CN115732235B - Electrolyte for long-life capacitor and preparation method thereof - Google Patents
Electrolyte for long-life capacitor and preparation method thereof Download PDFInfo
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- 239000003792 electrolyte Substances 0.000 title claims abstract description 63
- 239000003990 capacitor Substances 0.000 title claims abstract description 48
- 238000002360 preparation method Methods 0.000 title claims abstract description 14
- 238000010438 heat treatment Methods 0.000 claims abstract description 50
- 239000002253 acid Substances 0.000 claims abstract description 27
- -1 carboxylic acid ammonium salt Chemical class 0.000 claims abstract description 27
- 150000003863 ammonium salts Chemical class 0.000 claims abstract description 24
- SAOKZLXYCUGLFA-UHFFFAOYSA-N bis(2-ethylhexyl) adipate Chemical compound CCCCC(CC)COC(=O)CCCCC(=O)OCC(CC)CCCC SAOKZLXYCUGLFA-UHFFFAOYSA-N 0.000 claims abstract description 21
- 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 claims abstract description 9
- 239000003063 flame retardant Substances 0.000 claims abstract description 9
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 claims description 129
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 75
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims description 54
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 36
- 238000003756 stirring Methods 0.000 claims description 36
- 238000001816 cooling Methods 0.000 claims description 29
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 27
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims description 27
- STROTMSXXMEJJE-UHFFFAOYSA-N cyclopentanol;sodium Chemical compound [Na].OC1CCCC1 STROTMSXXMEJJE-UHFFFAOYSA-N 0.000 claims description 24
- 239000000126 substance Substances 0.000 claims description 23
- 239000002904 solvent Substances 0.000 claims description 19
- VPBZZPOGZPKYKX-UHFFFAOYSA-N 1,2-diethoxypropane Chemical compound CCOCC(C)OCC VPBZZPOGZPKYKX-UHFFFAOYSA-N 0.000 claims description 18
- 238000002156 mixing Methods 0.000 claims description 18
- 238000009423 ventilation Methods 0.000 claims description 18
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 18
- 238000006243 chemical reaction Methods 0.000 claims description 17
- UVECLJDRPFNRRQ-UHFFFAOYSA-N ethyl trifluoromethanesulfonate Chemical compound CCOS(=O)(=O)C(F)(F)F UVECLJDRPFNRRQ-UHFFFAOYSA-N 0.000 claims description 16
- 238000002390 rotary evaporation Methods 0.000 claims description 16
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims description 11
- BTJIUGUIPKRLHP-UHFFFAOYSA-N 4-nitrophenol Chemical compound OC1=CC=C([N+]([O-])=O)C=C1 BTJIUGUIPKRLHP-UHFFFAOYSA-N 0.000 claims description 9
- 150000001732 carboxylic acid derivatives Chemical class 0.000 claims description 9
- 239000007795 chemical reaction product Substances 0.000 claims description 9
- LXCYSACZTOKNNS-UHFFFAOYSA-N diethoxy(oxo)phosphanium Chemical group CCO[P+](=O)OCC LXCYSACZTOKNNS-UHFFFAOYSA-N 0.000 claims description 9
- 229920002401 polyacrylamide Polymers 0.000 claims description 9
- 238000010992 reflux Methods 0.000 claims description 9
- 230000001105 regulatory effect Effects 0.000 claims description 9
- 238000001291 vacuum drying Methods 0.000 claims description 9
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 6
- 239000006096 absorbing agent Substances 0.000 claims description 6
- 229910052739 hydrogen Inorganic materials 0.000 claims description 6
- 239000001257 hydrogen Substances 0.000 claims description 6
- 239000003960 organic solvent Substances 0.000 claims description 6
- 238000004519 manufacturing process Methods 0.000 claims description 4
- JKTYGPATCNUWKN-UHFFFAOYSA-N 4-nitrobenzyl alcohol Chemical compound OCC1=CC=C([N+]([O-])=O)C=C1 JKTYGPATCNUWKN-UHFFFAOYSA-N 0.000 claims description 2
- 239000002202 Polyethylene glycol Substances 0.000 claims description 2
- 239000004372 Polyvinyl alcohol Substances 0.000 claims description 2
- 229920001223 polyethylene glycol Polymers 0.000 claims description 2
- 229920002451 polyvinyl alcohol Polymers 0.000 claims description 2
- 238000010025 steaming Methods 0.000 claims description 2
- 239000000243 solution Substances 0.000 claims 10
- 239000008151 electrolyte solution Substances 0.000 claims 3
- KDWQLICBSFIDRM-UHFFFAOYSA-N 1,1,1-trifluoropropane Chemical compound CCC(F)(F)F KDWQLICBSFIDRM-UHFFFAOYSA-N 0.000 claims 1
- 230000007935 neutral effect Effects 0.000 claims 1
- 229910052760 oxygen Inorganic materials 0.000 abstract description 10
- 239000001301 oxygen Substances 0.000 abstract description 10
- 150000001335 aliphatic alkanes Chemical group 0.000 abstract description 4
- 125000001033 ether group Chemical group 0.000 abstract description 4
- 125000002843 carboxylic acid group Chemical group 0.000 abstract description 3
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical group [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 abstract description 2
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 abstract description 2
- 229910052731 fluorine Inorganic materials 0.000 abstract description 2
- 239000011737 fluorine Substances 0.000 abstract description 2
- 230000000052 comparative effect Effects 0.000 description 10
- 239000000498 cooling water Substances 0.000 description 7
- 230000007062 hydrolysis Effects 0.000 description 7
- 238000006460 hydrolysis reaction Methods 0.000 description 7
- PHTQWCKDNZKARW-UHFFFAOYSA-N isoamylol Chemical compound CC(C)CCO PHTQWCKDNZKARW-UHFFFAOYSA-N 0.000 description 4
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 2
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 229910052708 sodium Inorganic materials 0.000 description 2
- 239000011734 sodium Substances 0.000 description 2
- 230000009471 action Effects 0.000 description 1
- 238000007259 addition reaction Methods 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 229910052783 alkali metal Inorganic materials 0.000 description 1
- 125000000217 alkyl group Chemical group 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 1
- 230000002596 correlated effect Effects 0.000 description 1
- 230000000875 corresponding effect Effects 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 230000032050 esterification Effects 0.000 description 1
- 238000005886 esterification reaction Methods 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 238000000034 method Methods 0.000 description 1
- 238000006386 neutralization reaction Methods 0.000 description 1
- 125000004430 oxygen atom Chemical group O* 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 230000002035 prolonged effect Effects 0.000 description 1
- 125000006239 protecting group Chemical group 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 230000008439 repair process Effects 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
Landscapes
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention discloses an electrolyte for a long-life capacitor and a preparation method thereof; the invention prepares an electrolyte for a capacitor with long service life, wherein a branched chain polybasic carboxylic acid ammonium salt is synthesized as an electrolyte, adipic acid di (2-ethylhexyl) ester is taken as a basic carbon chain, an alkane group is grafted on the electrolyte, and the steric hindrance of the alkane group is utilized to protect the carboxylic acid group from being esterified at high temperature, so that the conductivity is prevented from being reduced, and the capacitor is prevented from heating and losing efficacy; meanwhile, in order to further improve the sparking voltage of the electrolyte and reduce the generation rate of oxygen anions, the invention introduces ether groups and fluorine elements into the branched polycarboxylic acid ammonium salt, and inhibits the generation of oxygen anions by means of higher potential so as to maintain the stability of the electrolyte. The electrolyte for the long-life capacitor, which is prepared by the invention, has long service life, stable conductive property, good flame retardant property and wide application space in the field of capacitor application.
Description
Technical Field
The invention relates to the technical field of electrolyte, in particular to electrolyte for a capacitor with long service life and a preparation method thereof.
Background
As one of the basic components of various electronic products, the capacitor has been increased in yield in recent years, but due to the development of the electronic technology field, the requirements for the working performance of the capacitor have also been increased. As an electrolyte determining the working performance of a capacitor, most of the electrolytes are not resistant to high temperature, have the electrical performance rapidly reduced along with the service time and have short usable lives, so that the working performance of the capacitor is greatly limited, and the manufacturing cost of related equipment is greatly increased, therefore, an electrolyte which can maintain the stable working performance for a long time and has long usable lives is needed to meet the market demands.
Disclosure of Invention
The invention aims to provide an electrolyte for a capacitor with long service life and a preparation method thereof, so as to solve the problems in the prior art.
In order to solve the technical problems, the invention provides the following technical scheme: an electrolyte for a long-life capacitor, comprising the following features: the electrolyte for the long-life capacitor comprises the following components in parts by weight: 52.5-65 parts of organic solvent, 16-22 parts of electrolyte, 0.1-0.3 part of hydrogen absorber, 1-10 parts of sparking voltage improver and 5-10 parts of flame retardant;
wherein the electrolyte is branched chain polybasic carboxylic acid ammonium salt.
Further, the organic solvent is any one or more of delta-butyrolactone and ethylene glycol; the hydrogen absorbing agent is one or more of p-nitrophenol and p-nitrobenzyl alcohol.
Further, the sparking voltage improver is any one or more of polyethylene glycol, polyvinyl alcohol and polyacrylamide; the flame retardant is diethyl phosphite.
A preparation method of electrolyte for long-life capacitor comprises the following steps:
s1, preparing branched chain polybasic carboxylic acid ammonium salt:
s11, dissolving sodium cyclopentanol in propylene glycol diethyl ether, adding adipic acid di (2-ethylhexyl) ester, fully stirring and mixing, heating to 60-80 ℃ in a water bath, reacting for 5-8h, and removing redundant solvent by rotary evaporation;
s12, adding a phosphoric acid solution, regulating the pH to 6-7, adding an N, N-dimethylformamide solution dissolved with ethyl triflate and sodium cyclopentanol, heating to 120-150 ℃ in a water bath, carrying out reflux reaction for 18-24, taking out and steaming a reaction product, and removing redundant solvent;
s13, adding the phosphoric acid solution again to adjust the pH value of the solution to 6-7, stirring for 3-5min under vigorous shaking, standing for 0.5-1h, and separating an upper oily substance;
s14, adding NaOH solution into the oily substance, heating to 60-80 ℃, preserving heat for 2-3 hours, cooling to room temperature, dropwise adding phosphoric acid solution to adjust pH to neutrality, adding ethyl acetate, stirring and mixing at a speed of 1000-1500rpm for 3-5 minutes, standing and extracting carboxylic acid in the solution, repeating for 3-5 times, introducing ammonia gas into the ethyl acetate solution for 18-24 hours, and performing vacuum drying after ventilation is finished to obtain branched-chain polycarboxylic acid ammonium salt;
s2, heating the organic solvent to 70-80 ℃, adding a sparking voltage improver, uniformly stirring, heating to 120-135 ℃, preserving heat for 0.5-1h, forcibly cooling to 80-90 ℃, adding electrolyte, continuously heating to 130-140 ℃, preserving heat for 1-2h, cooling to 60-80 ℃, adding a hydrogen absorber and a flame retardant, preserving heat for 0.5-1h, and cooling to room temperature to obtain the electrolyte for the long-life capacitor.
Most of the conventional capacitor electrolyte is linear polycarboxylic acid and ammonium salt thereof, and under the condition of long-time use, carboxyl groups at two ends of a linear polycarboxylic acid substance are gradually esterified due to no protecting group, so that carboxylate ion conduction cannot be continuously ionized, conductivity is reduced, and further the ESR value of the capacitor is increased, so that the capacitor generates serious heat, and the capacitor is invalid.
The invention takes adipic acid di (2-ethylhexyl) ester as a raw material to prepare the branched chain polybasic carboxylic acid ammonium salt electrolyte; the branched electrolyte has higher solubility in the electrolyte and can provide higher conductivity. According to the invention, firstly, adipic acid di (2-ethylhexyl) ester and alkali metal alkoxide are mixed for reaction, acid decomposition is carried out under the action of strong alkali, then acid is added for neutralization and alkalinity, then redundant solvent is removed, and then the adipic acid di (2-ethylhexyl) ester and ethyl triflate are mixed again for addition reaction, long-chain branches are grafted at alpha positions of adipic acid di (2-ethylhexyl) ester, and alkyl groups at alpha positions have larger steric hindrance effects, so that adjacent carboxylic acid groups can be effectively protected from esterification in a high-temperature environment.
In general, in the use process of the capacitor, the oxygen anion electron supply capability of the electrolyte is stronger, the repair effect on the oxide film of the capacitor is better, but the corresponding sparking voltage is lower, so in order to inhibit the oxygen anion generation rate of the electrolyte, the invention also adds ethyl triflate and sodium cyclopentanol, and at high temperature, the ethyl triflate and the sodium cyclopentanol can generate an ether reaction, and the branched chain polybasic carboxylic acid ammonium salt electrolyte prepared by the invention is introduced with an ether group which is a nonpolar group, wherein the oxygen atom potential is higher, and the oxygen anion generation can be blocked under the high temperature environment, so that the stability of the electrolyte is maintained, the damage of the oxygen anion on the oxide film of the capacitor is prevented, and the service life of the electrolyte is prolonged. Meanwhile, the ethyl triflate used in the invention also contains F element, has higher electronegativity, can also prevent oxygen anions from generating, can effectively improve the flame retardant property of the electrolyte and reduce the potential safety hazard.
Further, in the step S11, the molar ratio of sodium cyclopentanol, propylene glycol diethyl ether, di (2-ethylhexyl) adipate, ethyl triflate, and N, N-dimethylformamide is (1.6-2.3): (6-10): (0.5-1): (1-1.5): (10-15).
Further, the molar ratio of the sodium cyclopentanol in the step S11 to the sodium cyclopentanol in the step S12 is (1-1.5): (0.6-0.8).
Further, in step S14, the volume ratio of the oily substance to the NaOH solution is (1-1.2): 1, wherein the concentration of the NaOH solution is 35-45wt%.
Further, in step S14, the volume ratio of the oily substance to ethyl acetate is (1-1.2): (4-5).
Further, in the step S14, when ammonia gas is introduced, the ventilation rate of the ethyl acetate solution per liter is 0.2-0.4m < 3 >/min.
Compared with the prior art, the invention has the following beneficial effects: the invention prepares an electrolyte for a capacitor with long service life, wherein a branched chain polybasic carboxylic acid ammonium salt is synthesized as an electrolyte, adipic acid di (2-ethylhexyl) ester is taken as a basic carbon chain, an alkane group is grafted on the electrolyte, and the steric hindrance of the alkane group is utilized to protect the carboxylic acid group from being esterified at high temperature, so that the conductivity is prevented from being reduced, and the capacitor is prevented from heating and losing efficacy; meanwhile, in order to further improve the sparking voltage of the electrolyte and reduce the generation rate of oxygen anions, the invention introduces ether groups and fluorine elements into the branched polycarboxylic acid ammonium salt, and inhibits the generation of oxygen anions by means of higher potential so as to maintain the stability of the electrolyte. The electrolyte for the long-life capacitor, which is prepared by the invention, has long service life, stable conductive property, good flame retardant property and wide application space in the field of capacitor application.
Detailed Description
The following description of the technical solutions in the embodiments of the present invention will be clear and complete, and it is obvious that the described embodiments are only some embodiments of the present invention, but not all embodiments. All other embodiments, which can be made by those skilled in the art based on the embodiments of the invention without making any inventive effort, are intended to be within the scope of the invention.
Example 1.
A preparation method of electrolyte for long-life capacitor comprises the following steps:
s1, preparing branched chain polybasic carboxylic acid ammonium salt:
s11, 1 part of cyclopentanol sodium is dissolved in 6 parts of propylene glycol diethyl ether according to the mol parts, 0.5 part of adipic acid di (2-ethylhexyl) ester is added, and after full stirring and mixing, the temperature is raised to 60 ℃ in a water bath, the reaction is carried out for 5 hours, and the redundant solvent is removed by rotary evaporation;
s12, adding a phosphoric acid solution, regulating the pH to 7, dissolving 1 part of ethyl triflate and 0.6 part of cyclopentanol sodium in 10 parts of N, N-dimethylformamide to prepare an N, N-dimethylformamide solution, slowly dropwise adding the N, N-dimethylformamide solution into propylene glycol diethyl ether, heating the solution to 120 ℃ in a water bath, carrying out reflux reaction for 18 hours, taking out a reaction product, carrying out rotary evaporation treatment, and removing redundant solvent;
s13, adding the phosphoric acid solution again to adjust the pH value of the solution to 7, stirring for 5min under vigorous shaking, standing for 1h, and separating an upper oily substance;
s14, adding 1 part of NaOH solution with the concentration of 40wt% into one part of oily substance according to volume fraction, heating to 60 ℃, preserving heat for 2 hours for hydrolysis, cooling to room temperature, dropwise adding phosphoric acid solution to adjust pH to neutrality, adding 4 parts of ethyl acetate, stirring and mixing at the speed of 1000rpm for 3 minutes, standing and extracting carboxylic acid in the solution, repeating for 3 times, separating ethyl acetate, and introducing the ethyl acetate solution into the ethyl acetate solution with the ventilation rate of 0.2m per liter of the ethyl acetate solution 3 Introducing ammonia gas at the speed of/min for 18h, and vacuum drying after the ventilation is finished to obtain branched-chain polycarboxylic acid ammonium salt;
s2, according to parts by weight, heating 52.5 parts of ethylene glycol to 70 ℃, adding 1 part of polyacrylamide, uniformly stirring, heating to 120 ℃, preserving heat for 0.5h, then using cooling water to forcibly cool to 80 ℃, adding 16 parts of branched polycarboxylic acid ammonium salt, continuously heating to 130 ℃, preserving heat for 1h, cooling to 60 ℃, adding 0.1 part of p-nitrophenol and 5 parts of diethyl phosphite, preserving heat for 0.5h, and cooling to room temperature to obtain the long-life electrolyte for the capacitor.
Example 2.
In this example, the amount of di (2-ethylhexyl) adipate added in step S11 was increased as compared to example 1;
a preparation method of electrolyte for long-life capacitor comprises the following steps:
s1, preparing branched chain polybasic carboxylic acid ammonium salt:
s11, 1 part of cyclopentanol sodium is dissolved in 6 parts of propylene glycol diethyl ether according to the mol parts, 0.8 part of adipic acid di (2-ethylhexyl) ester is added, and after full stirring and mixing, the temperature is raised to 60 ℃ in a water bath, the reaction is carried out for 5 hours, and the redundant solvent is removed by rotary evaporation;
s12, adding a phosphoric acid solution, regulating the pH to 7, dissolving 1 part of ethyl triflate and 0.6 part of cyclopentanol sodium in 10 parts of N, N-dimethylformamide to prepare an N, N-dimethylformamide solution, slowly dropwise adding the N, N-dimethylformamide solution into propylene glycol diethyl ether, heating the solution to 120 ℃ in a water bath, carrying out reflux reaction for 18 hours, taking out a reaction product, carrying out rotary evaporation treatment, and removing redundant solvent;
s13, adding the phosphoric acid solution again to adjust the pH value of the solution to 7, stirring for 5min under vigorous shaking, standing for 1h, and separating an upper oily substance;
s14, adding 1 part of NaOH solution with the concentration of 40wt% into one part of oily substance according to volume fraction, heating to 60 ℃, preserving heat for 2 hours for hydrolysis, cooling to room temperature, dropwise adding phosphoric acid solution to adjust pH to neutrality, adding 4 parts of ethyl acetate, stirring and mixing at the speed of 1000rpm for 3 minutes, standing and extracting carboxylic acid in the solution, repeating for 3 times, separating ethyl acetate, and introducing the ethyl acetate solution into the ethyl acetate solution with the ventilation rate of 0.2m per liter of the ethyl acetate solution 3 Introducing ammonia gas at the speed of/min for 18h, and vacuum drying after the ventilation is finished to obtain branched-chain polycarboxylic acid ammonium salt;
s2, according to parts by weight, heating 52.5 parts of ethylene glycol to 70 ℃, adding 1 part of polyacrylamide, uniformly stirring, heating to 120 ℃, preserving heat for 0.5h, then using cooling water to forcibly cool to 80 ℃, adding 16 parts of branched polycarboxylic acid ammonium salt, continuously heating to 130 ℃, preserving heat for 1h, cooling to 60 ℃, adding 0.1 part of p-nitrophenol and 5 parts of diethyl phosphite, preserving heat for 0.5h, and cooling to room temperature to obtain the long-life electrolyte for the capacitor.
Example 3.
The present comparative example further increases the addition amount of di (2-ethylhexyl) adipate in step S11 compared to example 1;
a preparation method of electrolyte for long-life capacitor comprises the following steps:
s1, preparing branched chain polybasic carboxylic acid ammonium salt:
s11, 1 part of cyclopentanol sodium is dissolved in 6 parts of propylene glycol diethyl ether according to the mol parts, 1 part of adipic acid di (2-ethylhexyl) ester is added, and after full stirring and mixing, the temperature is raised to 60 ℃ in a water bath, the reaction is carried out for 5 hours, and the redundant solvent is removed by rotary evaporation;
s12, adding a phosphoric acid solution, regulating the pH to 7, dissolving 1 part of ethyl triflate and 0.6 part of cyclopentanol sodium in 10 parts of N, N-dimethylformamide to prepare an N, N-dimethylformamide solution, slowly dropwise adding the N, N-dimethylformamide solution into propylene glycol diethyl ether, heating the solution to 120 ℃ in a water bath, carrying out reflux reaction for 18 hours, taking out a reaction product, carrying out rotary evaporation treatment, and removing redundant solvent;
s13, adding the phosphoric acid solution again to adjust the pH value of the solution to 7, stirring for 5min under vigorous shaking, standing for 1h, and separating an upper oily substance;
s14, adding 1 part of NaOH solution with the concentration of 40wt% into one part of oily substance according to volume fraction, heating to 60 ℃, preserving heat for 2 hours for hydrolysis, cooling to room temperature, dropwise adding phosphoric acid solution to adjust pH to neutrality, adding 4 parts of ethyl acetate, stirring and mixing at the speed of 1000rpm for 3 minutes, standing and extracting carboxylic acid in the solution, repeating for 3 times, separating ethyl acetate, and introducing the ethyl acetate solution into the ethyl acetate solution with the ventilation rate of 0.2m per liter of the ethyl acetate solution 3 Introducing ammonia gas at the speed of/min for 18h, and vacuum drying after the ventilation is finished to obtain branched-chain polycarboxylic acid ammonium salt;
s2, according to parts by weight, heating 52.5 parts of ethylene glycol to 70 ℃, adding 1 part of polyacrylamide, uniformly stirring, heating to 120 ℃, preserving heat for 0.5h, then using cooling water to forcibly cool to 80 ℃, adding 16 parts of branched polycarboxylic acid ammonium salt, continuously heating to 130 ℃, preserving heat for 1h, cooling to 60 ℃, adding 0.1 part of p-nitrophenol and 5 parts of diethyl phosphite, preserving heat for 0.5h, and cooling to room temperature to obtain the long-life electrolyte for the capacitor.
Example 4.
Compared with example 1, the present comparative example increases the amount of the branched polycarboxylic acid ammonium salt added in step S2;
a preparation method of electrolyte for long-life capacitor comprises the following steps:
s1, preparing branched chain polybasic carboxylic acid ammonium salt:
s11, 1 part of cyclopentanol sodium is dissolved in 6 parts of propylene glycol diethyl ether according to the mol parts, 0.5 part of adipic acid di (2-ethylhexyl) ester is added, and after full stirring and mixing, the temperature is raised to 60 ℃ in a water bath, the reaction is carried out for 5 hours, and the redundant solvent is removed by rotary evaporation;
s12, adding a phosphoric acid solution, regulating the pH to 7, dissolving 1 part of ethyl triflate and 0.6 part of cyclopentanol sodium in 10 parts of N, N-dimethylformamide to prepare an N, N-dimethylformamide solution, slowly dropwise adding the N, N-dimethylformamide solution into propylene glycol diethyl ether, heating the solution to 120 ℃ in a water bath, carrying out reflux reaction for 18 hours, taking out a reaction product, carrying out rotary evaporation treatment, and removing redundant solvent;
s13, adding the phosphoric acid solution again to adjust the pH value of the solution to 7, stirring for 5min under vigorous shaking, standing for 1h, and separating an upper oily substance;
s14, adding 1 part of NaOH solution with the concentration of 40wt% into one part of oily substance according to volume fraction, heating to 60 ℃, preserving heat for 2 hours for hydrolysis, cooling to room temperature, dropwise adding phosphoric acid solution to adjust pH to neutrality, adding 4 parts of ethyl acetate, stirring and mixing at the speed of 1000rpm for 3 minutes, standing and extracting carboxylic acid in the solution, repeating for 3 times, separating ethyl acetate, and introducing the ethyl acetate solution into the ethyl acetate solution with the ventilation rate of 0.2m per liter of the ethyl acetate solution 3 Introducing ammonia gas at the speed of/min for 18h, and vacuum drying after the ventilation is finished to obtain branched-chain polycarboxylic acid ammonium salt;
s2, according to parts by weight, heating 52.5 parts of ethylene glycol to 70 ℃, adding 1 part of polyacrylamide, uniformly stirring, heating to 120 ℃, preserving heat for 0.5h, then using cooling water to forcibly cool to 80 ℃, adding 22 parts of branched polycarboxylic acid ammonium salt, continuously heating to 130 ℃, preserving heat for 1h, cooling to 60 ℃, adding 0.1 part of p-nitrophenol and 5 parts of diethyl phosphite, preserving heat for 0.5h, and cooling to room temperature to obtain the long-life electrolyte for the capacitor.
Example 5.
A preparation method of electrolyte for long-life capacitor comprises the following steps:
s1, preparing branched chain polybasic carboxylic acid ammonium salt:
s11, dissolving 1.5 parts of sodium cyclopentanol in 10 parts of propylene glycol diethyl ether, adding 1 part of adipic acid di (2-ethylhexyl) ester, fully stirring and mixing, heating to 80 ℃ in a water bath, reacting for 8 hours, and removing redundant solvent by rotary evaporation;
s12, adding a phosphoric acid solution, regulating the pH to 7, dissolving 1.5 parts of ethyl triflate and 0.8 part of cyclopentanol sodium in 15 parts of N, N-dimethylformamide to prepare an N, N-dimethylformamide solution, slowly dropwise adding the N, N-dimethylformamide solution into propylene glycol diethyl ether, heating the solution to 150 ℃ in a water bath, carrying out reflux reaction for 18 hours, taking out a reaction product, carrying out rotary evaporation treatment, and removing redundant solvent;
s13, adding the phosphoric acid solution again to adjust the pH value of the solution to 7, stirring for 5min under vigorous shaking, standing for 1h, and separating an upper oily substance;
s14, adding 1 part of NaOH solution with the concentration of 40wt% into one part of oily substance according to volume fraction, heating to 80 ℃, preserving heat for 3 hours for hydrolysis, cooling to room temperature, dropwise adding phosphoric acid solution to adjust pH to neutrality, adding 5 parts of ethyl acetate, stirring and mixing at the speed of 1000rpm for 3 minutes, standing and extracting carboxylic acid in the solution, repeating for 5 times, separating ethyl acetate, and introducing the ethyl acetate solution into the ethyl acetate solution with the ventilation rate of 0.4m per liter of the ethyl acetate solution 3 Introducing ammonia gas at the speed of/min for 24 hours, and vacuum drying after the ventilation is finished to obtain branched-chain polycarboxylic acid ammonium salt;
s2, according to parts by weight, heating 65 parts of ethylene glycol to 80 ℃, adding 10 parts of polyacrylamide, uniformly stirring, heating to 135 ℃, preserving heat for 0.5h, then using cooling water to forcibly cool to 90 ℃, adding 22 parts of branched chain polycarboxylic acid ammonium salt, continuously heating to 140 ℃, preserving heat for 1h, cooling to 80 ℃, adding 0.3 part of p-nitrophenol and 10 parts of diethyl phosphite, preserving heat for 0.5h, and cooling to room temperature to obtain the long-life electrolyte for the capacitor.
Comparative example 1.
Compared with example 1, this comparative example increases the amount of di (2-ethylhexyl) adipate added in step S11;
a preparation method of electrolyte for long-life capacitor comprises the following steps:
s1, preparing branched chain polybasic carboxylic acid ammonium salt:
s11, 1 part of cyclopentanol sodium is dissolved in 6 parts of propylene glycol diethyl ether according to the mol parts, 5 parts of adipic acid di (2-ethylhexyl) ester is added, and after full stirring and mixing, the temperature is raised to 60 ℃ in a water bath, the reaction is carried out for 5 hours, and the redundant solvent is removed by rotary evaporation;
s12, adding a phosphoric acid solution, regulating the pH to 7, dissolving 1 part of ethyl triflate and 0.6 part of cyclopentanol sodium in 10 parts of N, N-dimethylformamide to prepare an N, N-dimethylformamide solution, slowly dropwise adding the N, N-dimethylformamide solution into propylene glycol diethyl ether, heating the solution to 120 ℃ in a water bath, carrying out reflux reaction for 18 hours, taking out a reaction product, carrying out rotary evaporation treatment, and removing redundant solvent;
s13, adding the phosphoric acid solution again to adjust the pH value of the solution to 7, stirring for 5min under vigorous shaking, standing for 1h, and separating an upper oily substance;
s14, adding 1 part of NaOH solution with the concentration of 40wt% into one part of oily substance according to volume fraction, heating to 60 ℃, preserving heat for 2 hours for hydrolysis, cooling to room temperature, dropwise adding phosphoric acid solution to adjust pH to neutrality, adding 4 parts of ethyl acetate, stirring and mixing at the speed of 1000rpm for 3 minutes, standing and extracting carboxylic acid in the solution, repeating for 3 times, separating ethyl acetate, and introducing the ethyl acetate solution into the ethyl acetate solution with the ventilation rate of 0.2m per liter of the ethyl acetate solution 3 Introducing ammonia gas at the speed of/min for 18h, and vacuum drying after the ventilation is finished to obtain branched-chain polycarboxylic acid ammonium salt;
s2, according to parts by weight, heating 52.5 parts of ethylene glycol to 70 ℃, adding 1 part of polyacrylamide, uniformly stirring, heating to 120 ℃, preserving heat for 0.5h, then using cooling water to forcibly cool to 80 ℃, adding 16 parts of branched polycarboxylic acid ammonium salt, continuously heating to 130 ℃, preserving heat for 1h, cooling to 60 ℃, adding 0.1 part of p-nitrophenol and 5 parts of diethyl phosphite, preserving heat for 0.5h, and cooling to room temperature to obtain the long-life electrolyte for the capacitor.
Comparative example 2.
The comparative example increased the amount of ethyl triflate added compared to example 1;
a preparation method of electrolyte for long-life capacitor comprises the following steps:
s1, preparing branched chain polybasic carboxylic acid ammonium salt:
s11, 1 part of sodium isoamyl alcohol is dissolved in 6 parts of propylene glycol diethyl ether according to the mol parts, 0.5 part of adipic acid di (2-ethylhexyl) ester is added, and after full stirring and mixing, the temperature is raised to 60 ℃ in a water bath, the reaction is carried out for 5 hours, and the redundant solvent is removed by rotary evaporation;
s12, adding a phosphoric acid solution, regulating the pH to 7, dissolving 3 parts of ethyl triflate and 0.6 part of sodium isoamyl alcohol in 10 parts of N, N-dimethylformamide to prepare an N, N-dimethylformamide solution, slowly dropwise adding the N, N-dimethylformamide solution into propylene glycol diethyl ether, heating the solution to 120 ℃ in a water bath, carrying out reflux reaction for 18 hours, taking out a reaction product, carrying out rotary evaporation treatment, and removing redundant solvent;
s13, adding the phosphoric acid solution again to adjust the pH value of the solution to 7, stirring for 5min under vigorous shaking, standing for 1h, and separating an upper oily substance;
s14, adding 1 part of NaOH solution with the concentration of 40wt% into one part of oily substance according to volume fraction, heating to 60 ℃, preserving heat for 2 hours for hydrolysis, cooling to room temperature, dropwise adding phosphoric acid solution to adjust pH to neutrality, adding 4 parts of ethyl acetate, stirring and mixing at the speed of 1000rpm for 3 minutes, standing and extracting carboxylic acid in the solution, repeating for 3 times, separating ethyl acetate, and introducing the ethyl acetate solution into the ethyl acetate solution with the ventilation rate of 0.2m per liter of the ethyl acetate solution 3 Introducing ammonia gas at the speed of/min for 18h, and vacuum drying after the ventilation is finished to obtain branched-chain polycarboxylic acid ammonium salt;
s2, according to parts by weight, heating 52.5 parts of ethylene glycol to 70 ℃, adding 1 part of polyacrylamide, uniformly stirring, heating to 120 ℃, preserving heat for 0.5h, then using cooling water to forcibly cool to 80 ℃, adding 16 parts of branched polycarboxylic acid ammonium salt, continuously heating to 130 ℃, preserving heat for 1h, cooling to 60 ℃, adding 0.1 part of p-nitrophenol and 5 parts of diethyl phosphite, preserving heat for 0.5h, and cooling to room temperature to obtain the long-life electrolyte for the capacitor.
And (3) detection: electrolyte sparking voltage was measured using an electrolyte sparking tester, initial conductivity of the electrolyte was measured using a conductivity tester and conductivity at 130 ℃ for 1000 hours, the test results are shown in the following table:
| project | Sparking voltage (V) | Conductivity (ms/cm) | 1000h conductivity (ms/cm) |
| Example 1 | 510 | 2.4 | 1.9 |
| Example 2 | 510 | 2.2 | 1.6 |
| Example 3 | 520 | 2.1 | 1.5 |
| Example 4 | 530 | 2.5 | 2.0 |
| Example 5 | 530 | 2.3 | 1.9 |
| Comparative example 1 | 490 | 1.8 | 1.4 |
| Comparative example 2 | 540 | 2.4 | 1.9 |
As can be seen from the comparison of examples 1 to 5 with comparative example 1, the initial conductivity of the electrolyte prepared by the present invention is positively correlated with the addition amount of the branched polycarboxylic acid ammonium salt, but after a period of time at high temperature, it was found that the lower the conductivity, the more branches in the branched polycarboxylic acid ammonium salt, the better the stability thereof, with the increase of the branched substitution addition rate of di (2-ethylhexyl) adipate in the branched polycarboxylic acid ammonium salt; as can be seen from the comparison of the example 1 and the comparative example 2, the contents of the ether group and the f element in the branched polycarboxylic acid ammonium salt are increased along with the increase of the addition amount of the ethyl triflate, so that the generation rate of oxygen anions is inhibited, and the sparking voltage of the electrolyte is effectively improved.
Finally, it should be noted that: the foregoing description is only a preferred embodiment of the present invention, and the present invention is not limited thereto, but it is to be understood that modifications and equivalents of some of the technical features described in the foregoing embodiments may be made by those skilled in the art, although the present invention has been described in detail with reference to the foregoing embodiments. Any modification, equivalent replacement, improvement, etc. made within the spirit and principle of the present invention should be included in the protection scope of the present invention.
Claims (4)
1. The preparation method of the electrolyte for the long-life capacitor is characterized by comprising the following steps of:
s1, preparing branched chain polybasic carboxylic acid ammonium salt:
s11, dissolving sodium cyclopentanol in propylene glycol diethyl ether, adding adipic acid di (2-ethylhexyl) ester, fully stirring and mixing, heating to 60-80 ℃ in a water bath, reacting for 5-8h, and removing redundant solvent by rotary evaporation;
s12, adding a phosphoric acid solution, regulating the pH to 6-7, adding an N, N-dimethylformamide solution dissolved with ethyl triflate and sodium cyclopentanol, heating to 120-150 ℃ in a water bath, carrying out reflux reaction for 18-24, taking out and steaming a reaction product, and removing redundant solvent;
s13, adding the phosphoric acid solution again to adjust the pH value of the solution to 6-7, stirring for 3-5min under vigorous shaking, standing for 0.5-1h, and separating an upper oily substance;
s14, adding 35-45wt% NaOH solution into the oily substance, wherein the volume ratio of the oily substance to the NaOH solution is (1-1.2): 1, heating to 60-80 ℃, preserving heat for 2-3 hours, cooling to room temperature, dropwise adding a phosphoric acid solution to adjust the pH to be neutral, and adding ethyl acetate, wherein the volume ratio of oily substances to ethyl acetate is (1-1.2): (4-5), stirring and mixing at 1000-1500rpm for 3-5min, standing to extract carboxylic acid in the solution, repeating for 3-5 times, and introducing ammonia gas into ethyl acetate solution for 18-24 hr, wherein the ventilation rate of ammonia gas in each liter of ethyl acetate solution is 0.2-0.4m 3 Carrying out vacuum drying after ventilation is finished to obtain branched-chain polycarboxylic acid ammonium salt;
wherein in the step S1, the molar ratio of the sodium cyclopentanol, the propylene glycol diethyl ether, the adipic acid di (2-ethylhexyl) ester, the trifluoro ethyl methane sulfonate and the N, N-dimethylformamide is (1.6-2.3): (6-10): (0.5-1): (1-1.5): (10-15);
the molar ratio of the sodium cyclopentanol in the step S11 to the sodium cyclopentanol in the step S12 is (1-1.5): (0.6-0.8);
s2, heating the organic solvent to 70-80 ℃, adding a sparking voltage improver, uniformly stirring, heating to 120-135 ℃, preserving heat for 0.5-1h, cooling to 80-90 ℃, adding electrolyte, continuously heating to 130-140 ℃, preserving heat for 1-2h, cooling to 60-80 ℃, adding a hydrogen absorber and a flame retardant, preserving heat for 0.5-1h, and cooling to room temperature to obtain the electrolyte for the long-life capacitor.
2. The method for producing an electrolytic solution for capacitors having a long life according to claim 1, characterized in that: the electrolyte for the long-life capacitor comprises the following components in parts by weight: 52.5-65 parts of organic solvent, 16-22 parts of electrolyte, 0.1-0.3 part of hydrogen absorber, 1-10 parts of sparking voltage improver and 5-10 parts of flame retardant;
wherein the electrolyte is branched chain polybasic carboxylic acid ammonium salt.
3. The method for producing an electrolytic solution for capacitors having a long life according to claim 1, characterized in that: the organic solvent is any one or more of delta-butyrolactone and ethylene glycol; the hydrogen absorbing agent is one or more of p-nitrophenol and p-nitrobenzyl alcohol.
4. The method for producing an electrolytic solution for capacitors having a long life according to claim 1, characterized in that: the sparking voltage improver is one or more of polyethylene glycol, polyvinyl alcohol and polyacrylamide; the flame retardant is diethyl phosphite.
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Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH11233376A (en) * | 1998-02-12 | 1999-08-27 | Matsushita Electric Ind Co Ltd | Electrolyte for driving electrolytic capacitor and electrolytic capacitor using the same |
| CN101206955A (en) * | 2007-12-14 | 2008-06-25 | 广州市二轻工业科学技术研究所 | Branched chain polybasic carboxylic acid ammonium salt mixture as well as preparation method and application thereof |
| CN108538590A (en) * | 2018-04-09 | 2018-09-14 | 苏州松控电子科技有限公司 | A kind of electrolyte for aluminum electrolytic capacitor and preparation method thereof |
| CN114093674A (en) * | 2021-11-01 | 2022-02-25 | 赣州富之庆电子科技有限公司 | Electrolyte of ultra-high temperature long-life aluminum electrolytic capacitor and preparation method thereof |
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Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH11233376A (en) * | 1998-02-12 | 1999-08-27 | Matsushita Electric Ind Co Ltd | Electrolyte for driving electrolytic capacitor and electrolytic capacitor using the same |
| CN101206955A (en) * | 2007-12-14 | 2008-06-25 | 广州市二轻工业科学技术研究所 | Branched chain polybasic carboxylic acid ammonium salt mixture as well as preparation method and application thereof |
| CN108538590A (en) * | 2018-04-09 | 2018-09-14 | 苏州松控电子科技有限公司 | A kind of electrolyte for aluminum electrolytic capacitor and preparation method thereof |
| CN114093674A (en) * | 2021-11-01 | 2022-02-25 | 赣州富之庆电子科技有限公司 | Electrolyte of ultra-high temperature long-life aluminum electrolytic capacitor and preparation method thereof |
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