Bipolar organic electrode material and preparation method and application thereof
By preparing bipolar organic electrode materials, the energy density and stability problems of traditional lithium-ion batteries are solved, and high-capacity, low-cost and multifunctional battery applications are achieved, which are suitable for zinc-ion and lithium-ion batteries.
Patent Information
- Application Number
- CN202510699672.4
- Authority / Receiving Office
- CN · China
- Patent Type
- Applications(China)
- Current Assignee / Owner
- Filing Date
- 2025-05-28
- Publication Date
- 2025-09-16
AI Technical Summary
The energy density of traditional lithium-ion batteries is close to the theoretical limit, the cycle stability is poor, and they rely on scarce metal resources, making it difficult to meet the needs of high energy density, low cost and environmental friendliness.
Bipolar organic electrode materials are synthesized from 2-chloroquinoxaline and p-phenylenediamine, contain multiple redox active sites, are prepared by melt method or solvent method, and are used in zinc ion, lithium ion batteries, etc., and are combined with conductive additives and adhesives to prepare electrodes.
It significantly improves the battery's specific capacity and cycle stability, reduces production costs, broadens application scenarios, and achieves high energy density and environmentally friendly battery performance.
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Figure CN120647591A_ABST
Abstract
Description
Technical Field
[0001] The present invention belongs to the field of ion battery electrode materials, and in particular relates to a bipolar organic electrode material and a preparation method and application thereof. Background Art
[0002] As the global energy structure accelerates its transition toward a low-carbon and sustainable future, the proportion of renewable energy generation is increasing year by year. However, the intermittent nature of photovoltaic and wind power poses a serious challenge to grid stability. At the same time, the explosive growth of the electric vehicle market has further increased demand for high-performance power batteries. However, traditional lithium-ion batteries rely on scarce metal resources such as cobalt and nickel, and face multiple pressures from supply chain security, cost fluctuations, and environmental pollution. The energy density of traditional electrode materials, represented by graphite anodes and lithium cobalt oxide cathodes, is approaching its theoretical limit, making it difficult to meet the requirements of future energy storage systems for higher energy density, lower costs, and environmental friendliness.
[0003] In this context, organic materials have the characteristics of flexibility, designability and economic friendliness, which give them many advantages in the application of battery electrode materials. Due to their flexibility, organic molecular materials tend to have a stable structure when metal ions are embedded and removed, and there is no restriction on the type of metal ions, which is very beneficial for the cycle stability of batteries over a long period of time. In addition, bipolar electrodes are not only structural innovations, but can also be used as symmetrical electrodes to assemble symmetrical batteries. It breaks the physical boundaries of positive and negative electrodes and opens up new paths for the next generation of energy storage technologies with high energy density, low cost and high reliability through material multifunctionalization and structural integration. Therefore, the design and development of bipolar organic electrode materials with multiple active sites and structural diversity has become a key direction to break through the bottleneck of battery performance. Summary of the Invention
[0004] The purpose of the present invention is to provide a bipolar organic electrode material and a preparation method and application thereof, so as to solve the problem that inorganic electrode materials have always had low capacity and poor cycle stability.
[0005] The technical solution of the present invention:
[0006] A bipolar organic electrode material containing multiple redox active sites capable of multi-electron storage, thus having a high theoretical specific capacity. The structural formula of the bipolar organic electrode material is shown below:
[0007]
[0008] A method for preparing a bipolar organic electrode material, the synthesis reaction route of which is as follows:
[0009]
[0010] Furthermore, the reaction adopts a melting method or a solvent method.
[0011] Furthermore, the specific reaction steps of the melting method are as follows:
[0012] Grind p-phenylenediamine and 2-chloroquinoxaline until thoroughly mixed. Heat at 40-200°C under inert gas for 3-10 hours. After cooling to room temperature, add ethanol to form a slurry. Wash with anhydrous ethanol and water. Finally, dry under vacuum at 80°C for 12 hours to obtain the desired product.
[0013] Furthermore, the specific reaction steps of the solvent method are as follows:
[0014] Grind p-phenylenediamine and 2-chloroquinoxaline until thoroughly mixed, add them to a flask along with ethanol, and reflux at room temperature to 80°C under an inert atmosphere for 12-24 hours. After cooling to room temperature, wash with anhydrous ethanol and water. Finally, vacuum dry at 80°C for 12 hours. The molar ratio of 2-chloroquinoxaline to p-phenylenediamine is 1.8-2.2:1.
[0015] The invention discloses an application of a bipolar organic electrode material, wherein the bipolar organic electrode material is used for preparing electrodes of aqueous zinc ion batteries, organic zinc ion batteries or lithium ion batteries.
[0016] An application of a bipolar organic electrode material, a positive electrode preparation method: the bipolar organic electrode material, a conductive additive and a binder (the mass ratio of the three is ((3-8): (2-6): (0-1))) are uniformly dispersed in a solvent and coated on a current collector, and vacuum dried to obtain an organic positive electrode.
[0017] Furthermore, when applied to aqueous zinc ion batteries, the solvent is isopropyl alcohol or N-methylpyrrolidone (NMP), and the current collector is a 300-mesh stainless steel mesh or carbon paper; when applied to lithium ion batteries, the solvent is NMP, and the current collector is carbon paper, aluminum foil or copper foil.
[0018] Furthermore, the vacuum drying temperature is 60-80° C., and the drying time is 12-18 hours.
[0019] Furthermore, the conductive additive includes Ketjen black, carbon black, carbon nanotubes or graphene.
[0020] Furthermore, the adhesive includes polytetrafluoroethylene (PTFE) or polyvinylidene fluoride (PVDF).
[0021] The present invention provides a new bipolar organic electrode material, which is synthesized from 2-chloroquinoxaline and p-phenylenediamine. The bipolar organic electrode material contains multiple redox active sites and can store multiple electrons. When used to prepare battery electrodes, it has the following beneficial effects:
[0022] 1. Capacity breakthrough: The capacity of traditional inorganic electrodes is close to the theoretical limit, and the specific capacity of organic bipolar electrodes is low. However, the capacity of the material of this invention is increased to 370mAh g in lithium-ion batteries. -1 , significantly higher than similar organic electrodes.
[0023] 2. Improved cycle stability: Existing organic electrodes are prone to capacity decay because they and their discharge products are easily soluble in the electrolyte. However, the material of this invention stabilizes the charge and discharge process through a bipolar design (the capacity retention rate after cycling is better than similar technologies).
[0024] 3. Cost and environmental advantages: Existing inorganic electrode materials rely on scarce metals (such as cobalt and nickel). The present invention is completely based on organic raw materials, which reduces costs and has no heavy metal pollution in the production process.
[0025] 4. Multifunctional application: Existing bipolar electrodes are mostly limited to a single battery system (such as lithium ion), while the material of the present invention can be adapted to a variety of batteries such as zinc ion and lithium ion, broadening the application scenarios. BRIEF DESCRIPTION OF THE DRAWINGS
[0026] Figure 1 is the proton nuclear magnetic resonance spectrum of Example 1;
[0027] Figure 2 is the charge and discharge curve of the lithium-ion battery prepared with the corresponding organic cathode material in Example 1;
[0028] Figure 3 1 is a rate performance diagram of a lithium-ion battery prepared with the corresponding organic cathode material in Example 1 at different current densities;
[0029] Figure 4 This is a cycle stability diagram of a lithium-ion battery prepared using the corresponding organic cathode material in Example 1.
[0030] Figure 5 1 is the charge and discharge curve of the corresponding organic cathode material in the zinc ion battery in Example 1. DETAILED DESCRIPTION
[0031] 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 the following embodiments. It should be understood that the specific embodiments described herein are intended only to illustrate the present invention and are not intended to limit the present invention. In addition, the technical features described in the various embodiments of the present invention described below may be combined with each other as long as they do not conflict with each other.
[0032] Example 1
[0033] 0.6584 g (4 mmol) of 2-chloroquinoxaline and 0.2163 g (2 mmol) of p-phenylenediamine were ground in an agate mortar and pestle until thoroughly mixed. The mixture was then heated at 160°C under a nitrogen atmosphere for 5 hours. After cooling to room temperature, 40 mL of ethanol was added to form a slurry. The slurry was filtered and washed several times with deionized water and then ethanol. The slurry was then vacuum-dried at 80°C for 18 hours to obtain a brown solid, the bipolar organic electrode material. The yield was 78.2%. Figure 1 This is the hydrogen nuclear magnetic resonance spectrum of the bipolar organic electrode material. It can be seen that there are corresponding hydrogen nuclear magnetic resonance peaks at 7.45, 7.65, 7.74, 7.83, 8, 8.56 and 10.04.
[0034] The bipolar organic electrode material provided in this embodiment is used as a positive electrode material for zinc-ion batteries and lithium-ion batteries, and is not limited to its application in aqueous or organic potassium, sodium, magnesium, aluminum, and calcium ion batteries. Since lithium-ion batteries are widely studied and aqueous zinc-ion batteries are safe and abundant, the organic electrode material is preferably used in aqueous zinc-ion batteries and lithium-ion batteries.
[0035] Taking lithium-ion batteries as an example, a specific example is given below:
[0036] Preparation of the organic cathode for lithium-ion batteries: The organic cathode material, Ketjen black, and polyvinylidene fluoride (PVDF) were uniformly dispersed in NMP at a mass ratio of 4.5:4.5:1 and evenly coated on carbon paper. The organic cathode was then vacuum-dried at 60°C for 12 hours to obtain the organic cathode. A lithium-ion battery was assembled using the organic cathode, a lithium sheet as the anode, Celgard 2400 as the separator, a 1M lithium bistrifluoromethylsulfonyl imide (LiTFSI) solution and 0.3wt% lithium nitrate as the electrolyte, and a mixed solvent of 1,3-dioxolane (DOL) and ethylene glycol dimethyl ether (DME) in a volume ratio of 1:2 as the solvent.
[0037] Perform charge and discharge tests on the battery. Figure 2 for Figure 1 The lithium-ion battery prepared by the material in the current density is 0.1Ag -1 The charge and discharge curves below show that the organic electrode material has a high specific capacity and the discharge capacity can reach 370 mAh g -1 In addition, from Figure 3 It can be seen that the lithium-ion battery prepared by the organic electrode material has excellent rate performance. -1 The discharge capacity can still reach 191mAh g -1 When the current density returns to 0.1Ag -1 When the discharge capacity is 331mAh g-1 . Figure 4 This is the cycle performance diagram of the lithium-ion battery. It can be seen that the organic electrode material exhibits good cycle stability.
[0038] The preparation method of zinc-ion batteries is similar to that of lithium-ion batteries.
[0039] Preparation of the organic cathode for a zinc-ion battery: The organic cathode material, Ketjen black, and PVDF were uniformly dispersed in isopropyl alcohol at a mass ratio of 4.5:4.5:1. The resulting mixture was evenly coated onto carbon paper and then vacuum-dried at 60°C for 12 hours to obtain the organic cathode. A zinc-ion battery was assembled using the organic cathode, a zinc sheet as the anode, a glass fiber membrane as the separator, and a Zn(ClO4)2 solution as the electrolyte.
[0040] Perform charge and discharge tests on the battery. Figure 5 for Figure 1 The zinc ion battery prepared by the material in the current density is 0.05Ag -1 The charge-discharge curve below shows that the organic electrode material has a high specific capacity and the discharge capacity can reach 172 mAh g -1 .
[0041] Example 2
[0042] 0.6584 g (4 mmol) of 2-chloroquinoxaline and 0.2163 g (2 mmol) of p-phenylenediamine were ground in an agate mortar and pestle until thoroughly mixed. The mixture was added to a flask along with ethanol and refluxed at 45°C under nitrogen for 24 hours. After cooling to room temperature, the mixture was washed with anhydrous ethanol and then water. Finally, the mixture was vacuum-dried at 80°C for 18 hours to obtain a brown solid. The yield was 25.8%.
[0043] Example 3
[0044] A lithium-ion battery is made of the bipolar organic electrode material prepared in Example 1. The carbon paper current collector in the electrode preparation process is replaced with aluminum foil. The other steps are the same as the lithium-ion battery preparation method in Example 1. The discharge capacity is tested at a current density of 0.1Ag -1 The capacity can reach 135mAh g -1 .
[0045] Example 4
[0046] A zinc ion battery is prepared using the bipolar organic electrode material prepared in Example 1. The zinc ion battery is assembled. During the electrode preparation process, the mass ratio of the organic positive electrode material, Ketjen black, and PVDF is changed to 3:6:1. The other steps are the same as the zinc ion battery preparation method in Example 1. The discharge capacity is tested at a current density of 0.1Ag. -1 The capacity can reach 320mAhg-1 .
[0047] With the above-described preferred embodiments of the present invention as a guide, and with reference to the above description, relevant personnel are fully capable of making various changes and modifications without departing from the technical scope of this invention. The technical scope of this invention is not limited to the contents of the specification and must be determined according to the scope of the claims.
Claims
1. A bipolar organic electrode material, characterized in that The structure of the electrode material is as follows:
2. A method for preparing a bipolar organic electrode material according to claim 1, characterized in that: The bipolar organic electrode material is synthesized by a nucleophilic substitution reaction of 2-chloroquinoxaline and p-phenylenediamine.
3. The method for preparing a bipolar organic electrode material according to claim 2, wherein: The reaction adopts a melting method or a solvent method.
4. The method for preparing a bipolar organic electrode material according to claim 3, wherein: The steps of the melting preparation method are as follows: grinding 2-chloroquinoxaline and p-phenylenediamine until fully mixed, then heating them in an inert atmosphere for reaction, adding ethanol to form a slurry after cooling, and then washing and drying to obtain the bipolar organic electrode material.
5. The method for preparing a bipolar organic electrode material according to claim 3, wherein: The solvent preparation method comprises the following steps: grinding 2-chloroquinoxaline and p-phenylenediamine until fully mixed, then adding them into an ethanol solution and performing a reflux reaction in an inert atmosphere, cooling, washing, and drying to obtain the bipolar organic electrode material.
6. The preparation method according to claim 4 or 5, characterized in that The molar ratio of the 2-chloroquinoxaline to p-phenylenediamine is 1.8-2.2:
1.
7. The preparation method according to claim 4, characterized in that The heating reaction temperature is 40-200° C., and the reaction time is 3-10 hours.
8. The preparation method according to claim 5, characterized in that The reflux reaction temperature is room temperature to 80° C., and the reaction time is 12 to 24 hours.
9. A use of the bipolar organic electrode material according to claim 1, characterized in that: It is used to make electrodes for aqueous zinc ion batteries, organic zinc ion batteries or lithium ion batteries.
10. The use according to claim 9, characterized in that The preparation method of the electrode comprises the following steps: uniformly dispersing a bipolar organic electrode material, a conductive additive and an adhesive in a solvent, coating the mixture on a current collector, and drying the mixture to obtain the electrode.