Conductive / coordination dual polymer material and preparation method and application thereof
Patent Information
- Application Number
- CN202610910496.9
- Authority / Receiving Office
- CN · China
- Patent Type
- Applications(China)
- Current Assignee / Owner
- Filing Date
- 2026-06-23
- Publication Date
- 2026-10-27
Smart Images
Figure CN122978437A_ABST
Abstract
Description
Technical Field
[0001] This invention relates to the field of composite materials, specifically to a conductive / coordination dual polymer material, its preparation method, and its applications. Background Technology
[0002] As an emerging electrochemical energy storage technology, sodium-ion batteries have advantages such as abundant sodium resources, low cost, and high safety, and have shown good application prospects in large-scale energy storage and low-speed electric vehicles. Prussian blue analogues are cyano-bridged coordination polymers with a three-dimensional open framework structure, large-pore sodium storage sites, readily available raw materials, and low cost, making them one of the most promising cathode materials for sodium-ion batteries. However, Prussian blue analogue cathode materials still have the following two intrinsic problems that need to be solved in the process of large-scale use: (1) Prussian blue analogues prepared by traditional liquid phase method contain a large amount of crystal water and Fe(CN)6 vacancy defects, which will reduce the specific capacity of the material and lead to structural collapse and reduced cycle life; (2) The intrinsic electronic conductivity of Prussian blue analogues is extremely low, and the slow electron transport dynamics have become the key factor restricting its high current and low-temperature charge and discharge performance.
[0003] Therefore, introducing conductive polymers into Prussian blue analogues to form conductive / coordination bipolymer materials can improve structural stability and electronic conductivity, thereby enhancing the cycle life, rate capability, and low-temperature charge-discharge performance of the bipolymer materials. However, on the one hand, current conductive / coordination bipolymer materials are mainly prepared using liquid-phase methods, and the use of water solvents still introduces a certain amount of water of crystallization into the coordination polymer (Prussian blue analogue); on the other hand, the conductive polymer is mainly introduced into the Prussian blue analogue system through non-in-situ methods, and the composite uniformity of the two polymers needs further improvement. Moreover, the conductive polymer mainly coats the surface of the Prussian blue analogue, making it difficult to form an effective three-dimensional conductive network. Summary of the Invention
[0004] To address the inherent problems of poor structural stability and low electronic conductivity of Prussian blue analogues in existing technologies, this invention modifies Prussian blue analogues from a composite engineering perspective by in-situ introducing conductive polymers. This provides a conductive / coordination dual polymer material, its preparation method, and its applications. This invention generates a polymer in situ from a conductive polymer and a coordination polymer (Prussian blue analogue), avoiding the use of solvent water during synthesis. This reduces structural defects in the Prussian blue analogue, including water of crystallization, thereby improving the material's reversible specific capacity and cycle life. When used as a cathode material in sodium-ion batteries, it exhibits ideal comprehensive electrochemical sodium storage performance and has promising market prospects.
[0005] To address the problems in the existing technology, the technical solution adopted by this invention is as follows: A method for preparing a conductive / coordination dual polymer material involves adding conductive polymer monomer material, dopant, grinding aid, and transition metal salt into a ball mill jar and mixing them evenly. An oxidant is then added, and after ball milling, the product is washed and dried to obtain the conductive / coordination dual polymer material. The method further specifies that the molar ratio of the conductive polymer monomer material to the dopant is 1-1000:1; the molar ratio of the conductive polymer monomer material to the grinding aid is 1:1-20; the molar ratio of the conductive polymer monomer material to the transition metal salt is 1:1-5; and the molar ratio of the conductive polymer monomer material to the oxidant is 1:1-5.
[0006] Preferably, the conductive polymer monomer material is pyrrole or aniline.
[0007] Preferably, the dopant is tetrasodium phthalocyanine copper tetrasulfonate or phytic acid.
[0008] Preferably, the grinding aid is potassium chloride or sodium chloride.
[0009] Preferably, the metal ion of the transition metal salt is at least one selected from ferrous ion, manganese ion, nickel ion, cobalt ion, copper ion, and zinc ion; and the acid radical ion is at least one selected from chloride ion, sulfate ion, acetate ion, and nitrate ion.
[0010] Preferably, the oxidant is potassium ferricyanide or sodium ferricyanide.
[0011] Preferably, the ball milling reaction speed is 100~1000 rpm; the ball milling reaction time is 0.5~12 h.
[0012] The aforementioned conductive / coordination dual polymer material is composed of a conductive polymer and a Prussian blue analog (coordination polymer), with the Prussian blue analog uniformly distributed in a three-dimensional network formed by interconnected conductive polymer nanoparticles.
[0013] The above-mentioned conductive / coordination dual polymer material is used as a positive electrode material in sodium-ion batteries.
[0014] Beneficial effects: Compared with existing technologies, this invention discloses a conductive / coordination dual polymer material, its preparation method, and its application. It employs an in-situ composite mechanism using a bifunctional oxidant, where potassium ferrocyanide or sodium ferrocyanide simultaneously participates in the formation of both polymers. Potassium ferrocyanide acts as an oxidant to oxidize the monomer material, forming a conductive polymer, while its reduction product, ferrocyanide ions, reacts with a transition metal salt to form a coordination polymer (Prussian blue analogue). This in-situ composite route avoids the ex-situ introduction of the conductive polymer, achieving a uniform distribution of the Prussian blue analogue within a three-dimensional network of interconnected conductive polymer nanoparticles. The two polymers are generated in-situ in a solid-phase ball milling reaction, eliminating the need for water or other solvents during synthesis. This avoids the generation of crystal water and vacancy defects in the Prussian blue analogue from the source, reducing the structural defect density. Furthermore, when the conductive / coordination dual polymer material prepared by this invention is used as a cathode material for sodium-ion batteries, the three-dimensional network formed by the interconnection of conductive polymer nanoparticles can further enhance the structural stability and electron / ion transport capability of the cathode material during the sodium insertion / extraction process, thereby significantly improving the cycle life, rate capability, and low-temperature charge / discharge performance of the Prussian blue analog cathode material. In other words, when used as a cathode material for sodium-ion batteries, it can exhibit ideal comprehensive electrochemical sodium storage performance, including reversible specific capacity, lifespan, and rate capability. Attached Figure Description
[0015] Figure 1 This is a transmission electron microscope (TEM) image of the conductive / coordination dual polymer material prepared in Example 1. Figure 2 The cycling performance diagram (0.1 A·g) of the conductive / coordination dual polymer material prepared in Example 1 is shown. -1 ); Figure 3 The cycling performance diagram (1 A·g) of the conductive / coordination dual polymer material prepared in Example 1 is shown. -1 ); Figure 4 This is a rate performance graph of the conductive / coordination dual polymer material prepared in Example 1; Figure 5 This is a transmission electron microscope (TEM) image of the conductive / coordination dual polymer material prepared in Example 2; Figure 6 The cycling performance diagram (0.1 A·g) of the conductive / coordination dual polymer material prepared in Example 2 is shown. -1 ); Figure 7 This is a rate performance graph of the conductive / coordination bipolymer material prepared in Example 2. Detailed Implementation
[0016] Example 1 A method for preparing a conductive / coordination dual polymer material includes the following steps: Pyrrole, tetrasodium phthalocyanine tetrasulfonate, potassium chloride, and ferrous chloride were added to a ball mill jar and mixed thoroughly. Potassium ferricyanide was then added, and the mixture was ball-milled at 300 rpm for 3 hours. The product was washed with deionized water and dried at 80°C to obtain a conductive / coordination bipolymer material. The molar ratios of pyrrole to tetrasodium phthalocyanine tetrasulfonate were 705:1, pyrrole to potassium chloride, pyrrole to ferrous chloride, and pyrrole to potassium ferricyanide were all 1:2.
[0017] Depend on Figure 1 As can be seen, the conductive / coordination dual polymer material prepared in Example 1 is composed of a conductive polymer (polypyrrole) and a coordination polymer (Prussian blue analogue), wherein the Prussian blue analogue (ferrous ferrocyanide) is uniformly distributed in a three-dimensional network formed by interconnected polypyrrole nanoparticles.
[0018] An electrode sheet was prepared by mixing the conductive / coordination dual polymer material (active material), Super P carbon black (conductive agent), and polyvinylidene fluoride (binder) at a mass ratio of 8:1:1. Using this electrode sheet as the positive electrode, a sodium sheet as the negative electrode, a glass fiber membrane as the separator, and an EC / PC mixed solution (volume ratio 1:1) containing 1 M NaClO4 and 5% FEC as the electrolyte, a coin-type half-cell was assembled. Cyclic and rate performance (voltage range 2.0–4.2 V) was tested at room temperature.
[0019] From the cycle performance diagram ( Figure 2 and Figure 3 As can be seen, this conductive / coordination dual polymer material exhibits high reversible capacity and good cycling stability at 0.1 A·g2. -1 After 200 cycles at a current density, its discharge specific capacity reaches 104.2 mAh·g. -1 ; in 1A·g -1 After 1000 cycles at a current density, its discharge specific capacity remains as high as 72.7 mAh·g. -1 .
[0020] From the rate performance diagram ( Figure 4 As can be seen, this conductive / coordination dual polymer material exhibits good rate capability at 1 A·g. -1 At current densities of [specific values], its average discharge specific capacity remains as high as 72.9 mAh·g. -1 .
[0021] Example 2 A method for preparing a conductive / coordination dual polymer material includes the following steps: Pyrrole, tetrasodium phthalocyanine tetrasulfonate, potassium chloride, and manganese chloride were added to a ball mill jar and mixed thoroughly. Potassium ferricyanide was then added, and the mixture was ball-milled at 300 rpm for 3 hours. The product was washed with deionized water and dried at 80°C to obtain the conductive / coordination bipolymer material. The molar ratios of pyrrole to tetrasodium phthalocyanine tetrasulfonate were 705:1, pyrrole to potassium chloride, pyrrole to manganese chloride, and pyrrole to potassium ferricyanide were all 1:2.
[0022] Depend on Figure 5 As can be seen, the conductive / coordination dual polymer material prepared in Example 2 is composed of a conductive polymer (polypyrrole) and a coordination polymer (Prussian blue analogue), wherein the Prussian blue analogue (manganese ferrocyanide) is uniformly distributed in a three-dimensional network formed by interconnected polypyrrole nanoparticles.
[0023] An electrode sheet was prepared by mixing the conductive / coordination dual polymer material (active material), Super P carbon black (conductive agent), and polyvinylidene fluoride (binder) at a mass ratio of 8:1:1. Using this electrode sheet as the positive electrode, a sodium sheet as the negative electrode, a glass fiber membrane as the separator, and an EC / PC mixed solution (volume ratio 1:1) containing 1 M NaClO4 and 5% FEC as the electrolyte, a coin-type half-cell was assembled. Cyclic and rate performance (voltage range 2.0–4.2 V) was tested at room temperature.
[0024] From the cycle performance diagram ( Figure 6 As can be seen, this conductive / coordination dual polymer material exhibits high reversible capacity and good cycling stability at 0.1 A·g2. -1 After 200 cycles at a current density, its discharge specific capacity reaches as high as 97.3 mAh·g. -1 .
[0025] From the rate performance diagram ( Figure 7 As can be seen, this conductive / coordination dual polymer material exhibits good rate capability at 1 A·g. -1 At current densities of [specific values], its average discharge specific capacity remains as high as 62.5 mAh·g. -1 .
[0026] Example 3 A method for preparing a conductive / coordination dual polymer material includes the following steps: Aniline, phytic acid, sodium chloride, and nickel sulfate were added to a ball mill jar and mixed thoroughly. Sodium ferricyanide was then added, and the mixture was ball-milled at 100 rpm for 12 hours. The product was washed with deionized water and dried at 80°C to obtain the conductive / coordination bipolymer material. The molar ratios of aniline and phytic acid were 5:1, aniline and sodium chloride were 1:1, aniline and nickel sulfate were 1:5, and aniline and sodium ferricyanide were 1:5.
[0027] The conductive / coordination dual polymer material prepared in Example 3 has a structure and electrochemical properties that are basically the same as those prepared in Examples 1 and 2.
[0028] Example 4 A method for preparing a conductive / coordination dual polymer material includes the following steps: Aniline, phytic acid, sodium chloride, and manganese chloride were added to a ball mill jar and mixed thoroughly. Sodium ferricyanide was then added, and the mixture was ball-milled at 1000 rpm for 0.5 h. The product was washed with deionized water and dried at 80 °C to obtain the conductive / coordination bipolymer material. The molar ratios of aniline and phytic acid were 1:1, aniline and sodium chloride were 1:20, aniline and manganese chloride were 1:1, and aniline and sodium ferricyanide were 1:1.
[0029] The conductive / coordination dual polymer material prepared in Example 4 has a structure and electrochemical properties that are basically the same as those of the materials prepared in Examples 1 and 2.
[0030] Example 5
[0031] A method for preparing a conductive / coordination dual polymer material includes the following steps: Pyrrole, tetrasodium phthalocyanine tetrasulfonate, potassium chloride, and cobalt acetate were added to a ball mill jar and mixed thoroughly. Potassium ferricyanide was then added, and the mixture was ball-milled at 200 rpm for 6 hours. The product was washed with deionized water and dried at 80°C to obtain the conductive / coordination bipolymer material. The molar ratio of pyrrole to tetrasodium phthalocyanine tetrasulfonate was 1000:1, the molar ratio of pyrrole to potassium chloride was 1:10, the molar ratio of pyrrole to cobalt acetate was 1:2, and the molar ratio of pyrrole to potassium ferricyanide was 1:2.
[0032] The conductive / coordination dual polymer material prepared in Example 5 has a structure and electrochemical properties that are basically the same as those prepared in Examples 1 and 2.
Claims
1. A method for preparing a conductive / coordination dual polymer material, characterized in that, Conductive polymer monomer material, dopant, grinding aid, and transition metal salt are added to a ball mill jar and mixed evenly. Then, an oxidant is added, and after ball milling, the product is washed and dried to obtain a conductive / coordination dual polymer material. The molar ratio of the conductive polymer monomer material to the dopant is 1~1000:1; the molar ratio of the conductive polymer monomer material to the grinding aid is 1:1~20; the molar ratio of the conductive polymer monomer material to the transition metal salt is 1:1~5; and the molar ratio of the conductive polymer monomer material to the oxidant is 1:1~5.
2. The method for preparing the conductive / coordination dual polymer material according to claim 1, characterized in that: The conductive polymer monomer material is pyrrole or aniline.
3. The method for preparing the conductive / coordination dual polymer material according to claim 1, characterized in that: The dopant is tetrasodium phthalocyanine copper tetrasulfonate or phytic acid.
4. The method for preparing the conductive / coordination dual polymer material according to claim 1, characterized in that: The grinding aid is potassium chloride or sodium chloride.
5. The method for preparing the conductive / coordination dual polymer material according to claim 1, characterized in that: The transition metal salt contains at least one of the following metal ions: ferrous ion, manganese ion, nickel ion, cobalt ion, copper ion, and zinc ion; and at least one of the following acid radical ions: chloride ion, sulfate ion, acetate ion, and nitrate ion.
6. The method for preparing the conductive / coordination dual polymer material according to claim 1, characterized in that: The oxidant is potassium ferricyanide or sodium ferricyanide.
7. The method for preparing the conductive / coordination dual polymer material according to claim 1, characterized in that: The ball milling reaction speed is 100~1000 rpm; the ball milling reaction time is 0.5~12 h.
8. A conductive / coordination dual polymer material prepared by the method according to any one of claims 1-7, characterized in that, It is composed of a conductive polymer and a Prussian blue analogue, with the Prussian blue analogue uniformly distributed in a three-dimensional network formed by interconnected conductive polymer nanoparticles.
9. The application of the conductive / coordination dual polymer material according to claim 8 as a cathode material for sodium-ion batteries.