CN103560268B - A kind of boron doped graphene modified gel method for preparing polymer electrolytes - Google Patents
A kind of boron doped graphene modified gel method for preparing polymer electrolytes Download PDFInfo
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- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 62
- 229910021389 graphene Inorganic materials 0.000 title claims abstract description 39
- 239000005518 polymer electrolyte Substances 0.000 title claims abstract description 23
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 title claims abstract description 22
- 229910052796 boron Inorganic materials 0.000 title claims abstract description 22
- 238000000034 method Methods 0.000 title claims abstract description 17
- 239000000243 solution Substances 0.000 claims abstract description 59
- 229920000642 polymer Polymers 0.000 claims abstract description 22
- 239000004372 Polyvinyl alcohol Substances 0.000 claims abstract description 15
- 229920002451 polyvinyl alcohol Polymers 0.000 claims abstract description 15
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 12
- 239000008151 electrolyte solution Substances 0.000 claims abstract description 6
- 238000002360 preparation method Methods 0.000 claims description 11
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 6
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 6
- 238000007710 freezing Methods 0.000 claims description 6
- 230000008014 freezing Effects 0.000 claims description 6
- -1 polytetrafluoroethylene Polymers 0.000 claims description 6
- 229920001343 polytetrafluoroethylene Polymers 0.000 claims description 6
- 239000004810 polytetrafluoroethylene Substances 0.000 claims description 6
- 235000011114 ammonium hydroxide Nutrition 0.000 claims description 5
- 229910002804 graphite Inorganic materials 0.000 claims description 5
- 239000010439 graphite Substances 0.000 claims description 5
- NWZSZGALRFJKBT-KNIFDHDWSA-N (2s)-2,6-diaminohexanoic acid;(2s)-2-hydroxybutanedioic acid Chemical group OC(=O)[C@@H](O)CC(O)=O.NCCCC[C@H](N)C(O)=O NWZSZGALRFJKBT-KNIFDHDWSA-N 0.000 claims description 4
- CIWBSHSKHKDKBQ-JLAZNSOCSA-N Ascorbic acid Chemical compound OC[C@H](O)[C@H]1OC(=O)C(O)=C1O CIWBSHSKHKDKBQ-JLAZNSOCSA-N 0.000 claims description 4
- UORVGPXVDQYIDP-UHFFFAOYSA-N borane Chemical compound B UORVGPXVDQYIDP-UHFFFAOYSA-N 0.000 claims description 4
- 229910010277 boron hydride Inorganic materials 0.000 claims description 4
- 239000003638 chemical reducing agent Substances 0.000 claims description 4
- IKDUDTNKRLTJSI-UHFFFAOYSA-N hydrazine monohydrate Substances O.NN IKDUDTNKRLTJSI-UHFFFAOYSA-N 0.000 claims description 4
- 230000008569 process Effects 0.000 claims description 4
- BTBUEUYNUDRHOZ-UHFFFAOYSA-N Borate Chemical compound [O-]B([O-])[O-] BTBUEUYNUDRHOZ-UHFFFAOYSA-N 0.000 claims description 3
- 238000003756 stirring Methods 0.000 claims description 3
- ZZZCUOFIHGPKAK-UHFFFAOYSA-N D-erythro-ascorbic acid Natural products OCC1OC(=O)C(O)=C1O ZZZCUOFIHGPKAK-UHFFFAOYSA-N 0.000 claims description 2
- 239000002033 PVDF binder Substances 0.000 claims description 2
- 239000002202 Polyethylene glycol Substances 0.000 claims description 2
- 229930003268 Vitamin C Natural products 0.000 claims description 2
- 239000007864 aqueous solution Substances 0.000 claims description 2
- 239000004327 boric acid Substances 0.000 claims description 2
- 229910052810 boron oxide Inorganic materials 0.000 claims description 2
- JKWMSGQKBLHBQQ-UHFFFAOYSA-N diboron trioxide Chemical compound O=BOB=O JKWMSGQKBLHBQQ-UHFFFAOYSA-N 0.000 claims description 2
- CEYULKASIQJZGP-UHFFFAOYSA-L disodium;2-(carboxymethyl)-2-hydroxybutanedioate Chemical compound [Na+].[Na+].[O-]C(=O)CC(O)(C(=O)O)CC([O-])=O CEYULKASIQJZGP-UHFFFAOYSA-L 0.000 claims description 2
- 239000012467 final product Substances 0.000 claims description 2
- 150000004676 glycans Chemical class 0.000 claims description 2
- XMBWDFGMSWQBCA-UHFFFAOYSA-N hydrogen iodide Chemical compound I XMBWDFGMSWQBCA-UHFFFAOYSA-N 0.000 claims description 2
- 229910000043 hydrogen iodide Inorganic materials 0.000 claims description 2
- 239000002608 ionic liquid Substances 0.000 claims description 2
- INHCSSUBVCNVSK-UHFFFAOYSA-L lithium sulfate Inorganic materials [Li+].[Li+].[O-]S([O-])(=O)=O INHCSSUBVCNVSK-UHFFFAOYSA-L 0.000 claims description 2
- 239000000203 mixture Substances 0.000 claims description 2
- 229920003229 poly(methyl methacrylate) Polymers 0.000 claims description 2
- 229920002239 polyacrylonitrile Polymers 0.000 claims description 2
- 229920001223 polyethylene glycol Polymers 0.000 claims description 2
- 239000004926 polymethyl methacrylate Substances 0.000 claims description 2
- 229920001282 polysaccharide Polymers 0.000 claims description 2
- 239000005017 polysaccharide Substances 0.000 claims description 2
- 229920002981 polyvinylidene fluoride Polymers 0.000 claims description 2
- RBTVSNLYYIMMKS-UHFFFAOYSA-N tert-butyl 3-aminoazetidine-1-carboxylate;hydrochloride Chemical compound Cl.CC(C)(C)OC(=O)N1CC(N)C1 RBTVSNLYYIMMKS-UHFFFAOYSA-N 0.000 claims description 2
- 235000019154 vitamin C Nutrition 0.000 claims description 2
- 239000011718 vitamin C Substances 0.000 claims description 2
- 125000005619 boric acid group Chemical group 0.000 claims 1
- 239000000499 gel Substances 0.000 abstract description 36
- 239000003990 capacitor Substances 0.000 abstract description 12
- 230000000694 effects Effects 0.000 abstract description 7
- 239000003792 electrolyte Substances 0.000 abstract description 6
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 abstract description 5
- 229910001416 lithium ion Inorganic materials 0.000 abstract description 5
- 239000000446 fuel Substances 0.000 abstract description 4
- 239000011244 liquid electrolyte Substances 0.000 abstract description 4
- 239000011159 matrix material Substances 0.000 abstract description 3
- 239000000017 hydrogel Substances 0.000 abstract 2
- 229910052799 carbon Inorganic materials 0.000 description 14
- 229940068984 polyvinyl alcohol Drugs 0.000 description 11
- 235000019422 polyvinyl alcohol Nutrition 0.000 description 10
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 8
- 150000002500 ions Chemical class 0.000 description 6
- 238000002791 soaking Methods 0.000 description 5
- 239000006230 acetylene black Substances 0.000 description 4
- 238000000627 alternating current impedance spectroscopy Methods 0.000 description 4
- 238000011049 filling Methods 0.000 description 4
- 239000006260 foam Substances 0.000 description 4
- 239000011268 mixed slurry Substances 0.000 description 4
- 239000011259 mixed solution Substances 0.000 description 4
- 229910052759 nickel Inorganic materials 0.000 description 4
- 229920003023 plastic Polymers 0.000 description 4
- 239000004033 plastic Substances 0.000 description 4
- 229910001220 stainless steel Inorganic materials 0.000 description 4
- 239000010935 stainless steel Substances 0.000 description 4
- 238000001291 vacuum drying Methods 0.000 description 4
- 238000013019 agitation Methods 0.000 description 3
- 230000009514 concussion Effects 0.000 description 3
- 239000008367 deionised water Substances 0.000 description 3
- 229910021641 deionized water Inorganic materials 0.000 description 3
- 239000011245 gel electrolyte Substances 0.000 description 3
- OAKJQQAXSVQMHS-UHFFFAOYSA-N Hydrazine Chemical compound NN OAKJQQAXSVQMHS-UHFFFAOYSA-N 0.000 description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- 230000008901 benefit Effects 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 239000003153 chemical reaction reagent Substances 0.000 description 2
- 125000004122 cyclic group Chemical group 0.000 description 2
- 238000004146 energy storage Methods 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- 108010010803 Gelatin Proteins 0.000 description 1
- 102000004310 Ion Channels Human genes 0.000 description 1
- 229910018095 Ni-MH Inorganic materials 0.000 description 1
- 229910018477 Ni—MH Inorganic materials 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 230000002411 adverse Effects 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- 238000004220 aggregation Methods 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- KGBXLFKZBHKPEV-UHFFFAOYSA-N boric acid Chemical compound OB(O)O KGBXLFKZBHKPEV-UHFFFAOYSA-N 0.000 description 1
- 125000002091 cationic group Chemical group 0.000 description 1
- 238000010382 chemical cross-linking Methods 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 238000004132 cross linking Methods 0.000 description 1
- 239000003431 cross linking reagent Substances 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 239000002360 explosive Substances 0.000 description 1
- 239000008273 gelatin Substances 0.000 description 1
- 229920000159 gelatin Polymers 0.000 description 1
- 235000019322 gelatine Nutrition 0.000 description 1
- 235000011852 gelatine desserts Nutrition 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- 238000011068 loading method Methods 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
Classifications
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/056—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes
- H01M10/0564—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes the electrolyte being constituted of organic materials only
- H01M10/0565—Polymeric materials, e.g. gel-type or solid-type
-
- 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
- H01G11/56—Solid electrolytes, e.g. gels; Additives therein
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
- H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
- H01G11/84—Processes for the manufacture of hybrid or EDL capacitors, or components thereof
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M8/00—Fuel cells; Manufacture thereof
- H01M8/10—Fuel cells with solid electrolytes
- H01M8/1016—Fuel cells with solid electrolytes characterised by the electrolyte material
- H01M8/1018—Polymeric electrolyte materials
-
- 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
- Y02E60/10—Energy storage using batteries
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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
-
- 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
- Y02E60/30—Hydrogen technology
- Y02E60/50—Fuel cells
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- Engineering & Computer Science (AREA)
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- Power Engineering (AREA)
- Manufacturing & Machinery (AREA)
- Microelectronics & Electronic Packaging (AREA)
- General Chemical & Material Sciences (AREA)
- Sustainable Development (AREA)
- Sustainable Energy (AREA)
- Life Sciences & Earth Sciences (AREA)
- Physics & Mathematics (AREA)
- Condensed Matter Physics & Semiconductors (AREA)
- Dispersion Chemistry (AREA)
- General Physics & Mathematics (AREA)
- Inorganic Chemistry (AREA)
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Abstract
The invention discloses a kind of boron doped graphene modified gel method for preparing polymer electrolytes, can be applicable to the fields such as ultracapacitor, hybrid super capacitor, lithium ion battery and fuel cell.For polyvinyl alcohol as polymeric matrix, its feature comprises the steps: graphene oxide to be scattered in polyvinyl alcohol water solution, crosslinked method is adopted to carry out preforming, such as freeze-thaw legal system is for polyvinyl alcohol hydrogel, hydrogel is soaked in BAS and electrolyte solution successively, obtains gel polymer electrolyte.Inventive gel polymer dielectric has high ionic conductivity, strong mechanical performance intensity and good electrode/electrolyte interface effect, can be used for alternative liquid electrolyte solution.
Description
Technical field
The present invention relates to gel polymer electrolyte, more specifically, relates to a kind of boron doped graphene modified gel method for preparing polymer electrolytes.
Background technology
Electrolyte is one of important component part in electric energy storage and electric conversion devices, its dominant role of playing the part of is to provide the ion that can transmit or the passage as ion transfer, has important application in fields such as secondary cell (lead acid accumulator, Ni-MH battery and lithium ion battery etc.), capacitor (ultracapacitor, hybrid super capacitor), transducer and DSSC.Traditional electrolyte, mainly based on liquid electrolyte system, be because ionic conductivity is high under liquid medium, but its easy-to-leak liquid, the shortcoming such as inflammable and explosive makes people constantly find safer electrolyte system.Although all solid state electrolyte can fundamentally solve the problem, low ionic conductivity, the kind not only making it possible to really come into operation is few for counting, and the device performance of overall package is not good, greatly limit it and applies.Gel polymer electrolyte, or be called colloidal polymer electrolyte, both having remained the feature of liquid electrolyte high ionic conductivity in nature, having taken into account again all solid state electrolyte shape and can keep machinable advantage, thus having obtained the favor of more scholars and researcher.
Graphene oxide is considered to a kind of well cationic promoter, the ionic conductivity itself had can reach 2.1S/cm, the ionic conductivity of polymeric matrix can be significantly improved, but correlative study result shows, the graphene oxide of high-load to polymer intermediate ion transmission mechanism without obvious contribution, or even harmful.Self-assemble effect can be there is in this graphene oxide that mainly concentration is higher, although ion is fast in the surface delivery speed of graphene oxide, but building-up effect makes can to reduce for the path of ion transfer, elongated, thus improve little to the ionic conductivity of gel polymer electrolyte.The present invention adopts boron doped mode to open the ion channel got clogged in graphene oxide aggregation, thus under obtaining high-load graphene oxide loading, realizing the characteristic of macroion conduction efficiency, the gel polymer electrolyte of preparation can be applied to the fields such as ultracapacitor, hybrid super capacitor, lithium ion battery and fuel cell.
Summary of the invention
The invention provides a kind of boron doped graphene modified gel method for preparing polymer electrolytes of high ionic conductivity, comprise the following steps:
S1. by straight polymer solution or be poured in the mould of definite shape containing the polymer solution of graphene oxide, leave standstill to still; ;
S2. solution is carried out cryogenic freezing process, then in thawed at room temperature, repeatedly carry out freezing-solution freeze cycle operation 3-10 time, form gel;
S3. the gel of step S2 gained soaks through boron-containing solution and electrolyte solution successively, to obtain final product.
Described polymer is polyvinyl alcohol, or one or more blends formed in itself and polyethylene glycol oxide, polysaccharide, polyacrylonitrile, polymethyl methacrylate, polytetrafluoroethylene or polyvinylidene fluoride.
Described electrolyte solution is potassium hydroxide, lithium sulfate solution, methanol aqueous solution or ionic liquid.
The preparation method of the polymer solution containing graphene oxide described in S1 is as follows:
S11. graphite oxide is dissolved in certain density ammoniacal liquor, ultrasonic, obtain graphene oxide water solution;
S12. get polymer solution, add step S11 gained graphene oxide water solution under stirring, shake and adjust pH to 9 ~ 10, must containing the polymer solution of graphene oxide.
The quality of the graphene oxide in step S12 and polymer content is 0 ~ 10:1. than scope
The polymer solution containing graphene oxide described in step S1, can use reducing agent process further.
Described reducing agent is hydrazine hydrate, boron hydride, natrium citricum, vitamin C or hydrogen iodide.
Boron-containing solution described in step S3 is boric acid, borate, boron hydride or boron oxide.
Further, a kind of boron doped graphene modified gel polymer dielectric according to above-mentioned preparation method's gained is provided.
And according to the boron doped graphene modified gel polymer dielectric of above-mentioned gained, provide its application in ultracapacitor, hybrid super capacitor, lithium ion battery or fuel cell.
The present invention has the following advantages:
1. the invention provides a kind of boron doped with oxygen functionalized graphene method for preparing gel polymer electrolyte, the gel electrolyte of preparation can be applicable to the fields such as ultracapacitor, hybrid super capacitor, lithium ion battery and fuel cell.First graphene oxide/polyblend solution is prepared by the method for solution blending, then be cross-linked, carry out physical crosslinking as adopted freeze-thaw method or add the method preforming that crosslinking agent carries out chemical crosslinking, prepare polymer gel, subsequently boron doping is carried out to polymer gel, as adopted the method for the solution soaking containing borate, finally gelatin polymer being soaked electrolyte solution, obtaining gel polymer electrolyte.
2. the present invention adopts boron doped object to be to overcome the adverse effect of high-load graphene oxide to gel polymer electrolyte ionic conductivity, farthest play graphene oxide to the facilitation of ion transfer, and in some electric energy storage or electric conversion devices, electrode and electrolytical interfacial interaction can be improved significantly after gel polymer electrolyte carries out boron doping, reduce interface impedance.
3. the boron doped with oxygen functionalized graphene gel polymer electrolyte that prepared by the present invention has high ionic conductivity, good mechanical property, can be used for alternative traditional neat liquid electrolyte system.
Accompanying drawing explanation
Fig. 1 adopts the AC impedance curve of the ultracapacitor of the boron polyvinyl alcohol gel electrolyte of embodiment 1 (electrode is symmetrical active carbon electrode).
Fig. 2 adopts the Cyclic voltamogram curve of ultracapacitor under different voltage scan rate of the boron polyvinyl alcohol gel electrolyte of embodiment 1 (electrode is symmetrical active carbon electrode).
Fig. 3 is the mechanical curves of the boron polyvinyl alcohol gel of embodiment 1.
Embodiment
The present invention is further described below in conjunction with the drawings and specific embodiments.Unless stated otherwise, the present invention adopts reagent, equipment and method are conventional commercial reagent, equipment and the conventional method used of the art.
What embodiment was investigated is gel polymer electrolyte type double electric layer capacitor, and polymer electrolyte matrix selects polyvinyl alcohol.
Embodiment 1
Measure the poly-vinyl alcohol solution of 5mL0.1g/mL, be poured in plastic culture dish (Ф 90mm), leave standstill still.The refrigerating chamber culture dish filling solution being placed in-20 DEG C carries out freezing, then in thawed at room temperature, repeatedly carries out freezing-solution freeze cycle and operates 5 times.Gel in culture dish is taken out, is immersed in 1mg/mL BAS (pH ~ 11) about 48h.Gel after soaking is taken out, is immersed in 6mol/LKOH solution.Electrode adopts active carbon, and (specific area is about 1800cm
2/ g), stock quality proportioning is according to active carbon: acetylene black: the mixed slurry of polytetrafluoroethylene=82:10:8, and nickel foam suppresses film forming, by the film of compacting in vacuum drying chamber in 80 DEG C of more than freeze-day with constant temperature 24h.Collector adopts stainless steel briquetting, and collector/carbon electrode/gel polymer electrolyte/collector/spring plate group is dressed up button cell, the ac impedance spectroscopy of test capacitors by order, and as shown in Figure 1, calculating ionic conductivity is 0.134S/cm
2.The Cyclic voltamogram curve of test capacitors under different voltage scan rate, as shown in Figure 2.Fig. 3 is the mechanical curves of boron polyvinyl alcohol gel.
Embodiment 2
Precise is about 2.5mg graphite oxide, is dissolved in the mixed solution of 2.5mL deionized water and 0.05mL25% ammoniacal liquor, ultrasonic 20min.Measure the poly-vinyl alcohol solution of 5mL0.1g/mL, under magnetic agitation effect, drip toward in above-mentioned graphene oxide water solution, be mixed to appearance uniform, under room temperature condition, continue concussion solution 24h, pH value of solution is at 9.7-9.8.Solution being poured in plastic culture dish (Ф 90mm), leaving standstill still. the refrigerating chamber culture dish filling solution being placed in-20 DEG C carries out freezing, then in thawed at room temperature, repeatedly carries out freezing-solution freeze cycle and operates 5 times.Gel in culture dish is taken out, is immersed in 1mg/mL BAS (pH ~ 11) about 48h.Gel after soaking is taken out, is immersed in 6mol/LKOH solution.Electrode adopts active carbon, and (specific area is about 1800cm
2/ g), stock quality proportioning is according to active carbon: acetylene black: the mixed slurry of polytetrafluoroethylene=82:10:8, and nickel foam suppresses film forming, by the film of compacting in vacuum drying chamber in 80 DEG C of more than freeze-day with constant temperature 24h.Collector adopts stainless steel briquetting, and collector/carbon electrode/gel polymer electrolyte/collector/spring plate group is dressed up button cell, the ac impedance spectroscopy of test capacitors by order, and calculating ionic conductivity is 0.130S/cm
2.
Embodiment 3
Precise is about 100mg graphite oxide, is dissolved in the mixed solution of 2.5mL deionized water and 0.05mL25% ammoniacal liquor, ultrasonic 20min.Measure the poly-vinyl alcohol solution of 5mL0.1g/mL, under magnetic agitation effect, drip toward in above-mentioned graphene oxide water solution, be mixed to appearance uniform, under room temperature condition, continue concussion solution 24h, pH value of solution is at 9.7-9.8.Being poured in plastic culture dish (Ф 90mm), leaving standstill still. the refrigerating chamber culture dish filling solution being placed in-20 DEG C carries out freezing, then in thawed at room temperature, repeatedly carries out freezing-solution freeze cycle and operates 5 times.Gel in culture dish is taken out, is immersed in 1mg/mL BAS (pH ~ 11) about 48h.Gel after soaking is taken out, is immersed in 6mol/LKOH solution.Electrode adopts active carbon, and (specific area is about 1800cm
2/ g), stock quality proportioning is according to active carbon: acetylene black: the mixed slurry of polytetrafluoroethylene=82:10:8, and nickel foam suppresses film forming, by the film of compacting in vacuum drying chamber in 80 DEG C of more than freeze-day with constant temperature 24h.Collector adopts stainless steel briquetting, and collector/carbon electrode/gel polymer electrolyte/collector/spring plate group is dressed up button cell, the ac impedance spectroscopy of test capacitors by order, and calculating ionic conductivity is 0.195S/cm
2
Embodiment 4
Precise is about 2.5mg graphite oxide, is dissolved in the mixed solution of 2.5mL deionized water and 0.05mL25% ammoniacal liquor, ultrasonic 20min.Measure the poly-vinyl alcohol solution of 5mL0.1g/mL, under magnetic agitation effect, drip toward in above-mentioned graphene oxide water solution, be mixed to appearance uniform, under room temperature condition, continue concussion solution 24h, pH value of solution is at 9.7-9.8.On basis prepared by above-mentioned graphene oxide-polyvinyl alcohol water solution, adopt microsyringe (10 μ L or 100 μ L) according to hydrazine hydrate and the certain mass ratio (1:1) of graphene oxide toward a certain amount of hydrazine hydrate solution of mixed solution and dripping (hydrazine content 80%). after solution is continued to shake several minutes, under being placed in 90 DEG C of oil baths, stir reduction 1 ~ 1.5h.After cooling, solution being poured in plastic culture dish (Ф 90mm), leaving standstill still. the refrigerating chamber culture dish filling solution being placed in-20 DEG C carries out freezing, then in thawed at room temperature, repeatedly carries out freezing-solution freeze cycle and operates 5 times.Gel in culture dish is taken out, is immersed in 1mg/mL BAS (pH=~ 11) about 48h.Gel after soaking is taken out, is immersed in 6mol/LKOH solution.Electrode adopts active carbon, and (specific area is about 1800cm
2/ g), stock quality proportioning is according to active carbon: acetylene black: the mixed slurry of polytetrafluoroethylene=82:10:8, and nickel foam suppresses film forming, by the film of compacting in vacuum drying chamber in 80 DEG C of more than freeze-day with constant temperature 24h.Collector adopts stainless steel briquetting, and collector/carbon electrode/gel polymer electrolyte/collector/spring plate group is dressed up button cell, the ac impedance spectroscopy of test capacitors by order, and the ionic conductivity of calculating is 0.140S/cm
2.
Claims (7)
1. a boron doped graphene modified gel method for preparing polymer electrolytes, is characterized in that, comprise the following steps:
S1. the polymer solution containing graphene oxide is poured in the mould of definite shape, leaves standstill to still;
S2. solution is carried out cryogenic freezing process, then in thawed at room temperature, repeatedly carry out freezing-solution freeze cycle operation 3-10 time, form gel;
S3. the gel of step S2 gained soaks through boron-containing solution and electrolyte solution successively, to obtain final product;
Described polymer is polyvinyl alcohol, or one or more blends formed in itself and polyethylene glycol oxide, polysaccharide, polyacrylonitrile, polymethyl methacrylate, polytetrafluoroethylene or polyvinylidene fluoride.
2. preparation method according to claim 1, is characterized in that, described electrolyte solution is potassium hydroxide, lithium sulfate solution, methanol aqueous solution or ionic liquid.
3. preparation method according to claim 1, is characterized in that, the preparation method of the polymer solution containing graphene oxide described in step S1 is as follows:
S11. graphite oxide is dissolved in certain density ammoniacal liquor, ultrasonic, obtain graphene oxide water solution;
S12. get polymer solution, add step S11 gained graphene oxide water solution under stirring, shake and adjust pH to 9 ~ 10, must containing the polymer solution of graphene oxide.
4. preparation method according to claim 3, is characterized in that, the quality of the graphene oxide in step S12 and polymer content is 0 ~ 10:1 than scope, does not comprise zero.
5. preparation method according to claim 1, is characterized in that, the polymer solution containing graphene oxide described in step S1, can use reducing agent process further.
6. preparation method according to claim 5, is characterized in that, described reducing agent is hydrazine hydrate, boron hydride, natrium citricum, vitamin C or hydrogen iodide.
7. preparation method according to claim 1, is characterized in that, in the boron-containing solution described in step S3, solute is boric acid, borate, boron hydride or boron oxide.
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