A secondary aluminum ion battery, a Ni-PANI composite positive electrode material, a preparation method and applications

Abstract

The application relates to a secondary aluminum ion battery, a Ni-PANI composite positive electrode material, a preparation method and application. A nickel salt is introduced when polyaniline is synthesized through an oxidation polymerization reaction of an aniline mixed solution by a chemical oxidation polymerization method, and a Ni-PANI composite positive electrode material is obtained. In the oxidation polymerization reaction process, the chemical catalysis provided by nickel ions enables the prepared composite positive electrode material to have a fast charge transport capacity and an excellent honeycomb conductive structure. Meanwhile, the secondary aluminum ion battery assembled by the prepared Ni-PANI composite material has a discharge specific capacity of 185 mAh / g under the premise of a load of about 3 mg / cm 2 100 mA / g charging and discharging. The raw materials required in the whole preparation process of the composite material are easy to obtain, and the experimental conditions and operation steps are simple.

Description

TECHNICAL FIELD

[0001] The application belongs to the field of secondary battery positive electrode materials, and particularly relates to an aluminum ion battery capable of cyclic charge and discharge, a Ni-PANI composite positive electrode material and a preparation method thereof. BACKGROUND

[0002] An aluminum ion battery is a new type of secondary chemical battery. Since the aluminum resource reserves are abundant, accounting for 8.2% of the crust mass percentage, the aluminum ion battery has the advantages of low cost, high safety, environmental friendliness, high theoretical volume specific capacity of 8046 mAh / cm 3 and high theoretical mass specific capacity of 2980 mAh / g, and has great development potential in the fields of large-scale energy storage and power batteries. However, the development of the aluminum ion battery is restricted by the low discharge capacity and low working voltage platform of the existing aluminum ion battery. Therefore, it is crucial to develop a suitable positive electrode material for the research and development of the aluminum ion battery.

[0003] At present, the reported positive electrode materials of the aluminum ion battery mainly include carbon-based materials, oxides, sulfides and conductive polymers. The carbon-based materials have the advantages of cycle stability and high energy efficiency, but have the disadvantages of low specific capacity and low surface density. For example, a carbon-based positive electrode composite material, a positive electrode, an aluminum ion battery and a preparation method are disclosed in Chinese Invention Patent (CN114792787A). The carbon-based positive electrode composite material has high coulomb efficiency but low discharge specific capacity. The oxide positive electrode material has high discharge specific capacity but poor cycle performance. For example, a manganese oxide positive electrode material is disclosed in Chinese Invention Patent (CN106848295A). The 40-cycle capacity retention rate of the manganese oxide positive electrode material is only about 50%. The sulfide has high specific capacity and high coulomb efficiency, but has poor rate performance and poor cycle performance. For example, a sulfide positive electrode material is disclosed in Chinese Invention Patent (CN109786725A). The sulfide positive electrode material has poor cycle stability. The conductive organic polymer has the advantages of low surface density, low electrical conductivity, high mass specific capacity, stable cycle performance, high energy efficiency and simple preparation, and is one of the most studied positive electrode materials of the aluminum ion battery. For example, an aniline-based organic compound positive electrode material is introduced in Chinese Invention Patent (CN114784250A). The aniline-based organic compound positive electrode material has high discharge specific capacity and good cycle stability, but has a long pre-activation time. It is found that Ma et al. synthesized a composite material by using polyaniline and nickel oxide to improve the electrochemical performance of the original single material (Materials Research Bulletin, 2017, 96:301-305).

[0004] Therefore, a structure-stable Ni-PANI composite material is synthesized by using a chemical oxidation polymerization method with low cost and simple operation to introduce nickel ions into a polyaniline solution, so as to be used as a positive electrode of the aluminum ion battery. SUMMARY

[0005] In order to solve the structural instability and other deficiencies of the existing aluminum ion battery positive electrode material, the application provides a preparation method of a Ni-PANI composite material, which synthesizes polyaniline in a solution containing nickel ions by using a simple chemical oxidation polymerization method, and prepares the Ni-PANI composite material for the positive electrode of the aluminum ion battery. The structure of the composite material is more stable than that of a single polymer, forms a honeycomb conductive network, and thus improves the specific capacity of the aluminum ion battery and the pre-activation time of the conductive polymer positive electrode material.

[0006] In order to achieve the above purpose, the application adopts the following technical scheme:

[0007] A preparation method of a Ni-PANI composite positive electrode material, characterized in that it comprises the following steps:

[0008] (1) Two beakers are placed on two magnetic stirrers respectively and are labeled as A liquid and B liquid, and then an equal amount of dilute hydrochloric acid is added to each beaker;

[0009] (2) A certain amount of oxidizing agent is dissolved in B liquid;

[0010] (3) A certain amount of nickel salt and aniline monomer are dissolved in A liquid;

[0011] (4) A liquid is placed in an ice bath, and B liquid is slowly dropped into A liquid through a separatory funnel;

[0012] (5) After titration is completed, the polymerization reaction is waited for a certain period of time;

[0013] (6) After a certain period of time of polymerization reaction, the polymerization reaction solution is taken out and filtered and washed;

[0014] (7) The obtained solid medicine is placed in a vacuum drying box at a certain temperature;

[0015] (8) After a certain period of time, a dark green solid, i.e. the Ni-PANI composite material, can be obtained.

[0016] Further, in step (1), the speed of the magnetic stirrer is between 300 and 700 r / min, and the concentration of the dilute hydrochloric acid is between 0.5 mol / L and 2 mol / L.

[0017] Further, in step (2), the main components of the oxidizing agent include one of potassium persulfate, ammonium persulfate and ferric chloride, and the molar ratio of the oxidizing agent to the main component of the aniline monomer is between 2:1 and 1:20.

[0018] Further, in step (3), the nickel salt is one of nickel sulfate, nickel bromide, nickel chloride and nickel sulfamate, and the molar ratio of the nickel salt to the aniline monomer is between 1:20 and 6:1.

[0019] Further, the slow dropwise adding speed in step (4) is 0.1-2 mL / min.

[0020] Further, the polymerization reaction time in steps (5) and (6) is 4-24 h.

[0021] Further, the drying temperature in step (7) is 40-100 DEG C, and the drying time is 4-48 h.

[0022] The Ni-PANI composite positive electrode material prepared by the preparation method,

[0023] The application of the Ni-PANI composite positive electrode material, characterized in that the Ni-PANI aluminum ion battery composite positive electrode material is made into an aluminum ion battery positive electrode and used in a secondary aluminum ion battery.

[0024] The secondary aluminum ion battery made of the Ni-PANI composite positive electrode material.

[0025] The beneficial effects of the present application are:

[0026] The present application is based on a chemical oxidation polymerization preparation method, which utilizes the catalytic effect of nickel ions to form a more excellent honeycomb conductive structure in the polymerization process of polyaniline, increase the surface contact active sites, and the Ni-PANI composite material after filtration and washing shows obvious honeycomb structure under the microstructure, thereby improving the charge transmission capacity and ion diffusion capacity; at the same time, due to the introduction of nickel ions, the agglomeration phenomenon of polyaniline is greatly reduced, and the structural stability of the composite material is improved.

[0027] The Ni-PANI composite positive electrode material is mainly used for aluminum ion battery positive electrode material, high-purity aluminum is used as the negative electrode material, and the electrolyte is an organic electrolyte containing aluminum ions, and then an aluminum ion battery capable of cyclic charge and discharge is assembled. The secondary aluminum ion battery assembled by the Ni-PANI composite positive electrode material of the present application has a discharge specific capacity of 185 mAh / g at a load of about 3 mg / cm 2 at 100 mA / g.

[0028] In addition, the raw materials required for the preparation method of the Ni-PANI composite positive electrode material are easy to obtain, the experimental conditions and operation steps are simple, and the method can be widely applied in the fields of energy storage and electronic communication. BRIEF DESCRIPTION OF DRAWINGS

[0029] Figure 1 SEM image of the Ni-PANI composite material prepared in Example 1 of the present application.

[0030] Figure 2Charge-discharge test curve of the aluminum ion battery prepared for the embodiment 1 of the present application.

[0031] Figure 3 Cycle performance graph of the aluminum ion battery prepared for the embodiment 1 of the present application.

[0032] Figure 4 Aluminum ion CV curve graph prepared for the embodiment 1 of the present application.

[0033] Figure 5 Discharge cycle performance graph of the aluminum ion battery prepared for the embodiment 2 of the present application.

[0034] Figure 6 Discharge cycle performance graph of the aluminum ion battery prepared for the embodiment 3 of the present application.

[0035] Figure 7 Discharge cycle performance graph of the aluminum ion battery prepared for the embodiment 4 of the present application.

[0036] Figure 8 Discharge cycle performance graph of the aluminum ion battery prepared for the embodiment 5 of the present application.

[0037] Figure 9 SEM graph of the PANI positive electrode material prepared for the comparative example of the present application.

[0038] Figure 10 Discharge cycle performance graph of the aluminum ion battery prepared for the comparative example of the present application. DETAILED DESCRIPTION

[0039] The present application will be further described below in conjunction with the accompanying drawings and specific embodiments. It should be understood that the specific embodiments described herein are only used to illustrate and explain the present application, and are not used to limit the scope of the present application.

[0040] Embodiment 1:

[0041] The preparation method of the Ni-PANI composite positive electrode material for the aluminum ion battery specifically comprises the following steps:

[0042] (1) Take two beakers and place them on two 500 r / min magnetic stirrers, respectively, and label them A liquid and B liquid. Then add 50 mL of 1 mol / L concentrated hydrochloric acid to each beaker. Then, according to the molar ratio of nickel chloride: potassium persulfate: aniline of 1:20:20, weigh an appropriate amount of medicine for later use. Dissolve the nickel chloride in the A solution, and then dissolve the aniline solution in the A solution. Then, place the solution in an ice bath. Dissolve the potassium persulfate as an oxidizing agent in the B solution, and then add it to the A solution in the ice bath at a rate of 0.5 mL / min through a separatory funnel. Polymerize the solution in the ice bath for 12 hours. Then, filter and wash with deionized water until the solution is neutral. Place the filtered reaction product in a 65°C vacuum drying oven and dry for 25 hours to obtain a dark green Ni-PANI composite material. Figure 1 The SEM image of the Ni-PANI composite material prepared in this example is shown. The Ni-PANI composite material exhibits a clear honeycomb structure under a microscope, which improves the transmission capacity of electric charges and the diffusion capacity of ions. At the same time, the introduction of nickel ions greatly reduces the agglomeration of polyaniline and improves the structural stability of the composite material.

[0043] (2) Mix the Ni-PANI composite material powder, Super-P conductive agent, and polytetrafluoroethylene dispersion liquid (60%) in a mass ratio of 6:3:1 in a maroon mortar. Add an appropriate amount of anhydrous ethanol and grind until the mixture becomes a rubber-like paste. Then, roll the paste onto a molybdenum sheet to form a tab. Place the tab in a 60°C vacuum oven and dry for 12 hours. Then, take out the tab and place it in an argon-filled glove box to complete the addition of an organic electrolyte containing aluminum ions and the sealing work. Thus, an aluminum ion battery anode is obtained.

[0044] (3) Grind the high-purity aluminum sheet with sandpaper, clean the surface with anhydrous ethanol, and dry it as an aluminum ion battery cathode.

[0045] (4) Use whatman934-AH glass fiber as the aluminum ion battery separator. Assemble the positive electrode, separator, and negative electrode into a soft pack battery, and then place the battery in a 60°C oven and dry for 12 hours. Then, take out the battery and place it in an argon-filled glove box to complete the addition of an organic electrolyte containing aluminum ions and the sealing work. Thus, an aluminum ion soft pack battery is obtained.

[0046] (5) After 6 hours of standing, the assembled aluminum ion battery is subjected to cyclic charge and discharge testing, as shown in Figure 2 The electrochemical performance test results show that the first cycle discharge specific capacity is 95.83 mAh / g at a current density of 100 mA / g, and the tenth cycle increases to 155.48 mAh / g. As shown in Figure 3 The electrochemical performance test results show that the discharge specific capacity exceeds 174 mAh / g at a current density of 100 mA / g, and the discharge specific capacity is still 161 mAh / g after 200 cycles, with a coulombic efficiency of about 92%. As shown in Figure 4The CV test results show that there is a pair of obvious redox peaks, which corresponds to the charge and discharge platform in the above formula (1). Figure 2

[0047] Example 2

[0048] In this embodiment, the steps of preparing the Ni-PANI composite material and making the aluminum ion battery are the same as those of Example 1, and the only difference is that in this embodiment, two beakers are placed on two magnetic stirrers marked as A liquid and B liquid, respectively, at 700 r / min, 50 mL of dilute hydrochloric acid with a concentration of 1.2 mol / L is then added, and then an appropriate amount of drug is selected according to the molar ratio of nickel sulfate: ammonium persulfate: aniline of 3:2:1. When preparing the Ni-PANI composite positive electrode material, the nickel sulfate is dissolved in the A solution, the aniline solution is then dissolved in the A solution, and the solution is then placed in an ice bath. The ammonium persulfate is dissolved in the B solution as an oxidizing agent, and then added to the solution in the ice bath at a speed of 1.5 mL / min through a separatory funnel. The polymerization reaction is carried out in the ice bath environment for 4 h. Then, the reaction product is filtered and washed with deionized water until it is neutral. The filtered reaction product is placed in a vacuum drying oven at 55°C and dried for 30 h to obtain a dark green Ni-PANI composite material.

[0049] The positive electrode material prepared in this embodiment is assembled into an aluminum ion battery, and the cyclic charge and discharge test is carried out to obtain the results as shown in Figure 5 At a current density of 100 mA / g, the highest discharge specific capacity is 185.94 mAh / g.

[0050] In addition, this embodiment is completely the same as Example 1, and will not be described here.

[0051] Example 3

[0052] In this embodiment, the steps of preparing the Ni-PANI composite material and making the aluminum ion battery are the same as those of Example 1, and the only difference is that in this embodiment, two beakers are placed on two magnetic stirrers marked as A liquid and B liquid, respectively, at 600 r / min, 50 mL of dilute hydrochloric acid with a concentration of 0.5 mol / L is then added, and then an appropriate amount of drug is selected according to the molar ratio of nickel bromide: ferric chloride: aniline of 5:1:5. When preparing the Ni-PANI composite positive electrode material, the nickel bromide is dissolved in the A solution, the aniline solution is then dissolved in the above solution, and the solution is then placed in an ice bath. The ferric chloride is dissolved in the B solution as an oxidizing agent, and then added to the solution in the ice bath at a speed of 1 mL / min through a separatory funnel. The polymerization reaction is carried out in the ice bath environment for 10 h. Then, the reaction product is filtered and washed with deionized water until it is neutral. The filtered reaction product is placed in a vacuum drying oven at 80°C and dried for 12 h to obtain a dark green Ni-PANI composite material.

[0053] ​The positive electrode material prepared in this example was assembled into an aluminum ion battery, and the cyclic charge-discharge test was carried out, and the results are shown in Figure 6 At a current density of 100 mA / g, the highest discharge specific capacity was 143.58 mAh / g, and it could be stably cycled for more than 300 cycles.

[0054] In addition, the present embodiment is completely the same as embodiment 1, and will not be repeated here.

[0055] Example 4:

[0056] In this example, the preparation of Ni-PANI composite material and the steps of making aluminum ion battery are the same as example 1, the difference is that in this embodiment, two beakers are placed on two 400 r / min magnetic stirrers respectively, labeled as A liquid and B liquid, then 50 mL of 2 mol / L concentrated hydrochloric acid is added, then the appropriate amount of drugs is selected according to the molar ratio of nickel sulfamate: ammonium persulfate: aniline is 1:1:10. When preparing Ni-PANI composite positive electrode material, dissolve nickel sulfamate in A liquid, then dissolve aniline solution in the above solution, and then place it in an ice bath. Dissolve ammonium persulfate as an oxidizing agent in B solution, then add it to the solution in the ice bath environment through a separatory funnel at a speed of 0.1 mL / min, and polymerize in the ice bath environment for 20 h. Then filter and wash with deionized water until neutral, and the reaction product left after filtration is placed in a 40℃ vacuum drying oven for 48 h to obtain a dark green Ni-PANI composite material.

[0057] The positive electrode material prepared in this example was assembled into an aluminum ion battery, and the cyclic charge-discharge test was carried out, and the results are shown in Figure 7 At a current density of 100 mA / g, the highest discharge specific capacity was 143.59 mAh / g, and it could be stably cycled for more than 300 cycles.

[0058] In addition, the present embodiment is completely the same as embodiment 1, and will not be repeated here.

[0059] Example 5:

[0060] The steps of preparing the Ni-PANI composite material and manufacturing the aluminum ion battery in this example are the same as those in Example 1, and the only difference is that in this embodiment, two beakers are placed on two 300 r / min magnetic stirrers respectively, labeled as A liquid and B liquid, 50 mL of 1.5 mol / L dilute hydrochloric acid is then added, and then an appropriate amount of reagent is selected according to the molar ratio of nickel chloride: potassium persulfate: aniline of 120:1:20. When preparing the Ni-PANI composite positive electrode material, the nickel chloride is dissolved in the A liquid, the aniline solution is then dissolved in the above-mentioned solution, and then placed in an ice bath. The potassium persulfate is dissolved in the B solution as an oxidizing agent, and then added dropwise to the solution in the ice bath environment at a speed of 2 mL / min through a separatory funnel, and the polymerization reaction is carried out in the ice bath environment for 24 h. Then, the reaction product is filtered and washed with deionized water until it is neutral, and then placed in a 100°C vacuum drying oven for drying for 4 h, to obtain a dark green Ni-PANI composite material.

[0061] The positive electrode material prepared in this example is assembled into an aluminum ion battery, and the cyclic charge-discharge test is carried out, and the results are as shown in Figure 8 At a current density of 100 mA / g, the highest discharge specific capacity is 123.36 mAh / g, and it can be stably cycled for more than 100 cycles.

[0062] In addition, this embodiment is completely the same as Embodiment 1, and will not be repeated here.

[0063] Comparative Example:

[0064] The steps of preparing the PANI composite material and manufacturing the aluminum ion battery in this example are the same as those in Example 1, and the only difference is that in this embodiment, two beakers are placed on two 500 r / min magnetic stirrers respectively, labeled as A liquid and B liquid, 50 mL of 1 mol / L dilute hydrochloric acid is then added, and then an appropriate amount of reagent is selected according to the molar ratio of potassium persulfate: aniline of 1:20:20, the aniline solution is dissolved in the above-mentioned A solution, and then placed in an ice bath. The potassium persulfate is dissolved in the B solution as an oxidizing agent, and then added dropwise to the A solution in the ice bath environment at a speed of 0.5 mL / min through a separatory funnel, and the polymerization reaction is carried out in the ice bath environment for 12 h. Then, the reaction product is filtered and washed with deionized water until it is neutral, and then placed in a 65°C vacuum drying oven for drying for 25 h, to obtain a dark green PANI positive electrode material as shown in Figure 9 The PANI composite material exhibits obvious flaky and tangled agglomeration under the microstructure, which is not conducive to the transmission of electric charge and the diffusion of ions.

[0065] The positive electrode material prepared in this example is assembled into an aluminum ion battery, and the cyclic charge-discharge test is carried out, and the results are as shown in Figure 10The results are shown in the table. At a current density of 100 mA / g, the discharge specific capacity is all below 80 mAh / g, which is lower than that of the aluminum ion battery prepared by the Ni-PANI composite material.

[0066] In addition, the present embodiment is completely the same as embodiment 1, and will not be described here.

[0067] The above embodiments are preferred embodiments of the present application, but the present application is not limited to the above embodiments, and any obvious improvements, replacements or modifications made by those skilled in the art without departing from the essential content of the present application shall fall within the protection scope of the present application.

Claims

1. Use of Ni-PANI aluminum-ion battery composite cathode material in an aluminum-ion battery, characterized in that, The Ni-PANI aluminum ion battery composite positive electrode material is prepared by the following steps: (1) Take two beakers and place them on two magnetic stirrers, respectively, and label them as A liquid and B liquid, and then add the same amount of dilute hydrochloric acid to each; (2) A certain amount of oxidizing agent is weighed and dissolved in B liquid; (3) A certain amount of nickel salt and aniline monomer is weighed and dissolved in A liquid; (4) A liquid is placed in an ice bath, and B liquid is slowly dropped into A liquid through a separatory funnel; (5) After titration is completed, wait for a certain time for polymerization reaction; (6) After a certain time of polymerization reaction, the polymerization reaction solution is taken out and filtered and washed; (7) The filtered sample is placed in a vacuum drying oven at a certain temperature; (8) After a certain time, a dark green solid, namely Ni-PANI composite material, is obtained; The Ni-PANI aluminum ion battery composite positive electrode material is made into an aluminum ion battery positive electrode and used in a secondary aluminum ion battery.

2. Use of the Ni-PANI aluminum-ion battery composite cathode material according to claim 1 in an aluminum-ion battery, characterized in that, The speed of the magnetic stirrer in step (1) is between 300-700 r / min, and the concentration of dilute hydrochloric acid is 0.5 mol / L-2 mol / L.

3. Use of the Ni-PANI aluminum-ion battery composite cathode material according to claim 1 in an aluminum-ion battery, characterized in that, The oxidizing agent in step (2) contains any one of potassium persulfate, ammonium persulfate, and ferric chloride, and the molar ratio of oxidizing agent to aniline monomer is 2:1-1:

20.

4. Use of the Ni-PANI aluminum-ion battery composite cathode material according to claim 1 in an aluminum-ion battery, characterized in that, The nickel salt in step (3) is any one of nickel sulfate, nickel bromide, nickel chloride, and nickel sulfamate, and the molar ratio of nickel salt to aniline monomer is 1:20-6:

1.

5. Use of the Ni-PANI aluminum-ion battery composite cathode material according to claim 1 in an aluminum-ion battery, characterized in that, The speed of the slow drop in step (4) is 0.1-2 mL / min.

6. Use of the Ni-PANI aluminum-ion battery composite cathode material according to claim 1 in an aluminum-ion battery, characterized in that, The polymerization reaction time in step (5) is 4-24 h.

7. Use of the Ni-PANI aluminum-ion battery composite cathode material according to claim 1 in an aluminum-ion battery, characterized in that, The drying temperature in step (7) is 40-100°C, and the drying time is 4-48 h.

8. A secondary aluminum-ion battery, characterized by, The Ni-PANI aluminum ion battery composite positive electrode material is prepared by the following steps: (1) Take two beakers and place them on two magnetic stirrers, respectively, and label them as A liquid and B liquid, and then add the same amount of dilute hydrochloric acid to each; (2) A certain amount of oxidizing agent is weighed and dissolved in B liquid; (3) A certain amount of nickel salt and aniline monomer is weighed and dissolved in A liquid; (4) A liquid is placed in an ice bath, and B liquid is slowly dropped into A liquid through a separatory funnel; (5) After titration is completed, wait for a certain time for polymerization reaction; (6) After a certain time of polymerization reaction, the polymerization reaction solution is taken out and filtered and washed; (7) The filtered sample is placed in a vacuum drying oven at a certain temperature; (8) After a certain time, a dark green solid, namely Ni-PANI composite material, is obtained.

9. The secondary aluminum-ion battery of claim 8, wherein, The oxidizing agent contains any one of potassium persulfate, ammonium persulfate, and ferric chloride, and the molar ratio of oxidizing agent to aniline monomer is 2:1-1:

20.

10. The secondary aluminum-ion battery of claim 8, wherein, The nickel salt is any one of nickel sulfate, nickel bromide, nickel chloride, and nickel sulfamate, and the molar ratio of nickel salt to aniline monomer is 1:20-6:1.

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