CN113035586A - Low-temperature flame-retardant organic electrolyte for electric double layer capacitor and preparation method thereof - Google Patents
Low-temperature flame-retardant organic electrolyte for electric double layer capacitor and preparation method thereof Download PDFInfo
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- 239000003990 capacitor Substances 0.000 title claims abstract description 51
- 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 title claims abstract description 47
- 239000003063 flame retardant Substances 0.000 title claims abstract description 47
- 239000005486 organic electrolyte Substances 0.000 title claims abstract description 31
- 238000002360 preparation method Methods 0.000 title abstract description 5
- 239000003792 electrolyte Substances 0.000 claims abstract description 41
- 239000002904 solvent Substances 0.000 claims abstract description 21
- 239000000654 additive Substances 0.000 claims abstract description 18
- 230000000996 additive effect Effects 0.000 claims abstract description 18
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical group CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 claims abstract description 15
- 239000006184 cosolvent Substances 0.000 claims abstract description 14
- 239000003960 organic solvent Substances 0.000 claims abstract description 11
- YEJRWHAVMIAJKC-UHFFFAOYSA-N 4-Butyrolactone Chemical compound O=C1CCCO1 YEJRWHAVMIAJKC-UHFFFAOYSA-N 0.000 claims abstract description 8
- 229910019142 PO4 Inorganic materials 0.000 claims abstract description 7
- XBDQKXXYIPTUBI-UHFFFAOYSA-M Propionate Chemical compound CCC([O-])=O XBDQKXXYIPTUBI-UHFFFAOYSA-M 0.000 claims abstract description 7
- 239000010452 phosphate Substances 0.000 claims abstract description 7
- 150000003242 quaternary ammonium salts Chemical group 0.000 claims abstract description 7
- 150000002148 esters Chemical class 0.000 claims abstract description 6
- WNXJIVFYUVYPPR-UHFFFAOYSA-N 1,3-dioxolane Chemical compound C1COCO1 WNXJIVFYUVYPPR-UHFFFAOYSA-N 0.000 claims abstract description 4
- 125000002467 phosphate group Chemical group [H]OP(=O)(O[H])O[*] 0.000 claims abstract description 4
- -1 tetraethyl ammonium tetrafluoroborate Chemical compound 0.000 claims description 18
- DQWPFSLDHJDLRL-UHFFFAOYSA-N triethyl phosphate Chemical compound CCOP(=O)(OCC)OCC DQWPFSLDHJDLRL-UHFFFAOYSA-N 0.000 claims description 7
- FKRCODPIKNYEAC-UHFFFAOYSA-N ethyl propionate Chemical compound CCOC(=O)CC FKRCODPIKNYEAC-UHFFFAOYSA-N 0.000 claims description 6
- XZZNDPSIHUTMOC-UHFFFAOYSA-N triphenyl phosphate Chemical compound C=1C=CC=CC=1OP(OC=1C=CC=CC=1)(=O)OC1=CC=CC=C1 XZZNDPSIHUTMOC-UHFFFAOYSA-N 0.000 claims description 4
- OIFBSDVPJOWBCH-UHFFFAOYSA-N Diethyl carbonate Chemical compound CCOC(=O)OCC OIFBSDVPJOWBCH-UHFFFAOYSA-N 0.000 claims description 3
- KMTRUDSVKNLOMY-UHFFFAOYSA-N Ethylene carbonate Chemical compound O=C1OCCO1 KMTRUDSVKNLOMY-UHFFFAOYSA-N 0.000 claims description 3
- RJUFJBKOKNCXHH-UHFFFAOYSA-N Methyl propionate Chemical compound CCC(=O)OC RJUFJBKOKNCXHH-UHFFFAOYSA-N 0.000 claims description 3
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 3
- QLVWOKQMDLQXNN-UHFFFAOYSA-N dibutyl carbonate Chemical compound CCCCOC(=O)OCCCC QLVWOKQMDLQXNN-UHFFFAOYSA-N 0.000 claims description 3
- IEJIGPNLZYLLBP-UHFFFAOYSA-N dimethyl carbonate Chemical compound COC(=O)OC IEJIGPNLZYLLBP-UHFFFAOYSA-N 0.000 claims description 3
- VUPKGFBOKBGHFZ-UHFFFAOYSA-N dipropyl carbonate Chemical compound CCCOC(=O)OCCC VUPKGFBOKBGHFZ-UHFFFAOYSA-N 0.000 claims description 3
- JBTWLSYIZRCDFO-UHFFFAOYSA-N ethyl methyl carbonate Chemical compound CCOC(=O)OC JBTWLSYIZRCDFO-UHFFFAOYSA-N 0.000 claims description 3
- 229940017219 methyl propionate Drugs 0.000 claims description 3
- 238000002156 mixing Methods 0.000 claims description 3
- 239000001301 oxygen Substances 0.000 claims description 3
- 229910052760 oxygen Inorganic materials 0.000 claims description 3
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 claims description 3
- RUOJZAUFBMNUDX-UHFFFAOYSA-N propylene carbonate Chemical compound CC1COC(=O)O1 RUOJZAUFBMNUDX-UHFFFAOYSA-N 0.000 claims description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 3
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 claims description 2
- 238000000034 method Methods 0.000 claims description 2
- 238000002485 combustion reaction Methods 0.000 abstract description 10
- 238000002474 experimental method Methods 0.000 abstract description 6
- 238000012360 testing method Methods 0.000 abstract description 4
- 239000006227 byproduct Substances 0.000 abstract description 3
- 238000002484 cyclic voltammetry Methods 0.000 description 8
- 229940021013 electrolyte solution Drugs 0.000 description 5
- 239000008151 electrolyte solution Substances 0.000 description 4
- 239000011491 glass wool Substances 0.000 description 4
- 238000002844 melting Methods 0.000 description 3
- 230000008018 melting Effects 0.000 description 3
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 238000009472 formulation Methods 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 239000003575 carbonaceous material Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 239000007772 electrode material Substances 0.000 description 1
- 238000004146 energy storage Methods 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 238000012423 maintenance Methods 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 229910052698 phosphorus Inorganic materials 0.000 description 1
- 239000011574 phosphorus Substances 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 238000000197 pyrolysis Methods 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000007784 solid electrolyte Substances 0.000 description 1
- 238000007614 solvation Methods 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
-
- 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
- H01G11/84—Processes for the manufacture of hybrid or EDL capacitors, or components thereof
-
- 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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- Engineering & Computer Science (AREA)
- Power Engineering (AREA)
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- Microelectronics & Electronic Packaging (AREA)
- Manufacturing & Machinery (AREA)
- Electric Double-Layer Capacitors Or The Like (AREA)
Abstract
The invention provides a low-temperature flame-retardant organic electrolyte for an electric double layer capacitor and a preparation method thereof, wherein the low-temperature flame-retardant organic electrolyte comprises an electrolyte and an organic solvent, the organic solvent comprises a main solvent, a low-temperature cosolvent and a flame-retardant additive, the electrolyte is quaternary ammonium salt, the main solvent is acetonitrile, the low-temperature cosolvent is one or a combination of more of carbonic ester, gamma-butyrolactone, propionate and 1, 3-dioxolane, and the flame-retardant additive is phosphate. The invention can lead the electric double layer capacitor to have excellent low-temperature performance, and the discharge specific capacity of the electric double layer capacitor at minus 60 ℃ reaches at least 65 percent of the discharge specific capacity at 25 ℃, even can reach as high as 80 percent. Meanwhile, due to the use of the flame retardant, the electrolyte has good safety performance, no obvious combustion by-product is found in the low-temperature flame-retardant organic electrolyte for the double-electric-layer capacitor through combustion experiment tests, and the self-extinguishing time of the electrolyte is reduced by half compared with that of the electrolyte without the flame-retardant additive.
Description
Technical Field
The invention belongs to the technical field of double electric layer capacitors, and particularly relates to a low-temperature flame-retardant organic electrolyte for a double electric layer capacitor.
Background
The double-layer capacitor is a novel energy storage device between a traditional capacitor and a battery, generally adopts an active carbon material with a large specific surface area as an electrode, stores charges by a solid/liquid interface double-layer generated by a polarizable electrode/electrolyte, and has farad-level capacitance. The double-layer capacitor has higher energy density than the traditional capacitor, has higher power density than the secondary battery, has the advantages of no maintenance, high charge-discharge efficiency, long cycle life, wide use temperature range and the like, can be used as a power auxiliary device in occasions requiring high-power discharge, can also be used as a backup power source of electronic components, can also be used as a replacement power source, and is a main power source under the condition of continuous discharge for a few milliseconds. The electrolyte solution of the electric double layer capacitor can be classified into an aqueous electrolyte solution, an organic electrolyte solution, a colloidal electrolyte solution, and a solid electrolyte. The organic electrolyte has a wider electrochemical window and higher ionic conductivity, and can be used for preparing a double electric layer capacitor with higher working voltage and higher power density, so that the organic electrolyte is widely applied.
The current double electric layer capacitor widely uses an organic electrolyte, has high conductivity and excellent electrode surface wettability, but has poor thermal stability, easy leakage and poor safety, the working temperature range is usually only within minus 40-60 ℃, the discharge performance of the device is sharply reduced at minus 50 ℃, even the device cannot work, and therefore the working requirement under certain special temperature environments cannot be met. Most of organic electrolyte adopts aprotic liquid with high dielectric constant as solvent, however, the solvent has lower flash point, and is easy to generate heat and fire when the super capacitor is used for quick charge and discharge, so that higher potential safety hazard exists, and the application of the double electric layer capacitor in the fields of military industry, aerospace and the like is limited.
Disclosure of Invention
In view of the above-mentioned drawbacks of the prior art, an object of the present invention is to provide a low-temperature flame-retardant organic electrolyte for an electric double layer capacitor that can stably operate at-60 ℃ and can effectively prevent ignition.
In order to achieve the purpose, the technical scheme of the invention is as follows:
a low-temperature flame-retardant organic electrolyte for an electric double layer capacitor comprises an electrolyte and an organic solvent, wherein the concentration of the electrolyte in the electrolyte is 0.8-1.2 mol/L, the organic solvent comprises a main solvent, a low-temperature cosolvent and a flame-retardant additive, and the volume ratio of the main solvent to the low-temperature cosolvent to the flame-retardant additive is (6-8): (0.5-2): 0.5-2);
the electrolyte is quaternary ammonium salt, the main solvent is acetonitrile, the low-temperature cosolvent is one or a combination of more of carbonic ester, gamma-butyrolactone, propionate and 1, 3-dioxolane, and the flame retardant additive is phosphate.
Preferably, the quaternary ammonium salt is one or a combination of more of tetraethylammonium tetrafluoroborate, triethyl methyl tetrafluoroborate and spiro quaternary ammonium tetrafluoroborate.
Preferably, the carbonate is one or a combination of more of dimethyl carbonate, diethyl carbonate, ethyl methyl carbonate, dipropyl carbonate, dibutyl carbonate, ethylene carbonate and propylene carbonate.
Preferably, the propionate is one or two of methyl propionate and ethyl propionate.
Preferably, the phosphate is one or two of triethyl phosphate and triphenyl phosphate.
Preferably, the electrolyte is tetraethylammonium tetrafluoroborate with the concentration of 0.8-1.2 mol/L.
Preferably, the electrolyte is tetraethylammonium tetrafluoroborate with a concentration of 0.85 to 1.1 mol/L.
Preferably, the low-temperature electrolyte is triethyl methyl tetrafluoroborate with a concentration of 0.8 to 1.2 mol/L.
Preferably, the electrolyte is triethyl methyl tetrafluoroborate with a concentration of 0.9 to 1.15 mol/L.
Preferably, the flame retardant additive is triethyl phosphate.
The invention also provides a preparation method of the low-temperature flame-retardant organic electrolyte for the double electric layer capacitor, which comprises the following steps:
(1) mixing a main solvent and a low-temperature cosolvent according to a ratio in an environment with water and oxygen content lower than 1ppm, and then adding a flame retardant additive according to the ratio to form a final organic solvent;
(2) and adding electrolyte and completely dissolving to obtain the low-temperature flame-retardant organic electrolyte for the double-electric-layer capacitor.
The principle of the low-temperature electrolyte is as follows: firstly, the melting point of the AN-based solvent is reduced by directly adding the solvent with lower melting point, and the low-temperature performance of the electrolyte is improved. Secondly, by utilizing solvation, solvent molecules and solute ions are wrapped to form a new macromolecular structure, and the original chemical bond type is changed, so that the melting point of the system is reduced.
The low-temperature flame retardant principle of the invention is as follows: triethyl phosphate (TEP) and triphenyl phosphate (TPP) are non-combustible phosphorus-containing compounds, gaseous products formed by pyrolysis easily contain PO, the PO can capture main components H of a solvent combustion chain branching reaction such as carbonic ester and acetonitrile, and due to insufficient H, the solvent combustion chain branching reaction can be inhibited, so that the flammability of the electrolyte is reduced.
The invention has the beneficial effects that: compared with the prior art, the low-temperature flame-retardant organic electrolyte for the electric double layer capacitor can enable the electric double layer capacitor to have excellent low-temperature performance, and the discharge specific capacity of the electric double layer capacitor at the temperature of-60 ℃ reaches at least 65% of the discharge specific capacity at the temperature of 25 ℃, even can reach 80%. Meanwhile, due to the use of the flame retardant, the electrolyte has good safety performance, no obvious combustion by-product is found in the low-temperature flame-retardant organic electrolyte for the double-electric-layer capacitor through combustion experiment tests, and the self-extinguishing time of the electrolyte is reduced by half compared with that of the electrolyte without the flame-retardant additive.
Drawings
Fig. 1 (a) to (e) are graphs showing charge and discharge of the button type electric double layer capacitors prepared in examples 1 to 5 at-60 c and different current densities, respectively.
Fig. 1(f) is a graph showing the specific capacity at-60 c for button type electric double layer capacitors prepared in examples 1 to 5 at different current densities.
In fig. 2, (a) and (b) are a magnification graph and a cyclic voltammogram of the button type electric double layer capacitor prepared in example 6 at different temperatures, respectively;
in fig. 2, (c) and (d) are a magnification graph and a cyclic voltammogram of the button type electric double layer capacitor prepared in example 7 at different temperatures, respectively;
in fig. 2, (e) and (f) are a magnification graph and a cyclic voltammogram of the button type electric double layer capacitor prepared in example 8 at different temperatures, respectively;
Detailed Description
The embodiments of the present invention are described below with reference to specific embodiments, and other advantages and effects of the present invention will be easily understood by those skilled in the art from the disclosure of the present specification. The invention is capable of other and different embodiments and of being practiced or of being carried out in various ways, and its several details are capable of modification in various respects, all without departing from the spirit and scope of the present invention.
Examples
The embodiment provides a low-temperature flame-retardant organic electrolyte for an electric double layer capacitor, which comprises an electrolyte and an organic solvent, wherein the concentration of the electrolyte in the electrolyte is 0.8-1.2 mol/L, the organic solvent comprises a main solvent, a low-temperature cosolvent and a flame-retardant additive, and the volume ratio of the main solvent, the low-temperature cosolvent and the flame-retardant additive is (6-8): (0.5-2): 0.5-2;
the electrolyte is quaternary ammonium salt, and the quaternary ammonium salt is one or a combination of more of tetraethylammonium tetrafluoroborate, triethyl methyl tetrafluoroborate and spiro quaternary ammonium tetrafluoroborate.
The main solvent is acetonitrile;
the low-temperature cosolvent is one or a combination of more of carbonic ester, gamma-butyrolactone, propionate and 1, 3-dioxolane, and the carbonic ester is one or a combination of more of dimethyl carbonate, diethyl carbonate, ethyl methyl carbonate, dipropyl carbonate, dibutyl carbonate, ethylene carbonate and propylene carbonate. The propionate is one or two of methyl propionate and ethyl propionate.
The flame retardant additive is phosphate. The phosphate is one or two of triethyl phosphate and triphenyl phosphate.
Preferably, the electrolyte is tetraethylammonium tetrafluoroborate with the concentration of 0.8-1.2 mol/L.
Preferably, the electrolyte is tetraethylammonium tetrafluoroborate with the concentration of 0.85-1.1 mol/L.
Preferably, the low-temperature electrolyte is triethyl methyl tetrafluoroborate with the concentration of 0.8-1.2 mol/L.
Preferably, the electrolyte is triethyl methyl tetrafluoroborate with the concentration of 0.9-1.15 mol/L.
Preferably, the flame retardant additive is triethyl phosphate.
The embodiment also provides a preparation method of the low-temperature flame-retardant organic electrolyte for the electric double layer capacitor, which comprises the following steps:
(1) mixing a main solvent and a low-temperature cosolvent according to a ratio in an environment with water and oxygen content lower than 1ppm, and then adding a flame retardant additive according to the ratio to form a final organic solvent;
(2) and adding electrolyte and completely dissolving to obtain the low-temperature flame-retardant organic electrolyte for the double-electric-layer capacitor.
The formulations in the examples are shown in Table 1:
table 1 formulations of the examples
Second, Performance test experiment
1. Combustion experiment
The procedure for the combustion experiment was as follows:
glass wool is used as a raw material to prepare glass wool balls with the diameter of 5mm, the glass wool balls are weighed and arranged on a thin iron wire folded into an O shape, electrolyte solutions with different proportions are respectively taken out by a register and injected on the glass wool to be rapidly ignited, and the time from the moment when an ignition device is removed to the moment when flame is automatically extinguished is recorded.
Table 2 combustion experimental data and analysis:
| self-extinguishing time | Combustion by-products | |
| Control group 1 | 45s | Multiple |
| Control group | ||
| 2 | 44s | Multiple purpose |
| Example 1 | 33s | Small amount of |
| Example 2 | 20s | Is free of |
| Example 3 | 34s | Small amount of |
| Example 4 | 20s | Is free of |
| Example 5 | 22s | Is free of |
| Example 6 | 32s | Small amount of |
| Example 7 | 32s | Small amount of |
| Example 8 | 33s | Small amount of |
| Example 9 | 38s | Much more |
| Example 10 | 33s | Small amount of |
| Example 11 | 37s | Much more |
| Example 12 | 25s | Small amount of |
Third, Charge and discharge experiment
And preparing the prepared electrolyte into a formed button type double-layer capacitor according to the manufacturing standard of the double-layer capacitor, wherein the electrode material adopts active carbon. Testing specific capacity at 20 +/-5 ℃ at current densities of 0.1A/g, 0.2A/g, 0.5A/g, 1A/g and 2A/g, and testing cyclic voltammetry curve at 5 mV/s; after standing at a low temperature (0 ℃ C., -20 ℃ C., -40 ℃ C., -60 ℃ C.) for 16 hours, the specific capacity was measured at a current density of 0.1A/g, and the cyclic voltammogram was measured at 5 mV/s.
Fig. 1 (a) to (e) are graphs showing charge and discharge of the button type electric double layer capacitors prepared in examples 1 to 5 at-60 c and different current densities, respectively.
Fig. 1(f) is a graph showing the specific capacity at-60 c for button type electric double layer capacitors prepared in examples 1 to 5 at different current densities.
In fig. 2, (a) and (b) are a magnification graph and a cyclic voltammogram of the button type electric double layer capacitor prepared in example 6 at different temperatures, respectively;
in fig. 2, (c) and (d) are a magnification graph and a cyclic voltammogram of the button type electric double layer capacitor prepared in example 7 at different temperatures, respectively;
in fig. 2, (e) and (f) are a magnification graph and a cyclic voltammogram of the button type electric double layer capacitor prepared in example 8 at different temperatures, respectively;
the foregoing embodiments are merely illustrative of the principles and utilities of the present invention and are not intended to limit the invention. Any person skilled in the art can modify or change the above-mentioned embodiments without departing from the spirit and scope of the present invention. Accordingly, it is intended that all equivalent modifications or changes which can be made by those skilled in the art without departing from the spirit and technical spirit of the present invention be covered by the claims of the present invention.
Claims (10)
1. A low-temperature flame-retardant organic electrolyte for an electric double layer capacitor is characterized in that: the electrolyte is prepared from an electrolyte and an organic solvent, wherein the concentration of the electrolyte in an electrolyte is 0.8-1.2 mol/L, the organic solvent comprises a main solvent, a low-temperature cosolvent and a flame retardant additive, and the volume ratio of the main solvent to the low-temperature cosolvent to the flame retardant additive is (6-8): (0.5-2): 0.5-2);
the electrolyte is quaternary ammonium salt, the main solvent is acetonitrile, the low-temperature cosolvent is one or a combination of more of carbonic ester, gamma-butyrolactone, propionate and 1, 3-dioxolane, and the flame retardant additive is phosphate.
2. The low-temperature flame-retardant organic electrolyte for electric double layer capacitors according to claim 1, wherein: the quaternary ammonium salt is one or a combination of more of tetraethyl ammonium tetrafluoroborate, triethyl methyl tetrafluoroborate and spiro quaternary ammonium tetrafluoroborate.
3. The low-temperature-resistant flame-retardant organic electrolyte for electric double layer capacitors according to claim 1 or 2, characterized in that: the carbonate is one or a combination of more of dimethyl carbonate, diethyl carbonate, ethyl methyl carbonate, dipropyl carbonate, dibutyl carbonate, ethylene carbonate and propylene carbonate.
4. The low-temperature flame-retardant organic electrolyte for electric double layer capacitors according to claim 1, wherein: the propionate is one or two of methyl propionate and ethyl propionate.
5. The low-temperature flame-retardant organic electrolyte for electric double layer capacitors according to claim 1, wherein: the phosphate is one or two of triethyl phosphate and triphenyl phosphate.
6. The low-temperature flame-retardant organic electrolyte for electric double layer capacitors according to claim 1, wherein: the electrolyte is tetraethylammonium tetrafluoroborate with the concentration of 0.8-1.2 mol/L.
7. The low-temperature flame-retardant organic electrolyte for electric double layer capacitors according to claim 1, wherein: the electrolyte is tetraethylammonium tetrafluoroborate with the concentration of 0.85-1.1 mol/L.
8. The low-temperature flame-retardant organic electrolyte for electric double layer capacitors according to claim 1, characterized in that: the low-temperature electrolyte is triethyl methyl tetrafluoroborate with the concentration of 0.8-1.2 mol/L.
9. The low-temperature flame-retardant organic electrolyte for electric double layer capacitors according to claim 1, characterized in that: the electrolyte is triethyl methyl tetrafluoroborate with the concentration of 0.9-1.15 mol/L.
10. The method for preparing a low-temperature flame-retardant organic electrolyte for electric double layer capacitors as recited in any one of claims 1 to 9, comprising the steps of:
(1) mixing a main solvent and a low-temperature cosolvent according to a ratio in an environment with water and oxygen content lower than 1ppm, and then adding a flame retardant additive according to the ratio to form a final organic solvent;
(2) and adding electrolyte and completely dissolving to obtain the low-temperature flame-retardant organic electrolyte for the double-electric-layer capacitor.
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Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20150029640A1 (en) * | 2012-02-27 | 2015-01-29 | Panasonic Corporation | Electrolyte solution for electric double layer capacitors, and electric double layer capacitor |
| CN104584164A (en) * | 2012-09-04 | 2015-04-29 | 大金工业株式会社 | Electrolyte solution and electrochemical device |
| CN105336506A (en) * | 2015-11-11 | 2016-02-17 | 湖北诺邦科技股份有限公司 | Fire-retardant super capacitor electrolyte |
| CN109616325A (en) * | 2019-01-28 | 2019-04-12 | 江苏法拉电子有限公司 | A kind of take gamma-butyrolacton as the organic electrolyte of basic solvent |
| CN109727788A (en) * | 2017-10-30 | 2019-05-07 | 江苏国泰超威新材料有限公司 | A kind of double layer capacitor low-temperature electrolyte |
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2021
- 2021-03-17 CN CN202110285084.8A patent/CN113035586B/en active Active
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20150029640A1 (en) * | 2012-02-27 | 2015-01-29 | Panasonic Corporation | Electrolyte solution for electric double layer capacitors, and electric double layer capacitor |
| CN104584164A (en) * | 2012-09-04 | 2015-04-29 | 大金工业株式会社 | Electrolyte solution and electrochemical device |
| CN105336506A (en) * | 2015-11-11 | 2016-02-17 | 湖北诺邦科技股份有限公司 | Fire-retardant super capacitor electrolyte |
| CN109727788A (en) * | 2017-10-30 | 2019-05-07 | 江苏国泰超威新材料有限公司 | A kind of double layer capacitor low-temperature electrolyte |
| CN109616325A (en) * | 2019-01-28 | 2019-04-12 | 江苏法拉电子有限公司 | A kind of take gamma-butyrolacton as the organic electrolyte of basic solvent |
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| CN113035586B (en) | 2022-06-24 |
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