CN112457351B - Bipolar redox active organic ionic compound and preparation method and application thereof - Google Patents

Bipolar redox active organic ionic compound and preparation method and application thereof Download PDF

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CN112457351B
CN112457351B CN201910848463.6A CN201910848463A CN112457351B CN 112457351 B CN112457351 B CN 112457351B CN 201910848463 A CN201910848463 A CN 201910848463A CN 112457351 B CN112457351 B CN 112457351B
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智林杰
牛越
马英杰
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National Center for Nanosccience and Technology China
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    • C07F17/02—Metallocenes of metals of Groups 8, 9 or 10 of the Periodic System
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    • C07D213/00—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members
    • C07D213/02—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members
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Abstract

The invention relates to a bipolar redox active organic ionic compound and a preparation method and application thereof. The bipolar redox active organic ionic compound is composed of viologen cations and ferrocene-modified trifluoromethanesulfonimide anions, and the structure of the compound is shown in formula (I). The compound has reversible bipolar redox activity, namely contains a group capable of undergoing an oxidation reaction and a group capable of undergoing a reduction reaction. The compound is added into various super capacitor electrolytes as an additive, so that additional pseudo capacitance can be contributed, and the electrochemical performance of the super capacitor can be remarkably improved.

Description

Bipolar redox active organic ionic compound and preparation method and application thereof
Technical Field
The invention belongs to the technical field of super capacitors, relates to a bipolar redox active organic ionic compound, a preparation method and an application thereof, and particularly relates to a bipolar redox active organic ionic compound, a preparation method thereof, an electrolyte additive, an electrolyte and a super capacitor.
Background
With the shortage of fossil energy and the aggravation of environmental pollution, the development of clean energy such as solar energy and wind energy is urgent. This requires further performance enhancement of the corresponding energy storage device to accommodate the development of new energy sources. Currently, there are various commercially available energy storage devices, such as a primary battery including a manganese dry battery, a lead storage battery, a secondary battery including lithium ions, a fuel cell, a capacitor, and the like. Among these widely used and studied energy storage devices, super capacitors have been receiving much attention due to their advantages of fast charge and discharge capability, high power density, and long cycle life. However, the lower energy density compared to energy storage devices such as lithium ion batteries limits the application of supercapacitors. In order to improve the energy density of the super capacitor, researchers are continuously starting from the structural design of materials and the development of electrode materials with pseudo-capacitance activity, so that the specific capacitance of the electrode materials is improved, and the energy density of a device is further improved. The electrolyte of the super capacitor is a channel for ion transmission, and if the electrolyte can be endowed with redox activity, an extra pseudo capacitance is provided for a device, the specific capacitance of the super capacitor is greatly improved, and the energy density of the super capacitor is finally improved.
The most important method for preparing electrolytes having redox activity is to add molecules having redox activity to the base electrolyte. The method is very simple and convenient, and the specific capacitance of the super capacitor can be improved on the basis of not changing the electrode material and the structure of the conventional super capacitor. At present, most molecules applied to the electrolyte additive of the super capacitor are single redox active molecules, namely, in the charging process, oxidation/reduction reaction can only occur on one side of a positive electrode/a negative electrode, and an electrode on the other side is idle. Therefore, in order to prepare a super capacitor with high performance, it is very important to develop a novel electrolyte additive with bipolar redox activity, so that both electrodes of the device can perform redox reaction to obtain more pseudocapacitance.
Disclosure of Invention
Aiming at the defects of the prior art, the invention aims to provide a bipolar redox active organic ionic compound, a preparation method and application thereof, and particularly provides the bipolar redox active organic ionic compound, the preparation method thereof, an electrolyte additive, an electrolyte and a supercapacitor.
In order to achieve the purpose, the invention adopts the following technical scheme:
in a first aspect, the present invention provides a bipolar redox active organic ionic compound, which is composed of a viologen cation and a ferrocene-modified trifluoromethanesulfonimide anion, and has a structure represented by formula (I):
Figure BDA0002196102730000021
wherein R is 1 And R 2 Independently selected from substituted or unsubstituted alkyl, substituted or unsubstituted aryl, substituted or unsubstituted alkoxy.
When the above groups have substituents, the substituents are selected from one or a combination of at least two of halogen, cyano, nitro, carbonyl, ester, amino, C2-C6 alkenyl, C1-C6 alkoxy, C1-C6 thioalkoxy, C1-C12 alkanyl, C3-C12 cycloalkyl, C6-C30 aryl or C3-C30 heteroaryl.
The invention constructs a novel bipolar redox active organic ionic compound, which consists of a viologen cation and a ferrocene-modified trifluoromethanesulfonimide anion, and the compound has reversible bipolar redox activity, namely contains a group capable of undergoing an oxidation reaction and a group capable of undergoing a reduction reaction. The compound is used as the main component of the additive and added into various super capacitor electrolytes, so that the compound can contribute to extra pseudo capacitance and remarkably improve the electrochemical performance of the super capacitor.
Preferably, said R is 1 And R 2 Independently selected from any one of the following structural formulas:
Figure BDA0002196102730000031
wherein the curve represents the attachment position of the group.
Wherein n is selected from any integer of 0-12, and n =0, 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11 or 12.
Figure BDA0002196102730000032
When n is 0, it is methyl.
In a second aspect, the present invention provides a method for preparing a bipolar redox active organic ionic compound as described above, the method comprising:
and carrying out ion exchange reaction on the viologen ionic compound and the ferrocene-modified trifluoromethanesulfonimide ionic compound to obtain the bipolar redox active organic ionic compound.
Wherein the viologen compound can be prepared by a method known in the art, for example, the literature (D.Taffa, M.Kathersan, L.Walder, tuning the Hydrophilic, hydrophobic, and Ion Exchange Properties of Mesoporous TiO) 2 Langmuir,2009,25, 5371-5379) disclose methods for preparing viologen ion compounds.
The ferrocene-modified trifluoromethanesulfonimide ionic compound can also be prepared by referring to related preparation methods disclosed in the prior art, for example, a preparation method of ferrocene sequentially reacted with chlorosulfonic acid, phosphorus trichloride and trifluoromethanesulfonamide to obtain the ferrocene-modified trifluoromethanesulfonimide ionic compound is disclosed in the literature (j.zhang, b.yang, y.yang, b.zhang, synthesis, characterization and crystal structure of 1-ferrine sulfonyl-2-long carbon chain alkyl benzene amide, frontiers of chem.china 4 (2009) 52-57).
The preparation method of the bipolar redox active organic ionic compound has the advantages of few steps, simple operation and high reaction yield.
Preferably, the molar ratio of the viologen ionic compound to ferrocene-modified trifluoromethanesulfonimide ionic compound is 1 (2-3), such as 1.
Preferably, the ion exchange reaction is carried out in a solvent.
Preferably, the solvent is deionized water.
Preferably, the ion exchange reaction is performed at 10-40 ℃, such as 10 ℃, 15 ℃,20 ℃,25 ℃, 30 ℃, 35 ℃ or 40 ℃.
Preferably, the time of the ion exchange reaction is 20-40min, such as 20min, 25min, 30min, 35min or 40min, etc.
In a third aspect, the present invention provides an electrolyte additive comprising a bipolar redox-active organic ionic compound as described above.
The bipolar redox active organic ionic compound is added into various super capacitor electrolytes as a main component of an additive, so that additional pseudo capacitance can be contributed, and the electrochemical performance of the super capacitor is remarkably improved. And the dosage is very small when the performance of the super capacitor is improved. The electrolyte additive has wide application range and can effectively improve the specific capacitance and energy density of the conventional super capacitor.
In a fourth aspect, the present invention provides an electrolyte comprising a base electrolyte and an electrolyte additive as described above.
Preferably, the electrolyte additive is present in the electrolyte at a concentration of 0.01 to 3000mmol/L, such as 0.01mmol/L, 0.05mmol/L, 0.1mmol/L, 0.5mmol/L, 1mmol/L, 10mmol/L, 50mmol/L, 100mmol/L, 200mmol/L, 400mmol/L, 800mmol/L, 1000mmol/L, 1500mmol/L, 2000mmol/L, 2500mmol/L or 3000mmol/L, etc.
Preferably, the base electrolyte is an organic system base electrolyte.
Preferably, the organic system base electrolyte comprises 1-butyl-3-methylimidazole bistrifluoromethylsulfonyl imide ionic liquid, 1-butyl-3-methylimidazole tetrafluoroborate ionic liquid or an acetonitrile solution containing LiTFSI.
The supercapacitor electrolyte according to the present invention is prepared according to conventional methods known to those skilled in the art. For example, the additive of the present invention may be dissolved in the base electrolyte.
In a fifth aspect, the present invention provides a supercapacitor comprising an electrolyte as described above.
The supercapacitors to which the invention relates are also assembled according to conventional methods known to those skilled in the art.
Compared with the prior art, the invention has the following beneficial effects:
the invention constructs a novel bipolar redox active organic ionic compound, which consists of a viologen cation and a ferrocene-modified trifluoromethanesulfonimide anion, and the compound has reversible bipolar redox activity, namely contains a group capable of undergoing an oxidation reaction and a group capable of undergoing a reduction reaction. The compound is used as the main component of the additive and added into various super capacitor electrolytes, so that the compound can contribute to extra pseudo capacitance, the electrochemical performance of the super capacitor is remarkably improved, and the specific capacitance of the ionic liquid electrolyte can be improved to more than 10 times by 0.2M of the compound.
The bipolar redox active organic ionic compound is added into various super capacitor electrolytes as a main component of an additive, so as to provide extra pseudo capacitance for the super capacitor and greatly increase the energy density of the device. And when the performance of the super capacitor is improved, a remarkable improvement effect can be obtained under the condition of less dosage, and the energy density of the super capacitor can be improved by 4 times by using millimole dosage. The electrolyte additive has good solubility in the existing electrolyte, is wide in application range, can effectively improve the specific capacitance and energy density of the existing super capacitor, and has very considerable application prospect.
Drawings
FIG. 1 is a nuclear magnetic hydrogen spectrum of the product obtained in example 1;
FIG. 2 is a graph comparing the specific capacitance of the supercapacitors obtained in test 1;
fig. 3 is a graph comparing the rate performance of the supercapacitors obtained from test 2.
Detailed Description
The technical solution of the present invention is further described below by way of specific embodiments. It should be understood by those skilled in the art that the examples are only for the understanding of the present invention and should not be construed as the specific limitations of the present invention.
The instruments used in the following examples were all Bio-Logic VSP electrochemical workstations.
Example 1
This example provides a bipolar redox active organic ionic compound (expressed as PV-FcNtf) having the structure shown in formula (A).
Figure BDA0002196102730000061
The preparation method comprises the following steps:
(1) 1-bromopentane and 4,4' -bipyridine were reacted to produce viologen compounds, according to the methods described in the literature (D.Taffa, M.Katliresan, L.Walder, tuning the Hydrophilic, hydrophobic, and Ion Exchange Properties of Mesoporous TiO 2 Langmuir,2009,25, 5371-5379).
(2) Ferrocene is sequentially reacted with chlorosulfonic acid, phosphorus trichloride and trifluoromethanesulfonamide to obtain a ferrocene-modified trifluoromethanesulfonimide ionic compound, which is specifically prepared by a preparation method in references (j.zhang, b.yang, y.yang, b.zhang, synthesis, characterization and crystal structure of 1-ferricenesulfonyl-2-long carbon chain alkyl benzene sulfonic acid, frontiers of chem.china 4 (2009) 52-57).
(3) And (3) dissolving 1g of the product prepared in the step (1) in 5mL of deionized water, dissolving 2.67g of the product prepared in the step (2) in 15mL of deionized water, mixing the two solutions, stirring at 25 ℃ for 20min, and filtering to obtain the product PV-FcNTf.
Performing nuclear magnetic hydrogen spectrum characterization on the prepared product PV-FcNtf as shown in figure 1: 1 h NMR (400mhz, dmso) δ 9.37 (s, 4H), 8.77 (s, 4H), 4.68 (s, 4H), 4.54 (s, 4H), 4.28 (d, J =9.0hz, 14h), 1.99 (s, 4H), 1.34 (d, J =7.0hz, 8h), 0.89 (t, J =6.3hz, 6h). The synthesis of PV-FcNtf was proved to be successful.
Example 2
This example provides a bipolar redox active organic ionic compound (expressed by BV-FcNtf), the structure of which is shown in formula (B).
Figure BDA0002196102730000081
The preparation method comprises the following steps:
(1) Will be provided withReaction of 1-bromobutane with 4,4' -bipyridine to produce viologen compounds, a method described in the literature (D.Taffa, M.Kathersan, L.Walder, tuning the Hydrophlic, hydrophobic, and Ion Exchange Properties of meso TiO 2 Langmuir,2009,25, 5371-5379).
(2) Ferrocene is reacted with chlorosulfonic acid, phosphorus trichloride, and trifluoromethanesulfonamide in this order to obtain a ferrocene-modified trifluoromethanesulfonimide ionic compound, which is prepared by a method described in the literature (j.zhang, b.yang, y.yang, b.zhang, synthesis, chromatography and crystal structure of 1-ferrocenesulfonyl-2-long carbon chain alkyl benzimidazole, frontiers of chem.china 4 (2009) 52-57.).
(3) And (3) dissolving 1g of the product prepared in the step (1) in 5mL of deionized water, dissolving 2.55g of the product prepared in the step (2) in 15mL of deionized water, mixing the two solutions, stirring at 30 ℃ for 30min, and filtering to obtain the product BV-FcNTf.
Example 3
The embodiment provides four types of supercapacitor electrolytes, and the preparation method comprises the following steps: 0.05mmol, 0.1mmol, 0.2mmol and 0.3mmol of PV-FcNtf obtained in example 1 were weighed and dissolved in 1mL of 1-butyl-3-methylimidazolium bistrifluoromethanesulfonylimide ionic liquid (BmimFSI) as an organic electrolyte for a supercapacitor to obtain an organic electrolyte containing PV-FcNtf at concentrations of 0.05M, 0.1M, 0.2M and 0.3M, respectively.
The embodiment also provides four super capacitors, and the preparation method thereof comprises: the four electrolytes prepared by using commercial ordered mesoporous carbon CMK-3 as an electrode material and a glass fiber membrane as a diaphragm are respectively used as electrolytes to respectively prepare 2032 type button supercapacitors.
Example 4
The embodiment provides a supercapacitor electrolyte, and a preparation method thereof comprises the following steps: 0.05mmol of PV-FcNTf prepared in example 1 was weighed and dissolved in 1mL of acetonitrile solution of organic electrolyte 1M LiTFSI for a supercapacitor to obtain an organic electrolyte containing PV-FcNTf (concentration: 0.05M).
The embodiment also provides a supercapacitor, and a preparation method thereof is as follows: and (3) taking the commercial ordered mesoporous carbon CMK-3 as an electrode material, taking a glass fiber membrane as a diaphragm, and taking the prepared electrolyte as an electrolyte to manufacture the 2032 type button supercapacitor.
Example 5
The embodiment provides a supercapacitor electrolyte, and a preparation method thereof comprises the following steps: 0.05mmol of BV-FcNTf prepared in example 2 was weighed and dissolved in 1mL of acetonitrile solution of organic electrolyte 1M LiTFSI for a supercapacitor to obtain an organic electrolyte containing BV-FcNTf (concentration: 0.05M).
The embodiment also provides a super capacitor, and the preparation method thereof comprises the following steps: the 2032 type button supercapacitor is manufactured by taking a commercial multi-walled carbon nanotube (MWCNT) as an electrode material, a glass fiber film as a diaphragm and the prepared electrolyte as an electrolyte.
Comparative example 1
The comparative example provides a supercapacitor electrolyte, which is an organic electrolyte 1-butyl-3-methylimidazole bistrifluoromethanesulfonylimide ionic liquid (BmimTFSI) for a supercapacitor, and does not contain any additive.
The comparative example also provides a supercapacitor, and the preparation method thereof comprises: and (3) taking the commercial ordered mesoporous carbon CMK-3 as an electrode material, taking a glass fiber membrane as a diaphragm, and taking the electrolyte as an electrolyte to manufacture the 2032 type button type supercapacitor.
Comparative example 2
The comparative example provides a supercapacitor electrolyte, and the preparation method comprises the following steps: 0.2mmol of the monoredox active ionic compound (using PV-NTf) was weighed out 2 The structure is shown as formula (C), and the compound is dissolved in 1mL of organic electrolyte 1-butyl-3-methylimidazole bistrifluoromethanesulfonylimide ionic liquid (BmimFSI) for a super capacitor to obtain the compound containing PV-NTf 2 (concentration: 0.2M) of an organic electrolytic solution.
Figure BDA0002196102730000101
The comparative example also provides a supercapacitor, and the preparation method thereof comprises: and (3) taking the commercial ordered mesoporous carbon CMK-3 as an electrode material, taking a glass fiber membrane as a diaphragm, and taking the electrolyte as an electrolyte to manufacture the 2032 type button type supercapacitor.
Comparative example 3
The comparative example provides a supercapacitor electrolyte, and the preparation method comprises the following steps: 0.2mmol of single redox active ionic compound (represented by Bmim-FcNTf, the structure of which is shown as formula (D)) is weighed and dissolved in 1mL of organic electrolyte 1-butyl-3-methylimidazolium bistrifluoromethylsulfonyl imide ionic liquid (Bmim TFSI) for a super capacitor to obtain the organic electrolyte containing Bmim-FcNTf (the concentration is 0.2M).
Figure BDA0002196102730000111
The comparative example also provides a supercapacitor, and the preparation method thereof comprises: and (3) taking the commercial ordered mesoporous carbon CMK-3 as an electrode material, taking a glass fiber membrane as a diaphragm, and taking the electrolyte as an electrolyte to manufacture the 2032 type button type supercapacitor.
Test 1: the specific capacitance of the four supercapacitors produced in comparative example 3 were tested and the results are shown in figure 2. As can be seen from fig. 2: compared with a super capacitor (0M) without PV-FcNTf in the electrolyte, the specific capacitance of the super capacitor is greatly increased after the PV-FcNTf is added, wherein the specific capacitance of the super capacitor containing 0.2M PV-FcNTf is up to 1120F/g.
And (3) testing 2: four types of supercapacitors prepared in comparative example 1, comparative example 2, comparative example 3 and example 3 (the electrolyte is an organic electrolyte containing 0.2M of a compound of formula (A)) were tested for rate capability, and the results are shown in FIG. 3 (shown by BmimFSI, PV-NTf 2 Bmim-FcNtf and PV-FcNtf). As can be seen from fig. 3: the electrochemical performance of the bipolar redox-active molecule-based capacitor (PV-FcNtf) greatly exceeds that of the mono-redox-active molecule-based capacitor (Bmim-FcNtf and PV-NTf) at the same concentration of additive molecules 2 ). Bipolar redox active molecule based capacitors (PV-F) at a current density of 0.5A/gcNTf) has a specific capacitance of 273F/g, and capacitors based on bipolar redox-active molecules (Bmim-Fcntf and PV-NTf) 2 ) The specific capacitances of (A) are only 114F/g and 124F/g.
The applicant states that the present invention is illustrated by the above examples to a bipolar redox active organic ionic compound of the present invention and its preparation method and application, but the present invention is not limited to the above examples, i.e. it does not mean that the present invention must be implemented by relying on the above examples. It should be understood by those skilled in the art that any modification of the present invention, equivalent substitutions of the raw materials of the product of the present invention, addition of auxiliary components, selection of specific modes, etc., are within the scope and disclosure of the present invention.
The preferred embodiments of the present invention have been described in detail, however, the present invention is not limited to the specific details of the above embodiments, and various simple modifications may be made to the technical solution of the present invention within the technical idea of the present invention, and these simple modifications are within the protective scope of the present invention.
It should be noted that the various technical features described in the above embodiments can be combined in any suitable manner without contradiction, and the invention is not described in any way for the possible combinations in order to avoid unnecessary repetition.

Claims (10)

1. The electrolyte is characterized by comprising a base electrolyte and an electrolyte additive, wherein the electrolyte additive is a bipolar redox active organic ionic compound which is composed of viologen cations and ferrocene-modified trifluoromethanesulfonimide anions, and the structure of the bipolar redox active organic ionic compound is shown in formula (I):
Figure FDA0003897276450000011
wherein R is 1 And R 2 Independently selected from the following structural formulae:
Figure FDA0003897276450000012
wherein n is selected from any integer of 0-12; wherein the curve represents the attachment position of the group;
the basic electrolyte is selected from 1-butyl-3-methylimidazole bistrifluoromethanesulfonimide salt ionic liquid, 1-butyl-3-methylimidazole tetrafluoroborate ionic liquid or acetonitrile solution containing LiTFSI.
2. The electrolyte of claim 1, wherein the bipolar redox active organic ionic compound is prepared by a method comprising:
and (3) carrying out ion exchange reaction on the viologen ionic compound and the ferrocene-modified trifluoromethanesulfonimide ionic compound to obtain the bipolar redox active organic ionic compound.
3. The electrolyte of claim 2, wherein the molar ratio of the viologen ionic compound to the ferrocene-modified trifluoromethanesulfonimide ionic compound is 1 (2-3).
4. The electrolyte of claim 2, wherein the molar ratio of the viologen ionic compound to the ferrocene-modified trifluoromethanesulfonimide ionic compound is 1.
5. The electrolyte of claim 2, wherein the ion exchange reaction is carried out in a solvent.
6. The electrolyte of claim 5, wherein the solvent is deionized water.
7. The electrolyte of claim 2, wherein the ion exchange reaction is carried out at 10-40 ℃.
8. The electrolyte of claim 2, wherein the ion exchange reaction time is 20-40min.
9. The electrolyte of claim 1, wherein the electrolyte additive is present in the electrolyte at a concentration of 0.01 to 3000mmol/L.
10. A supercapacitor, characterized in that it comprises an electrolyte according to any one of claims 1 to 9.
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