CN112837944B - High-voltage-resistant capacitor electrolyte and capacitor - Google Patents
High-voltage-resistant capacitor electrolyte and capacitor Download PDFInfo
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- CN112837944B CN112837944B CN202110012145.3A CN202110012145A CN112837944B CN 112837944 B CN112837944 B CN 112837944B CN 202110012145 A CN202110012145 A CN 202110012145A CN 112837944 B CN112837944 B CN 112837944B
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- 239000003990 capacitor Substances 0.000 title claims abstract description 38
- 239000003792 electrolyte Substances 0.000 title claims abstract description 35
- NUJOXMJBOLGQSY-UHFFFAOYSA-N manganese dioxide Chemical compound O=[Mn]=O NUJOXMJBOLGQSY-UHFFFAOYSA-N 0.000 claims abstract description 67
- GOPYZMJAIPBUGX-UHFFFAOYSA-N [O-2].[O-2].[Mn+4] Chemical class [O-2].[O-2].[Mn+4] GOPYZMJAIPBUGX-UHFFFAOYSA-N 0.000 claims abstract description 36
- 239000000654 additive Substances 0.000 claims abstract description 26
- 230000000996 additive effect Effects 0.000 claims abstract description 26
- DBMJMQXJHONAFJ-UHFFFAOYSA-M Sodium laurylsulphate Chemical compound [Na+].CCCCCCCCCCCCOS([O-])(=O)=O DBMJMQXJHONAFJ-UHFFFAOYSA-M 0.000 claims abstract description 24
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 24
- OFOBLEOULBTSOW-UHFFFAOYSA-N Propanedioic acid Natural products OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 claims abstract description 20
- VZCYOOQTPOCHFL-UPHRSURJSA-N maleic acid Chemical compound OC(=O)\C=C/C(O)=O VZCYOOQTPOCHFL-UPHRSURJSA-N 0.000 claims abstract description 20
- 239000011976 maleic acid Substances 0.000 claims abstract description 20
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 claims abstract description 20
- 239000002904 solvent Substances 0.000 claims abstract description 17
- 229940071125 manganese acetate Drugs 0.000 claims abstract description 10
- UOGMEBQRZBEZQT-UHFFFAOYSA-L manganese(2+);diacetate Chemical compound [Mn+2].CC([O-])=O.CC([O-])=O UOGMEBQRZBEZQT-UHFFFAOYSA-L 0.000 claims abstract description 10
- 239000012286 potassium permanganate Substances 0.000 claims abstract description 10
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 45
- 239000002994 raw material Substances 0.000 claims description 27
- BDJRBEYXGGNYIS-UHFFFAOYSA-N nonanedioic acid Chemical compound OC(=O)CCCCCCCC(O)=O BDJRBEYXGGNYIS-UHFFFAOYSA-N 0.000 claims description 26
- CXMXRPHRNRROMY-UHFFFAOYSA-N sebacic acid Chemical compound OC(=O)CCCCCCCCC(O)=O CXMXRPHRNRROMY-UHFFFAOYSA-N 0.000 claims description 26
- 239000000203 mixture Substances 0.000 claims description 25
- YEJRWHAVMIAJKC-UHFFFAOYSA-N 4-Butyrolactone Chemical compound O=C1CCCO1 YEJRWHAVMIAJKC-UHFFFAOYSA-N 0.000 claims description 14
- WPYMKLBDIGXBTP-UHFFFAOYSA-N benzoic acid Chemical compound OC(=O)C1=CC=CC=C1 WPYMKLBDIGXBTP-UHFFFAOYSA-N 0.000 claims description 14
- 238000003756 stirring Methods 0.000 claims description 14
- FBPFZTCFMRRESA-KVTDHHQDSA-N D-Mannitol Chemical compound OC[C@@H](O)[C@@H](O)[C@H](O)[C@H](O)CO FBPFZTCFMRRESA-KVTDHHQDSA-N 0.000 claims description 12
- 229930195725 Mannitol Natural products 0.000 claims description 12
- 235000010355 mannitol Nutrition 0.000 claims description 12
- 239000000594 mannitol Substances 0.000 claims description 12
- 230000003213 activating effect Effects 0.000 claims description 11
- 238000002360 preparation method Methods 0.000 claims description 10
- RGHNJXZEOKUKBD-UHFFFAOYSA-N D-gluconic acid Natural products OCC(O)C(O)C(O)C(O)C(O)=O RGHNJXZEOKUKBD-UHFFFAOYSA-N 0.000 claims description 8
- RGHNJXZEOKUKBD-SQOUGZDYSA-N Gluconic acid Natural products OC[C@@H](O)[C@@H](O)[C@H](O)[C@@H](O)C(O)=O RGHNJXZEOKUKBD-SQOUGZDYSA-N 0.000 claims description 8
- OTRAYOBSWCVTIN-UHFFFAOYSA-N OB(O)O.OB(O)O.OB(O)O.OB(O)O.OB(O)O.N.N.N.N.N.N.N.N.N.N.N.N.N.N.N Chemical compound OB(O)O.OB(O)O.OB(O)O.OB(O)O.OB(O)O.N.N.N.N.N.N.N.N.N.N.N.N.N.N.N OTRAYOBSWCVTIN-UHFFFAOYSA-N 0.000 claims description 8
- 239000000174 gluconic acid Substances 0.000 claims description 8
- 235000012208 gluconic acid Nutrition 0.000 claims description 8
- 239000005711 Benzoic acid Substances 0.000 claims description 7
- GRKXSKURFIUBAK-UHFFFAOYSA-N OB(O)O.OB(O)O.OB(O)O.OB(O)O.OB(O)O.OB(O)O.OB(O)O.OB(O)O.OB(O)O.OB(O)O.OB(O)O.OB(O)O.N.N.N.N.N.N.N.N.N.N.N.N.N.N.N.N.N.N.N.N.N.N.N.N.N.N.N.N.N.N.N.N.N.N.N.N Chemical compound OB(O)O.OB(O)O.OB(O)O.OB(O)O.OB(O)O.OB(O)O.OB(O)O.OB(O)O.OB(O)O.OB(O)O.OB(O)O.OB(O)O.N.N.N.N.N.N.N.N.N.N.N.N.N.N.N.N.N.N.N.N.N.N.N.N.N.N.N.N.N.N.N.N.N.N.N.N GRKXSKURFIUBAK-UHFFFAOYSA-N 0.000 claims description 7
- 239000002202 Polyethylene glycol Substances 0.000 claims description 7
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 7
- 235000010233 benzoic acid Nutrition 0.000 claims description 7
- 238000001354 calcination Methods 0.000 claims description 7
- 238000006356 dehydrogenation reaction Methods 0.000 claims description 7
- 238000001035 drying Methods 0.000 claims description 7
- 238000001914 filtration Methods 0.000 claims description 7
- 238000000227 grinding Methods 0.000 claims description 7
- 239000004570 mortar (masonry) Substances 0.000 claims description 7
- 229920001223 polyethylene glycol Polymers 0.000 claims description 7
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 7
- GVGUFUZHNYFZLC-UHFFFAOYSA-N dodecyl benzenesulfonate;sodium Chemical compound [Na].CCCCCCCCCCCCOS(=O)(=O)C1=CC=CC=C1 GVGUFUZHNYFZLC-UHFFFAOYSA-N 0.000 claims description 6
- 229940080264 sodium dodecylbenzenesulfonate Drugs 0.000 claims description 6
- BTJIUGUIPKRLHP-UHFFFAOYSA-N 4-nitrophenol Chemical group OC1=CC=C([N+]([O-])=O)C=C1 BTJIUGUIPKRLHP-UHFFFAOYSA-N 0.000 claims description 5
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 5
- 229910017604 nitric acid Inorganic materials 0.000 claims description 5
- QAOWNCQODCNURD-UHFFFAOYSA-N sulfuric acid Substances OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 5
- 239000012190 activator Substances 0.000 claims 1
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 abstract description 6
- 239000010407 anodic oxide Substances 0.000 abstract description 6
- 239000000693 micelle Substances 0.000 abstract description 6
- 230000000694 effects Effects 0.000 abstract description 4
- 239000001569 carbon dioxide Substances 0.000 abstract description 3
- 229910002092 carbon dioxide Inorganic materials 0.000 abstract description 3
- 230000008439 repair process Effects 0.000 abstract description 3
- 238000005054 agglomeration Methods 0.000 abstract description 2
- 230000002776 aggregation Effects 0.000 abstract description 2
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 abstract 1
- 239000001257 hydrogen Substances 0.000 abstract 1
- 229910052739 hydrogen Inorganic materials 0.000 abstract 1
- -1 solute Substances 0.000 abstract 1
- 230000000052 comparative effect Effects 0.000 description 43
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 description 24
- 235000019333 sodium laurylsulphate Nutrition 0.000 description 20
- FEWJPZIEWOKRBE-UHFFFAOYSA-N Tartaric acid Natural products [H+].[H+].[O-]C(=O)C(O)C(O)C([O-])=O FEWJPZIEWOKRBE-UHFFFAOYSA-N 0.000 description 5
- 239000011975 tartaric acid Substances 0.000 description 5
- 235000002906 tartaric acid Nutrition 0.000 description 5
- 229910052782 aluminium Inorganic materials 0.000 description 4
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 4
- 230000015572 biosynthetic process Effects 0.000 description 4
- 239000011888 foil Substances 0.000 description 4
- 230000005684 electric field Effects 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- FEWJPZIEWOKRBE-JCYAYHJZSA-N Dextrotartaric acid Chemical compound OC(=O)[C@H](O)[C@@H](O)C(O)=O FEWJPZIEWOKRBE-JCYAYHJZSA-N 0.000 description 2
- 150000001991 dicarboxylic acids Chemical class 0.000 description 2
- 239000006185 dispersion Substances 0.000 description 2
- 238000002474 experimental method Methods 0.000 description 2
- 230000001965 increasing effect Effects 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 230000002195 synergetic effect Effects 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 239000007772 electrode material Substances 0.000 description 1
- 230000003028 elevating effect Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 239000010410 layer Substances 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 238000000034 method Methods 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- DVEKCXOJTLDBFE-UHFFFAOYSA-N n-dodecyl-n,n-dimethylglycinate Chemical compound CCCCCCCCCCCC[N+](C)(C)CC([O-])=O DVEKCXOJTLDBFE-UHFFFAOYSA-N 0.000 description 1
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 239000007774 positive electrode material Substances 0.000 description 1
- 239000011241 protective layer Substances 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- 229910000314 transition metal oxide Inorganic materials 0.000 description 1
Classifications
-
- 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
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
- H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
- H01G11/54—Electrolytes
- H01G11/58—Liquid electrolytes
- H01G11/64—Liquid electrolytes characterised by additives
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/13—Energy storage using capacitors
Landscapes
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- Engineering & Computer Science (AREA)
- Power Engineering (AREA)
- Microelectronics & Electronic Packaging (AREA)
- Inorganic Compounds Of Heavy Metals (AREA)
- Battery Electrode And Active Subsutance (AREA)
Abstract
The invention discloses a high-voltage-resistant capacitor electrolyte and a capacitor, wherein the electrolyte comprises the following components: solvent, solute, additive and hydrogen eliminating agent. The capacitor electrolyte has extremely high sparking voltage, and the highest sparking voltage reaches 692V; the modified manganese dioxide, the maleic acid and the sodium dodecyl sulfate in the additive are added to obviously improve the sparking voltage, and manganese dioxide is synthesized by adopting manganese acetate and potassium permanganate and then subjected to subsequent treatment, so that the surface of the manganese dioxide can be activated, the surface distribution of carbon dioxide is more uniform, and the agglomeration of the manganese dioxide is prevented, thereby further improving the sparking voltage; the addition of the maleic acid can quickly repair the damage of the dielectric film and eliminate the edge effect, thereby improving the sparking voltage; when the sodium dodecyl sulfate is added into the system, the sodium dodecyl sulfate can form a small amount of micelles, and the micelles can adsorb the surface of the anodic oxide film, so that the sparking voltage is improved.
Description
Technical Field
The invention relates to the technical field of capacitors, in particular to a high-voltage-resistant capacitor electrolyte and a capacitor.
Background
With the rapid development of the electronic industry, the application of the aluminum electrolytic capacitor is wider, and the performance requirement is higher and higher. The formation foil for the aluminum electrolytic capacitor is an electronic main material of basic component products in the electronic information industry, and the quality of the formation foil directly influences the performance of the capacitor. The formed foil is a product which is formed by expanding the surface area of a special high-purity aluminum foil after electrochemical or chemical corrosion, putting the corroded anode into a certain solution, and forming a layer of oxide film (aluminum oxide) on the surface of the anode by adopting multi-level voltage energization. When the aluminum electrolytic capacitor is used, if the flashover occurs under high voltage, the electrode can be punctured, so that the capacitor fails, and therefore, the improvement of the flashover voltage of the electrolyte has great significance.
Manganese dioxide, an important transition metal oxide, is receiving attention because of its abundant reserves, various crystal forms, and excellent properties. After the manganese dioxide is nanocrystallized, the particle size of the manganese dioxide is reduced, the specific surface area is increased, the material performance is optimized, and the application field is widened. Because the manganese dioxide-based supercapacitor has the characteristics of high theoretical specific capacitance, good chemical stability, environmental friendliness and the like, the manganese dioxide-based supercapacitor is widely used as a positive electrode material of a battery and an electrode material of the supercapacitor, and no report is found on the application of nano manganese dioxide to an electrolyte at present.
Disclosure of Invention
The invention provides a high-voltage-resistant capacitor electrolyte and a capacitor.
The invention adopts the following technical scheme for solving the technical problems:
the high-voltage-resistant capacitor electrolyte comprises the following components in parts by weight: 55-70 parts of solvent, 20-30 parts of solute, 6-12 parts of additive and 0.5-1.5 parts of dehydrogenating agent;
the additive comprises the following raw materials in parts by weight: 10-15 parts of modified manganese dioxide, 3-6 parts of maleic acid, 1-3 parts of mannitol and 1-3 parts of sodium dodecyl sulfate.
The inventor of the present invention surprisingly found in a great number of experiments that the modified manganese dioxide can be adsorbed to the pores on the surface of the anodic oxide film in the electrolyte of the solvent and solute system of the present invention, thereby effectively increasing the sparking voltage of the electrolyte.
The addition of the maleic acid can quickly repair the damage of the dielectric film and eliminate the edge effect, thereby improving the flash voltage, and the inventor finds out in a large number of experiments, in the solvent, solute system of the present invention, citric acid, tartaric acid, for example, has been found to be almost ineffective in elevating the flash fire voltage, because the citric acid and the tartaric acid can obviously improve the sparking voltage in the sparking voltage electrolyte below 500V (low and medium voltage), however, citric acid, tartaric acid, hardly play a role once the sparking voltage is above 500V, because in high-voltage electrolytes (above 500V), the discharge voltage reached by the electrolyte under the action of the electric field force can break down the protective layer formed by the citric acid, the tartaric acid and the oxide film, so that the citric acid and the tartaric acid hardly play a role in the high-voltage electrode liquid system.
When the sodium dodecyl sulfate is added into the system, the sodium dodecyl sulfate can form a small amount of micelles which can adsorb the surface of the anodic oxide film, so that the sparking voltage is improved, and meanwhile, the formation of the micelles can further improve the dispersion performance of the modified manganese dioxide, so that the sodium dodecyl sulfate and the modified manganese dioxide can play a good synergistic effect.
As an effective scheme, the high-voltage-resistant capacitor electrolyte comprises the following components in parts by weight: 64 parts of solvent, 25 parts of solute, 10 parts of additive and 1 part of dehydrogenation agent.
As an effective scheme, the preparation method of the modified manganese dioxide comprises the following steps:
adding 1-4 parts of manganese acetate and 2-5 parts of potassium permanganate into an agate mortar, grinding until the color is not deepened, transferring the mixture into a beaker, keeping the mixture in a water bath at 70-90 ℃ for 6-9 hours, transferring the mixture into a muffle furnace, and calcining the mixture for 2-6 hours at 350-400 ℃ to obtain manganese dioxide;
adding 1-4 parts of manganese dioxide into 6-10 parts of activating agent, stirring at the rotating speed of 80-150 rpm for 60-100 min, adding 0.2-0.5 part of sodium dodecyl benzene sulfonate, stirring at the rotating speed of 80-150 rpm for 40-80 min, filtering, and drying to obtain the modified manganese dioxide.
Manganese dioxide (nano alpha-manganese dioxide) is synthesized by adopting manganese acetate and potassium permanganate, and the chemical reaction equation is as follows: 2KMnO4+3Mm(CH3COO)2·4H2O→5MnO2+2CH3COOK+10H2O；
And through subsequent treatment, the surface of manganese dioxide can be activated, the surface distribution of carbon dioxide is more uniform (the surface is dendritic), and manganese dioxide is prevented from agglomerating, so that the sparking voltage is further improved.
As an effective scheme, the activating agent is prepared from concentrated sulfuric acid and concentrated nitric acid according to a weight ratio of 1: 0.5 to 2.
As an effective scheme, the solvent consists of the following raw materials in parts by weight: 60-70 parts of ethylene glycol, 15-25 parts of gamma-butyrolactone, 6-10 parts of polyethylene glycol and 4-8 parts of benzoic acid.
As an effective scheme, the solvent consists of the following raw materials in parts by weight: 62 parts of ethylene glycol, 23 parts of gamma-butyrolactone, 9 parts of polyethylene glycol and 6 parts of benzoic acid.
As an effective scheme, the solute comprises the following raw materials in parts by weight: 25-40 parts of sebacic acid, 25-40 parts of azelaic acid, 10-18 parts of ammonium pentaborate, 10-15 parts of ammonium dodecaborate and 2-5 parts of gluconic acid.
The invention further selects sebacic acid and azelaic acid as main solutes, wherein the sebacic acid and the azelaic acid are dicarboxylic acids, have more atomic numbers and large radius, and are adsorbed on the surface of the anodic oxide film after ionization, so that the surface electric field is uniformly distributed, and the sparking voltage is improved.
As an effective scheme, the solute comprises the following raw materials in parts by weight: 30 parts of sebacic acid, 30 parts of azelaic acid, 15 parts of ammonium pentaborate, 12 parts of ammonium dodecaborate and 3 parts of gluconic acid.
As an effective scheme, the dehydrogenating agent is p-nitrophenol.
The invention also provides a capacitor, and the electrolyte of the capacitor is the electrolyte.
The invention has the beneficial effects that: (1) the capacitor electrolyte has extremely high sparking voltage, and the highest sparking voltage reaches 692V; (2) the modified manganese dioxide, the maleic acid and the sodium dodecyl sulfate in the additive are added to obviously improve the sparking voltage, manganese dioxide is synthesized by adopting manganese acetate and potassium permanganate, and the subsequent treatment is carried out to activate the surface of the manganese dioxide, so that the surface distribution of the carbon dioxide is more uniform (the surface is dendritic), and the agglomeration of the manganese dioxide is prevented, thereby further improving the sparking voltage; the addition of the maleic acid can quickly repair the damage of the dielectric film and eliminate the edge effect, thereby improving the sparking voltage; when the sodium dodecyl sulfate is added into the system, the sodium dodecyl sulfate can form a small amount of micelles which can adsorb the surface of an anodic oxide film, so that the sparking voltage is improved, and meanwhile, the formation of the micelles can further improve the dispersion performance of the modified manganese dioxide, so that the sodium dodecyl sulfate and the modified manganese dioxide can play a good synergistic effect; (4) the invention further selects sebacic acid and azelaic acid as main solutes, wherein the sebacic acid and the azelaic acid are dicarboxylic acids, have more atomic numbers and large radius, and are adsorbed on the surface of the anodic oxide film after ionization, so that the surface electric field is uniformly distributed, and the sparking voltage is improved.
Detailed Description
In order to make the objects, technical solutions and advantages of the embodiments of the present invention clearer, the technical solutions in the embodiments of the present invention will be clearly and completely described below, and it is obvious that the described embodiments are a part of the embodiments of the present invention, but 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.
In the present invention, the parts are all parts by weight unless otherwise specified.
Example 1
The high-voltage-resistant capacitor electrolyte comprises the following components in parts by weight: 64 parts of solvent, 25 parts of solute, 10 parts of additive and 1 part of dehydrogenation agent.
In this embodiment, the additive is composed of the following raw materials in parts by weight: 12 parts of modified manganese dioxide, 4 parts of maleic acid, 2 parts of mannitol and 2 parts of sodium dodecyl sulfate.
In this embodiment, the preparation method of the modified manganese dioxide comprises:
adding 2 parts of manganese acetate and 3 parts of potassium permanganate into an agate mortar, grinding until the color is not deepened, transferring the mixture into a beaker, keeping the mixture in a water bath at 85 ℃ for 8 hours, transferring the mixture into a muffle furnace, and calcining the mixture for 5 hours at 380 ℃ to obtain manganese dioxide;
adding 2 parts of manganese dioxide into 7.6 parts of activating agent, stirring for 90min at the rotating speed of 100rpm, adding 0.4 part of sodium dodecyl benzene sulfonate, stirring for 60min at the rotating speed of 100rpm, filtering and drying to obtain the modified manganese dioxide.
In this embodiment, the activating agent is prepared from concentrated sulfuric acid and concentrated nitric acid in a weight ratio of 1: 1 is configured.
In this embodiment, the solvent is composed of the following raw materials in parts by weight: 62 parts of ethylene glycol, 23 parts of gamma-butyrolactone, 9 parts of polyethylene glycol and 6 parts of benzoic acid.
In this embodiment, the solute comprises the following raw materials in parts by weight: 30 parts of sebacic acid, 30 parts of azelaic acid, 15 parts of ammonium pentaborate, 12 parts of ammonium dodecaborate and 3 parts of gluconic acid.
In this embodiment, the dehydrogenation agent is p-nitrophenol.
Example 2
The high-voltage-resistant capacitor electrolyte comprises the following components in parts by weight: 55 parts of solvent, 20 parts of solute, 6 parts of additive and 0.5 part of dehydrogenating agent.
In this embodiment, the additive is composed of the following raw materials in parts by weight: 12 parts of modified manganese dioxide, 4 parts of maleic acid, 2 parts of mannitol and 2 parts of sodium dodecyl sulfate.
In this embodiment, the preparation method of the modified manganese dioxide comprises:
adding 2 parts of manganese acetate and 3 parts of potassium permanganate into an agate mortar, grinding until the color is not deepened, transferring the mixture into a beaker, keeping the mixture in a water bath at 85 ℃ for 8 hours, transferring the mixture into a muffle furnace, and calcining the mixture for 5 hours at 380 ℃ to obtain manganese dioxide;
adding 2 parts of manganese dioxide into 7.6 parts of activating agent, stirring for 90min at the rotating speed of 100rpm, adding 0.4 part of sodium dodecyl benzene sulfonate, stirring for 60min at the rotating speed of 100rpm, filtering and drying to obtain the modified manganese dioxide.
In this embodiment, the activating agent is prepared from concentrated sulfuric acid and concentrated nitric acid in a weight ratio of 1: 1 is configured.
In this embodiment, the solvent is composed of the following raw materials in parts by weight: 62 parts of ethylene glycol, 23 parts of gamma-butyrolactone, 9 parts of polyethylene glycol and 6 parts of benzoic acid.
In this embodiment, the solute comprises the following raw materials in parts by weight: 30 parts of sebacic acid, 30 parts of azelaic acid, 15 parts of ammonium pentaborate, 12 parts of ammonium dodecaborate and 3 parts of gluconic acid.
In this embodiment, the dehydrogenation agent is p-nitrophenol.
Example 3
The high-voltage-resistant capacitor electrolyte comprises the following components in parts by weight: 70 parts of solvent, 30 parts of solute, 9 parts of additive and 1.5 parts of dehydrogenation agent.
In this embodiment, the additive is composed of the following raw materials in parts by weight: 12 parts of modified manganese dioxide, 4 parts of maleic acid, 2 parts of mannitol and 2 parts of sodium dodecyl sulfate.
In this embodiment, the preparation method of the modified manganese dioxide comprises:
adding 2 parts of manganese acetate and 3 parts of potassium permanganate into an agate mortar, grinding until the color is not deepened, transferring the mixture into a beaker, keeping the mixture in a water bath at 85 ℃ for 8 hours, transferring the mixture into a muffle furnace, and calcining the mixture for 5 hours at 380 ℃ to obtain manganese dioxide;
adding 2 parts of manganese dioxide into 7.6 parts of activating agent, stirring for 90min at the rotating speed of 100rpm, adding 0.4 part of sodium dodecyl benzene sulfonate, stirring for 60min at the rotating speed of 100rpm, filtering and drying to obtain the modified manganese dioxide.
In this embodiment, the activating agent is prepared from concentrated sulfuric acid and concentrated nitric acid in a weight ratio of 1: 1 is configured.
In this embodiment, the solvent is composed of the following raw materials in parts by weight: 62 parts of ethylene glycol, 23 parts of gamma-butyrolactone, 9 parts of polyethylene glycol and 6 parts of benzoic acid.
In this embodiment, the solute comprises the following raw materials in parts by weight: 30 parts of sebacic acid, 30 parts of azelaic acid, 15 parts of ammonium pentaborate, 12 parts of ammonium dodecaborate and 3 parts of gluconic acid.
In this embodiment, the dehydrogenation agent is p-nitrophenol.
Comparative example 1
Comparative example 1 differs from example 1 in that the modified manganese dioxide in the additive described in comparative example 1 is replaced with an equal amount of ethylene glycol, i.e. no modified manganese dioxide is present in this comparative example, all else being equal.
In the comparative example, the additive consists of the following raw materials in parts by weight: 12 parts of ethylene glycol, 4 parts of maleic acid, 2 parts of mannitol and 2 parts of sodium dodecyl sulfate.
Comparative example 2
Comparative example 2 is different from example 1 in that modified manganese dioxide in the additive described in comparative example 2 is replaced with manganese dioxide, and the others are the same.
In the comparative example, the additive consists of the following raw materials in parts by weight: 12 parts of manganese dioxide, 4 parts of maleic acid, 2 parts of mannitol and 2 parts of sodium dodecyl sulfate.
In this comparative example, the preparation method of manganese dioxide was:
adding 2 parts of manganese acetate and 3 parts of potassium permanganate into an agate mortar, grinding until the color is not deepened, transferring into a beaker, keeping in a water bath at 85 ℃ for 8 hours, transferring into a muffle furnace, and calcining at 380 ℃ for 5 hours to obtain manganese dioxide.
Comparative example 3
Comparative example 3 is different from example 1 in that the modified manganese dioxide prepared by modifying commercially available manganese dioxide was prepared differently from example 1 in comparative example 3, which was purchased from mixcrystal materials technologies ltd.
In the comparative example, the additive consists of the following raw materials in parts by weight: 12 parts of modified manganese dioxide, 4 parts of maleic acid, 2 parts of mannitol and 2 parts of sodium dodecyl sulfate.
In this comparative example, the preparation method of the modified manganese dioxide was:
adding 2 parts of manganese dioxide into 7.6 parts of activating agent, stirring for 90min at the rotating speed of 100rpm, adding 0.4 part of sodium dodecyl benzene sulfonate, stirring for 60min at the rotating speed of 100rpm, filtering and drying to obtain the modified manganese dioxide.
Comparative example 4
Comparative example 4 is different from example 1 in that the modified manganese dioxide was prepared by the same method as example 1.
In the comparative example, the additive consists of the following raw materials in parts by weight: 12 parts of modified manganese dioxide, 4 parts of maleic acid, 2 parts of mannitol and 2 parts of sodium dodecyl sulfate.
In this comparative example, the preparation method of the modified manganese dioxide was:
adding 2 parts of manganese acetate and 3 parts of potassium permanganate into an agate mortar, grinding until the color is not deepened, transferring the mixture into a beaker, keeping the mixture in a water bath at 85 ℃ for 8 hours, transferring the mixture into a muffle furnace, and calcining the mixture for 5 hours at 380 ℃ to obtain manganese dioxide;
adding 2 parts of manganese dioxide into 7.6 parts of activating agent, stirring at 100rpm for 90min, adding 0.4 part of dodecyl betaine, stirring at 100rpm for 60min, filtering, and drying to obtain modified manganese dioxide.
Comparative example 5
Comparative example 5 differs from example 1 in that comparative example 5 replaces maleic acid with citric acid, all other things being equal.
In the comparative example, the additive consists of the following raw materials in parts by weight: 12 parts of modified manganese dioxide, 4 parts of citric acid, 2 parts of mannitol and 2 parts of sodium dodecyl sulfate.
Comparative example 6
Comparative example 6 differs from example 1 in that the maleic acid in the additive described in comparative example 6 was replaced with an equal amount of ethylene glycol, i.e. no maleic acid was contained in this comparative example, all else being identical.
In the comparative example, the additive consists of the following raw materials in parts by weight: 12 parts of ethylene glycol, 4 parts of ethylene glycol, 2 parts of mannitol and 2 parts of sodium dodecyl sulfate.
Comparative example 7
Comparative example 7 differs from example 1 in that the sodium lauryl sulfate in the additive described in comparative example 7 was replaced with an equal amount of ethylene glycol, i.e., in this comparative example, sodium lauryl sulfate was not included, and the other was the same.
In the comparative example, the additive consists of the following raw materials in parts by weight: 12 parts of ethylene glycol, 4 parts of maleic acid, 2 parts of mannitol and 2 parts of ethylene glycol.
Comparative example 8
Comparative example 8 differs from example 1 in that the solute is the same as in example 1, i.e., in this comparative example, the solute does not contain sebacic acid, azelaic acid.
In the present comparative example, the solute consisted of the following raw materials in parts by weight: 5 parts of ammonium pentaborate, 12 parts of ammonium dodecadicarboxylate and 3 parts of gluconic acid.
To further demonstrate the effect of the present invention, the following test methods were provided:
1. the highest sparking voltage of the capacitors made with the electrolytes of examples 1-3 and comparative examples 1-8 was tested. The specification of the capacitor core is 400V/4.7 muF, and the test result is shown in Table 1.
TABLE 1 test results
As can be seen from table 1, the high voltage capacitor electrolyte according to the present invention has a good sparking voltage.
As can be seen from comparison of examples 1-3, the ratios of different electrolytes can affect the sparking voltage, wherein example 1 is the best ratio.
Comparing example 1 with comparative example 1, it can be seen that the modified manganese dioxide according to the present invention can significantly improve the sparking voltage.
Compared with the comparative examples 2 to 4, the modified manganese dioxide prepared by the preparation method disclosed by the invention can obviously improve the sparking voltage, and if the preparation method is replaced, the sparking voltage can be obviously reduced.
Comparing example 1 with comparative examples 5 and 6, it can be seen that the addition of maleic acid can significantly increase the flash voltage, and when the maleic acid is replaced by citric acid, the flash voltage is significantly decreased.
Comparing example 1 with comparative example 7, it can be seen that the addition of sodium lauryl sulfate can significantly increase the sparking voltage.
Comparing example 1 with comparative example 8, it can be seen that adopting sebacic acid and azelaic acid in the solute of the invention can significantly improve the sparking voltage.
In light of the foregoing description of preferred embodiments according to the invention, it is clear that many changes and modifications can be made by the person skilled in the art without departing from the scope of the invention. The technical scope of the present invention is not limited to the contents of the specification, and must be determined according to the scope of the claims.
Claims (9)
1. The high-voltage-resistant capacitor electrolyte is characterized by comprising the following components in parts by weight: 55-70 parts of solvent, 20-30 parts of solute, 6-12 parts of additive and 0.5-1.5 parts of dehydrogenating agent;
the additive comprises the following raw materials in parts by weight: 10-15 parts of modified manganese dioxide, 3-6 parts of maleic acid, 1-3 parts of mannitol and 1-3 parts of sodium dodecyl sulfate;
the preparation method of the modified manganese dioxide comprises the following steps:
adding 1-4 parts of manganese acetate and 2-5 parts of potassium permanganate into an agate mortar, grinding until the color is not deepened, transferring the mixture into a beaker, keeping the mixture in a water bath at 70-90 ℃ for 6-9 hours, transferring the mixture into a muffle furnace, and calcining the mixture for 2-6 hours at 350-400 ℃ to obtain manganese dioxide;
adding 1-4 parts of manganese dioxide into 6-10 parts of activating agent, stirring at the rotating speed of 80-150 rpm for 60-100 min, adding 0.2-0.5 part of sodium dodecyl benzene sulfonate, stirring at the rotating speed of 80-150 rpm for 40-80 min, filtering, and drying to obtain the modified manganese dioxide.
2. The high voltage resistant capacitor electrolyte of claim 1, comprising the following components in parts by weight: 64 parts of solvent, 25 parts of solute, 10 parts of additive and 1 part of dehydrogenation agent.
3. The high voltage tolerant capacitor electrolyte of claim 1 wherein the activator is a mixture of concentrated sulfuric acid and concentrated nitric acid in a weight ratio of 1: 0.5 to 2.
4. The high-voltage-resistant capacitor electrolyte as claimed in claim 1, wherein the solvent is composed of the following raw materials in parts by weight: 60-70 parts of ethylene glycol, 15-25 parts of gamma-butyrolactone, 6-10 parts of polyethylene glycol and 4-8 parts of benzoic acid.
5. The high-voltage-resistant capacitor electrolyte as claimed in claim 4, wherein the solvent is composed of the following raw materials in parts by weight: 62 parts of ethylene glycol, 23 parts of gamma-butyrolactone, 9 parts of polyethylene glycol and 6 parts of benzoic acid.
6. The high-voltage-resistant capacitor electrolyte as claimed in claim 5, wherein the solute comprises the following raw materials in parts by weight: 25-40 parts of sebacic acid, 25-40 parts of azelaic acid, 10-18 parts of ammonium pentaborate, 10-15 parts of ammonium dodecaborate and 2-5 parts of gluconic acid.
7. The high voltage resistant capacitor electrolyte of claim 6, wherein the solute comprises the following raw materials in parts by weight: 30 parts of sebacic acid, 30 parts of azelaic acid, 15 parts of ammonium pentaborate, 12 parts of ammonium dodecaborate and 3 parts of gluconic acid.
8. The high voltage tolerant capacitor electrolyte of claim 1 wherein said dehydrogenating agent is p-nitrophenol.
9. A capacitor, characterized in that the electrolyte of the capacitor is the electrolyte of any one of claims 1 to 8.
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