CN105590759A - Method of preparing ionic liquid gel electrolyte by semiconductor through self-initiated polymerization - Google Patents
Method of preparing ionic liquid gel electrolyte by semiconductor through self-initiated polymerization Download PDFInfo
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Abstract
The invention relates to a method of preparing an ionic liquid gel electrolyte by a semiconductor through ultraviolet initiated polymerization. The semiconductor and a monomer are added to the ionic liquid, uniform mixing is carried out, the semiconductor generates electrons and holes through ultraviolet irradiation, free radicals are formed, the monomer is thus initiated to be subjected to free radical polymerization, and an ionic liquid gel electrolyte with a three-dimensional network structure is generated. Compared with the prior art, the method of the invention has the advantages that the preparation process is simple; the reaction condition is mild; the prepared ionic liquid gel electrolyte is characterized in high mechanical strength, good thermal stability, large polymer skeleton pore, high conductivity and the like, and important promotion significance is achieved in the fields of a super capacitor, a lithium battery, a solar cell, a flexible wearable device and the like.
Description
Technical field
The invention belongs to technical field of new energies, relate to a kind of method of gel electrolyte, especially relate to oneSemiconductor causes ultraviolet polymerization and prepares the electrolytical method of ionic liquid gel.
Background technology
Ionic liquid has many good characteristics, higher heat endurance, and almost without vapour pressure, electrochemical windowWide, electrical conductivity is high, is widely used in the fields such as biology, catalysis, synthetic and electrochemistry, especially can be used as electrolyteFor lithium battery, ultracapacitor, fuel cell etc. Although but ionic liquid can solve biography as electrolyteThe problem of system organic electrolyte volatilization, but as liquid electrolyte, still exist electrolyte leakage and encapsulation skillThe problem of art.
Ionic liquid gel is that one can absorb and retain a large amount of ionic liquids (conventionally ionic liquid content is greater than70%) the material with three-dimensional network polymer molecule chain structure. Than liquid electrolyte (water system andOrganic electrolyte), ionic liquid gel belongs to solid electrolyte, can avoid the leakage problem of electrolyte, andDuring encapsulation on more simple and easy convenient. Meanwhile, ionic liquid gel macroscopic view is solid-state, and part is full of liquid electricityXie Zhi, is a kind of between liquid and pure solid-state material, thereby possesses than the better mechanical strength of liquid electrolyte,And than the better chemical property of pure solid electrolyte.
The preparation of ionic liquid gel is generally divided into two kinds of physical crosslinking and chemical crosslinkings. Physical crosslinking mainly passes throughMechanical blending and film forming immersion process, as added the swelling covalently cross-linked polymethyl methacrylate system of ionic liquidStandby ionic liquid gel, the machinery that the ionic liquid gel that these class methods obtain greatly reduces ionic liquid gel is steadyQualitative. Chemical crosslinking often, by add initator, monomer (crosslinking agent) in ionic liquid solution, is drawn by heatSend out the methods such as polymerization, make the comonomer polymerisation in solution that contains unsaturated double-bond be formed with the three dimensional network of chemical crosslinkingNetwork. But conventional initiator (as benzoyl peroxide) residual in system often caused chemical propertyReduce; And ionic liquid cation group has obvious electrophilic, ionic liquid is known from experience and is made free radical cancellation brokenBad polymerization process, therefore, is used conventional method to carry out in-situ polymerization, is difficult to the synthetic ionic liquid that has larger expansion rateBody gel (J.Am.Chem.Soc., 2005,127,4976-4983; Chem.Mater., 2004,16,3091-3097). These shortcomings have limited the ionic liquid gel of preparing with said method to a great extent in electrificationThe application in field.
Ultraviolet light irradiation can produce free electron and hole free radical by vitalizing semiconductor, and then causes ionic liquidThe polymerization of middle vinyl monomer. By utilizing the raw free radical of ultraviolet irradiation semiconductor product, prepare with trigger monomer polymerizationIonic liquid gel can be realized in ionic liquid, and ionic liquid, releaser and comonomer are selectedScope is larger, and operation is easy, gel forming is controlled, and product ion content liquid is high, chemical property good,Can be used for preparing high-intensity nano combined ionic liquid gel, be used for flexible energy storage device tool as solid electrolyteThere is good application prospect.
Summary of the invention
Object of the present invention is exactly to provide a kind of semiconductor to cause in order to overcome the defect that above-mentioned prior art existsUltraviolet polymerization is prepared the electrolytical method of ionic liquid gel.
Object of the present invention can be achieved through the following technical solutions:
A kind of semiconductor causes ultraviolet polymerization and prepares the electrolytical method of ionic liquid gel, and the method is partly to leadBody, monomer join in ionic liquid, mix, then by ultraviolet light irradiation, make semiconductor produce electronics andHole, form free radical, and then trigger monomer generation Raolical polymerizable generates and has three-dimensional net structureIonic liquid gel electrolyte.
A kind of semiconductor causes ultraviolet polymerization and prepares the electrolytical method of ionic liquid gel, the method specifically comprise withLower step:
(1) semiconductor, monomer are joined in ionic liquid, magnetic agitation 0.5～1h, to mixing, is preparedObtain mixed solution;
(2) mixed solution step (1) being prepared is under 25 DEG C of conditions, and adopting light intensity is 25～30mW/cm2Ultraviolet light carry out irradiation, reaction 1～60min, prepare ionic liquid gel electrolyte.
Step also adds crosslinking agent, inorganic nano material or lithium salts in (1).
The described semiconductor of step (1) comprises the one in titania nanoparticles, tin oxide nano particle,Described semi-conductive addition is 0.05～5% of reaction raw materials gross weight.
The described monomer of step (1) is acrylamide monomers or acrylic ester monomer, described acrylamideClass monomer comprises N,N-DMAA (DMAA), and described acrylic ester monomer comprises metering systemAcid methyl esters (MMA), hydroxyethyl methacrylate (HEMA), polyethylene glycol methacrylate-styrene polymer (PEGMA)In one or more, the addition of described monomer is 5～25% of reaction raw materials gross weight.
The described ionic liquid of step (1) comprises the one in imidazolium ionic liquid or pyridine radicals ionic liquid,Anion in described ionic liquid comprises BF4 -、PF6 -Or TFSI-In one.
Described crosslinking agent is the intermiscibility compound of monomer, contains two or more two keys, comprises N, N-One or more in methylene-bisacrylamide (MBA), polyethyleneglycol diacrylate (PEGDA), describedThe addition of crosslinking agent is 0～6% of total monomer weight.
Described inorganic nano material comprises the one in aluminium oxide, silica or zirconia, and preferably average grain diameter isThe nano particle of 10～100nm, the addition of described inorganic nano material is 0～10% of reaction raw materials gross weight.
Described lithium salts comprises lithium hexafluoro phosphate (LiPF6) or two (trimethyl fluoride sulfonyl) (LiTFSI) imine lithiumIn one.
The present invention is a kind of novel method of preparing ionic liquid gel, using semiconductor as without organic initiators, and canTo solve the adverse effect of conventional initiator remnants to follow-up chemical property, meanwhile, semiconductor nanoparticle canIn polymerization process, play the effect of inorganic crosslinking agent, by providing covalent effect power to strengthen the mechanical strength of gel;What in preparation process, adopt is the method for ultraviolet light irradiation, can produce electronics by vitalizing semiconductor by ultraviolet light irradiationThen generate free radical trigger monomer polymerisation with hole, the method is gentleer, controllability good, is convenient to implement behaviourDo. The electrolytical polymer backbone of ionic liquid gel of gained has three-dimensional net structure, this space porous knotStructure can provide passage more easily for the transmission of ion, is conducive to keep chemical property. In mechanical property sideFace, prepares the ionic liquid gel electrolysis mass-energy of gained and resists the compressive strength of 30～515kPa and can return to formerShape.
Compared with prior art, the present invention has following characteristics:
1) compared with preparing polymer ions liquid gel method with traditional swelling absorption of physical crosslinking, preparation processSimply, reaction condition gentleness, not only mechanical strength is high to prepare the ionic liquid gel electrolyte of gained, and hasHigher electrolyte content;
2) because the semiconductor adopting is without organic initiators, be conducive to keep the electrolytical electrification of ionic liquid gelLearn performance, and can be used as inorganic filler and provide crosslinking points to strengthen gel mechanical performance;
3) owing to adopting ultraviolet light irradiation, can realize the regulation and control to the reaction time, make to prepare the ionic liquid of gainedBody gel electrolyte has controllability;
4) reaction raw materials wide material sources, can prepare high-intensity nano combined ionic liquid gel, haveHigh electrical conductivity, can be used as solid electrolyte, has good application prospect in pure solid-state flexible energy storing devices field.
Brief description of the drawings
Fig. 1 is embodiment 1 electron paramagnetic resonance spectrum figure (EPR);
Fig. 2 is that embodiment 1 prepares the electrolytical field emission scanning electron microscope spectrogram of gained ionic liquid gel;
Fig. 3 is that embodiment 1 prepares the circulation of gained ionic liquid gel electrolyte as double electric layers supercapacitorVolt-ampere curve spectrogram;
Fig. 4 is that embodiment 1 prepares the constant current of gained ionic liquid gel electrolyte as double electric layers supercapacitorCharging and discharging curve spectrogram.
Detailed description of the invention
Below in conjunction with the drawings and specific embodiments, the present invention is described in detail.
Embodiment 1:
Get ionic liquid (BMIMPF6), titania nanoparticles, DMAA (containing 3%MBA) according to89: 1: 10 magnetic agitation of mass ratio mix half an hour, under 25 DEG C of conditions, and ultraviolet light irradiation in addition, light intensityAbout 25mW/cm2, reaction 10min prepares ionic liquid gel electrolyte. Gained ionic liquid gel electrolyteElectrical conductivity is 0.84mS/cm, with specific area 2100m2The active carbon of/g is assembled into electric double layer as active materialUltracapacitor, under current density 1A/g, gained specific capacity is 128F/g.
As shown in Figure 1, produced in can explanation system according to the sweep signal of EPR by the semiconductor product that is stimulatedRaw electronics, the free carbon Propagating Radical that hole derives then. Shown in Fig. 2, the present embodiment prepare gained fromSub-liquid gel electrolyte has loose structure, and this transmission that is ion provides passage more easily, is conducive toKeep chemical property.
Using gained ionic liquid gel electrolyte as integrated barrier film and electrolyte, taking specific surface as 2100m2The active carbon of/g, as electrode activity thing, is assembled into double electric layers supercapacitor, carry out cyclic voltammetry andConstant current charge-discharge test, test result respectively as shown in Figure 3, Figure 4. According to the electrochemistry of selected ionic liquidCharacteristic, in test, test voltage is chosen for 0～3V. As seen from Figure 3, cyclic voltammetry curve approaches rectangle,Show good double layer capacitor behavior, also shown the good transfer ability of electrolyte intermediate ion. As Fig. 4Shown in, constant current charge-discharge curve approaches isosceles triangle, demonstrates the good behavior that discharges and recharges. Therefore, this ionLiquid gel has good ion transmission performance under electric field, has feasibility as the electrolyte of energy storage device.
Embodiment 2:
Get ionic liquid (BMIMPF6), tin oxide nano particle, DMAA (containing 3%MBA) is according to matterAmount mixes than 89: 1: 10 magnetic agitation half an hour, under 25 DEG C of conditions, and in addition ultraviolet light irradiation, light intensity is approximately25mW/cm2, reaction 40min, prepares ionic liquid gel electrolyte. Gained ionic liquid gel electrolyte electricityConductance is 0.83mS/cm, with specific area 2100m2It is super that the active carbon of/g is assembled into electric double layer as active materialLevel capacitor, under current density 1A/g, gained specific capacity is 127F/g.
Embodiment 3:
Get ionic liquid (BMIMPF6), titania nanoparticles, methyl methacrylate (contains 3%MBA) mix half an hour according to 89: 1: 10 magnetic agitation of mass ratio, under 25 DEG C of conditions, ultraviolet in additionLight irradiation, the about 25mW/cm of light intensity2, reaction 40min, prepares ionic liquid gel electrolyte. Gained ionLiquid gel electrolytic conductivity is 0.86mS/cm, with specific area 2100m2The active carbon of/g is as active matterMatter is assembled into double electric layers supercapacitor, and under current density 1A/g, gained specific capacity is 128F/g.
Embodiment 4:
Get ionic liquid (BMIMPF6), titania nanoparticles, polyethylene glycol methacrylate-styrene polymer (contains5%PEGDA) mix half an hour according to 89: 1: 10 magnetic agitation of mass ratio, at ambient temperature, addWith ultraviolet light irradiation, the about 25mW/cm of light intensity2, reaction 40min, prepares ionic liquid gel electrolyte. InstituteObtaining ionic liquid gel electrolytic conductivity is 0.84mS/cm, with specific area 2100m2The active carbon conduct of/gActive material is assembled into double electric layers supercapacitor, and under current density 1A/g, gained specific capacity is 129F/g.
Embodiment 5:
Get ionic liquid (BMIMPF6), titania nanoparticles, hydroxyethyl methacrylate (contains 3%MBA) mix half an hour according to 89: 1: 10 magnetic agitation of mass ratio, at ambient temperature, ultraviolet light in additionIrradiation, the about 25mW/cm of light intensity2, reaction 50min, prepares ionic liquid gel electrolyte. Gained ionic liquidBody gel electrolyte electrical conductivity is 0.82mS/cm, with specific area 2100m2The active carbon of/g is as active materialBe assembled into double electric layers supercapacitor, under current density 1A/g, gained specific capacity is 129F/g.
Embodiment 6:
Get ionic liquid (BMIMBF4), titania nanoparticles, DMAA (containing 3%MBA) according to89: 1: 10 magnetic agitation of mass ratio mix half an hour, at ambient temperature, and ultraviolet light irradiation in addition, light intensityAbout 25mW/cm2, reaction 15min, prepares ionic liquid gel electrolyte. The electrolysis of gained ionic liquid gelMatter electrical conductivity is 0.91mS/cm, with specific area 2100m2The active carbon of/g is assembled into two electricity as active materialLayer ultracapacitor, under current density 1A/g, gained specific capacity is 132F/g.
Embodiment 7:
Get ionic liquid (BMIMTFSI), titania nanoparticles, DMAA (containing 3%MBA) pressesMix half an hour according to 89: 1: 10 magnetic agitation of mass ratio, at ambient temperature, ultraviolet light irradiation in addition, lightStrong about 25mW/cm2, reaction 40min, prepares ionic liquid gel electrolyte. Gained ionic liquid gel electricitySeparating matter electrical conductivity is 0.92mS/cm, with specific area 2100m2The active carbon of/g is assembled into two as active materialElectricity layer ultracapacitor, under current density 1A/g, gained specific capacity is 134F/g.
Embodiment 8:
Get ionic liquid (BMIMPF6), titania nanoparticles, DMAA (containing 3%MBA), threeAl 2 O nano particle was according to mass ratio 88.9: 1: 10: 0.1 magnetic agitation mixes half an hour, at room temperature barUnder part, ultraviolet light irradiation in addition, the about 25mW/cm of light intensity2, reaction 40min, can prepare mixed nanometer ionLiquid gel electrolyte. Gained ionic liquid gel electrolytic conductivity is 0.82mS/cm, with specific area 2100m2The active carbon of/g is assembled into double electric layers supercapacitor as active material, gained under current density 1A/gSpecific capacity is 127F/g.
Embodiment 9:
Get ionic liquid (BMIMPF6), titania nanoparticles, DMAA (containing 3%MBA), threeAl 2 O nano particle was according to mass ratio 84: 1: 10: 5 magnetic agitation mix half an hour, at ambient temperature,Ultraviolet light irradiation in addition, the about 25mW/cm of light intensity2, reaction 60min, prepares ionic liquid gel electrolyte.Gained ionic liquid gel electrolytic conductivity is 0.83mS/cm, with specific area 2100m2The active carbon of/g is doneFor active material is assembled into double electric layers supercapacitor, under current density 1A/g, gained specific capacity is 126F/g.
Embodiment 10:
Get ionic liquid (BMIMPF6), titania nanoparticles, DMAA (containing 3%MBA), oxygenChange zirconium nano particle according to mass ratio 88.9: 1: 10: 0.1 magnetic agitation mixes half an hour, at ambient temperature,Ultraviolet light irradiation in addition, the about 25mW/cm of light intensity2, reaction 40min, prepares ionic liquid gel electrolyte.Gained ionic liquid gel electrolytic conductivity is 0.83mS/cm, with specific area 2100m2The active carbon of/g is doneFor active material is assembled into double electric layers supercapacitor, under current density 1A/g, gained specific capacity is 126F/g.
Embodiment 11:
Get ionic liquid (BMIMPF6), titania nanoparticles, DMAA (containing 3%MBA), oxygenChange zirconium nano particle according to mass ratio 84: 1: 10: 5 magnetic agitation mix half an hour, at ambient temperature, addWith ultraviolet light irradiation, the about 25mW/cm of light intensity2, reaction 60min, prepares ionic liquid gel electrolyte. InstituteObtaining ionic liquid gel electrolytic conductivity is 0.84mS/cm, with specific area 2100m2The active carbon conduct of/gActive material is assembled into double electric layers supercapacitor, and under current density 1A/g, gained specific capacity is 125F/g.
Embodiment 12:
Get ionic liquid (BMIMTFSI), titania nanoparticles, MMA (containing 3%MBA) according to89: 1: 10 magnetic agitation of mass ratio mix half an hour, and adding lithium salts (liTFSI) content is 0.6M, in chamberUnder temperature condition, in addition ultraviolet light irradiation, the about 25mW/cm of light intensity2, after 30min, can prepare ionic liquid gelElectrolyte. The nano combined ionic liquid gel electrolyte that visible the present embodiment is prepared gained has good phase to lithium saltsDissolubility, can be used as integrated barrier film and electrolyte for lithium battery.
Nano combined ionic liquid gel sample for above preparation (is of a size of diameter 20mm, high 1～3mmCylinder), use electronic universal tester carry out compression performance test, various performance parameters is as shown in table 1. WithControl sample is compared, and it has good mechanical property as seen.
The mechanical property of the nano combined ionic liquid gel of table 1
| Sample | Compressive strength (kPa) | Modulus of compressibility (kPa) |
| 1 | 93.8 | 3.6 |
| 2 | 515.4 | 6.5 |
| 4 | 30.2 | 2.6 |
| 7 | 489.5 | 5.6 |
| 10 | 102.5 | 4.1 |
| 11 | 123.6 | 4.9 |
Embodiment 13:
Get ionic liquid (BMIMTFSI), tin oxide nano particle, MMA (containing 3%MBA) is according to matterAmount than 70: 5: 25 magnetic agitation 1h to mixing, under 25 DEG C of conditions, in addition ultraviolet light irradiation, light intensity is approximately30mW/cm2, after 60min, can prepare ionic liquid gel electrolyte.
Embodiment 14:
Get ionic liquid (BMIMTFSI), tin oxide nano particle, MMA (containing 3%MBA) is according to matterAmount than 94.95: 0.05: 5 magnetic agitation 1h to mixing, under 25 DEG C of conditions, in addition ultraviolet light irradiation, lightStrong about 28mW/cm2, after 1min, can prepare ionic liquid gel electrolyte.
Embodiment 15:
Get ionic liquid (BMIMTFSI), tin oxide nano particle, MMA (containing 3%MBA), oxidationSilicon was according to mass ratio 79: 1: 10: 10 magnetic agitation 0.5h are to mixing, under 25 DEG C of conditions, and ultraviolet light in additionIrradiation, the about 25mW/cm of light intensity2, after 60min, can prepare ionic liquid gel electrolyte.
In the present embodiment, silica is that average grain diameter is the monox nanometer particle of 10～100nm.
Embodiment 16:
Get ionic liquid (BMIMTFSI), titania nanoparticles, MMA (containing 3%MBA), N,N-methylene-bisacrylamide, aluminium oxide was according to mass ratio 78.4: 1: 10: within 0.6: 10, magnetic agitation 0.5h is to mixing allEven, under 25 DEG C of conditions, ultraviolet light irradiation in addition, the about 25mW/cm of light intensity2, after 40min, can prepare ionLiquid gel electrolyte.
In the present embodiment, aluminium oxide is that average grain diameter is the aluminum oxide nanoparticle of 10～100nm.
Embodiment 17:
Get ionic liquid (BMIMTFSI), titania nanoparticles, MMA (containing 3%MBA), poly-Glycol diacrylate, aluminium oxide was according to mass ratio 78.4: 1: 10: 0.4: 10 magnetic agitation 0.5h is to mixing,Under 25 DEG C of conditions, ultraviolet light irradiation in addition, the about 25mW/cm of light intensity2, after 50min, can prepare ionic liquid solidifyingGlue electrolyte.
In the present embodiment, aluminium oxide is that average grain diameter is the aluminum oxide nanoparticle of 10～100nm.
Above the present invention has been done to exemplary description, but embodiments of the present invention are not subject to the limit of above-described embodimentSystem. Other any do not deviate from amendment, replacement, combination, the simplification under principle essence of the present invention, done, all shouldFor equivalent substitute mode, within being included in protection scope of the present invention.
Claims (9)
1. semiconductor initiation ultraviolet polymerization is prepared the electrolytical method of ionic liquid gel, it is characterized in that,The method is that semiconductor, monomer are joined in ionic liquid, mixes, then by ultraviolet light irradiation, makes halfConductor produces electronics and hole, forms free radical, and then trigger monomer generation Raolical polymerizable, and generation hasThe ionic liquid gel electrolyte of three-dimensional net structure.
2. a kind of semiconductor initiation ultraviolet polymerization according to claim 1 is prepared ionic liquid gel electrolyteMethod, it is characterized in that, the method specifically comprises the following steps:
(1) semiconductor, monomer are joined in ionic liquid, magnetic agitation 0.5～1h, to mixing, is preparedObtain mixed solution;
(2) mixed solution step (1) being prepared is under 25 DEG C of conditions, and adopting light intensity is 25～30mW/cm2Ultraviolet light carry out irradiation, reaction 1～60min, prepare ionic liquid gel electrolyte.
3. a kind of semiconductor initiation ultraviolet polymerization according to claim 1 is prepared ionic liquid gel electrolyteMethod, it is characterized in that, step also adds crosslinking agent, inorganic nano material or lithium salts in (1).
4. a kind of semiconductor initiation ultraviolet polymerization according to claim 1 is prepared ionic liquid gel electrolyteMethod, it is characterized in that, the described semiconductor of step (1) comprises titania nanoparticles, oxidation sijnaOne in rice grain, described semi-conductive addition is 0.05～5% of reaction raw materials gross weight.
5. a kind of semiconductor initiation ultraviolet polymerization according to claim 1 is prepared ionic liquid gel electrolyteMethod, it is characterized in that, the described monomer of step (1) is acrylamide monomers or acrylic ester monomer,Described acrylamide monomers comprises N,N-DMAA, and described acrylic ester monomer comprises firstOne or more in base methyl acrylate, hydroxyethyl methacrylate, polyethylene glycol methacrylate-styrene polymer, described inThe addition of monomer be 5～25% of reaction raw materials gross weight.
6. a kind of semiconductor initiation ultraviolet polymerization according to claim 1 is prepared ionic liquid gel electrolyteMethod, it is characterized in that, the described ionic liquid of step (1) comprise imidazolium ionic liquid or pyridine radicals fromOne in sub-liquid, the anion in described ionic liquid comprises BF4 -、PF6 -Or TFSI-In one.
7. cause ultraviolet polymerization according to a kind of semiconductor described in claim 1 or 3 and prepare ionic liquid gel electricityThe method of separating matter, is characterized in that the intermiscibility compound that described crosslinking agent is monomer contains two or manyIndividual pair of key, comprises N, one or more in N-methylene-bisacrylamide, polyethyleneglycol diacrylate, instituteThe addition of the crosslinking agent of stating is 0～6% of total monomer weight.
8. a kind of semiconductor initiation ultraviolet polymerization according to claim 3 is prepared ionic liquid gel electrolyteMethod, it is characterized in that, described inorganic nano material comprises the one in aluminium oxide, silica or zirconia,The nano particle that preferably average grain diameter is 10～100nm, the addition of described inorganic nano material is for reacting former0～10% of material gross weight.
9. a kind of semiconductor initiation ultraviolet polymerization according to claim 3 is prepared ionic liquid gel electrolyteMethod, it is characterized in that, described lithium salts comprises in lithium hexafluoro phosphate or two (trimethyl fluoride sulfonyl) imine lithiumOne.
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| CN106252078A (en) * | 2016-08-31 | 2016-12-21 | 湖南艾华集团股份有限公司 | A kind of electrolyte of photocuring gel state aluminium electrolutic capacitor and preparation method thereof |
| CN106229556A (en) * | 2016-09-05 | 2016-12-14 | 南方科技大学 | Flexible battery and the preparation method of flexible battery |
| CN108630461A (en) * | 2018-04-25 | 2018-10-09 | 同济大学 | A kind of preparation method of the full gel ultracapacitor of ionic liquid gel base |
| CN109904010A (en) * | 2019-03-13 | 2019-06-18 | 同济大学 | A kind of gel electrolyte supercapacitor of high-low temperature resistant and preparation method thereof |
| CN112086296A (en) * | 2019-06-13 | 2020-12-15 | 南京理工大学 | Hydrogel electrolyte film with physical crosslinking and preparation method and application thereof |
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| CN110600280A (en) * | 2019-10-28 | 2019-12-20 | 锦州凯美能源有限公司 | Gel electrolyte precursor and application thereof in preparation of low-internal-resistance standard solid-state supercapacitor |
| CN110600279A (en) * | 2019-10-28 | 2019-12-20 | 锦州凯美能源有限公司 | Safe gel electrolyte precursor and application thereof in preparing quasi-solid supercapacitor |
| CN110600279B (en) * | 2019-10-28 | 2021-10-12 | 锦州凯美能源有限公司 | Gel electrolyte precursor and application thereof in preparing quasi-solid supercapacitor |
| CN110600280B (en) * | 2019-10-28 | 2022-03-08 | 锦州凯美能源有限公司 | Gel electrolyte precursor and application thereof in preparation of supercapacitor |
| CN111261425A (en) * | 2020-02-07 | 2020-06-09 | 齐鲁工业大学 | Antifreeze hydrogel solid electrolyte, preparation method and application in supercapacitor |
| CN111261425B (en) * | 2020-02-07 | 2022-02-08 | 齐鲁工业大学 | Antifreeze hydrogel solid electrolyte, preparation method and application in supercapacitor |
| CN115819911A (en) * | 2022-11-24 | 2023-03-21 | 同济大学 | Ionic gel and preparation method thereof, and preparation method and application of ionic gel film |
| CN115819911B (en) * | 2022-11-24 | 2023-10-20 | 同济大学 | Ionic gel and preparation method thereof, and preparation method and application of ionic gel film |
| CN115819911B9 (en) * | 2022-11-24 | 2024-05-17 | 同济大学 | Ionic gel and preparation method thereof, and preparation method and application of ionic gel film |
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