugated composite organic anode material for hydrogen-ion batteries, the specific structure of which is shown below:
[0007]
[0008] The preparation steps of the π-conjugated composite organic anode material are as follows:
[0009] Thionium and organic ketone compounds are mixed and ground, and then refluxed in a solvent at 80-200℃ for 6-12 hours. After the reaction is completed, centrifugation, washing and drying are performed to obtain π-conjugated composite organic anode material.
[0010] Preferably, the molar ratio of the thionine to the organic ketone compound is 3:1-3.
[0011] Preferably, the organic ketone compound is one of acetophenone, cyclohexanehexaone, methyl acetophenone, 1-benzocycloheptanone, benzocyclobutenone, 4-phenyl-2-butanone, and cyclohexanedione.
[0012] Preferably, the solvent is one of methanol, glacial acetic acid, N,N-dimethylformamide, dimethyl sulfoxide, and water.
[0013] Preferably, the centrifugation is performed at 8000 rpm for 10 minutes.
[0014] Preferably, the washing process involves sequentially washing with glacial acetic acid, ethanol, and deionized water.
[0015] Preferably, the drying temperature is 60°C.
[0016] Furthermore, the present invention also provides an application of a π-conjugated composite organic anode material in a hydrogen-ion battery.
[0017] Preferably, the present invention also provides a method for preparing a composite organic negative electrode sheet, comprising mixing a π-conjugated composite organic negative electrode material, conductive carbon black, and a binder, dispersing them in an organic solvent to obtain a slurry, and then coating the slurry onto a conductive agent fluid and drying it.
[0018] Preferably, the conductive current collector is one of carbon paper, titanium mesh, carbon cloth, or nickel foam.
[0019] Preferably, the organic solvent is one of N-methylpyrrolidone and polyvinylidene fluoride.
[0020] Preferably, the weight ratio of the π-conjugated composite organic negative electrode material, conductive carbon black, binder, and organic solvent is 6-8g:1-3g:1g:10-20g.
[0021] The beneficial effects of this invention are:
[0022] The π-conjugated composite organic anode material proposed in this invention constructs a stable framework with an extended conjugated system and abundant active sites through a controllable condensation reaction of thionine and organic ketone compounds. The highly conjugated aromatic framework in the material forms a continuous electron delocalization network with imine bonds, providing a large number of reversible hydrogen storage active sites. Moreover, the extensibility of the conjugated structure ensures the rapid transport of electrons within the molecule, significantly improving the high specific capacity and efficient charge transport capability of hydrogen ion batteries.
[0023] The π-conjugated composite organic anode material proposed in this invention has a rigid framework that can buffer the volumetric strain during hydrogen ion insertion / extraction, while the cross-linked chemical bond network prevents electrolyte penetration of active materials, thus maintaining the structural integrity of the material during long-term cycling.
[0024] This invention utilizes a synthesized, low-cost composite organic material with π-conjugated phenothiazine molecular characteristics as the negative electrode and readily available, inexpensive MnO2 as the positive electrode to assemble a hydrogen-ion battery. This battery exhibits a wide voltage window and a high open-circuit voltage, achieving a proton storage capacity of up to 163.4 mAh g⁻¹. -1 The full battery can reach 6Ag -1 It can stably cycle more than 6,000 times at current density, far exceeding most existing hydrogen-ion batteries. Attached Figure Description
[0025] To more clearly illustrate the technical solutions in this invention or the prior art, the accompanying drawings used in the description of the embodiments or the prior art will be briefly introduced below.
[0026] Figure 1 This is a structural diagram of the π-conjugated composite organic anode material prepared in Example 1 of the present invention.
[0027] Figure 2 This is a schematic scanning electron microscope image of the π-conjugated composite organic anode material prepared in Example 1 of the present invention;
[0028] Figure 3 The infrared spectra of the π-conjugated composite organic anode material (APTH) prepared in Example 1 of this invention and two monomers, thionine and cyclohexanehexanone (hexanecyclohexane), are shown.
[0029] Figure 4The image shows the hydrogen NMR spectrum of the π-conjugated composite organic anode material prepared in Example 1 of this invention.
[0030] Figure 5 The images show the cyclic voltammetry curves (a) and (b) of the positive and negative electrodes of an aqueous hydrogen ion battery assembled using the π-conjugated composite organic negative electrode material as the electrode material in Example 1 of this invention, and the cyclic voltammetry curves at different scan rates.
[0031] Figure 6 This is a rate performance diagram of an aqueous hydrogen-ion battery assembled from electrode sheets prepared using π-conjugated composite organic anode material as electrode material in Example 1 of this invention.
[0032] Figure 7 This is a graph showing the long-cycle charge-discharge performance of an aqueous hydrogen-ion battery assembled from electrode sheets prepared using π-conjugated composite organic anode material as electrode material in Example 1 of this invention.
[0033] Figure 8 The charge-discharge capacity performance curves of aqueous hydrogen ion batteries assembled with electrode sheets prepared by using π-conjugated composite organic negative electrode materials as electrode materials in Example 1 of the present invention, compared with those in Examples 2 and 3. Detailed Implementation
[0034] In order to make the objectives, technical solutions and advantages of the present invention more clearly understood, the present invention is further described in detail below with reference to specific embodiments.
[0035] Example 1: A π-conjugated composite organic anode material for hydrogen ion batteries, the specific preparation steps are as follows:
[0036] 0.861 g of thionine and 0.312 g of cyclohexanehexanone were placed in a mortar and ground thoroughly to obtain a premix. Then, 110 mL of glacial acetic acid was added to the premix, and the mixture was ultrasonically dispersed for 30 min. The mixture was then heated to 80 °C in an oil bath and reacted for 12 h. After the reaction was completed, the mixture was cooled to room temperature and centrifuged at 8000 rpm for 10 min. The resulting precipitate was washed successively with glacial acetic acid, ethanol, and deionized water. Finally, the mixture was vacuum dried at 60 °C for 12 h to obtain the π-conjugated composite organic anode material.
[0037] Example 2: A π-conjugated composite organic anode material for hydrogen ion batteries, the specific preparation steps are as follows:
[0038] 0.861 g of thionine and 0.624 g of cyclohexanehexanone were placed in a mortar and ground thoroughly to obtain a premix. Then, 120 mL of glacial acetic acid was added to the premix, and the mixture was ultrasonically dispersed for 50 min. The mixture was then heated to 150 °C in an oil bath and reacted for 9 h. After the reaction was completed, the mixture was cooled to room temperature and centrifuged at 8000 rpm for 10 min. The resulting precipitate was washed successively with glacial acetic acid, ethanol, and deionized water. Finally, the mixture was vacuum dried at 60 °C for 12 h to obtain the π-conjugated composite organic anode material.
[0039] Example 3: A π-conjugated composite organic anode material for hydrogen ion batteries, the specific preparation steps are as follows:
[0040] 0.861 g of thionine and 0.936 g of cyclohexanehexanone were placed in a mortar and ground thoroughly to obtain a premix. Then, 30 mL of glacial acetic acid was added to the premix, and the mixture was ultrasonically dispersed for 60 min. The mixture was then heated to 200 °C in an oil bath and reacted for 6 h. After the reaction was completed, the mixture was cooled to room temperature and centrifuged at 8000 rpm for 10 min. The resulting precipitate was washed successively with glacial acetic acid, ethanol, and deionized water. Finally, the mixture was vacuum dried at 60 °C for 12 h to obtain the π-conjugated composite organic anode material.
[0041] Example 4: An aqueous hydrogen-ion battery, the specific preparation steps are as follows:
[0042] 6g of π-conjugated composite organic anode material, 3g of acetylene black, and 1g of polyvinylidene fluoride were dispersed in 10g of N-methylpyrrolidone. After stirring and dispersing evenly, the mixture was uniformly coated onto carbon cloth and dried under vacuum at 60°C to obtain an electrode sheet. Subsequently, an aqueous hydrogen ion battery was assembled using the electrode sheet as the working electrode, sulfuric acid solution (2M) as the electrolyte, a carbon rod as the counter electrode, and Ag / AgCl as the reference electrode.
[0043] Example 5: An aqueous hydrogen-ion battery, the specific preparation steps are as follows:
[0044] 7g of π-conjugated composite organic anode material, 2g of acetylene black, and 1g of polyvinylidene fluoride were dispersed in 15g of N-methylpyrrolidone. After stirring and dispersing evenly, the mixture was uniformly coated onto carbon cloth and dried under vacuum at 60°C to obtain an electrode sheet. Subsequently, an aqueous hydrogen ion battery was assembled using the electrode sheet as the working electrode, sulfuric acid solution (2M) as the electrolyte, a carbon rod as the counter electrode, and Ag / AgCl as the reference electrode.
[0045] Example 6: An aqueous hydrogen-ion battery, the specific preparation steps are as follows:
[0046] 8g of π-conjugated composite organic anode material, 1g of acetylene black, and 1g of polyvinylidene fluoride were dispersed in 20g of N-methylpyrrolidone. After stirring and dispersing evenly, the mixture was uniformly coated onto carbon cloth and dried under vacuum at 60°C to obtain an electrode sheet. Subsequently, an aqueous hydrogen ion battery was assembled using the electrode sheet as the working electrode, sulfuric acid solution (2M) as the electrolyte, a carbon rod as the counter electrode, and Ag / AgCl as the reference electrode.
[0047] Performance testing
[0048] The aqueous hydrogen-ion batteries assembled in Examples 4-6 were subjected to charge-discharge performance tests using an electrochemical workstation and a charge-discharge tester.
[0049] Data analysis: such as Figure 2 As shown, the π-conjugated composite organic material prepared in Example 1 exhibits an irregular blocky microstructure, which is beneficial for the full exposure of active sites, thereby endowing the material with excellent electrochemical performance; as Figure 3 As shown, the infrared spectra of APTH, thionine, and hexaketonecyclohexane, the π-conjugated composite organic materials prepared in Example 1, indicate that the π-conjugated composite organic materials were successfully prepared; Figure 4 As shown, the 1H nuclear magnetic resonance spectrum analysis of the π-conjugated composite organic material APTH prepared in Example 1 is presented. The spectrum shows seven different proton environments with chemical shifts of δ = 8.60, 7.90, 7.47, 7.39, 7.21, 7.13, and 6.63 ppm, which is consistent with the aromatic and imine linkage framework of the proposed π-conjugated composite organic anode material structure.
[0050] like Figure 5 As shown, the cyclic voltammetry (CV) curves of an aqueous hydrogen-ion battery assembled from an electrode sheet prepared using the π-conjugated composite organic anode material in Example 1 are displayed under different scan rates on the same device. It can be seen that the CV curves of this battery exhibit obvious redox peaks at different scan rates, indicating that the electrode sheet has high redox activity. Figure 6 As shown in the figure, the rate performance diagram of the aqueous hydrogen-ion battery assembled from electrode sheets prepared using the π-conjugated composite organic anode material in Example 1 demonstrates excellent adaptability at different rates. Even under high-rate charge-discharge conditions, it maintains stable capacity output and low capacity decay, exhibiting superior rate performance. Figure 7As shown in the figure, the long-cycle charge-discharge performance of the aqueous hydrogen-ion battery assembled from electrode sheets prepared by using the π-conjugated composite organic anode material as the electrode material in Example 1 can be seen. It can be seen that the capacity of the battery did not decrease significantly after 6000 cycles, indicating that the battery has good cycle stability. This fully demonstrates that the introduction of the π-conjugated system after polymerization helps to enhance the conjugated structure of molecules in the material, improve electron transport performance and charge transport. In addition, since there are a large number of active sites for hydrogen ion insertion / extraction in the π-conjugated composite organic anode material, the solubility problem is solved. The π-conjugated composite organic anode material can effectively improve the specific capacity of the battery and has ultra-long cycle capability as an electrode material.
[0051] like Figure 8 As shown, the aqueous hydrogen-ion battery assembled from the electrode sheet prepared by Example 1 using the π-conjugated composite organic anode material as the electrode material in Examples 2 and 3 exhibits a higher charge-discharge capacity. In Example 1, the monomers thionine and hexaketonecyclohexane are mixed in a molar ratio of 3:1. The meta-reaction has unique advantages. From the perspective of structural stability, the molecular structure formed by the meta-reaction allows the conjugated system to be extended to the maximum extent, reducing intramolecular tension and avoiding excessive steric hindrance that may be caused by ortho- or para-reactions, thus providing a stable framework for the material. From the perspective of active site exposure, the meta-reaction can ensure the orderly distribution of active groups (such as imine bonds), which is conducive to the full exposure of active sites. This is crucial for improving the performance of the material in energy storage, catalysis and other fields. At this molar ratio, the meta-reaction has higher selectivity, which can effectively suppress the occurrence of side reactions and make the reaction path clearer, thereby ensuring the consistency and purity of the product. As a result, the aqueous hydrogen-ion battery using this material as the electrode material can exhibit excellent electrochemical performance.
[0052] In summary, the π-conjugated composite organic anode material prepared in this invention exhibits significant advantages in rate performance and cycle stability as an electrode material for aqueous hydrogen-ion batteries. Under different charge-discharge rate conditions, the battery can not only maintain high capacity output and achieve rapid charge-discharge response, but also maintain high capacity retention and slow capacity decay during long-term cycling, thus overcoming the technical bottlenecks in electrochemical performance of existing aqueous hydrogen-ion batteries.
[0053] Those skilled in the art should understand that the discussion of any of the above embodiments is merely illustrative and is not intended to imply that the scope of the present invention is limited to these examples. Within the scope of the present invention, the technical features in the above embodiments or different embodiments may be combined, the steps may be implemented in any order, and there are many other variations of the different aspects of the present invention as described above, which are not provided in detail for the sake of simplicity.
Claims
1. A π-conjugated composite organic anode material for hydrogen-ion batteries, characterized in that, The specific structure is shown below: ； The preparation steps of the π-conjugated composite organic anode material are as follows: Thionium and organic ketone compounds are mixed and ground, and then refluxed in a solvent at 80-200℃ for 6-12 hours. After the reaction is completed, the mixture is purified and dried to obtain the π-conjugated composite organic anode material.
2. The π-conjugated composite organic anode material for hydrogen-ion batteries according to claim 1, characterized in that, The molar ratio of the thionine to the organic ketone compound is 3:1-3.
3. The π-conjugated composite organic anode material for hydrogen-ion batteries according to claim 1, characterized in that, The organic ketone compound is one of acetophenone, cyclohexanehexaone, methyl acetophenone, 1-benzocycloheptanone, benzocyclobutenone, 4-phenyl-2-butanone, and cyclohexanedione.
4. The π-conjugated composite organic anode material for hydrogen-ion batteries according to claim 1, characterized in that, The solvent is one of methanol, glacial acetic acid, N,N-dimethylformamide, dimethyl sulfoxide, or water.
5. An application of the π-conjugated composite organic anode material for hydrogen-ion batteries according to any one of claims 1-4, characterized in that, It is used in hydrogen-ion batteries.
6. A method for preparing a negative electrode for a hydrogen-ion battery, characterized in that, The following steps are involved: A slurry is obtained by mixing π-conjugated composite organic anode material, conductive carbon black, and binder, dispersing them in an organic solvent, and then coating the slurry onto a conductive agent fluid and drying it.
7. The method for preparing the negative electrode of a hydrogen-ion battery according to claim 6, characterized in that, The conductive current collector is one of carbon paper, titanium mesh, carbon cloth, or nickel foam.
8. The method for preparing the negative electrode of a hydrogen-ion battery according to claim 6, characterized in that, The organic solvent is one of N-methylpyrrolidone and polyvinylidene fluoride.
9. The method for preparing the negative electrode of a hydrogen-ion battery according to claim 6, characterized in that, The weight ratio of the π-conjugated composite organic anode material, conductive carbon black, binder, and organic solvent is 6-8g:1-3g:1g:10-20g.