CN110379645B - Mixed salt electrolyte for high-voltage super capacitor and application thereof - Google Patents
Mixed salt electrolyte for high-voltage super capacitor and application thereof Download PDFInfo
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- 239000003792 electrolyte Substances 0.000 title claims abstract description 54
- 150000003839 salts Chemical class 0.000 title claims abstract description 32
- 239000003990 capacitor Substances 0.000 title abstract description 64
- -1 triethyl methyl ammonium hexafluorophosphate Chemical group 0.000 claims abstract description 51
- 150000003242 quaternary ammonium salts Chemical class 0.000 claims abstract description 26
- 239000003960 organic solvent Substances 0.000 claims abstract description 24
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 23
- 229910002804 graphite Inorganic materials 0.000 claims abstract description 18
- 239000010439 graphite Substances 0.000 claims abstract description 18
- 159000000000 sodium salts Chemical class 0.000 claims abstract description 17
- 229910021384 soft carbon Inorganic materials 0.000 claims abstract description 12
- RUOJZAUFBMNUDX-UHFFFAOYSA-N propylene carbonate Chemical group CC1COC(=O)O1 RUOJZAUFBMNUDX-UHFFFAOYSA-N 0.000 claims abstract description 10
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical group [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 30
- 239000003365 glass fiber Substances 0.000 claims description 10
- 239000002931 mesocarbon microbead Substances 0.000 claims description 10
- 239000000463 material Substances 0.000 claims description 3
- 239000012528 membrane Substances 0.000 claims 1
- 150000002500 ions Chemical class 0.000 abstract description 5
- 230000004913 activation Effects 0.000 abstract description 4
- 238000001179 sorption measurement Methods 0.000 abstract description 3
- 230000005518 electrochemistry Effects 0.000 abstract description 2
- 229910001415 sodium ion Inorganic materials 0.000 abstract description 2
- 238000007614 solvation Methods 0.000 abstract description 2
- 230000000052 comparative effect Effects 0.000 description 14
- 238000001994 activation Methods 0.000 description 10
- 238000012360 testing method Methods 0.000 description 10
- 238000004519 manufacturing process Methods 0.000 description 7
- 238000000034 method Methods 0.000 description 5
- 229910052799 carbon Inorganic materials 0.000 description 4
- 238000010586 diagram Methods 0.000 description 4
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 description 3
- 230000014759 maintenance of location Effects 0.000 description 3
- 230000008569 process Effects 0.000 description 3
- 238000004146 energy storage Methods 0.000 description 2
- 239000006230 acetylene black Substances 0.000 description 1
- 239000013543 active substance Substances 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- 238000013459 approach Methods 0.000 description 1
- 230000002238 attenuated effect Effects 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000003575 carbonaceous material Substances 0.000 description 1
- 238000004891 communication Methods 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 230000007123 defense Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000007599 discharging Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000012983 electrochemical energy storage Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 229910003002 lithium salt Inorganic materials 0.000 description 1
- 159000000002 lithium salts Chemical class 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000007773 negative electrode material Substances 0.000 description 1
- 230000010287 polarization Effects 0.000 description 1
- 239000007774 positive electrode material Substances 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 238000003825 pressing Methods 0.000 description 1
- 230000001681 protective effect Effects 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 239000000126 substance Substances 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
- H01G11/60—Liquid electrolytes characterised by the solvent
-
- 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
- H01G11/62—Liquid electrolytes characterised by the solute, e.g. salts, anions or cations therein
-
- 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
A mixed salt electrolyte for a high-voltage super capacitor and application thereof belong to the field of electrochemistry, and the mixed salt electrolyte comprises a solute and an organic solvent; the solute comprises quaternary ammonium salt and sodium salt, the quaternary ammonium salt is triethyl methyl ammonium hexafluorophosphate or tetraethyl ammonium hexafluorophosphate, and the sodium salt is sodium hexafluorophosphate; the organic solvent is propylene carbonate. The mixed salt electrolyte is applied to a nonporous soft carbon/graphite super capacitor, has better compatibility with the super capacitor, can reach 4V at the highest working voltage, and can stably output about 50mAh g after hundreds of cycles‑1The specific capacity of (A). The invention not only improves the discharge capacity of the super capacitor, but also reduces the cost of the electrolyte; meanwhile, as the size of sodium ions is smaller and the solvation degree is lower, more ion adsorption can be realized in the subsequent cycle on the premise of ensuring good electrochemical activation of quaternary ammonium salt cations to the negative electrode in the first cycle, and the total capacity is further improved.
Description
Technical Field
The invention belongs to the technical field of electrochemistry, and particularly relates to a mixed salt electrolyte for a high-voltage super capacitor and application thereof.
Background
In recent years, the development of renewable energy has been driven by increasing human attention to environmental issues. As an electrochemical energy storage device, the super capacitor has gained wide attention due to the advantages of high charging speed, long cycle life, small environmental pollution and the like. The method is gradually applied to the fields of traffic, communication, national defense and the like, and plays a more important role in the future energy field.
The super capacitor consists of a positive electrode, a negative electrode, electrolyte and a diaphragm between the two electrodes. The most common organic super capacitor generally uses porous carbon as a positive electrode material and a negative electrode material, quaternary ammonium salt is dissolved in propylene carbonate or acetonitrile solvent to be used as electrolyte, and the working voltage range is 0-2.7V. However, the energy density and power density achieved by the current system cannot fully meet the energy supply requirement in practical application, and people try to further increase the working voltage of the super capacitor to get rid of the limitation. One possible approach is to replace the porous carbon with other carbon materials to form an asymmetric supercapacitor; the activated nonporous soft carbon or graphite is used for replacing a porous carbon electrode on one side, and the working voltage range can be expanded to 0-3.5V; activated nonporous soft carbon and graphite are used for replacing porous carbon of the cathode and the anode respectively, and the range can be continuously expanded to 0-4V.
In a 4V high-voltage capacitor, the energy storage basis of the positive electrode is that negative ions in quaternary ammonium salt are inserted into graphite, the negative electrode needs larger quaternary ammonium salt cations to be inserted into nonporous soft carbon in the first polarization process, so that a sufficient electrochemical activation effect is generated, and energy storage is realized through ion adsorption in the subsequent cycle. However, the capacity generated by the negative electrode is generally inversely related to the size of the adsorbed ions, and the number of quaternary ammonium cations that can achieve a good balance between activation and capacity is not large, and the price of the electrolyte corresponding to them is also relatively expensive.
Disclosure of Invention
In order to solve the problems of the existing high-voltage super capacitor in practical application, the invention provides a mixed salt electrolyte for a high-voltage super capacitor and application thereof.
The technical scheme adopted by the invention for solving the technical problem is as follows:
the mixed salt electrolyte for the high-voltage super capacitor comprises a solute and an organic solvent; the solute comprises quaternary ammonium salt and sodium salt; the organic solvent is propylene carbonate.
In a preferred embodiment, the quaternary ammonium salt is triethylmethylammonium hexafluorophosphate or tetraethylammonium hexafluorophosphate, and the sodium salt is sodium hexafluorophosphate.
In a preferred embodiment, the total molar concentration of the solute in the organic solvent is 0.5 to 2.5 mol/L.
In a preferred embodiment, the molar concentration of the quaternary ammonium salt in the organic solvent is 0.01-2.5 mol/L; the molar concentration of the sodium salt in the organic solvent is 0.01-2.5 mol/L.
In a preferred embodiment, the molar ratio of the quaternary ammonium salt to the sodium salt in the organic solvent is 100 (0.1 to 50).
In a more preferred embodiment, the molar ratio of the quaternary ammonium salt to the sodium salt in the organic solvent is 100 (0.5 to 35).
The invention relates to application of a mixed salt electrolyte in a high-voltage super capacitor.
As a preferred embodiment, the high voltage supercapacitor comprises an activated non-porous soft carbon negative electrode, a graphite positive electrode, a mixed salt electrolyte and a separator.
In a preferred embodiment, the activated nonporous soft carbon negative electrode is potassium hydroxide activated mesocarbon microbeads.
In a preferred embodiment, the diaphragm is made of a glass fiber material.
The invention has the beneficial effects that: the invention provides a mixed salt electrolyte for a high-voltage super capacitor, which mainly comprises a solute and an organic solvent; wherein the solute is two electrolyte salts, one is quaternary ammonium salt, and the quaternary ammonium salt is preferably triethylmethyl ammonium hexafluorophosphate (TEMAPF)6) Or tetraethylammonium hexafluorophosphate (TEAPF)6) (ii) a The other is sodium salt, preferably sodium hexafluorophosphate (NaPF)6) (ii) a The organic solvent is preferably Propylene Carbonate (PC).
The mixed salt electrolyte is applied to a nonporous soft carbon/graphite supercapacitor, and tests prove that the mixed salt electrolyte has high compatibility with the supercapacitor, the working voltage range of the supercapacitor is 0-4V, the highest working voltage can reach 4V, and about 50mAh g can be stably output after hundreds of cycles of circulation-1Specific capacity of, i.e. 0.1Ag-1The discharge specific capacity can exceed 50mAh g under the current density-1。
The mixed salt electrolyte of the invention uses a proper amount of sodium hexafluorophosphate to replace triethyl methyl ammonium hexafluorophosphate or tetraethyl ammonium hexafluorophosphate, and compared with a single quaternary ammonium salt electrolyte, the mixed salt electrolyte not only improves the discharge capacity of the super capacitor, but also reduces the cost of the electrolyte; meanwhile, as the size of sodium ions is smaller and the solvation degree is lower, more ion adsorption can be realized in the subsequent cycle on the premise of ensuring good electrochemical activation of quaternary ammonium salt cations to the negative electrode in the first cycle, and the total capacity is further improved.
Drawings
FIG. 1 is a graph of the charge and discharge cycles for a capacitor made in accordance with example 1 of the present invention.
FIG. 2 is a graph of the charge and discharge cycles for a capacitor made in accordance with example 2 of the present invention.
FIG. 3 is a graph of the charge and discharge cycles for a capacitor made in accordance with example 3 of the present invention.
FIG. 4 is a graph of the charge and discharge cycles for a capacitor made in accordance with example 4 of the present invention.
Fig. 5 is a graph of the charge and discharge for some number of cycles of the capacitor prepared in comparative example 1.
Fig. 6 is a graph of the charge and discharge for some number of cycles of the capacitor prepared in comparative example 2.
Fig. 7 is a graph of the charge and discharge for some number of cycles of the capacitor made in comparative example 3.
FIG. 8 is a graph showing the discharge specific capacity of the capacitors prepared in examples 1, 2 and 3 of the present invention and comparative examples 1 and 2 as a function of the number of cycles.
FIG. 9 is a graph of specific discharge capacity versus number of cycles for capacitors prepared in example 4 of the present invention and comparative example 3.
Detailed Description
The invention provides a mixed salt electrolyte for a high-voltage super capacitor, which mainly comprises a solute and an organic solvent; wherein the solute is two electrolyte salts, one is quaternary ammonium salt, and the quaternary ammonium salt is preferably triethylmethyl ammonium hexafluorophosphate (TEMAPF)6) Or tetraethylammonium hexafluorophosphate (TEAPF)6) More preferably triethylmethylammonium hexafluorophosphate; the other is sodium salt, preferably sodium hexafluorophosphate (NaPF)6) (ii) a The organic solvent is preferably Propylene Carbonate (PC).
The total molar concentration of the solute in the organic solvent is preferably 0.5-2.5 mol/L, namely the sum of the molar concentrations of the quaternary ammonium salt and the sodium salt in the organic solvent is preferably 0.5-2.5 mol/L, and more preferably 1-2.2 mol/L.
The molar concentration of the quaternary ammonium salt and the sodium salt in the organic solvent is preferably 0.01-2.5 mol/L.
The molar ratio of the quaternary ammonium salt to the sodium salt in the organic solvent is preferably 100 (0.1-50), more preferably 100 (0.5-35), and most preferably 100 (0.5-20).
The mixed salt electrolyte can be applied to a high-voltage super capacitor. The high-voltage super capacitor is an asymmetric super capacitor and consists of an activated nonporous soft carbon cathode, a graphite anode, the mixed salt electrolyte and a diaphragm. The nonporous soft carbon cathode used in the present invention is not particularly limited, and is activated by a strong alkali substance well known to those skilled in the art, and the present invention preferably uses potassium hydroxide activated mesocarbon microbeads. The graphite anode used in the invention is not particularly limited, and those skilled in the art can select and adjust the graphite anode according to actual conditions, product performance, quality requirements and the like. The material of the separator used in the present invention is not particularly limited, and glass fiber is preferably used in the present invention.
The preparation method of the electrode and the super capacitor is not particularly limited, and the method for preparing the battery well known to the technical personnel in the field can be adopted, and the specific steps are preferably as follows: mixing an electrode active substance and a conductive adhesive, namely polytetrafluoroethylene acetylene black according to a mass ratio of 2:1, and pressing the mixture on an aluminum mesh current collector to prepare an electrode, wherein the mass ratio of positive to negative is 1: 1; and preparing the mixed salt electrolyte in a glove box filled with protective atmosphere, and assembling the activated nonporous soft carbon negative electrode, the graphite positive electrode, the diaphragm and the mixed salt electrolyte into the supercapacitor.
The super capacitor provided by the invention is subjected to charge and discharge tests to represent the capacity and the cycle performance of the capacitor adopting the mixed salt electrolyte, and the current density is 0.1Ag-1The voltage range is 0-4V, and the test temperature is 25 ℃. The experimental result shows that compared with the quaternary ammonium salt electrolyte with the same total molar concentration or the quaternary ammonium salt and lithium salt electrolyte mixed in the same molar ratio, the mixed salt electrolyte provided by the invention has higher specific discharge capacity when the circulation is stable.
The technical solutions in the embodiments of the present invention will be clearly and completely described below with reference to the embodiments of the present invention, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all of the embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
All the raw materials used in the present invention, the sources of which are not particularly limited, may be purchased commercially or prepared according to conventional methods well known to those skilled in the art.
Example 1
A mixed salt propylene carbonate solution is prepared in a glove box, wherein solutes are triethyl methyl ammonium hexafluorophosphate and sodium hexafluorophosphate, the concentration of the triethyl methyl ammonium hexafluorophosphate is 1.9mol/L, and the concentration of the sodium hexafluorophosphate is 0.1 mol/L. And (3) taking the solution as an electrolyte, and manufacturing the super capacitor in a glove box, wherein the cathode is the potassium hydroxide activated mesocarbon microbeads, the anode is graphite, and the diaphragm is glass fiber. And (4) standing the capacitor for 12 hours, and then carrying out constant current charge-discharge cycle test until the voltage is 4V.
Fig. 1 is a charge-discharge curve diagram of some cycles of the capacitor prepared in example 1, and it can be seen from fig. 1 that the first cycle is distinguished from the electrochemical activation process of the subsequent cycle, and the compatibility of the electrolyte and the electrode is good; FIG. 8 shows the relationship between the number of cycles and the discharge capacity of the capacitor prepared in example 1, and it can be seen from FIG. 8 that the discharge was substantially stabilized to a capacity of about 48mAh g after 200 cycles-1。
Example 2
A mixed salt propylene carbonate solution is prepared in a glove box, wherein solutes are triethyl methyl ammonium hexafluorophosphate and sodium hexafluorophosphate, the concentration of the triethyl methyl ammonium hexafluorophosphate is 1.8mol/L, and the concentration of the sodium hexafluorophosphate is 0.2 mol/L. And (3) taking the solution as an electrolyte, and manufacturing the super capacitor in a glove box, wherein the cathode is the potassium hydroxide activated mesocarbon microbeads, the anode is graphite, and the diaphragm is glass fiber. And (4) standing the capacitor for 12 hours, and then carrying out constant current charge-discharge cycle test until the voltage is 4V.
Fig. 2 is a charge-discharge curve diagram of some cycles of the capacitor prepared in example 2, and it can be seen from fig. 2 that the first cycle is distinguished from the electrochemical activation process of the subsequent cycle, and the compatibility of the electrolyte and the electrode is good; FIG. 8 shows the relationship between the number of cycles and the discharge capacity of the capacitor prepared in example 2. from FIG. 8, it can be seen that after 200 cycles, the discharge substantially stabilized to a capacity of about 52mAh g-1。
Example 3
A mixed salt propylene carbonate solution is prepared in a glove box, wherein solutes are triethyl methyl ammonium hexafluorophosphate and sodium hexafluorophosphate, the concentration of the triethyl methyl ammonium hexafluorophosphate is 1.6mol/L, and the concentration of the sodium hexafluorophosphate is 0.4 mol/L. And (3) taking the solution as an electrolyte, and manufacturing the super capacitor in a glove box, wherein the cathode is the potassium hydroxide activated mesocarbon microbeads, the anode is graphite, and the diaphragm is glass fiber. And (4) standing the capacitor for 12 hours, and then carrying out constant current charge-discharge cycle test until the voltage is 4V.
Fig. 3 is a charge-discharge curve diagram of some cycles of the capacitor prepared in example 3, and it can be seen from fig. 3 that the first cycle is distinguished from the electrochemical activation process of the subsequent cycle, and the compatibility of the electrolyte and the electrode is good; FIG. 8 shows the relationship between the number of cycles and the discharge capacity of the capacitor prepared in example 3. from FIG. 8, it can be seen that after 200 cycles, the discharge substantially stabilized to a capacity of about 51mAh g-1。
Example 4
A mixed salt propylene carbonate solution is prepared in a glove box, wherein solutes are tetraethylammonium hexafluorophosphate and sodium hexafluorophosphate, the concentration of the tetraethylammonium hexafluorophosphate is 0.95mol/L, and the concentration of the sodium hexafluorophosphate is 0.05 mol/L. And (3) taking the solution as an electrolyte, and manufacturing the super capacitor in a glove box, wherein the cathode is the potassium hydroxide activated mesocarbon microbeads, the anode is graphite, and the diaphragm is glass fiber. And (4) standing the capacitor for 12 hours, and then carrying out constant current charge-discharge cycle test until the voltage is 4V.
Fig. 4 is a charge-discharge curve diagram of some cycles of the capacitor prepared in example 4, and it can be seen from fig. 4 that the first cycle is distinguished from the electrochemical activation process of the subsequent cycle, and the compatibility of the electrolyte and the electrode is good; FIG. 9 shows the relationship between the number of cycles and the discharge capacity of the capacitor prepared in example 4. from FIG. 9, it can be seen that after 200 cycles, the discharge process gradually stabilized to a capacity of about 42mAh g-1。
Comparative example 1
A propylene carbonate solution of quaternary ammonium salt is prepared in a glove box, the solute is triethyl methyl ammonium hexafluorophosphate, and the concentration is 2 mol/L. And (3) taking the solution as an electrolyte, and manufacturing the super capacitor in a glove box, wherein the cathode is the potassium hydroxide activated mesocarbon microbeads, the anode is graphite, and the diaphragm is glass fiber. And (4) standing the capacitor for 12 hours, and then carrying out constant current charge-discharge cycle test until the voltage is 4V.
Fig. 5 is a charge-discharge graph of the capacitor prepared in comparative example 1 for some cycles, and it can be seen from fig. 5 that the first cycle is distinguished from the electrochemical activation process of the subsequent cycle, and the compatibility of the electrolyte and the electrode is good; FIG. 8 shows the relationship between the number of cycles and the discharge capacity of the capacitor prepared in comparative example 1, and it can be seen from FIG. 8 that the discharge tends to be stable after 200 cycles and the capacity is about 38mAh g-1The capacity retention is lower than that of a supercapacitor using the mixed salt electrolyte of the present invention.
Comparative example 2
A mixed salt propylene carbonate solution is prepared in a glove box, wherein solutes are triethyl methyl ammonium hexafluorophosphate and lithium hexafluorophosphate, the concentration of the triethyl methyl ammonium hexafluorophosphate is 1.8mol/L, and the concentration of the lithium hexafluorophosphate is 0.2 mol/L. And (3) taking the solution as an electrolyte, and manufacturing the super capacitor in a glove box, wherein the cathode is the potassium hydroxide activated mesocarbon microbeads, the anode is graphite, and the diaphragm is glass fiber. And (4) standing the capacitor for 12 hours, and then carrying out constant current charge-discharge cycle test until the voltage is 4V.
FIG. 6 is a graph showing the number of cycles of charging and discharging the capacitor prepared in comparative example 2, and it can be seen from FIG. 6 thatThe first circle is different from the subsequent circulating electrochemical activation process, and the compatibility of the electrolyte and the electrode is good; FIG. 8 shows the relationship between the number of cycles and the discharge capacity of the capacitor prepared in comparative example 2, and it can be seen from FIG. 8 that the capacity after 200 cycles is about 46mAhg-1The capacity retention is lower than that of a supercapacitor using the mixed salt electrolyte of the present invention.
Comparative example 3
A propylene carbonate solution of quaternary ammonium salt is prepared in a glove box, the solute is tetraethylammonium hexafluorophosphate, and the concentration is 1 mol/L. And (3) taking the solution as an electrolyte, and manufacturing the super capacitor in a glove box, wherein the cathode is the potassium hydroxide activated mesocarbon microbeads, the anode is graphite, and the diaphragm is glass fiber. And (4) standing the capacitor for 12 hours, and then carrying out constant current charge-discharge cycle test until the voltage is 4V.
Fig. 7 is a charge-discharge graph of the capacitor prepared in comparative example 3 for some cycles, and it can be seen from fig. 7 that the first cycle is distinguished from the electrochemical activation process of the subsequent cycle, and the compatibility of the electrolyte and the electrode is good; FIG. 9 shows the relationship between the number of cycles and the discharge capacity of the capacitor prepared in comparative example 3, and it can be seen from FIG. 9 that the discharge capacity is continuously attenuated to about 26mAh g after 200 cycles-1The stability and capacity retention rate are lower than those of the super capacitor adopting the mixed salt electrolyte.
The invention discloses a mixed salt electrolyte for a high-voltage super capacitor and application thereof, and a person skilled in the art can appropriately improve process parameters by referring to the content. It is expressly intended that all such similar substitutes and modifications which would be obvious to one skilled in the art are deemed to be included in the invention. While the invention has been described in terms of preferred embodiments, it will be apparent to those skilled in the art that the technology can be practiced and applied by modifying or appropriately combining the products described herein without departing from the spirit and scope of the invention.
Claims (6)
1. A mixed salt electrolyte for a high voltage supercapacitor, comprising a solute and an organic solvent; the solute comprises quaternary ammonium salt and sodium salt; the organic solvent is propylene carbonate;
the total molar concentration of the solute in the organic solvent is 0.5-2.5 mol/L;
the molar concentration of the quaternary ammonium salt in the organic solvent is 0.01-2.5 mol/L;
the molar concentration of the sodium salt in the organic solvent is 0.01-2.5 mol/L;
the molar ratio of the quaternary ammonium salt to the sodium salt in the organic solvent is 100 (0.1-50);
the molar ratio of the quaternary ammonium salt to the sodium salt in the organic solvent is 100 (0.5-35).
2. The mixed salt electrolyte for a high voltage supercapacitor according to claim 1, wherein the quaternary ammonium salt is triethylmethylammonium hexafluorophosphate or tetraethylammonium hexafluorophosphate and the sodium salt is sodium hexafluorophosphate.
3. Use of a mixed salt electrolyte according to any of claims 1 and 2 in a high voltage supercapacitor.
4. The use according to claim 3, wherein the high voltage supercapacitor comprises an activated non-porous soft carbon negative electrode, a graphite positive electrode, a mixed salt electrolyte and a separator.
5. The use of claim 4, wherein the activated nonporous soft carbon negative electrode is potassium hydroxide activated mesocarbon microbeads.
6. Use according to claim 4, wherein the membrane is made of a glass fibre material.
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