Conductive conjugated coordination polymer based on imide as well as preparation method and application of conductive conjugated coordination polymer

Abstract

The invention discloses an imide-based conductive conjugated coordination polymer as well as a preparation method and application thereof, and belongs to the technical field of battery materials. The preparation method of the conductive conjugated coordination polymer comprises the following steps: adding N, N '-dihydroxy naphthalene diimide into a solvent, then adding metal salt, mixing and heating to obtain the conductive conjugated coordination polymer. In addition, the invention also provides the conductive conjugated coordination polymer which is prepared by the preparation method. In addition, the invention also provides the conductive conjugated coordination polymer prepared by the preparation method or application of the conductive conjugated coordination polymer as a lithium ion battery positive electrode material or a sodium ion battery positive electrode material. The polymer has high specific capacity as a lithium ion battery positive electrode material or a sodium ion battery positive electrode material.

Description

Technical Field

[0001] The present invention relates to the technical field of battery materials, and particularly relates to an imide-based conductive conjugated coordination polymer, a preparation method thereof, and an application thereof. Background Art

[0002] As two important electrochemical energy storage devices, lithium-ion batteries and sodium-ion batteries have the advantages of high energy density, long cycle life, and environmental friendliness, and have been widely used. However, traditional cathode electrode materials have problems such as scarce resources, high costs, and limited specific capacity, which limit their further development and application. Organic electrode materials have the advantages of high theoretical capacity, renewable, and environmental friendliness, and are one of the key research materials for lithium / sodium-ion batteries.

[0003] Among organic electrode materials, conductive conjugated coordination polymer materials not only inherit the advantages of high specific surface area and porous structure of traditional coordination polymers, but also have excellent electron transport performance and rich redox active sites, which can effectively improve the specific capacity, rate performance, and cycle stability of electrode materials. In lithium / sodium-ion batteries, as a cathode material, conductive conjugated coordination polymer materials can provide high specific capacity and excellent cycle stability. Their porous structure is beneficial to the infiltration of electrolytes and ion transport, while conjugated ligands can achieve efficient electron transport and reduce the internal resistance of the electrode. Therefore, developing an efficient and stable conductive conjugated coordination polymer material and exploring its application in the cathode material of lithium-sodium batteries have important scientific significance and practical value.

[0004] At present, some conductive conjugated coordination polymer materials have been studied as cathode materials in lithium / sodium-ion batteries to achieve high specific capacity and excellent cycle stability of electrode materials. However, there is still a need to develop new conductive conjugated coordination polymers with high specific capacity and excellent cycle stability. Summary of the Invention

[0005] The purpose of the present invention is to overcome the above technical deficiencies, provide an imide-based conductive conjugated coordination polymer, a preparation method thereof, and an application thereof, and solve the technical problem of how to achieve high specific capacity and excellent cycle stability of battery materials in the prior art.

[0006] To achieve the above technical purpose, the technical solution of the present invention provides a preparation method of an imide-based conductive conjugated coordination polymer, including the following steps:

[0007] Add N,N'-dihydroxynaphthalenedicarboximide to a solvent, and then add a metal salt and mix and heat to obtain an imide-based conductive conjugated coordination polymer.

[0008] In any embodiment, the solvent is DMF.

[0009] In any embodiment, the metal salt is one or more of a soluble nickel salt, a soluble manganese salt, a soluble calcium salt, a soluble copper salt, and a soluble cobalt salt.

[0010] In any embodiment, the soluble nickel salt includes nickel nitrate; and / or, the soluble manganese salt includes manganese chloride; and / or, the soluble calcium salt includes calcium nitrate; and / or, the soluble copper salt includes copper nitrate; and / or, the soluble cobalt salt includes cobalt chloride.

[0011] In any embodiment, the molar ratio of the N,N'-dihydroxynaphthalenedicarboximide to the metal salt is 1:(1 - 1.5); and / or, the temperature of the heating reaction is 100 - 120 °C, and the time is 48 - 72 h.

[0012] In any embodiment, the N,N'-dihydroxynaphthalenedicarboximide is prepared by the following steps:

[0013] 1,4,5,8-Naphthalenetetracarboxylic dianhydride and hydroxylamine hydrochloride are added to a solvent and mixed and heated to obtain the N,N'-dihydroxynaphthalenedicarboximide.

[0014] In any embodiment, the molar ratio of the 1,4,5,8-naphthalenetetracarboxylic dianhydride to the hydroxylamine hydrochloride is 1:(2 - 2.5); and / or, the temperature of the mixed heating is 65 - 70 °C, and the time is 5 - 7 h.

[0015] In addition, the present invention also provides an imide-based conductive conjugated coordination polymer prepared by the above preparation method.

[0016] In addition, the present invention also provides the use of the imide-based conductive conjugated coordination polymer prepared by the above preparation method or the above imide-based conductive conjugated coordination polymer as a cathode material for a lithium-ion battery or a sodium-ion battery.

[0017] In any embodiment, the conductive conjugated coordination polymer, super P, and polyvinylidene fluoride are ground and mixed, and then an NMP solution is added dropwise and grinding is continued. The obtained slurry is coated on an aluminum foil and dried in vacuum to obtain a cathode for a lithium or sodium ion battery.

[0018] Compared with the prior art, the beneficial effects of the present invention include: In the preparation method of the imide-based conductive conjugated coordination polymer proposed by the present invention, N,N'-dihydroxynaphthalenedicarboximide is added to a solvent, and then a metal salt is added and mixed and heated to obtain the imide-based conductive conjugated coordination polymer. This polymer has a high specific capacity, excellent charge and discharge curves, and cycling performance as a cathode material for a lithium-ion battery or a sodium-ion battery, indicating its extremely excellent electrochemical performance. Description of the Drawings

[0019] Figure 1 It is the thermogravimetric curve of the N,N'-dihydroxynaphthalenediimide conductive conjugated nickel coordination polymer and N,N'-dihydroxynaphthalenediimide prepared in Example 1.

[0020] Figure 2 It is the infrared absorption spectrum of the N,N'-dihydroxynaphthalenediimide conductive conjugated nickel coordination polymer and N,N'-dihydroxynaphthalenediimide prepared in Example 1.

[0021] Figure 3 It is the powder X-ray diffraction analysis pattern of the N,N'-dihydroxynaphthalenediimide conductive conjugated nickel coordination polymer prepared in Example 1.

[0022] Figure 4 It is the cyclic capacity diagram of the N,N'-dihydroxynaphthalenediimide conductive conjugated nickel coordination polymer Ni-ONDI prepared in Example 1 as the positive electrode of a lithium-ion battery.

[0023] Figure 5 It is the charge-discharge curve of the N,N'-dihydroxynaphthalenediimide conductive conjugated nickel coordination polymer Ni-ONDI prepared in Example 1 as the positive electrode of a lithium-ion battery.

[0024] Figure 6 It is the cyclic capacity diagram of the N,N'-dihydroxynaphthalenediimide conductive conjugated nickel coordination polymer Ni-ONDI prepared in Example 1 as the positive electrode of a sodium-ion battery.

[0025] Figure 7 It is the charge-discharge curve of the N,N'-dihydroxynaphthalenediimide conductive conjugated nickel coordination polymer Ni-ONDI prepared in Example 1 as the positive electrode of a sodium-ion battery.

[0026] Figure 8 It is the thermogravimetric curve of the N,N'-dihydroxynaphthalenediimide conductive conjugated manganese coordination polymer and N,N'-dihydroxynaphthalenediimide prepared in Example 2.

[0027] Figure 9 It is the infrared absorption spectrum of the N,N'-dihydroxynaphthalenediimide conductive conjugated manganese coordination polymer and N,N'-dihydroxynaphthalenediimide prepared in Example 2.

[0028] Figure 10 It is the powder X-ray diffraction analysis pattern of the N,N'-dihydroxynaphthalenediimide conductive conjugated manganese coordination polymer prepared in Example 2.

[0029] Figure 11 It is the cyclic capacity diagram of the N,N'-dihydroxynaphthalenediimide conductive conjugated manganese coordination polymer Mn-ONDI prepared in Example 2 as the positive electrode of a lithium-ion battery.

[0030] Figure 12 It is the charge-discharge curve of the N,N'-dihydroxynaphthalenediimide conductive conjugated manganese coordination polymer Mn-ONDI prepared in Example 2 as the positive electrode of a lithium-ion battery.

[0031] Figure 13 It is the cyclic capacity diagram of the N,N'-dihydroxynaphthalenediimide conductive conjugated manganese coordination polymer Mn-ONDI prepared in Example 2 as the positive electrode of a sodium-ion battery.

[0032] Figure 14 It is the charge-discharge curve of the N,N'-dihydroxynaphthalenediimide conductive conjugated manganese coordination polymer Mn-ONDI prepared in Example 2 as the positive electrode of a sodium-ion battery.

[0033] Figure 15 It is the thermogravimetric curve diagram of the N,N'-dihydroxynaphthalenediimide conductive conjugated calcium coordination polymer and N,N'-dihydroxynaphthalenediimide prepared in Example 3.

[0034] Figure 16 It is the infrared absorption spectrum diagram of the N,N'-dihydroxynaphthalenediimide conductive conjugated calcium coordination polymer and N,N'-dihydroxynaphthalenediimide prepared in Example 3.

[0035] Figure 17 It is the powder X-ray diffraction analysis diagram of the N,N'-dihydroxynaphthalenediimide conductive conjugated calcium coordination polymer prepared in Example 3.

[0036] Figure 18 It is the cyclic capacity diagram of the N,N'-dihydroxynaphthalenediimide conductive conjugated calcium coordination polymer Ca-ONDI prepared in Example 3 as the positive electrode of a lithium-ion battery.

[0037] Figure 19 It is the charge-discharge curve of the N,N'-dihydroxynaphthalenediimide conductive conjugated calcium coordination polymer Ca-ONDI prepared in Example 3 as the positive electrode of a lithium-ion battery.

[0038] Figure 20 It is the cyclic capacity diagram of the N,N'-dihydroxynaphthalenediimide conductive conjugated calcium coordination polymer Ca-ONDI prepared in Example 3 as the positive electrode of a sodium-ion battery.

[0039] Figure 21 It is the charge-discharge curve of the N,N'-dihydroxynaphthalenediimide conductive conjugated calcium coordination polymer Ca-ONDI prepared in Example 3 as the positive electrode of a sodium-ion battery.

[0040] Figure 22 It is the thermogravimetric curve diagram of the N,N'-dihydroxynaphthalenediimide conductive conjugated copper coordination polymer and N,N'-dihydroxynaphthalenediimide prepared in Example 4.

[0041] Figure 23 The infrared absorption spectra of the N,N'-dihydroxynaphthalenediimide conductive conjugated copper coordination polymer and N,N'-dihydroxynaphthalenediimide prepared in Example 4.

[0042] Figure 24 The powder X-ray diffraction analysis pattern of the N,N'-dihydroxynaphthalenediimide conductive conjugated copper coordination polymer prepared in Example 4.

[0043] Figure 25 The cycle capacity diagram of the N,N'-dihydroxynaphthalenediimide conductive conjugated copper coordination polymer Cu-ONDI prepared in Example 4 as the positive electrode of a lithium-ion battery.

[0044] Figure 26 The charge-discharge curve of the N,N'-dihydroxynaphthalenediimide conductive conjugated copper coordination polymer Cu-ONDI prepared in Example 4 as the positive electrode of a lithium-ion battery.

[0045] Figure 27 The cycle capacity diagram of the N,N'-dihydroxynaphthalenediimide conductive conjugated copper coordination polymer Cu-ONDI prepared in Example 4 as the positive electrode of a sodium-ion battery.

[0046] Figure 28 The charge-discharge curve of the N,N'-dihydroxynaphthalenediimide conductive conjugated copper coordination polymer Cu-ONDI prepared in Example 4 as the positive electrode of a sodium-ion battery.

[0047] Figure 29 The thermogravimetric curve of the N,N'-dihydroxynaphthalenediimide conductive conjugated cobalt coordination polymer and N,N'-dihydroxynaphthalenediimide prepared in Example 5.

[0048] Figure 30 The infrared absorption spectra of the N,N'-dihydroxynaphthalenediimide conductive conjugated cobalt coordination polymer and N,N'-dihydroxynaphthalenediimide prepared in Example 5.

[0049] Figure 31 The powder X-ray diffraction analysis pattern of the N,N'-dihydroxynaphthalenediimide conductive conjugated cobalt coordination polymer prepared in Example 5.

[0050] Figure 32 The cycle capacity diagram of the N,N'-dihydroxynaphthalenediimide conductive conjugated cobalt coordination polymer Co-ONDI prepared in Example 5 as the positive electrode of a lithium-ion battery.

[0051] Figure 33 The charge-discharge curve of the N,N'-dihydroxynaphthalenediimide conductive conjugated cobalt coordination polymer Co-ONDI prepared in Example 5 as the positive electrode of a lithium-ion battery.

[0052] Figure 34 It is the cycle capacity diagram of the N,N'-dihydroxynaphthalenediimide conductive conjugated cobalt coordination polymer Co-ONDI prepared in Example 5 as the positive electrode of a sodium-ion battery.

[0053] Figure 35 It is the charge-discharge curve of the N,N'-dihydroxynaphthalenediimide conductive conjugated cobalt coordination polymer Co-ONDI prepared in Example 5 as the positive electrode of a sodium-ion battery. Detailed implementation manners

[0054] The "ranges" disclosed in this application are defined in the form of lower and upper limits. A given range is defined by selecting a lower limit and an upper limit, and the selected lower and upper limits define the boundaries of a particular range. The ranges defined in this way can include or exclude the end values and can be combined arbitrarily, that is, any lower limit can be combined with any upper limit to form a range. For example, if ranges of 60-120 and 80-110 are listed for a particular parameter, ranges of 60-110 and 80-120 are also contemplated. In addition, if the minimum range values 1 and 2 are listed, and if the maximum range values 3, 4, and 5 are listed, then the following ranges are all contemplated: 1-3, 1-4, 1-5, 2-3, 2-4, and 2-5. In this application, unless otherwise stated, the numerical range "a-b" represents an abbreviated representation of any real number combination between a and b, where a and b are both real numbers. For example, the numerical range "0-5" means that all real numbers between "0-5" have been fully listed herein, and "0-5" is only an abbreviated representation of these numerical combinations. Additionally, when stating that a certain parameter is an integer ≥2, it is equivalent to disclosing that the parameter is, for example, the integer 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, etc.

[0055] Unless otherwise specified, the "including" and "comprising" mentioned in this application are open-ended and can also be closed-ended. For example, the "including" and "comprising" can mean that other components not listed can also be included or comprised, or it can only include or comprise the listed components.

[0056] Unless otherwise specified, in this application, the term "or" is inclusive. For example, the phrase "A or B" means "A, B, or both A and B". More specifically, any of the following conditions satisfies the condition "A or B": A is true (or exists) and B is false (or does not exist); A is false (or does not exist) while B is true (or exists); or both A and B are true (or exist).

[0057] This detailed implementation manner provides a preparation method of an imide-based conductive conjugated coordination polymer, including the following steps:

[0058] N,N'-dihydroxynaphthalenedicarboximide is added to the solvent DMF (i.e., dimethylformamide), and then a metal salt is added and heated to obtain an imide-based conductive conjugated coordination polymer; the metal salt is one or more of a soluble nickel salt, a soluble manganese salt, a soluble calcium salt, a soluble copper salt, and a soluble cobalt salt; the molar ratio of the N,N'-dihydroxynaphthalenedicarboximide to the metal salt is 1:(1 - 1.5); the temperature of the heating reaction is 100 - 120 °C, and the time is 48 - 72 h.

[0059] In some embodiments, the soluble nickel salt includes nickel nitrate; the soluble manganese salt includes manganese chloride; the soluble calcium salt includes calcium nitrate; the soluble copper salt includes copper nitrate; the soluble cobalt salt includes cobalt chloride.

[0060] In some embodiments, the N,N'-dihydroxynaphthalenedicarboximide is prepared by the following steps:

[0061] 1,4,5,8-Naphthalenetetracarboxylic dianhydride and hydroxylamine hydrochloride are added to a solvent and heated to obtain the N,N'-dihydroxynaphthalenedicarboximide; the molar ratio of the 1,4,5,8-naphthalenetetracarboxylic dianhydride to the hydroxylamine hydrochloride is 1:(2 - 2.5); the temperature of the heating is 65 - 70 °C, and the time is 5 - 7 h; the solvent is DMF.

[0062] The reactions involved in the above preparation method are as follows:

[0063]

[0064] Among them, M represents a metal ion, such as a nickel ion, a manganese ion, a calcium ion, a copper ion, or a cobalt ion.

[0065] This specific embodiment also provides an imide-based conductive conjugated coordination polymer prepared by the above preparation method.

[0066] This specific embodiment also provides the application of the imide-based conductive conjugated coordination polymer prepared by the above preparation method or the above imide-based conductive conjugated coordination polymer as a cathode material for a lithium-ion battery or a sodium-ion battery. The imide-based conductive conjugated coordination polymer, super P, and polyvinylidene fluoride are ground and mixed, and then an NMP solution is added dropwise and grinding is continued. The obtained slurry is coated on an aluminum foil and dried in vacuum to obtain a cathode for a lithium-ion battery or a sodium-ion battery.

[0067] In order to make the objectives, technical solutions, and advantages of the present invention clearer, the present invention will be further described in detail below with reference to the accompanying drawings and embodiments. It should be understood that the specific embodiments described herein are only used to explain the present invention and are not used to limit the present invention.

[0068] In the present invention, reference is made to "some embodiments", "this embodiment", and examples, etc., which describe subsets of all possible embodiments. However, it is understood that "some embodiments" may be the same subset or different subsets of all possible embodiments, and may be combined with each other without conflict.

[0069] If a similar description such as "first / second" appears in the application document, the following explanation shall be added. In the following description, the terms "first / second / third" only distinguish similar objects and do not represent a specific order for the objects. It is understood that "first / second / third" can be interchanged in a specific order or sequence when permitted, so that the embodiments described herein can be implemented in an order other than that illustrated or described herein.

[0070] In this embodiment, the term "and / or" only describes the association relationship of associated objects, indicating that there can be three relationships. For example, object A and / or object B can represent three situations: object A exists alone, object A and object B exist simultaneously, and object B exists alone.

[0071] Hereinafter, embodiments of the present application will be described. The embodiments described below are exemplary and are only used to explain the present application and should not be construed as a limitation of the present application. For those technologies or conditions not specified in the embodiments, they shall be carried out according to the technologies or conditions described in the literature in the art or according to the product specifications. For reagents or instruments not specified by the manufacturer, they are all conventional products that can be obtained through commercial purchase.

[0072] Example 1

[0073] This embodiment provides a conductive conjugated coordination polymer based on imide, which is prepared by the following steps:

[0074] (1) 10 mmol of 1,4,5,8-naphthalenetetracarboxylic dianhydride and 21 mmol of hydroxylamine hydrochloride are added to 20 ml of DMF and mixed evenly. The mixture is refluxed at 65 °C for 8 h, and the crude product is filtered, washed, and dried to obtain N,N'-dihydroxynaphthalenediimide (i.e., H 2 ONDI);

[0075] (2) 0.2 mmol of H 2ONDI was dissolved in a reaction kettle containing 10 ml of DMF. Then, 0.2 mmol of nickel nitrate was weighed and dissolved in 10 ml of deionized water and added to the reaction kettle. After mixing evenly, the reaction kettle was placed in an oven for reaction. The temperature was raised from room temperature to 100 °C and kept at this temperature for 48 h. After the reaction was completed, it was cooled to room temperature. The product was filtered by suction and washed and dried with deionized water and DMF. The precipitate was dried in a vacuum drying oven at 60 °C for 12 h to obtain nickel N,N'-dihydroxynaphthalenedicarboximide coordination polymer (i.e., Ni-ONDI).

[0076] The thermogravimetric curves of the nickel N,N'-dihydroxynaphthalenedicarboximide coordination polymer and N,N'-dihydroxynaphthalenedicarboximide obtained in this example are as shown in Figure 1 shown, and the infrared absorption spectra are as shown in Figure 2 shown, and the X-ray diffraction analysis diagrams are as shown in Figure 3 shown. The thermogravimetric curves, infrared absorption spectra and X-ray diffraction analysis diagrams show that the prepared nickel N,N'-dihydroxynaphthalenedicarboximide coordination polymer is different from N,N'-dihydroxynaphthalenedicarboximide and is a new composite material.

[0077] Performance test on the application of the nickel N,N'-dihydroxynaphthalenedicarboximide coordination polymer obtained in this example as a cathode material for lithium / sodium ion batteries:

[0078] (1) Ni-ONDI, super P and polyvinylidene fluoride were ground and mixed in an agate mortar for 10 min at a mass ratio of 6:3:1. Then, an appropriate amount of NMP solution was added dropwise and grinding was continued for 10 min. The obtained slurry was coated on an aluminum foil and dried in a vacuum drying oven at 60 °C for 12 h, and then cut into circular pieces to obtain a cathode for lithium / sodium ion batteries. The content of the electrode active material Ni-ONDI was about 1.0 mg.

[0079] (2) A two-electrode system was adopted. The working electrode prepared in step (1) was used as the cathode, a lithium sheet was used as the anode, a glass fiber was used as the separator, and 1 M LiTFSI-DOL+DME (VDOL:VDME = 1:1) was used as the electrolyte. A button battery was assembled in a glove box filled with argon.

[0080] (3) Constant current charge and discharge test. The test condition parameters were: the constant current charge and discharge density was 100 mA·g -1 , and the charge and discharge potential range was 1.5 V - 3.8 V. All charge and discharge performance tests were carried out at room temperature.

[0081] (4) The anode material was replaced with a sodium sheet and the electrolyte was replaced with NaPF6-DME. Steps (1) to (3) were repeated. The charge and discharge potential range was 1 - 3.5 V. All charge and discharge performance tests were carried out at room temperature.

[0082] The constant current charge-discharge curves and cyclic capacity diagrams of the N,N'-dihydroxynaphthalenediimide nickel coordination polymer electrode obtained by testing with a lithium sheet as the negative electrode are shown in Figure 4 and Figure 5 respectively. The results of the electrochemical performance test are as follows: the initial discharge specific capacity is 133.1 mAh·g -1 , and the Coulombic efficiency of the first cycle is 101.55%. At a current density of 100 mA·g -1 , after 300 cycles, the reversible capacity is 92.7 mAh·g -1 . The constant current charge-discharge curves and cyclic capacity diagrams of the N,N'-dihydroxynaphthalenediimide nickel coordination polymer electrode obtained by testing with a sodium sheet as the negative electrode are shown in Figure 6 and Figure 7 respectively. The results of the electrochemical performance test are as follows: the initial discharge specific capacity is 142.2 mAh·g -1 , and the Coulombic efficiency of the first cycle is 93.7%. At a current density of 100 mA·g -1 , after 200 cycles, the reversible capacity is 132.5 mAh·g -1 .

[0083] It can be seen from the above results that the N,N'-dihydroxynaphthalenediimide nickel coordination polymer obtained in this example has excellent electrochemical performance as a cathode material for lithium / sodium ion batteries.

[0084] Example 2

[0085] This example proposes a conductive conjugated coordination polymer based on imide, which is prepared by the following steps:

[0086] (1) 10 mmol of 1,4,5,8-naphthalenetetracarboxylic dianhydride and 21 mmol of hydroxylamine hydrochloride are added to 20 ml of DMF and mixed evenly. The mixture is refluxed at 65 °C for 8 h. The crude product is filtered, washed and dried to obtain N,N'-dihydroxynaphthalenediimide (H 2 ONDI);

[0087] (2) 0.2 mmol of H 2 ONDI is dissolved in a reaction kettle containing 10 ml of DMF. Then, 0.2 mmol of manganese chloride is weighed and dissolved in 10 ml of deionized water and added to the reaction kettle. The mixture is stirred evenly. The reaction kettle is placed in an oven for reaction. The temperature is raised from room temperature to 100 °C and kept for 48 h. After the reaction is completed, it is cooled to room temperature. The product is filtered and washed with deionized water and DMF and then dried. The precipitate is dried in a vacuum drying oven at 60 °C for 12 h to obtain N,N'-dihydroxynaphthalenediimide manganese coordination polymer (i.e., Mn-ONDI).

[0088] The thermogravimetric curves of the N,N'-dihydroxynaphthalenediimide manganese coordination polymer and N,N'-dihydroxynaphthalenediimide obtained in this example are as follows Figure 8 shown, and the infrared absorption spectra are as follows Figure 9 shown, and the X-ray diffraction analysis diagrams are as follows Figure 10 shown. The thermogravimetric curves, infrared absorption spectra and X-ray diffraction analysis diagrams show that the prepared N,N'-dihydroxynaphthalenediimide manganese coordination polymer is different from N,N'-dihydroxynaphthalenediimide and is a new composite material.

[0089] Performance test on the application of the N,N'-dihydroxynaphthalenediimide manganese coordination polymer obtained in this example as a cathode material for lithium / sodium ion batteries:

[0090] (1) Mix Mn-ONDI, super P and polyvinylidene fluoride in a mass ratio of 6:3:1 in an agate mortar and grind for 10 min, then add an appropriate amount of NMP solution and continue to grind for 10 min. Coat the obtained slurry on an aluminum foil, dry it in a vacuum drying oven at 60 °C for 12 h, and cut it into discs to obtain the cathode of the lithium / sodium ion battery. The content of the electrode active material Mn-ONDI is about 1.0 mg.

[0091] (2) Adopt a two-electrode system. The working electrode prepared in step (1) is used as the cathode, a lithium sheet is used as the anode, a glass fiber is used as the separator, and 1M LiTFSI-DOL+DME (VDOL:VDME = 1:1) is used as the electrolyte. Assemble a button battery in a glove box filled with argon.

[0092] (3) Constant current charge and discharge test. The test condition parameters are: the constant current charge and discharge density is 100 mA·g -1 , and the charge and discharge potential range is 1.5 V - 3.8 V. All charge and discharge performance tests are carried out at room temperature.

[0093] (4) Replace the anode material with a sodium sheet and the electrolyte with NaPF6-DME, and repeat steps (1) to (3). The charge and discharge potential range is 1 - 3.6 V. All charge and discharge performance tests are carried out at room temperature.

[0094] The constant current charge and discharge curves and cyclic capacity diagrams of the N,N'-dihydroxynaphthalenediimide manganese coordination polymer electrode with a lithium sheet as the anode obtained by testing are respectively as follows Figure 11 and Figure 12 shown. The results of the electrochemical performance test are as follows: the initial discharge specific capacity is 91.9 mAh·g -1 , and the first-cycle Coulombic efficiency is 127.26%. At a current density of 100 mA·g -1 , it cycles 500 times, and the reversible capacity is 89.4 mAh·g -1。The constant current charge-discharge curves and cyclic capacity diagrams of the N,N'-dihydroxynaphthalenediimide manganese coordination polymer electrode obtained by testing with a sodium sheet as the negative electrode are shown in Figure 13 and Figure 14 respectively. The results of the electrochemical performance test are as follows: the initial discharge specific capacity is 88.7 mAh·g -1 , and the first-cycle Coulombic efficiency is 114.4%. At a current density of 100 mA·g -1 , after 200 cycles, the reversible capacity is 126.4 mAh·g -1 .

[0095] It can be seen from the above results that the N,N'-dihydroxynaphthalenediimide manganese coordination polymer obtained in this example has excellent electrochemical performance as a cathode material for lithium / sodium ion batteries.

[0096] Example 3

[0097] This example presents a conductive conjugated coordination polymer based on imide, which is prepared by the following steps:

[0098] (1) 10 mmol of 1,4,5,8-naphthalenetetracarboxylic dianhydride and 21 mmol of hydroxylamine hydrochloride are added to 20 ml of DMF and mixed evenly. The mixture is refluxed at 65 °C for 8 h. The crude product is filtered, washed, and dried to obtain N,N'-dihydroxynaphthalenediimide (H 2 ONDI);

[0099] (2) 0.2 mmol of H 2 ONDI is dissolved in a reaction kettle containing 10 ml of DMF. Then, 0.2 mmol of calcium nitrate is weighed and dissolved in 10 ml of deionized water and added to the reaction kettle. The mixture is stirred evenly. The reaction kettle is placed in an oven for reaction. The temperature is raised from room temperature to 100 °C and kept at this temperature for 48 h. After the reaction is completed, it is cooled to room temperature. The product is filtered, washed with deionized water and DMF, and dried. The precipitate is dried in a vacuum drying oven at 60 °C for 12 h to obtain N,N'-dihydroxynaphthalenediimide calcium coordination polymer (i.e., Ca-ONDI).

[0100] The thermogravimetric curves of the N,N'-dihydroxynaphthalenediimide calcium coordination polymer and N,N'-dihydroxynaphthalenediimide obtained in this example are shown in Figure 15 , the infrared absorption spectra are shown in Figure 16 , and the X-ray diffraction analysis diagrams are shown in Figure 17 . The thermogravimetric curves, infrared absorption spectra, and X-ray diffraction analysis diagrams show that the prepared N,N'-dihydroxynaphthalenediimide calcium coordination polymer is different from N,N'-dihydroxynaphthalenediimide and is a new composite material.

[0101] Application performance test of the N,N'-dihydroxynaphthalenedicarboximide calcium coordination polymer obtained in this example as a cathode material for lithium / sodium ion batteries:

[0102] (1) Mix Ca-ONDI, super P, and polyvinylidene fluoride in a mass ratio of 6:3:1 in an agate mortar and grind for 10 min. Then, add an appropriate amount of NMP solution and continue grinding for 10 min. Coat the resulting slurry onto an aluminum foil, dry it in a vacuum drying oven at 60 °C for 12 h, and cut it into circular pieces to obtain the cathode of the lithium / sodium ion battery. The content of the electrode active material Ca-ONDI is approximately 1.0 mg.

[0103] (2) Adopt a two-electrode system. The working electrode prepared in step (1) is used as the cathode, a lithium sheet is used as the anode, a glass fiber is used as the separator, and 1 M LiTFSI-DOL+DME (VDOL:VDME = 1:1) is used as the electrolyte. Assemble the coin cell in a glove box filled with argon.

[0104] (3) Constant current charge-discharge test. The test condition parameters are: the constant current charge-discharge density is 100 mA·g -1 , and the charge-discharge potential range is 1 V - 3.5 V. All charge-discharge performance tests are carried out at room temperature.

[0105] (4) Replace the anode material with a sodium sheet and the electrolyte with NaPF6-DME, and repeat steps (1) to (3). The charge-discharge potential range is 1 - 3.6 V. All charge-discharge performance tests are carried out at room temperature.

[0106] The constant current charge-discharge curve and cyclic capacity diagram of the N,N'-dihydroxynaphthalenedicarboximide calcium coordination polymer electrode with a lithium sheet as the anode are shown in Figure 18 and Figure 19 respectively. The results of the electrochemical performance test are as follows: the initial discharge specific capacity is 56.6 mAh·g -1 , and the first-cycle Coulombic efficiency is 122%. At a current density of 100 mA·g -1 , cycle 200 times, and the reversible capacity is 56.8 mAh·g -1 . The constant current charge-discharge curve and cyclic capacity diagram of the N,N'-dihydroxynaphthalenedicarboximide calcium coordination polymer electrode with a sodium sheet as the anode are shown in Figure 20 and Figure 21 respectively. The results of the electrochemical performance test are as follows: the initial discharge specific capacity is 69.6 mAh·g -1 , and the first-cycle Coulombic efficiency is 131.96%. At a current density of 100 mA·g -1 , cycle 300 times, and the reversible capacity is 106.3 mAh·g -1 .

[0107] As can be seen from the above results, the N,N'-dihydroxynaphthalenedicarboximide calcium coordination polymer obtained in this example has excellent electrochemical performance as a cathode material for lithium / sodium ion batteries.

[0108] Example 4

[0109] This example presents a conductive conjugated coordination polymer based on imide, which is prepared by the following steps:

[0110] (1) Add 10 mmol of 1,4,5,8-naphthalenetetracarboxylic dianhydride and 21 mmol of hydroxylamine hydrochloride to 20 ml of DMF, mix evenly, reflux at 65 °C for 8 h, filter, wash and dry the crude product to obtain N,N'-dihydroxynaphthalenedicarboximide (H 2 ONDI);

[0111] (2) Dissolve 0.2 mmol of H 2 ONDI in a reaction kettle containing 10 ml of DMF, then weigh 0.2 mmol of copper nitrate, dissolve it in 10 ml of deionized water and add it to the reaction kettle, mix evenly, place the reaction kettle in an oven for reaction, heat it from room temperature to 100 °C, keep the temperature for reaction for 48 h, cool it to room temperature after the reaction is completed, filter the product, wash and dry it with deionized water and DMF, and dry the precipitate in a vacuum drying oven at 60 °C for 12 h to obtain N,N'-dihydroxynaphthalenedicarboximide copper coordination polymer (i.e., Cu-ONDI).

[0112] The thermogravimetric curves of the N,N'-dihydroxynaphthalenedicarboximide copper coordination polymer and N,N'-dihydroxynaphthalenedicarboximide obtained in this example are as Figure 22 shown, the infrared absorption spectra are as Figure 23 shown, and the X-ray diffraction analysis diagrams are as Figure 24 shown. The thermogravimetric curves, infrared absorption spectra and X-ray diffraction analysis diagrams show that the prepared N,N'-dihydroxynaphthalenedicarboximide copper coordination polymer is different from N,N'-dihydroxynaphthalenedicarboximide and is a new composite material.

[0113] Performance test of the N,N'-dihydroxynaphthalenedicarboximide copper coordination polymer obtained in this example as a cathode material for lithium / sodium ion batteries:

[0114] (1) Mix Cu-ONDI, super P and polyvinylidene fluoride in a mass ratio of 6:3:1 in an agate mortar, grind and mix for 10 min, then add an appropriate amount of NMP solution and continue to grind for 10 min. Coat the obtained slurry on an aluminum foil, dry it in a vacuum drying oven at 60 °C for 12 h, and cut it into circular pieces to obtain a cathode for lithium / sodium ion batteries. The content of the electrode active material Cu-ONDI is about 1.0 mg.

[0115] (2) A two-electrode system is adopted. The working electrode prepared in step (1) serves as the positive electrode, the lithium sheet serves as the negative electrode, the glass fiber serves as the separator, and 1M LiTFSI-DOL+DME (VDOL:VDME = 1:1) serves as the electrolyte. The coin cell is assembled in a glove box filled with argon gas.

[0116] (3) Constant current charge-discharge test. The test condition parameters are as follows: the constant current charge-discharge density is 100 mA·g -1 , and the charge-discharge potential range is 1.5 V - 3.8 V. All charge-discharge performance tests are carried out at room temperature.

[0117] (4) Replace the negative electrode material with a sodium sheet and the electrolyte with NaPF6-DME, and repeat steps (1) to (3). The charge-discharge potential range is 1 - 3.6 V. All charge-discharge performance tests are carried out at room temperature.

[0118] The constant current charge-discharge curve and the cycling capacity diagram of the N,N'-dihydroxynaphthalenediimide copper coordination polymer electrode with a lithium sheet as the negative electrode obtained by testing are respectively as Figure 25 and Figure 26 shown. The results of the electrochemical performance test are as follows: the initial discharge specific capacity is 170.4 mAh·g -1 , and the first-cycle Coulombic efficiency is 101.76%. Cycling 120 times at a current density of 100 mA·g -1 , the reversible capacity is 101.3 mAh·g -1 . The constant current charge-discharge curve and the cycling capacity diagram of the N,N'-dihydroxynaphthalenediimide copper coordination polymer electrode with a sodium sheet as the negative electrode obtained by testing are respectively as Figure 27 and Figure 28 shown. The results of the electrochemical performance test are as follows: the initial discharge specific capacity is 98.9 mAh·g -1 , and the first-cycle Coulombic efficiency is 127.49%. Cycling 200 times at a current density of 100 mA·g -1 , the reversible capacity is 150.4 mAh·g -1 .

[0119] It can be seen from the above results that the N,N'-dihydroxynaphthalenediimide copper coordination polymer obtained in this example has excellent electrochemical performance as the positive electrode material for lithium / sodium ion batteries.

[0120] Example 5

[0121] This example proposes a conductive conjugated coordination polymer based on imide, which is prepared by the following steps:

[0122] (1) Add 10 mmol of 1,4,5,8-naphthalenetetracarboxylic dianhydride and 21 mmol of hydroxylamine hydrochloride to 20 ml of DMF, mix evenly, reflux at 65 °C for 8 h, filter, wash, and dry the crude product to obtain N,N'-dihydroxynaphthalenediimide (H 2 ONDI);

[0123] (2) Dissolve 0.2 mmol of H 2 ONDI in a reaction kettle containing 10 ml of DMF. Weigh 0.2 mmol of cobalt chloride, dissolve it in 10 ml of deionized water, and add it to the reaction kettle. Mix evenly. Place the reaction kettle in an oven for reaction. Heat from room temperature to 100 °C and keep the temperature for 48 h. After the reaction is completed, cool to room temperature. Filter the product, wash it with deionized water and DMF, and dry it. Dry the precipitate in a vacuum drying oven at 60 °C for 12 h to obtain cobalt N,N'-dihydroxynaphthalenediimide coordination polymer (i.e., Co-ONDI).

[0124] The thermogravimetric curves of the cobalt N,N'-dihydroxynaphthalenediimide coordination polymer and N,N'-dihydroxynaphthalenediimide obtained in this example are as shown in Figure 29 The infrared absorption spectra are as shown in Figure 30 The X-ray diffraction analysis patterns are as shown in Figure 31 As shown by the thermogravimetric curves, infrared absorption spectra, and X-ray diffraction analysis patterns, the prepared cobalt N,N'-dihydroxynaphthalenediimide coordination polymer is different from N,N'-dihydroxynaphthalenediimide and is a new composite material.

[0125] Application performance test of the cobalt N,N'-dihydroxynaphthalenediimide coordination polymer obtained in this example as a cathode material for lithium / sodium ion batteries:

[0126] (1) Mix Co-ONDI, super P, and polyvinylidene fluoride in a mass ratio of 6:3:1 in an agate mortar and grind for 10 min. Then add an appropriate amount of NMP solution and continue grinding for 10 min. Coat the obtained slurry on an aluminum foil, dry it in a vacuum drying oven at 60 °C for 12 h, and cut it into circular pieces to obtain the cathode of a lithium / sodium ion battery. The content of the electrode active material Co-ONDI is about 1.0 mg.

[0127] (2) Adopt a two-electrode system. The working electrode prepared in step (1) is used as the cathode, a lithium sheet is used as the anode, a glass fiber is used as the separator, and 1 M LiTFSI-DOL+DME (VDOL:VDME = 1:1) is used as the electrolyte. Assemble a button battery in a glove box filled with argon.

[0128] (3) Constant current charge and discharge test. The test condition parameters are: the constant current charge and discharge density is 100 mA·g -1, the charge-discharge potential range is 1.5V - 4V. All charge-discharge performance tests were carried out at room temperature.

[0129] (4) Replace the negative electrode material with a sodium sheet and the electrolyte with NaPF6-DME, and repeat steps (1) to (3). The charge-discharge potential range is 1 - 3.6V. All charge-discharge performance tests were carried out at room temperature.

[0130] The constant current charge-discharge curve and cyclic capacity diagram of the N,N'-dihydroxynaphthalenediimide cobalt coordination polymer electrode obtained by testing with a lithium sheet as the negative electrode are respectively as Figure 32 and Figure 33 shown. The results of the electrochemical performance tests are as follows: the initial discharge specific capacity is 112.2 mAh·g -1 , and the Coulombic efficiency of the first cycle is 97.41%. At a current density of 100 mA·g -1 , after cycling 200 times, the reversible capacity is 59.9 mAh·g -1 . The constant current charge-discharge curve and cyclic capacity diagram of the N,N'-dihydroxynaphthalenediimide cobalt coordination polymer electrode obtained by testing with a sodium sheet as the negative electrode are respectively as Figure 34 and Figure 35 shown. The results of the electrochemical performance tests are as follows: the initial discharge specific capacity is 133 mAh·g -1 , and the Coulombic efficiency of the first cycle is 91.58%. At a current density of 100 mA·g -1 , after cycling 100 times, the reversible capacity is 132.5 mAh·g -1 .

[0131] It can be seen from the above results that the N,N'-dihydroxynaphthalenediimide cobalt coordination polymer obtained in this example has excellent electrochemical performance as a cathode material for lithium / sodium ion batteries.

[0132] Compared with the prior art, the beneficial effects of the present invention also include:

[0133] 1) The method of the present invention uses a simple one-step hydrothermal method to prepare N,N'-dihydroxynaphthalenediimide conductive conjugated coordination polymers. The synthesis route is very simple, the treatment is convenient, the equipment requirements are low, and it is environmentally friendly.

[0134] 2) The charge-discharge curve and cyclic performance of the N,N'-dihydroxynaphthalenediimide conductive conjugated coordination polymer of the present invention as a cathode material for lithium / sodium ion batteries show that it has extremely excellent electrochemical performance.

[0135] 3) The N,N'-dihydroxynaphthalenediimide conductive conjugated coordination polymer of the present invention does not contain polluting or radioactive heavy metal ions, is environmentally friendly, green, and has a low cost.

[0136] The specific embodiments of the present invention described above do not limit the protection scope of the present invention. Any other corresponding changes and deformations made according to the technical concept of the present invention shall be included in the protection scope of the claims of the present invention.

Claims

1. A method for preparing an imide-based conductive conjugated coordination polymer, characterized in that: The following steps are involved: N,N'-dihydroxynaphthalene diimide is added into a solvent, and then a metal salt is added, mixed and heated to obtain an imide-based conductive conjugated coordination polymer.

2. The method for preparing an imide-based conductive conjugated coordination polymer according to claim 1, characterized in that: The solvent is DMF.

3. The method for preparing an imide-based conductive conjugated coordination polymer according to claim 1, characterized in that: The metal salt is one or more of a soluble nickel salt, a soluble manganese salt, a soluble calcium salt, a soluble copper salt and a soluble cobalt salt.

4. The method for preparing an imide-based conductive conjugated coordination polymer according to claim 3, characterized in that: The soluble nickel salt includes nickel nitrate; and / or, the soluble manganese salt includes manganese chloride; and / or, the soluble calcium salt includes calcium nitrate; and / or, the soluble copper salt includes copper nitrate; and / or, the soluble cobalt salt includes cobalt chloride.

5. The method for preparing an imide-based conductive conjugated coordination polymer according to claim 1, characterized in that: The molar ratio of the N,N'-dihydroxynaphthalene diimide to the metal salt is 1:(1-1.5); and / or the temperature of the heating reaction is 100-120°C and the time is 48-72h.

6. The method for preparing an imide-based conductive conjugated coordination polymer according to claim 1, characterized in that: The N,N'-dihydroxynaphthalene diimide is prepared by the following steps: 1,4,5,8-naphthalenetetracarboxylic anhydride and hydroxylamine hydrochloride are added into a solvent, mixed and heated to obtain the N,N'-dihydroxynaphthalene diimide.

7. The method for preparing an imide-based conductive conjugated coordination polymer according to claim 6, characterized in that: The molar ratio of 1,4,5,8-naphthalenetetracarboxylic anhydride to hydroxylamine hydrochloride is 1:(2-2.5); and / or the temperature of the mixed heating is 65-70° C. and the time is 5-7 hours.

8. An imide-based conductive conjugated coordination polymer, characterized in that: The invention is prepared by the preparation method according to any one of claims 1 to 7.

9. Use of the imide-based conductive conjugated coordination polymer prepared by the preparation method according to any one of claims 1 to 7 or the imide-based conductive conjugated coordination polymer according to claim 8 as a positive electrode material for lithium ion batteries or a positive electrode material for sodium ion batteries.

10. The use according to claim 9, characterized in that: The imide-based conductive conjugated coordination polymer, super P and polyvinylidene fluoride are ground and mixed, and then NMP solution is added dropwise and grinding is continued. The obtained slurry is coated on aluminum foil and vacuum dried to obtain a lithium ion battery positive electrode or a sodium ion battery positive electrode.

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