CN111599609B - Supercapacitor electrolyte additive, supercapacitor electrolyte and application of supercapacitor electrolyte additive - Google Patents
Supercapacitor electrolyte additive, supercapacitor electrolyte and application of supercapacitor electrolyte additive Download PDFInfo
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- 239000003792 electrolyte Substances 0.000 title claims abstract description 86
- 239000002000 Electrolyte additive Substances 0.000 title claims abstract description 61
- ROFVEXUMMXZLPA-UHFFFAOYSA-N Bipyridyl Chemical class N1=CC=CC=C1C1=CC=CC=N1 ROFVEXUMMXZLPA-UHFFFAOYSA-N 0.000 claims abstract description 25
- 125000003118 aryl group Chemical group 0.000 claims abstract description 6
- 125000003545 alkoxy group Chemical group 0.000 claims abstract description 5
- 125000000217 alkyl group Chemical group 0.000 claims abstract description 5
- 150000001450 anions Chemical class 0.000 claims abstract description 5
- 125000001072 heteroaryl group Chemical group 0.000 claims abstract description 5
- 125000000623 heterocyclic group Chemical group 0.000 claims abstract description 5
- 238000004519 manufacturing process Methods 0.000 claims description 12
- KRHYYFGTRYWZRS-UHFFFAOYSA-M Fluoride anion Chemical compound [F-] KRHYYFGTRYWZRS-UHFFFAOYSA-M 0.000 claims description 3
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 abstract 1
- 229910052731 fluorine Inorganic materials 0.000 abstract 1
- 239000011737 fluorine Substances 0.000 abstract 1
- 239000003990 capacitor Substances 0.000 description 48
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 22
- 150000001875 compounds Chemical class 0.000 description 20
- 238000002360 preparation method Methods 0.000 description 17
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 description 12
- 239000007772 electrode material Substances 0.000 description 11
- 239000003365 glass fiber Substances 0.000 description 11
- 239000012528 membrane Substances 0.000 description 11
- 239000005486 organic electrolyte Substances 0.000 description 10
- 239000000243 solution Substances 0.000 description 10
- 230000000052 comparative effect Effects 0.000 description 9
- 239000000654 additive Substances 0.000 description 7
- 229910003473 lithium bis(trifluoromethanesulfonyl)imide Inorganic materials 0.000 description 7
- QSZMZKBZAYQGRS-UHFFFAOYSA-N lithium;bis(trifluoromethylsulfonyl)azanide Chemical compound [Li+].FC(F)(F)S(=O)(=O)[N-]S(=O)(=O)C(F)(F)F QSZMZKBZAYQGRS-UHFFFAOYSA-N 0.000 description 7
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 6
- 238000012360 testing method Methods 0.000 description 6
- NJMWOUFKYKNWDW-UHFFFAOYSA-N 1-ethyl-3-methylimidazolium Chemical compound CCN1C=C[N+](C)=C1 NJMWOUFKYKNWDW-UHFFFAOYSA-N 0.000 description 5
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 5
- 230000000996 additive effect Effects 0.000 description 5
- 239000002608 ionic liquid Substances 0.000 description 5
- 229910001416 lithium ion Inorganic materials 0.000 description 5
- 238000000034 method Methods 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 3
- 230000015572 biosynthetic process Effects 0.000 description 3
- 239000002131 composite material Substances 0.000 description 3
- 239000008151 electrolyte solution Substances 0.000 description 3
- 238000004146 energy storage Methods 0.000 description 3
- 238000012986 modification Methods 0.000 description 3
- 230000004048 modification Effects 0.000 description 3
- 238000003786 synthesis reaction Methods 0.000 description 3
- 238000012512 characterization method Methods 0.000 description 2
- 229920000642 polymer Polymers 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 230000002468 redox effect Effects 0.000 description 2
- 238000006722 reduction reaction Methods 0.000 description 2
- 150000003839 salts Chemical class 0.000 description 2
- 125000005415 substituted alkoxy group Chemical group 0.000 description 2
- 125000000547 substituted alkyl group Chemical group 0.000 description 2
- 125000003107 substituted aryl group Chemical group 0.000 description 2
- RNFJDJUURJAICM-UHFFFAOYSA-N 2,2,4,4,6,6-hexaphenoxy-1,3,5-triaza-2$l^{5},4$l^{5},6$l^{5}-triphosphacyclohexa-1,3,5-triene Chemical compound N=1P(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP=1(OC=1C=CC=CC=1)OC1=CC=CC=C1 RNFJDJUURJAICM-UHFFFAOYSA-N 0.000 description 1
- 241000589516 Pseudomonas Species 0.000 description 1
- 230000002238 attenuated effect Effects 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 150000001768 cations Chemical class 0.000 description 1
- 230000001351 cycling effect Effects 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000007599 discharging Methods 0.000 description 1
- 238000010494 dissociation reaction Methods 0.000 description 1
- 230000005593 dissociations Effects 0.000 description 1
- 238000012983 electrochemical energy storage Methods 0.000 description 1
- 239000003063 flame retardant Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 125000004435 hydrogen atom Chemical class [H]* 0.000 description 1
- 230000002209 hydrophobic effect Effects 0.000 description 1
- 238000005342 ion exchange Methods 0.000 description 1
- 125000005647 linker group Chemical group 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 230000001681 protective effect Effects 0.000 description 1
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N titanium dioxide Inorganic materials O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 1
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 1
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
- H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
- H01G11/54—Electrolytes
- H01G11/58—Liquid electrolytes
- H01G11/64—Liquid electrolytes characterised by additives
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/13—Energy storage using capacitors
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- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- Engineering & Computer Science (AREA)
- Power Engineering (AREA)
- Microelectronics & Electronic Packaging (AREA)
- Electric Double-Layer Capacitors Or The Like (AREA)
Abstract
本发明涉及一种超级电容器电解液添加剂、电解液及其应用，所述超级电容器电解液添加剂包括双吡啶盐共轭有机分子；所述双吡啶盐共轭有机分子的结构如式(I)所示，其中，R1和R1'独立地选自取代或未取代的烷基、取代或未取代的芳基、取代或未取代的烷氧基；R2选自取代或未取代的杂芳基、取代或未取代的五元杂环基团；X1和X2独立地选自含氟阴离子。该电解液添加剂及电解液能极大地提升超级电容器的电化学性能，有效地降低电解液内阻，增强电流密度，提升超级电容器的比电容、能量密度、倍率性能和循环稳定性。
The invention relates to a supercapacitor electrolyte additive, electrolyte and application thereof. The supercapacitor electrolyte additive comprises a bipyridine salt conjugated organic molecule; the structure of the bipyridine salt conjugated organic molecule is as shown in formula (I). shown, wherein, R 1 and R 1 ' are independently selected from substituted or unsubstituted alkyl, substituted or unsubstituted aryl, substituted or unsubstituted alkoxy; R 2 is selected from substituted or unsubstituted heteroaryl group, a substituted or unsubstituted five-membered heterocyclic group; X 1 and X 2 are independently selected from fluorine-containing anions. The electrolyte additive and electrolyte can greatly improve the electrochemical performance of the supercapacitor, effectively reduce the internal resistance of the electrolyte, enhance the current density, and improve the specific capacitance, energy density, rate performance and cycle stability of the supercapacitor.
Description
Technical Field
The invention belongs to the technical field of super capacitors, and particularly relates to a super capacitor electrolyte additive, electrolyte and application thereof.
Background
With the rapid development of portable electronic equipment, wearable equipment and electric vehicles, people have higher and higher requirements on energy storage devices of various electronic equipment, and among a plurality of energy storage devices, a supercapacitor is a high-efficiency electrochemical energy storage device and has the advantages of high charge-discharge rate, high power density, long cycle life, quick charging, stable performance and the like. Therefore, the super capacitor is receiving an increasingly wide attention and is widely used, but compared with energy storage devices such as lithium ion batteries, the super capacitor has a lower energy density, and this disadvantage greatly limits the application of the super capacitor. Therefore, how to further increase the energy density of the super capacitor is the key of the current research under the advantages of ensuring the long cycle life and high power density of the super capacitor.
The addition of the electrolyte additive can reduce the internal resistance of the electrolyte and effectively improve the specific capacitance of the super capacitor, and the electrolyte additive is convenient to use without changing the structure and process conditions of the conventional super capacitor. In addition, the dosage of the electrolyte additive is small, and the electrochemical performance of the super capacitor can be greatly improved only by adding a small amount of the electrolyte additive.
CN105006377A discloses a composite electrolyte using azo substances as additives and a preparation method thereof, wherein the composite electrolyte is composed of a blank electrolyte and an electrolyte additive, the blank electrolyte is KOH solution, and the electrolyte additive is azo substances. The concentration of KOH in the composite electrolyte is 1-6mol/L, and the concentration of azo substances is 1-10 mmol/L. The method is easy to operate, the raw materials are cheap and easy to obtain, and the azo substances are used as the electrolyte additive, so that the ionic conductivity of the electrolyte can be improved, the internal resistance of the electrolyte can be reduced, and the electrochemical performance of the super capacitor can be obviously improved.
CN107275120A discloses an electrolyte additive and a lithium ion hybrid super capacitor containing the same, wherein a small amount of additive is added into the electrolyte of the lithium ion hybrid super capacitor, so that the charge and discharge performance of the lithium ion hybrid super capacitor is greatly improved, and the lithium ion hybrid super capacitor containing the electrolyte additive has flame retardant capability and improves the use safety.
In the prior art, the strategy for effectively improving the energy density of the super capacitor is limited, so that it is significant to develop an electrolyte additive for further improving the energy density of the super capacitor on the premise of ensuring the long cycle life and high power density of the super capacitor.
Disclosure of Invention
Aiming at the defects of the prior art, the invention aims to provide a super capacitor electrolyte additive, an electrolyte and application thereof.
In order to achieve the purpose, the invention adopts the following technical scheme:
in one aspect, the present invention provides a supercapacitor electrolyte additive comprising a bipyridylium conjugated organic molecule; the structure of the bipyridyl salt conjugated organic molecule is shown as the formula (I):
wherein R is1And R1' is independently selected from substituted or unsubstituted alkyl, substituted or unsubstituted aryl, substituted or unsubstituted alkoxy, in particular: r1May be selected from substituted alkyl, unsubstituted alkyl, substituted aryl, unsubstituted aryl, substituted alkoxy, or unsubstituted alkoxy; r1' may be selected from substituted alkyl, unsubstitutedSubstituted alkyl, substituted aryl, unsubstituted aryl, substituted alkoxy, or unsubstituted alkoxy.
R2Selected from single bonds, substituted or unsubstituted heteroaryl groups, and substituted or unsubstituted five-membered heterocyclic groups, and specifically: r2May be selected from a single bond, a substituted heteroaryl group, an unsubstituted heteroaryl group, a substituted five-membered heterocyclic group or an unsubstituted five-membered heterocyclic group.
X1And X2Independently selected from fluoride-containing anions.
X1And X2The fluoride-containing anion is selected because it makes the electrolyte additive of formula (I) more soluble in organic solvents, less dissociative, and forms a salt that readily dissociates in the solvent.
The electrolyte additive comprises bipyridyl salt conjugated organic molecules which have redox properties and can be reduced during charging and oxidized during discharging. The oxidation/reduction reaction of the molecules in the charge and discharge process provides pseudo capacitance for the capacitor, and further enhances the specific capacitance of the capacitor. The molecule has the advantages of good solubility in an organic system, simpler synthesis, higher performance and the like. Therefore, the super capacitor prepared by the method has long cycle life, cycle stability, high power density and high energy density.
Preferably, said R is1Selected from any one of the following structural formulas:
wherein the curve represents the attachment position of the group.
Wherein n is selected from any integer from 0 to 10, such as 0,1, 2, 3, 4, 5, 6, 7, 8, 9 or 10.
The groups have different electronic structures and electronegativities, and can influence the electronic structure of the pyridine-containing conjugated group, further influence the redox property of molecules, and finally influence the performance of the molecules in a capacitor.
Preferably, said R is1' is selected from any one of the following structural formulae:
wherein the curve represents the attachment position of the group.
Wherein n is selected from any integer from 0 to 10, such as 0,1, 2, 3, 4, 5, 6, 7, 8, 9 or 10.
The value of n should not exceed 10, and if it exceeds 10, the solubility of the electrolyte additive is greatly reduced.
Preferably, said R is2Selected from any one of the following structural formulas:
wherein the curve represents the attachment position of the group.
Wherein m is selected from any integer from 1 to 4, such as 1, 2, 3 or 4.
The structure can stabilize the pyridine ring in a reduction state, so that the circulation stability of additive molecules is improved, the dissociation of anions and cations is facilitated, the resistance of the electrolyte is improved, and the performance of the electrolyte is improved.
The value of m cannot exceed 4, and if the value of m exceeds 4, the solubility of the electrolyte additive is greatly reduced due to the overlarge conjugated ring.
Preferably, said X1Selected from any one of the following structural formulas:
preferably, said X2Selected from any one of the following structural formulas:
reference is made to the bipyridylium salt conjugated organic molecules (K.Takahashi, T.Nihira, K.Akiyama, Y.Ikegami, E.Fukuyo, Synthesis and Characterization of New Conjugation-Extended virology, Involution a Central Aromatic Linking Group, J.chem.Commun, 1992,620-622, Terry L.Prime, J.and Harder W.Gibson, Supermolecular Pseudomonas Polymers from Biscoryutan Bisaraaquats, J.Am.Soc.2018, 140,12,4455-4465, D.Taffa, M.Kathesean, L.Walder, Tug, Hydrogen, and humidity of moisture TiO, of moisture2Langmuir,2009,25, 5371-5379).
In another aspect, the present invention provides a supercapacitor electrolyte comprising a base electrolyte and a supercapacitor electrolyte additive as described above.
Preferably, the concentration of the supercapacitor electrolyte additive in the supercapacitor electrolyte is 0.01-2000mmol/L, such as 0.01mmol/L, 0.1mmol/L, 1mmol/L, 5mmol/L, 10mmol/L, 50mmol/L, 100mmol/L, 200mmol/L, 500mmol/L, 800mmol/L, 1000mmol/L, 1500mmol/L or 2000mmol/L, and the like.
Preferably, the concentration of the supercapacitor electrolyte additive in the supercapacitor electrolyte is 5-1000mmol/L, such as 5mmol/L, 10mmol/L, 20mmol/L, 50mmol/L, 100mmol/L, 200mmol/L, 500mmol/L or 1000mmol/L, etc.
Preferably, the base electrolyte is an organic system electrolyte, i.e. the supercapacitor electrolyte additive is applicable to all organic system electrolytes.
The basic electrolyte not only comprises the above electrolyte, but also is applicable to all organic system electrolytes, and the electrolyte additive is applicable to all organic system electrolytes and has a wide application range.
In a further aspect, the invention provides the use of a supercapacitor electrolyte as described above in the preparation of a supercapacitor.
Compared with the prior art, the invention has the following beneficial effects:
the electrolyte additive provided by the invention can greatly improve the electrochemical performance of the super capacitor, effectively reduce the internal resistance of the electrolyte, enhance the current density, and improve the specific capacitance, energy density, rate capability and cycle stability of the super capacitor.
The electrolyte additive needs a small amount of use when improving the performance of the super capacitor, is suitable for all organic system electrolytes, and has a wide application range.
Drawings
FIG. 1 is a graph showing the results of comparing the specific capacitances of the capacitors obtained in examples 1 and 2 with those of comparative example 1 at different current densities;
FIG. 2 is a graph showing the results of comparing the cycle characteristics of the capacitors obtained in example 1 with those of comparative example 1.
Detailed Description
The technical solution of the present invention is further explained by the following 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.
Example 1
The embodiment provides a supercapacitor electrolyte additive, which comprises a bipyridyl salt conjugated organic molecule; the bipyridylium conjugated organic molecule has a structure shown in formula (A), and is prepared according to the preparation method in the literature (K.TAKAHASHI, T.NIHIRA, K.AKIYAMA, Y.IKEGAMI, E.FUKUYO, Synthesis and Characterization of New coupling-Extended virology Involution, J.chem.Commun.,1992, 620-plus 622.).
Preparing an electrolyte containing the electrolyte additive: 0.02mmol of the compound of formula (A) was weighed and dissolved in 100mL of a base electrolyte solution for a supercapacitor (acetonitrile solution containing 1M LiTFSI), to obtain an organic electrolyte solution containing 0.2M of the compound of formula (A).
Assembling the super capacitor: and (3) taking the 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 type supercapacitor.
Example 2
The embodiment provides a supercapacitor electrolyte additive, which comprises a bipyridyl salt conjugated organic molecule; the structure of the bipyridyl salt conjugated organic molecule is shown as a formula (B), and the bipyridyl salt conjugated organic molecule is prepared by a preparation method in a reference literature (Terry L.price, Jr.and Harry W.Gibson, Supramolecular pseudotaxane Polymers from Biscrypands and Bisparaquats, J.Am.chem.Soc.2018,140(12), 4455-4465):
preparing an electrolyte containing the electrolyte additive: 0.02mmol of the compound of formula (B) was weighed and dissolved in 100mL of a base electrolyte solution for a supercapacitor (acetonitrile solution containing 1M LiTFSI), to obtain an organic electrolyte solution containing 0.2M of the compound of formula (B).
Assembling the super capacitor: and (3) taking the 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 type supercapacitor.
Example 3
The embodiment provides a supercapacitor electrolyte additive, which comprises a bipyridyl salt conjugated organic molecule; the structure of the bipyridyl salt conjugated organic molecule is shown as the formula (A):
preparing an electrolyte containing the electrolyte additive: 0.02mmol of the compound of the formula (A) is weighed and dissolved in 100mL of a basic electrolyte (ionic liquid: 1-ethyl-3-methylimidazolium bistrifluoromethanesulfonylimide) for a super capacitor, so as to obtain an organic electrolyte containing 0.2M of the compound of the formula (A).
Assembling the super capacitor: and (3) taking the 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 type supercapacitor.
Example 4
The embodiment provides a supercapacitor electrolyte additive, which comprises a bipyridyl salt conjugated organic molecule; the structure of the bipyridine salt conjugated organic molecule is shown as a formula (C), and the preparation method is prepared by referring to the preparation method disclosed in the document in example 1.
Preparing an electrolyte containing the electrolyte additive: 0.02mmol of the compound of the formula (C) is weighed and dissolved in 100mL of a basic electrolyte (ionic liquid: 1-ethyl-3-methylimidazolium bistrifluoromethanesulfonylimide) for a super capacitor, so as to obtain an organic electrolyte containing 0.2M of the compound of the formula (C).
Assembling the super capacitor: and (3) taking the 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 type supercapacitor.
Example 5
The embodiment provides a supercapacitor electrolyte additive, which comprises a bipyridyl salt conjugated organic molecule; the structure of the bipyridine salt conjugated organic molecule is shown as a formula (D), and the preparation method thereof is referred to a literature (D.Taffa, M.Kathiresan, L.Walder, Tuning the Hy)drophilic,Hydrophobic,and Ion Exchange Properties of Mesoporous TiO2Langmuir,2009,25, 5371-5379).
Preparing an electrolyte containing the electrolyte additive: 0.02mmol of the compound of the formula (D) was weighed and dissolved in 100mL of a base electrolyte for a supercapacitor (ionic liquid: 1-ethyl-3-methylimidazolium bistrifluoromethanesulfonylimide) to obtain an organic electrolyte containing 0.2M of the compound of the formula (D).
Assembling the super capacitor: and (3) taking the 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 type supercapacitor.
Example 6
The embodiment provides a supercapacitor electrolyte additive, which comprises a bipyridyl salt conjugated organic molecule; the structure of the bipyridine salt conjugated organic molecule is shown as a formula (E), and the preparation method is prepared by referring to the preparation method in the literature in example 5.
Preparing an electrolyte containing the electrolyte additive: 0.02mmol of the compound of formula (E) was weighed and dissolved in 100mL of a base electrolyte for a supercapacitor (ionic liquid: 1-ethyl-3-methylimidazolium bistrifluoromethanesulfonylimide) to obtain an organic electrolyte containing 0.2M of the compound of formula (E).
Assembling the super capacitor: and (3) taking the 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 type supercapacitor.
Example 7
The embodiment provides a supercapacitor electrolyte additive, which comprises a bipyridyl salt conjugated organic molecule; the structure of the bipyridyl salt conjugated organic molecule is shown as a formula (F), and the preparation method is prepared by referring to the preparation method in the literature in example 1.
Preparing an electrolyte containing the electrolyte additive: 0.02mmol of the compound of formula (F) was weighed and dissolved in 100mL of a base electrolyte for a supercapacitor (ionic liquid: 1-ethyl-3-methylimidazolium bistrifluoromethanesulfonylimide) to obtain an organic electrolyte containing 0.2M of the compound of formula (F).
Assembling the super capacitor: and (3) taking the 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 type supercapacitor.
Example 8
The embodiment provides a supercapacitor electrolyte additive, which comprises a bipyridyl salt conjugated organic molecule; the structure of the bipyridyl salt conjugated organic molecule is shown as a formula (G), and the preparation method is prepared by referring to the preparation method in the literature in example 1.
Preparing an electrolyte containing the electrolyte additive: 0.02mmol of the compound of formula (G) was weighed and dissolved in 100mL of a base electrolyte solution for a supercapacitor (a dimethyl sulfoxide solution containing 1M LiTFSI), to obtain an organic electrolyte solution containing 0.2M of the compound of formula (G).
Assembling the super capacitor: and (3) taking the 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 type supercapacitor.
Example 9
The embodiment provides a supercapacitor electrolyte additive, which comprises a bipyridyl salt conjugated organic molecule; the structure of the bipyridine salt conjugated organic molecule is shown as a formula (H), and the preparation method is prepared by referring to the preparation method in the literature in example 1.
Preparing an electrolyte containing the electrolyte additive: 0.02mmol of the compound of formula (H) was weighed and dissolved in 100mL of a base electrolyte for a supercapacitor (a dimethyl sulfoxide solution containing 1M LiTFSI), to obtain an organic electrolyte containing 0.2M of the compound of formula (H).
Assembling the super capacitor: and (3) taking the 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 type supercapacitor.
Example 10
The embodiment provides a supercapacitor electrolyte additive, which comprises a bipyridyl salt conjugated organic molecule; the structure of the bipyridyl salt conjugated organic molecule is shown as a formula (I), and the preparation method is prepared by referring to the preparation method in the literature in example 1.
Preparing an electrolyte containing the electrolyte additive: 0.02mmol of the compound of formula (I) was weighed and dissolved in 100mL of a base electrolyte for a supercapacitor (1M solution of LiTFSI in dimethylsulfoxide) to obtain an organic electrolyte containing 0.2M of the compound of formula (I).
Assembling the super capacitor: and (3) taking the 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 type supercapacitor.
Comparative example 1
This comparative example provides an electrolyte: this electrolyte contained only the base electrolyte (acetonitrile solution containing 1M LiTFSI) and no additive, compared to example 1.
Assembling the super capacitor: and (3) taking the 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 type supercapacitor.
Electrochemical properties (specific capacitance, rate capability and cycle stability) of the supercapacitors prepared in examples 1-2 and comparative example 1 were tested as follows:
test 1: the specific capacitance of each supercapacitor was tested at different current densities, and the test results are shown in fig. 1: the results of this test are comparative results of specific capacitance at different current densities for the capacitors made in examples 1 and 2 and comparative example 1. As can be seen from FIG. 1, the addition of the additives A and B to the blank electrolyte (acetonitrile solution containing 1M LiTFSI) can greatly improve the specific capacitance of the capacitor under different current densities, and can be up to more than twice as high as that of the blank electrolyte. At the same time, at very high current densities (20A g)-1) The specific capacitance attenuation of the electrolyte containing the additive is extremely small, and the prepared electrolyte containing the additive not only can greatly improve the specific capacitance of the super capacitor, but also has excellent rate performance, so that the power density of the capacitor is improved.
And (3) testing 2: the cycling stability of each supercapacitor was tested, and the test results are shown in fig. 2: the results of this test are the results of comparing the cycle performance of the capacitors made in example 1 with those made in comparative example 1. As can be seen from fig. 2, the capacitor of example 1 has more excellent cycle performance. At 2 A.g-1After 10000 cycles, the specific capacitance is not attenuated and is still more than doubled compared with the specific capacitance of the capacitor of the comparative example 1.
The applicant states that the present invention is illustrated by the above examples of the supercapacitor electrolyte additive, the electrolyte and the application thereof, but the present invention is not limited to the above examples, i.e. it does not mean that the present invention must rely on the above examples to be implemented. 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. A supercapacitor electrolyte additive, comprising a bipyridylium conjugated organic molecule; the structure of the bipyridyl salt conjugated organic molecule is shown as the formula (I):
wherein R is1And R1' is independently selected from substituted or unsubstituted alkyl, substituted or unsubstituted aryl, substituted or unsubstituted alkoxy;
R2selected from the group consisting of a single bond, a substituted or unsubstituted heteroaryl, and a substituted or unsubstituted five-membered heterocyclic group;
X1and X2Independently selected from fluoride-containing anions.
2. The supercapacitor electrolyte additive of claim 1, wherein R is1Selected from any one of the following structural formulas:
wherein n is selected from any integer of 0-10.
3. The supercapacitor electrolyte additive according to claim 1 or 2, wherein R is1' is selected from any one of the following structural formulae:
wherein n is selected from any integer of 0-10.
4. The supercapacitor electrolyte additive of claim 1, wherein R is2Selected from any one of the following structural formulas:
wherein m is selected from any integer of 1-4.
5. The supercapacitor electrolyte additive of claim 1, wherein X is1Selected from any one of the following structural formulas:
6. the supercapacitor electrolyte additive of claim 1, wherein X is2Selected from any one of the following structural formulas:
7. a supercapacitor electrolyte, comprising a base electrolyte and the supercapacitor electrolyte additive of any one of claims 1 to 6.
8. The supercapacitor electrolyte of claim 7, wherein the supercapacitor electrolyte additive is present in the supercapacitor electrolyte at a concentration of 0.01 to 2000 mmol/L.
9. The supercapacitor electrolyte of claim 7, wherein the supercapacitor electrolyte additive is present in the supercapacitor electrolyte at a concentration of 5 to 1000 mmol/L.
10. Use of the supercapacitor electrolyte according to any one of claims 7 to 9 in the manufacture of a supercapacitor.
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