CN115775689B - Solid polymer electrolyte, preparation method and solid-liquid mixed capacitor - Google Patents
Solid polymer electrolyte, preparation method and solid-liquid mixed capacitor Download PDFInfo
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- 239000003990 capacitor Substances 0.000 title claims abstract description 35
- 239000007787 solid Substances 0.000 title claims abstract description 30
- 239000005518 polymer electrolyte Substances 0.000 title claims abstract description 24
- 239000007788 liquid Substances 0.000 title claims abstract description 13
- 238000002360 preparation method Methods 0.000 title claims abstract description 10
- 229920000642 polymer Polymers 0.000 claims abstract description 35
- 239000007784 solid electrolyte Substances 0.000 claims abstract description 26
- WXZMFSXDPGVJKK-UHFFFAOYSA-N pentaerythritol Chemical compound OCC(CO)(CO)CO WXZMFSXDPGVJKK-UHFFFAOYSA-N 0.000 claims abstract description 19
- 229910002126 La0.6Sr0.4Co0.2Fe0.8O3-x Inorganic materials 0.000 claims abstract description 3
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 claims description 54
- 238000010438 heat treatment Methods 0.000 claims description 44
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 30
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 claims description 24
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 18
- 229910017604 nitric acid Inorganic materials 0.000 claims description 18
- 238000009987 spinning Methods 0.000 claims description 18
- 238000003756 stirring Methods 0.000 claims description 18
- 238000005245 sintering Methods 0.000 claims description 16
- 239000003792 electrolyte Substances 0.000 claims description 14
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims description 12
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 12
- 229920002565 Polyethylene Glycol 400 Polymers 0.000 claims description 12
- 229920002593 Polyethylene Glycol 800 Polymers 0.000 claims description 12
- 235000011114 ammonium hydroxide Nutrition 0.000 claims description 12
- 239000012510 hollow fiber Substances 0.000 claims description 12
- 239000012528 membrane Substances 0.000 claims description 12
- JLFNLZLINWHATN-UHFFFAOYSA-N pentaethylene glycol Chemical compound OCCOCCOCCOCCOCCO JLFNLZLINWHATN-UHFFFAOYSA-N 0.000 claims description 12
- 239000000843 powder Substances 0.000 claims description 12
- 239000002243 precursor Substances 0.000 claims description 12
- 239000002131 composite material Substances 0.000 claims description 8
- -1 imidazole cation Chemical class 0.000 claims description 8
- 238000002156 mixing Methods 0.000 claims description 8
- 230000000630 rising effect Effects 0.000 claims description 8
- 238000001035 drying Methods 0.000 claims description 7
- 229910002651 NO3 Inorganic materials 0.000 claims description 6
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 claims description 6
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 claims description 6
- 239000002608 ionic liquid Substances 0.000 claims description 6
- 229910052746 lanthanum Inorganic materials 0.000 claims description 6
- 238000004519 manufacturing process Methods 0.000 claims description 6
- 229910021645 metal ion Inorganic materials 0.000 claims description 6
- 229910052757 nitrogen Inorganic materials 0.000 claims description 6
- 229920001223 polyethylene glycol Polymers 0.000 claims description 6
- 238000003825 pressing Methods 0.000 claims description 6
- 239000000376 reactant Substances 0.000 claims description 6
- 238000000967 suction filtration Methods 0.000 claims description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 6
- 239000002994 raw material Substances 0.000 claims description 5
- 150000001450 anions Chemical class 0.000 claims description 4
- 150000001768 cations Chemical class 0.000 claims description 4
- RAXXELZNTBOGNW-UHFFFAOYSA-N imidazole Natural products C1=CNC=N1 RAXXELZNTBOGNW-UHFFFAOYSA-N 0.000 claims description 4
- 229920000867 polyelectrolyte Polymers 0.000 claims description 3
- 239000002245 particle Substances 0.000 claims description 2
- XYFCBTPGUUZFHI-UHFFFAOYSA-O phosphonium Chemical group [PH4+] XYFCBTPGUUZFHI-UHFFFAOYSA-O 0.000 claims description 2
- 239000004014 plasticizer Substances 0.000 claims description 2
- 239000002904 solvent Substances 0.000 claims description 2
- 238000000034 method Methods 0.000 abstract description 2
- 239000000126 substance Substances 0.000 abstract description 2
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 description 15
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 6
- 239000002041 carbon nanotube Substances 0.000 description 6
- 229910021393 carbon nanotube Inorganic materials 0.000 description 6
- AMWRITDGCCNYAT-UHFFFAOYSA-L hydroxy(oxo)manganese;manganese Chemical compound [Mn].O[Mn]=O.O[Mn]=O AMWRITDGCCNYAT-UHFFFAOYSA-L 0.000 description 6
- 229920001940 conductive polymer Polymers 0.000 description 5
- KMTRUDSVKNLOMY-UHFFFAOYSA-N Ethylene carbonate Chemical compound O=C1OCCO1 KMTRUDSVKNLOMY-UHFFFAOYSA-N 0.000 description 4
- 229910052782 aluminium Inorganic materials 0.000 description 4
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 4
- 229920002678 cellulose Polymers 0.000 description 4
- 239000001913 cellulose Substances 0.000 description 4
- 239000012982 microporous membrane Substances 0.000 description 4
- 229920000128 polypyrrole Polymers 0.000 description 3
- NUJOXMJBOLGQSY-UHFFFAOYSA-N manganese dioxide Chemical compound O=[Mn]=O NUJOXMJBOLGQSY-UHFFFAOYSA-N 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 239000004020 conductor Substances 0.000 description 1
- 230000008602 contraction Effects 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 239000011244 liquid electrolyte Substances 0.000 description 1
- 229910052758 niobium Inorganic materials 0.000 description 1
- 239000010955 niobium Substances 0.000 description 1
- GUCVJGMIXFAOAE-UHFFFAOYSA-N niobium atom Chemical compound [Nb] GUCVJGMIXFAOAE-UHFFFAOYSA-N 0.000 description 1
- 238000003672 processing method Methods 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 229910052715 tantalum Inorganic materials 0.000 description 1
- GUVRBAGPIYLISA-UHFFFAOYSA-N tantalum atom Chemical compound [Ta] GUVRBAGPIYLISA-UHFFFAOYSA-N 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
Classifications
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- 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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Abstract
The invention relates to the technical field of capacitors, in particular to a solid polymer electrolyte, a preparation method and a solid-liquid mixed capacitor, wherein the solid polymer electrolyte comprises 200-250 parts of solid electrolyte and 25-30 parts of polymer; the solid electrolyte is La 0.6 Sr 0.4 Co 0.2 Fe 0.8 O 3‑x The method comprises the steps of carrying out a first treatment on the surface of the The mass ratio of the polymer is (0.1-10): 100 pentaerythritol and PEG; the solid electrolyte is a spongy asymmetric structure with finger holes at two sides and a spongy middle, so that the solid electrolyte has excellent chemical stability and high ionic conductivity, and the manufactured capacitor has the characteristics of lower equivalent series resistance and long service life.
Description
Technical Field
The invention relates to the technical field of capacitors, in particular to a solid polymer electrolyte, a preparation method and a solid-liquid mixed capacitor.
Background
Electrolytic capacitors are one of the most widely used basic components in the electronics industry, and are widely used in various types of electronic circuits. The most original capacitor is a Lyon bottle invented by the university of Holland Leton, P. Mu Senbu Rog, 1745, which is a corrugated glass capacitor, was developed successfully by Bell laboratories in the United states in the fifth sixty of twentieth century, and in 1949, a liquid sintered aluminum electrolytic capacitor was developed by the Michelin and Ball laboratories in the United states in 1955, the first solid electrolyte aluminum capacitor in the industry was developed by taking manganese dioxide as an electrolyte, the problem of "drying" of the liquid electrolyte was overcome, the stability and the frequency characteristics of the capacitor were greatly improved, and the foundation was laid for the future commercialization and wide application of the aluminum capacitor. Electrolytic capacitors are classified into various types, and can be classified into aluminum electrolytic capacitors, tantalum electrolytic capacitors, niobium electrolytic capacitors, and the like according to materials, and liquid electrolytic capacitors, solid electrolytic capacitors, and the like according to the form of internal conductors. The liquid electrolytic capacitor mainly uses electrolyte as electrolyte, and along with the extension of the service time, the electrolyte serving as the electrolyte is easy to volatilize, so that the capacity of the liquid electrolytic capacitor is reduced, the resistivity is increased, and compared with the liquid electrolytic capacitor, the solid electrolytic capacitor has the characteristics of more outstanding electrical performance, longer service life, more stable safety and the like. In the prior art, the solid electrolytic capacitor mostly adopts conductive polymers as electrolytes, mainly because the conductive polymers have the advantages of simple synthesis process, good stability and the like. However, the conductivity of a pure conductive polymer is not high, and the volume of the conductive polymer is changed by expansion/contraction during charge and discharge cycles of a capacitor, so that a polymer chain is broken, and the conductivity of the conductive polymer is reduced.
Disclosure of Invention
In order to overcome the defects in the background technology, the invention provides a solid polymer electrolyte, a preparation method and a solid-liquid mixed capacitor.
On one hand, the invention provides a solid polymer electrolyte, which is characterized in that: the material comprises the following raw materials in parts by mass: 200-250 parts of solid electrolyte and 25-30 parts of polymer; the solid electrolyte is La 0.6 Sr 0.4 Co 0.2 Fe 0.8 O 3-x ；
The mass ratio of the polymer is (0.1-10): 100 pentaerythritol and PEG.
Preferably, the solid electrolyte has a particle size of 1-5 μm and a relative density of > 97%.
On the other hand, the invention provides a preparation method of solid polyelectrolyte, which is characterized by comprising the following steps:
s1, adding PEG400, PEG800, pentaerythritol and methylene dichloride into a dry three-neck flask, stirring and adding KOH at 15-40 ℃ under the protection of nitrogen after the pentaerythritol is dissolved, reacting for 12-24 hours, removing the methylene dichloride under reduced pressure, dissolving reactants, and carrying out suction filtration to obtain a polymer;
s2, dissolving nitrate of La, sr, co, fe in a metering ratio in water, adding citric acid and glycol, stirring, heating to form a uniform transparent solution, sequentially adding nitric acid and ammonia water, continuously stirring and heating, preserving heat at 70-80 ℃ to form composite sol, then heating to 210-240 ℃ to obtain precursor powder, pressing the precursor powder into a sheet-shaped blank at 8-12Mpa, and sintering the sheet-shaped blank at 900-1600 ℃ to obtain the composite sol;
s3, after the polymer is dissolved in a solvent, adding a plasticizer and a solid electrolyte, fully mixing to form a polymer solution, injecting the polymer solution into a spinning device, and preparing the hollow fiber membrane at a spinning rate of 1.0-1.5 m/min;
s4, drying the hollow fiber membrane, heating to 1100-1400 ℃ by adopting a step heating mode, and sintering for 2-10 hours to obtain the solid polymer electrolyte.
Preferably, in the S1, the mass ratio of the PEG400 to the PEG800 is 1:9-9:1.
Preferably, the ratio of the total molar quantity of the citric acid to the metal ions in the S2 is 1-4:1, and the molar ratio of the ethylene glycol to the citric acid is 1-2:1; the molar ratio of nitric acid to organic matters is 4-6; the molar ratio of the ammonia water to the nitric acid is 0.8-1.3.
Preferably, the sintering conditions in S2 are: heating to 900-1600 ℃ at a heating rate of 1-5 ℃/min, and sintering for 4-8h.
Preferably, the inside diameter and outside diameter of the spinneret of the spinning device in S3 are 0.3mm and 0.42mm, respectively.
Preferably, the step heating of S4 specifically includes: when T is less than or equal to 200 ℃, the temperature rising rate is less than 10 ℃/h; when T is more than 200 ℃, the temperature rising rate is less than or equal to 1 ℃/h, and the temperature reducing rate is less than or equal to 2 ℃/h.
On the other hand, the invention also provides a solid-liquid mixing capacitor, which is characterized in that: the solid polymer electrolyte and the ionic liquid electrolyte prepared by the scheme are included.
Preferably, the ionic liquid electrolyte is any combination of anions and cations of any two or more of the following: the cation is imidazole cation, quaternary phosphonium cation and sulfonium cation; the anions are F3COO, sbF6, CIO4, C3F7COO and CF3SO3.
The beneficial effects are that: compared with the prior art, the solid electrolyte provided by the invention has the advantages that finger holes are formed at two sides, a spongy asymmetric structure is formed in the middle, the chemical stability is excellent, the ion conductivity is high, and the manufactured capacitor has the characteristics of low equivalent series resistance and long service life.
Detailed Description
The present invention will be described in detail below with reference to the drawings and detailed description to enable those skilled in the art to better understand the technical scheme of the present invention. The instruments and devices referred to in the following examples are conventional instruments and devices unless otherwise specified; the industrial raw materials (reagents and raw materials are selected according to the situation) are all conventional industrial raw materials sold in the market unless otherwise specified; the processing and manufacturing methods (detection, test, preparation method, etc. are optional) are conventional methods unless otherwise specified.
EXAMPLE 1 solid Polymer electrolyte
S1, adding PEG400, PEG800, pentaerythritol and methylene dichloride into a dry three-neck flask, stirring and adding KOH at 15 ℃ under the protection of nitrogen after the pentaerythritol is dissolved, reacting for 12-14h, removing the methylene dichloride under reduced pressure, dissolving reactants, and carrying out suction filtration to obtain a polymer; wherein the mass ratio of PEG400 to PEG800 is 1:9; the ratio of pentaerythritol to the total mass of PEG was 0.1:100;
s2, dissolving nitrate of La, sr, co, fe in a metering ratio in water, adding citric acid and glycol, stirring, heating to form a uniform transparent solution, sequentially adding nitric acid and ammonia water, continuously stirring and heating, preserving heat at 70-80 ℃ to form composite sol, then heating to 210 ℃ to obtain precursor powder, pressing the precursor powder into a sheet-shaped blank at 8-12Mpa, heating the sheet-shaped blank to 900 ℃ at a heating rate of 1 ℃/min, and sintering for 4-8h; wherein the ratio of the total molar quantity of the citric acid to the metal ions in the S2 is 1:1, and the molar ratio of the glycol to the citric acid is 1:1; the molar ratio of nitric acid to organic matters is 4:1; the molar ratio of the ammonia water to the nitric acid is 0.8:1;
s3, after the polymer is dissolved in acetonitrile, adding ethylene carbonate and solid electrolyte, and fully mixing to form a high polymer solution, wherein the mass ratio of the polymer to the solid electrolyte is 1:15, injecting the polymer solution into a spinning device, wherein the inner diameter and the outer diameter of a spinning head are respectively 0.3mm and 0.42mm, and a hollow fiber membrane is prepared at a spinning rate of 1.0 m/min;
s4, drying the hollow fiber membrane, and adopting a step heating mode, wherein when T is less than or equal to 200 ℃, the heating rate is less than 10 ℃/h; when T is more than 200 ℃, the temperature rising rate is less than or equal to 1 ℃/h, the temperature reducing rate is less than or equal to 2 ℃/h, the temperature is raised to 1100 ℃, and the solid polymer electrolyte is obtained after sintering for 2 h.
EXAMPLE 2 solid Polymer electrolyte
S1, adding PEG400, PEG800, pentaerythritol and methylene dichloride into a dry three-neck flask, stirring and adding KOH at 40 ℃ under the protection of nitrogen after the pentaerythritol is dissolved, reacting for 22-24 hours, removing the methylene dichloride under reduced pressure, dissolving reactants, and carrying out suction filtration to obtain a polymer; wherein the mass ratio of PEG400 to PEG800 is 9:1; the ratio of pentaerythritol to PEG total mass is 10:100;
s2, dissolving nitrate of La, sr, co, fe in a metering ratio in water, adding citric acid and ethylene glycol, stirring, heating to form a uniform transparent solution, sequentially adding nitric acid and ammonia water, continuously stirring and heating, preserving heat at 70-80 ℃ to form composite sol, then heating to 240 ℃ to obtain precursor powder, pressing the precursor powder into a sheet-shaped blank at 8-12Mpa, heating the sheet-shaped blank to 1600 ℃ at a heating rate of 5 ℃/min, and sintering for 4-8h; wherein the ratio of the total molar quantity of citric acid to metal ions in the S2 is 4:1, and the molar ratio of glycol to citric acid is 2:1; the molar ratio of nitric acid to organic matters is 6:1; the molar ratio of the ammonia water to the nitric acid is 1.3:1;
s3, after the polymer is dissolved in acetonitrile, adding ethylene carbonate and solid electrolyte, and fully mixing to form a high polymer solution, wherein the mass ratio of the polymer to the solid electrolyte is 1:20, injecting a polymer solution into a spinning device, wherein the inner diameter and the outer diameter of a spinning head are respectively 0.3mm and 0.42mm, and a hollow fiber membrane is prepared at a spinning rate of 1.5 m/min;
s4, drying the hollow fiber membrane, and adopting a step heating mode, wherein when T is less than or equal to 200 ℃, the heating rate is less than 10 ℃/h; when T is more than 200 ℃, the temperature rising rate is less than or equal to 1 ℃/h, the temperature reducing rate is less than or equal to 2 ℃/h, the temperature is raised to 1400 ℃, and the solid polymer electrolyte is obtained after sintering for 8-10 h.
EXAMPLE 3 solid Polymer electrolyte
S1, adding PEG400, PEG800, pentaerythritol and methylene dichloride into a dry three-neck flask, stirring and adding KOH at 28 ℃ under the protection of nitrogen after the pentaerythritol is dissolved, reacting for 15-18h, removing the methylene dichloride under reduced pressure, dissolving reactants, and carrying out suction filtration to obtain a polymer; wherein, the mass ratio of PEG400 to PEG800 is 4:7; the ratio of pentaerythritol to PEG total mass is 3:100;
s2, dissolving nitrate of La, sr, co, fe in a metering ratio in water, adding citric acid and ethylene glycol, stirring, heating to form a uniform transparent solution, sequentially adding nitric acid and ammonia water, continuously stirring and heating, preserving heat at 70-80 ℃ to form composite sol, then heating to 220 ℃ to obtain precursor powder, pressing the precursor powder into a sheet-shaped blank at 8-12Mpa, heating the sheet-shaped blank to 1000 ℃ at a heating rate of 3 ℃/min, and sintering for 4-8h; wherein the ratio of the total molar amount of citric acid to metal ions is 2:1, and the molar ratio of ethylene glycol to citric acid is 1.2:1; the molar ratio of nitric acid to organic matters is 5:1; the molar ratio of the ammonia water to the nitric acid is 0.9:1;
s3, after the polymer is dissolved in acetonitrile, adding ethylene carbonate and solid electrolyte, and fully mixing to form a high polymer solution, wherein the mass ratio of the polymer to the solid electrolyte is 1:18, injecting a polymer solution into a spinning device, wherein the inner diameter and the outer diameter of a spinning head are respectively 0.3mm and 0.42mm, and a hollow fiber membrane is prepared at a spinning rate of 1.1 m/min;
s4, drying the hollow fiber membrane, and adopting a step heating mode, wherein when T is less than or equal to 200 ℃, the heating rate is less than 10 ℃/h; when T is more than 200 ℃, the temperature rising rate is less than or equal to 1 ℃/h, the temperature reducing rate is less than or equal to 2 ℃/h, the temperature is raised to 1200 ℃, and the solid polymer electrolyte is obtained after sintering for 5 h.
EXAMPLE 4 solid Polymer electrolyte
S1, adding PEG400, PEG800, pentaerythritol and methylene dichloride into a dry three-neck flask, stirring and adding KOH at 15 ℃ under the protection of nitrogen after the pentaerythritol is dissolved, reacting for 12-14 hours, removing the methylene dichloride under reduced pressure, dissolving reactants, and carrying out suction filtration to obtain a polymer; wherein, the mass ratio of PEG400 to PEG800 is 8:1; the ratio of pentaerythritol to the total mass of PEG was 0.8:100;
s2, dissolving nitrate of La, sr, co, fe in a metering ratio in water, adding citric acid and ethylene glycol, stirring, heating to form a uniform transparent solution, sequentially adding nitric acid and ammonia water, continuously stirring and heating, preserving heat at 70-80 ℃ to form composite sol, then heating to 210 ℃ to obtain precursor powder, pressing the precursor powder into a sheet-shaped blank at 8-12Mpa, heating the sheet-shaped blank to 1600 ℃ at a heating rate of 5 ℃/min, and sintering for 4-8h; wherein the ratio of the total molar amount of citric acid to metal ions is 3:1, and the molar ratio of ethylene glycol to citric acid is 1:1; the molar ratio of nitric acid to organic matters is 6:1; the molar ratio of the ammonia water to the nitric acid is 0.8:1;
s3, after the polymer is dissolved in acetonitrile, adding ethylene carbonate and solid electrolyte, and fully mixing to form a high polymer solution, wherein the mass ratio of the polymer to the solid electrolyte is 1:20, injecting a polymer solution into a spinning device, wherein the inner diameter and the outer diameter of a spinning head are respectively 0.3mm and 0.42mm, and a hollow fiber membrane is prepared at a spinning rate of 1.4 m/min;
s4, drying the hollow fiber membrane, and adopting a step heating mode, wherein when T is less than or equal to 200 ℃, the heating rate is less than 10 ℃/h; when T is more than 200 ℃, the temperature rising rate is less than or equal to 1 ℃/h, the temperature reducing rate is less than or equal to 2 ℃/h, the temperature is raised to 1400 ℃, and the solid polymer electrolyte is obtained after sintering for 2 h.
Example 5
The capacitor is assembled by taking manganese oxide/oriented carbon nano tube as an anode, polypyrrole/oriented carbon nano tube as a cathode, taking ionic liquid tetraethyl hexafluorophosphate quaternary ammonium salt and the solid electrolyte prepared in the embodiment 1 as electrolytes, taking a cellulose microporous membrane as a diaphragm and taking a CR2025 battery shell as a shell.
Example 6
The solid electrolyte prepared in the example 2 and the ionic liquid 1-ethyl-3-methylimidazole tetrafluoroborate are selected as electrolyte, the cellulose microporous membrane is a diaphragm, and the CR2025 battery shell is a shell, so that the capacitor is assembled.
Example 7
Taking manganese oxide/oriented carbon nano tube as an anode, polypyrrole/oriented carbon nano tube as a cathode, selecting acetonitrile solution of tetraethyl hexafluorophosphate quaternary ammonium salt with the concentration of 1mol/L and the solid electrolyte prepared in the embodiment 3 as electrolyte, taking a cellulose microporous membrane as a diaphragm, and taking a CR2025 battery shell as a shell to assemble the capacitor.
Example 8
Taking manganese oxide/oriented carbon nano tube as an anode, polypyrrole/oriented carbon nano tube as a cathode, selecting 1mol/L of 1-ethyl-3-methylimidazole tetrafluoroborate and the solid electrolyte prepared in the embodiment 4 as electrolyte, taking a cellulose microporous membrane as a diaphragm and taking a CR2025 battery shell as a shell, and assembling the capacitor.
DC voltage is applied at 100 ℃ and 20V rated voltage, equivalent Series Resistance (ESR) and high temperature load performance are tested, 100 data are tested to obtain average value, and comparison result with initial performance is shown in the following table.
Finally, it should be noted that the above description is only a preferred embodiment of the present invention, and that many similar changes can be made by those skilled in the art without departing from the spirit and scope of the invention as defined in the appended claims.
Claims (8)
1. The preparation method of the solid polyelectrolyte is characterized in that the solid polyelectrolyte comprises the following raw materials in parts by mass: 200-250 parts of solid electrolyte and 25-30 parts of polymer; the solid electrolyte is La 0.6 Sr 0.4 Co 0.2 Fe 0.8 O 3-x The polymer is of massThe ratio is (0.1-10): 100 pentaerythritol and PEG; the particle size of the solid electrolyte is 1-5 mu m, and the relative density is more than 97%;
the preparation method comprises the following steps:
s1, adding PEG400, PEG800, pentaerythritol and methylene dichloride into a dry three-neck flask, stirring and adding KOH at 15-40 ℃ under the protection of nitrogen after the pentaerythritol is dissolved, reacting for 12-24 hours, removing the methylene dichloride under reduced pressure, dissolving reactants, and carrying out suction filtration to obtain a polymer;
s2, dissolving nitrate of La, sr, co, fe in a metering ratio in water, adding citric acid and glycol, stirring, heating to form a uniform transparent solution, sequentially adding nitric acid and ammonia water, continuously stirring and heating, preserving heat at 70-80 ℃ to form composite sol, then heating to 210-240 ℃ to obtain precursor powder, pressing the precursor powder into a sheet-shaped blank at 8-12Mpa, and sintering the sheet-shaped blank at 900-1600 ℃ to obtain the composite sol;
s3, after the polymer is dissolved in a solvent, adding a plasticizer and a solid electrolyte, fully mixing to form a polymer solution, injecting the polymer solution into a spinning device, and preparing the hollow fiber membrane at a spinning rate of 1.0-1.5 m/min;
s4, drying the hollow fiber membrane, heating to 1100-1400 ℃ by adopting a step heating mode, and sintering for 2-10 hours to obtain the solid polymer electrolyte.
2. The method for producing a solid polymer electrolyte according to claim 1, wherein: in the S1, the mass ratio of the PEG400 to the PEG800 is 1:9-9:1.
3. The method for producing a solid polymer electrolyte according to claim 1, wherein: the ratio of the total molar weight of the citric acid to the metal ions in the S2 is 1-4:1, and the molar ratio of the glycol to the citric acid is 1-2:1; the molar ratio of nitric acid to organic matters is 4-6; the molar ratio of the ammonia water to the nitric acid is 0.8-1.3.
4. The method for producing a solid polymer electrolyte according to claim 1, wherein: the sintering conditions in the step S2 are as follows: heating to 900-1600 ℃ at a heating rate of 1-5 ℃/min, and sintering for 4-8h.
5. The method for producing a solid polymer electrolyte according to claim 1, wherein: the spinning device in S3 has an inner diameter and an outer diameter of 0.3mm and 0.42mm, respectively.
6. The method for producing a solid polymer electrolyte according to claim 1, wherein: the step heating of the S4 is specifically as follows: when T is less than or equal to 200 ℃, the temperature rising rate is less than 10 ℃/h; when T is more than 200 ℃, the temperature rising rate is less than or equal to 1 ℃/h, and the temperature reducing rate is less than or equal to 2 ℃/h.
7. The solid-liquid mixing capacitor is characterized in that: comprising the solid polymer electrolyte and the ionic liquid electrolyte obtained by the preparation method according to any one of claims 1 to 6.
8. The solid-liquid hybrid capacitor according to claim 7, wherein: the ionic liquid electrolyte is any combination of anions and cations of any two or more of the following: the cation is imidazole cation, quaternary phosphonium cation and sulfonium cation; the anions are F3COO, sbF6, CIO4, C3F7COO and CF3SO3.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202211362247.9A CN115775689B (en) | 2022-11-02 | 2022-11-02 | Solid polymer electrolyte, preparation method and solid-liquid mixed capacitor |
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