CN104966621A - Solvent co-intercalated sodium ion capacitor - Google Patents
Solvent co-intercalated sodium ion capacitor Download PDFInfo
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- CN104966621A CN104966621A CN201510242864.9A CN201510242864A CN104966621A CN 104966621 A CN104966621 A CN 104966621A CN 201510242864 A CN201510242864 A CN 201510242864A CN 104966621 A CN104966621 A CN 104966621A
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- Prior art keywords
- ion capacitor
- sodium ion
- sodium
- electrolyte
- porous
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- 239000003990 capacitor Substances 0.000 title claims abstract description 63
- 229910001415 sodium ion Inorganic materials 0.000 title claims abstract description 62
- FKNQFGJONOIPTF-UHFFFAOYSA-N Sodium cation Chemical compound [Na+] FKNQFGJONOIPTF-UHFFFAOYSA-N 0.000 title claims abstract description 59
- 239000002904 solvent Substances 0.000 title claims abstract description 16
- 239000011734 sodium Substances 0.000 claims abstract description 28
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 claims abstract description 25
- 229910052708 sodium Inorganic materials 0.000 claims abstract description 25
- 239000003792 electrolyte Substances 0.000 claims abstract description 23
- 239000000463 material Substances 0.000 claims abstract description 11
- -1 hexafluorophosphate Chemical compound 0.000 claims abstract description 8
- 239000002028 Biomass Substances 0.000 claims abstract description 5
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims abstract description 4
- VLTRZXGMWDSKGL-UHFFFAOYSA-M perchlorate Inorganic materials [O-]Cl(=O)(=O)=O VLTRZXGMWDSKGL-UHFFFAOYSA-M 0.000 claims abstract description 3
- VLTRZXGMWDSKGL-UHFFFAOYSA-N perchloric acid Chemical compound OCl(=O)(=O)=O VLTRZXGMWDSKGL-UHFFFAOYSA-N 0.000 claims abstract description 3
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 33
- 230000004888 barrier function Effects 0.000 claims description 19
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 claims description 14
- 229910001416 lithium ion Inorganic materials 0.000 claims description 14
- 229910052799 carbon Inorganic materials 0.000 claims description 11
- 239000000835 fiber Substances 0.000 claims description 9
- ZUHZGEOKBKGPSW-UHFFFAOYSA-N tetraglyme Chemical compound COCCOCCOCCOCCOC ZUHZGEOKBKGPSW-UHFFFAOYSA-N 0.000 claims description 8
- 239000011230 binding agent Substances 0.000 claims description 7
- 229910002804 graphite Inorganic materials 0.000 claims description 7
- 239000010439 graphite Substances 0.000 claims description 7
- 239000006258 conductive agent Substances 0.000 claims description 6
- 239000002002 slurry Substances 0.000 claims description 6
- SBZXBUIDTXKZTM-UHFFFAOYSA-N diglyme Chemical compound COCCOCCOC SBZXBUIDTXKZTM-UHFFFAOYSA-N 0.000 claims description 5
- 229910021389 graphene Inorganic materials 0.000 claims description 5
- 239000005030 aluminium foil Substances 0.000 claims description 4
- 239000011148 porous material Substances 0.000 claims description 4
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 3
- 229910000831 Steel Inorganic materials 0.000 claims description 3
- 239000002174 Styrene-butadiene Substances 0.000 claims description 3
- DPXJVFZANSGRMM-UHFFFAOYSA-N acetic acid;2,3,4,5,6-pentahydroxyhexanal;sodium Chemical compound [Na].CC(O)=O.OCC(O)C(O)C(O)C(O)C=O DPXJVFZANSGRMM-UHFFFAOYSA-N 0.000 claims description 3
- 239000001768 carboxy methyl cellulose Substances 0.000 claims description 3
- 229910021382 natural graphite Inorganic materials 0.000 claims description 3
- 235000019812 sodium carboxymethyl cellulose Nutrition 0.000 claims description 3
- 229920001027 sodium carboxymethylcellulose Polymers 0.000 claims description 3
- 239000010959 steel Substances 0.000 claims description 3
- 229920003048 styrene butadiene rubber Polymers 0.000 claims description 3
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 2
- 239000006230 acetylene black Substances 0.000 claims description 2
- 239000011149 active material Substances 0.000 claims description 2
- 150000001450 anions Chemical class 0.000 claims description 2
- MTAZNLWOLGHBHU-UHFFFAOYSA-N butadiene-styrene rubber Chemical compound C=CC=C.C=CC1=CC=CC=C1 MTAZNLWOLGHBHU-UHFFFAOYSA-N 0.000 claims description 2
- 239000002041 carbon nanotube Substances 0.000 claims description 2
- 229910021393 carbon nanotube Inorganic materials 0.000 claims description 2
- 150000001768 cations Chemical class 0.000 claims description 2
- 229910052802 copper Inorganic materials 0.000 claims description 2
- 239000010949 copper Substances 0.000 claims description 2
- 239000004816 latex Substances 0.000 claims description 2
- 229920000126 latex Polymers 0.000 claims description 2
- 239000007773 negative electrode material Substances 0.000 claims description 2
- 229920001343 polytetrafluoroethylene Polymers 0.000 claims description 2
- 239000004810 polytetrafluoroethylene Substances 0.000 claims description 2
- 239000007774 positive electrode material Substances 0.000 claims description 2
- 229910001220 stainless steel Inorganic materials 0.000 claims description 2
- 239000010935 stainless steel Substances 0.000 claims description 2
- 239000004575 stone Substances 0.000 claims description 2
- 239000011115 styrene butadiene Substances 0.000 claims description 2
- 239000010936 titanium Substances 0.000 claims description 2
- 229910052719 titanium Inorganic materials 0.000 claims description 2
- ITMCEJHCFYSIIV-UHFFFAOYSA-N triflic acid Chemical compound OS(=O)(=O)C(F)(F)F ITMCEJHCFYSIIV-UHFFFAOYSA-N 0.000 claims description 2
- 238000007599 discharging Methods 0.000 abstract description 16
- LCGLNKUTAGEVQW-UHFFFAOYSA-N Dimethyl ether Chemical compound COC LCGLNKUTAGEVQW-UHFFFAOYSA-N 0.000 abstract description 6
- 238000004519 manufacturing process Methods 0.000 abstract description 6
- 239000010406 cathode material Substances 0.000 abstract description 3
- 150000002148 esters Chemical class 0.000 abstract description 2
- 150000002500 ions Chemical class 0.000 abstract 2
- 125000004122 cyclic group Chemical group 0.000 abstract 1
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 abstract 1
- ITMCEJHCFYSIIV-UHFFFAOYSA-M triflate Chemical compound [O-]S(=O)(=O)C(F)(F)F ITMCEJHCFYSIIV-UHFFFAOYSA-M 0.000 abstract 1
- 229910052744 lithium Inorganic materials 0.000 description 11
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 9
- 238000004146 energy storage Methods 0.000 description 7
- 238000000034 method Methods 0.000 description 7
- 230000014759 maintenance of location Effects 0.000 description 6
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 4
- 238000002156 mixing Methods 0.000 description 4
- 230000008569 process Effects 0.000 description 4
- QGHDLJAZIIFENW-UHFFFAOYSA-N 4-[1,1,1,3,3,3-hexafluoro-2-(4-hydroxy-3-prop-2-enylphenyl)propan-2-yl]-2-prop-2-enylphenol Chemical group C1=C(CC=C)C(O)=CC=C1C(C(F)(F)F)(C(F)(F)F)C1=CC=C(O)C(CC=C)=C1 QGHDLJAZIIFENW-UHFFFAOYSA-N 0.000 description 3
- 229910019142 PO4 Inorganic materials 0.000 description 3
- KEAYESYHFKHZAL-UHFFFAOYSA-N Sodium Chemical compound [Na] KEAYESYHFKHZAL-UHFFFAOYSA-N 0.000 description 3
- 229910052782 aluminium Inorganic materials 0.000 description 3
- 230000008901 benefit Effects 0.000 description 3
- 230000008859 change Effects 0.000 description 3
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 3
- 239000010452 phosphate Substances 0.000 description 3
- 238000003756 stirring Methods 0.000 description 3
- 238000003466 welding Methods 0.000 description 3
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 2
- 238000001354 calcination Methods 0.000 description 2
- 230000005611 electricity Effects 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 239000007770 graphite material Substances 0.000 description 2
- 239000002931 mesocarbon microbead Substances 0.000 description 2
- 229910052759 nickel Inorganic materials 0.000 description 2
- KMTRUDSVKNLOMY-UHFFFAOYSA-N Ethylene carbonate Chemical compound O=C1OCCO1 KMTRUDSVKNLOMY-UHFFFAOYSA-N 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 239000004411 aluminium Substances 0.000 description 1
- 229910052786 argon Inorganic materials 0.000 description 1
- 239000003575 carbonaceous material Substances 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 239000011889 copper foil Substances 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- IEJIGPNLZYLLBP-UHFFFAOYSA-N dimethyl carbonate Chemical compound COC(=O)OC IEJIGPNLZYLLBP-UHFFFAOYSA-N 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000003487 electrochemical reaction Methods 0.000 description 1
- 239000007772 electrode material Substances 0.000 description 1
- 239000000839 emulsion Substances 0.000 description 1
- 238000005538 encapsulation Methods 0.000 description 1
- 238000011049 filling Methods 0.000 description 1
- 239000011888 foil Substances 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 150000002632 lipids Chemical class 0.000 description 1
- 238000006138 lithiation reaction Methods 0.000 description 1
- 229910000476 molybdenum oxide Inorganic materials 0.000 description 1
- 239000002127 nanobelt Substances 0.000 description 1
- 239000002071 nanotube Substances 0.000 description 1
- 230000006855 networking Effects 0.000 description 1
- 239000011368 organic material Substances 0.000 description 1
- PQQKPALAQIIWST-UHFFFAOYSA-N oxomolybdenum Chemical compound [Mo]=O PQQKPALAQIIWST-UHFFFAOYSA-N 0.000 description 1
- 230000000737 periodic effect Effects 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 230000001172 regenerating effect Effects 0.000 description 1
- GROMGGTZECPEKN-UHFFFAOYSA-N sodium metatitanate Chemical compound [Na+].[Na+].[O-][Ti](=O)O[Ti](=O)O[Ti]([O-])=O GROMGGTZECPEKN-UHFFFAOYSA-N 0.000 description 1
- PNGLEYLFMHGIQO-UHFFFAOYSA-M sodium;3-(n-ethyl-3-methoxyanilino)-2-hydroxypropane-1-sulfonate;dihydrate Chemical compound O.O.[Na+].[O-]S(=O)(=O)CC(O)CN(CC)C1=CC=CC(OC)=C1 PNGLEYLFMHGIQO-UHFFFAOYSA-M 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
- H01G11/22—Electrodes
- H01G11/24—Electrodes characterised by structural features of the materials making up or comprised in the electrodes, e.g. form, surface area or porosity; characterised by the structural features of powders or particles used therefor
-
- 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
- H01G11/22—Electrodes
- H01G11/30—Electrodes characterised by their material
- H01G11/32—Carbon-based
-
- 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
- H01G11/52—Separators
-
- 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
- H01G11/60—Liquid electrolytes characterised by the solvent
-
- 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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- Engineering & Computer Science (AREA)
- Power Engineering (AREA)
- Chemical & Material Sciences (AREA)
- Microelectronics & Electronic Packaging (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- Materials Engineering (AREA)
- Electric Double-Layer Capacitors Or The Like (AREA)
- Secondary Cells (AREA)
Abstract
The invention provides a solvent co-intercalated sodium ion capacitor comprising an anode, a cathode, a sodium auxiliary electrode, an electrolyte, and a diaphragm between the anode and the cathode. The concentration of the electrolyte is between 0.5 and 3mol/L. A solvent is selected from one or more of a group including diethanol dimethyl ether, tetraethanol dimethyl ether, and tetrahydrofuran. The electrolyte positive ions in the electrolyte are sodium ions. The negative ions in electrolyte are hexafluorophosphate, tetrafluoroborate, triflate, and perchlorate. The diaphragm is biomass cellulosic material and has 10 to 100 micrometers of thickness, 30% to 95% of porosity, and 20 to 200 nanometers of average diameters. The solvent used in the electrolyte and the sodium ions can be co-intercalated into graphite-kind cathode material and a problem is effectively solved that sodium ions cannot be intercalated into the graphite-kind cathode material in a conventional esters solvent. The biomass cellulosic diaphragm material improves the ionic conductivity of the electrolyte so as to further improve the large-current charging and discharging capability of the sodium ion capacitor, and is low in cost. The sodium ion capacitor is simple in production process, high in specific energy, good in cyclic stability, and has good application prospect in the field of new energy.
Description
Technical field
The present invention relates to a kind of electrochemical energy storing device, particularly a kind of solvent embedded type sodium ion capacitor altogether.
Background technology
In the trend that climate change and carbon reduction are paid much attention in the whole world, one of New Energy Industry strategic new industry becoming the new century.As important support and the ancillary technique of New Energy Industry, energy storage device is paid close attention to by each side.In China, along with pure
The fast development of electric automobile and hybrid vehicle, the moving forward steadily of intelligent grid, the regenerative resource such as wind energy and solar energy
The growth of extensive networking, regional peak load, various application problem also occurs thereupon, to energy density, the merit of energy storage device
Rate density, useful life and cost are had higher requirement.
Lithium ion battery is the electrochemical energy storing device that current technical development is the most ripe, be most widely used, but the abundance in the earth's crust of lithium is very low.Along with new forms of energy industry is to the increase day by day of lithium ion battery demand, the amount of lithium resource is carried
Gone out larger demand, and the rarity of lithium resource greatly limit the fast development of lithium ion battery in large-scale energy storage device,
And lithium ion battery power density is low, also limit it in high power applications.Therefore, alternative lithium resource, development is found
Novel high-performance energy storage device of future generation becomes extremely urgent problem.
Sodium metal and lithium metal are in the Ith main group together in the periodic table of elements, have similar behavior in electrochemical reaction process, therefore the lithium in existing lithium-ion energy storage battery can be replaced to sodium completely, and the abundance of sodium metal in the earth's crust is wanted
Far above lithium metal, in wide ocean, contain abundant lithium resource, with low cost.Therefore, the height based on sodium ion is developed
The energy storage device of energy density, high power density, more seems particularly important.
In recent years, hybrid super capacitor development day by day comes into one's own.Lithium-ion capacitor belongs to the one of hybrid super capacitor, its operation principle is that positive pole adopts the porous carbon electrode material of double electric layer capacitor by physical absorption lithium ion store electrical energy, and negative pole adopts graphite negative material of lithium ion battery to adopt by Electrochemical lithiation store electrical energy, the energy storage device of the type
Advantage be taken into account high-energy-density and the high-power advantage of double electric layer capacitor of lithium ion battery.If adopt sodium ion to replace
Forming a kind of novel sodium ion capacitor for lithium ion, is feasible from principle.But, based on organic molten in conventional ester class
In agent, because sodium ion radius is much larger than lithium ion radius, sodium ion is difficult to be embedded in graphite negative electrodes material crystal structure.
From published patent, patent CN103198928 discloses a kind of sodium ion capacitor, and its negative material is preferred
Molybdenum oxide nanobelt, sodium titanate nanotubes, need loaded down with trivial details calcination process, not only complex process, and cost is also high, and work electricity
Pressure is only up to 3V, and the performance of energy density is also restricted.Patent CN104036961 and CN104036965 is public respectively
Open a kind of sodium ion hybrid super capacitor positive electrode Na
4mn
9o
18preparation method and adopt this positive electrode mixing surpass
Level capacitor, there is the same complex techniques process such as plurality of raw materials mixing, calcining, drying, and calcine technology is to material
Energy, product batches consistency create significant impact, and be unfavorable for that scale is applied, and this sodium ion hybrid super capacitor uses in aqueous electrolyte, the charging/discharging voltage upper limit is only 1.7V, and energy density plays and is restricted equally.
Summary of the invention
The present invention, in order to solve above-mentioned Problems existing, provides a kind of solvent embedded type lithium-ion capacitor altogether.
To achieve these goals, technical scheme of the present invention is:
A kind of solvent is embedded type sodium ion capacitor altogether, comprising: positive pole, negative pole, sodium auxiliary electrode, electrolyte and between both positive and negative polarity it
Between barrier film.
Described sodium ion capacitor, concentration of electrolyte 0.5 ~ 3 mol/L, solvent is one or more in diethylene glycol dimethyl ether, tetraethyleneglycol dimethyl ether, oxolane, and in electrolyte, electrolyte cation is sodium ion, and anion is hexafluorophosphoric acid
One in root, tetrafluoroborate, trifluoromethane sulfonic acid root, perchlorate.
Described sodium ion capacitor, barrier film is biomass fiber cellulosic material, and thickness is 10 ~ 100 microns, and porosity is 30%-95%, and average pore size is 5-200 nanometer.
Described sodium ion capacitor, positive pole and negative pole are mixed into slurry by active material, conductive agent, binding agent 70 ~ 90%:5 in mass ratio ~ 20%:5% ~ 10% ratio, and are coated on positive pole porous current collector respectively and negative pole porous current collector obtains.
Described sodium ion capacitor, positive active material is one or more in porous activated carbon, porous graphene, porous graphite plate, porous carbon nanotube.
Described sodium ion capacitor, negative electrode active material is one or more in native graphite, Delanium, graphitized intermediate-phase carbon microballoon, porous stone ink film, modified natural graphite, graphitized carbon fibre.
Described sodium ion capacitor, conductive agent is one or more in acetylene black, Super P, graphitized carbon fibre, gas-phase growth of carbon fibre, Graphene; Described lithium-ion capacitor, binding agent is one or more in Kynoar, polytetrafluoroethylene, carboxylic styrene butadiene latex, sodium carboxymethylcellulose.
Described sodium ion capacitor, positive pole porous current collector is porous aluminium foil, porous stainless steel mesh, preferred porous aluminium foil, and percent opening is 30 ~ 50%.
Described sodium ion capacitor, sodium auxiliary electrode passes through lithium compacting and is filled in copper mesh, titanium net or stainless (steel) wire collector, is drawn by lug.
Described sodium ion capacitor, internal structure form is sodium auxiliary electrode/barrier film/negative pole/barrier film/positive pole/barrier film/negative pole/barrier film/positive pole/barrier film/negative pole ... and negative pole always encases positive pole, capacitor unit structure both can be stacked, also can be takeup type.
The advantage that the present invention has and good effect are: compared with prior art, the present invention with the graphite material cheap and easy to get of routine for negative pole, take porous carbon material as positive pole, electrolyte with diethanol dimethyl ether, tetraethyleneglycol dimethyl ether, oxolane ethers organic material for solvent, under sodium ion electrolyte exists situation, by common embedded mode, sodium ion is inserted in graphite cathode material, thus forming the sodium ion capacitor of a kind of operating voltage up to 4V, energy density is greatly enhanced.Adopt in addition high, the stable performance of ionic conductivity, cheap biomass fiber cellulosic material as sodium ion capacitor both positive and negative polarity between barrier film, be not only conducive to the performance of capacitor high rate performance, also help and reduce sodium ion capacitor production cost.
Accompanying drawing explanation
Sodium ion capacitor pre-embedding sodium figure first in Fig. 1 embodiment 1.
The charging and discharging curve of sodium ion capacitor in Fig. 2 embodiment 1,2,3,4,5.
Sodium ion capacitor charging/discharging curve in Fig. 3 comparative example 1.
Sodium ion capacitor pre-embedding sodium curve first in Fig. 4 comparative example 2.
Embodiment
Embodiment
1
Electrolyte is allocated: be full of in argon gas glove box, taking 167.95 grams of sodium hexafluoro phosphate (NaPF
6), afterwards under at the uniform velocity stirring state, sodium hexafluoro phosphate is slowly joined in the beaker filling 1 liter of diethylene glycol dimethyl ether (DEGDME) solvent, until completely dissolved, form the NaPF of 1mol/L
6/ DEGDME electrolyte.
The making of negative plate: be SBR emulsion in 85:10:5(binding agent in mass ratio by graphitized intermediate-phase carbon microballoon, conductive agent Super P, binding agent: ratio mixing and stirring form slurry sodium carboxymethylcellulose mass ratio=3.5:1.5), this slurry is evenly coated on percent opening 30%, thickness is in the copper foil current collector of 15 μm, pole piece is of a size of 3cm × 5cm, nickel strap lug in welding.
The making of positive plate: by the ratio mixing and stirring form slurry of porous activated carbon, conductive agent Super P, binding agent Kynoar 85:10:5 in mass ratio, is evenly coated on this slurry that percent opening is 30%, thickness is in the aluminum foil current collector of 20 μm.Pole piece is of a size of 3cm × 5cm, aluminium strip lug in welding.
Sodium auxiliary electrode makes: be 50 μm by thickness, be of a size of the sodium metal sheet of 3cm × 5cm, be compacted on stainless (steel) wire, and the upper nickel strap lug of welding.
Barrier film between both positive and negative polarity adopts thickness to be 25 microns, the cellulosic separator of porosity 60%, average pore size 40 nanometer.
Sodium ion capacitor package: according to the order of sodium auxiliary electrode/barrier film/negative pole/barrier film/positive pole/barrier film/negative pole, form capacitor unit according to pad mode, two negative lug are welded together, is placed in plastic-aluminum housing, encapsulation.
The pre-embedding sodium method of negative pole: sodium auxiliary electrode and negative pole are formed loop, with 0.02C multiplying power electric current, embedding lithium in negative pole, until negative electricity potential drop is to 0.05V vs. Na
+/ Na, Fig. 1 are the discharge curve first of pre-embedding sodium.
Sodium ion capacitor charging/discharging is tested: after pre-embedding sodium, positive pole, negative pole are formed loop, 1C multiplying power electric current is adopted to carry out discharge and recharge, voltage range is 1 ~ 4V, accompanying drawing 2 is its charging and discharging curve, this sodium ion capacitor under 1C multiplying power electric current, based on the energy density of the two poles of the earth active matter quality sum up to 97.8Wh/kg; Under 40C multiplying power electric current, energy density is 65.7Wh/kg; After lower 1000 discharge and recharges of 40C multiplying power electric current, capability retention is 97.8%.
Embodiment
2
By in embodiment 1, it is identical with embodiment 1 that the solvent in electrolyte changes all the other manufacturing process of tetraethyleneglycol dimethyl ether into.
Sodium ion capacitor charging/discharging is tested: after pre-embedding sodium, positive pole, negative pole are formed loop, 1C multiplying power electric current is adopted to carry out discharge and recharge, voltage range is 1 ~ 4V, charging and discharging curve is shown in accompanying drawing 2, this sodium ion capacitor under 1C multiplying power electric current, based on the energy density of the two poles of the earth active matter quality sum up to 91.5Wh/kg; Under 40C multiplying power electric current, energy density is 62.8Wh/kg; After lower 1000 discharge and recharges of 40C multiplying power electric current, capability retention is 96.5%.
Embodiment
3
By in embodiment 1, negative material MCMB changes modified natural graphite into, and all the other manufacturing process are identical with embodiment 1.
Sodium ion capacitor charging/discharging is tested: after pre-embedding sodium, positive pole, negative pole are formed loop, 1C multiplying power electric current is adopted to carry out discharge and recharge, voltage range is 1 ~ 4V, charging and discharging curve is shown in accompanying drawing 2, this sodium ion capacitor under 1C multiplying power electric current, based on the energy density of the two poles of the earth active matter quality sum up to 113.8 Wh/kg; Under 40C multiplying power electric current, energy density is 70.3Wh/kg; After lower 1000 discharge and recharges of 40C multiplying power electric current, capability retention is 97.5%.
Embodiment
4
By in embodiment 1, diaphragm material changes that thickness is 30 microns, the cellulosic separator of porosity 50%, average pore size 30 nanometer into, and all the other manufacturing process are identical with embodiment 1.
Sodium ion capacitor charging/discharging is tested: after pre-embedding sodium, positive pole, negative pole are formed loop, 1C multiplying power electric current is adopted to carry out discharge and recharge, voltage range is 1 ~ 4V, charging and discharging curve is shown in accompanying drawing 2, this sodium ion capacitor under 1C multiplying power electric current, based on the energy density of the two poles of the earth active matter quality sum up to 97.2 Wh/kg; Under 40C multiplying power electric current, energy density is 60.4Wh/kg; After lower 1000 discharge and recharges of 40C multiplying power electric current, capability retention is 95.5%.
Embodiment
5
By in embodiment 1, change positive electrode into porous graphene, all the other manufacturing process are identical with embodiment 1.
Sodium ion capacitor charging/discharging is tested: after pre-embedding sodium, positive pole, negative pole are formed loop, 1C multiplying power electric current is adopted to carry out discharge and recharge, voltage range is 1 ~ 4V, charging and discharging curve is shown in accompanying drawing 2, this sodium ion capacitor under 1C multiplying power electric current, based on the energy density of the two poles of the earth active matter quality sum up to 103.8 Wh/kg; Under 30C multiplying power electric current, energy density is 75.3Wh/kg; After 1000 discharge and recharges, capability retention is 98.5%.
Comparative example
1
Change charging/discharging voltage scope in embodiment 1 into 1-3.7 V, charging and discharging curve is shown in accompanying drawing 3, this sodium ion capacitor under 1C multiplying power electric current, based on the energy density of the two poles of the earth active matter quality sum up to 87.6 Wh/kg; Under 30C multiplying power electric current, energy density is 46.8Wh/kg; After 1000 discharge and recharges, capability retention is 99.6%.
Comparative example
2
Electrolyte in embodiment 1 is changed into sodium hexafluoro phosphate/(ethylene carbonate: dimethyl carbonate=volume ratio 1:1) of 1mol/L, pre-embedding sodium first discharge curve is shown in accompanying drawing 4, MCMB first pre-embedding lithium capacity is only 11.8mAh/g, the electrolyte of conventional lipid solvent is described, sodium ion almost can not be embedded in the good graphite material of crystallinity.
Claims (9)
1. a solvent embedded type sodium ion capacitor altogether, comprising: positive pole, negative pole, sodium auxiliary electrode, electrolyte and the barrier film between both positive and negative polarity; Described sodium ion capacitor, concentration of electrolyte 0.5 ~ 3 mol/L, solvent is one or more in diethylene glycol dimethyl ether, tetraethyleneglycol dimethyl ether, oxolane, in electrolyte, electrolyte cation is sodium ion, and anion is the one in hexafluoro-phosphate radical, tetrafluoroborate, trifluoromethane sulfonic acid root, perchlorate; Described sodium ion capacitor, barrier film is biomass fiber cellulosic material, and thickness is 10 ~ 100 microns, and porosity is 30%-95%, and average pore size is 5-200 nanometer.
2. according to the sodium ion capacitor described in claim 1, it is characterized in that: described positive pole and negative pole by active material, conductive agent, binding agent in mass ratio 70 ~ 90%: 5 ~ 20%: 5% ~ 10% ratio be mixed into slurry, and be coated on positive pole porous current collector respectively and negative pole porous current collector obtains.
3. according to the sodium ion capacitor described in claim 2, it is characterized in that: described positive active material is one or more in porous activated carbon, porous graphene, porous graphite plate, porous carbon nanotube.
4. according to the sodium ion capacitor described in claim 2, it is characterized in that: described negative electrode active material is one or more in native graphite, Delanium, graphitized intermediate-phase carbon microballoon, porous stone ink film, modified natural graphite, graphitized carbon fibre.
5. according to the sodium ion capacitor described in claim 2, it is characterized in that: described conductive agent is one or more in acetylene black, Super P, graphitized carbon fibre, gas-phase growth of carbon fibre, Graphene.
6. according to the lithium-ion capacitor described in claim 2, it is characterized in that: described binding agent is one or more in Kynoar, polytetrafluoroethylene, carboxylic styrene butadiene latex, sodium carboxymethylcellulose.
7. according to the sodium ion capacitor described in claim 2, it is characterized in that: described porous current collector is porous aluminium foil, porous stainless steel mesh, preferred porous aluminium foil, and percent opening is 30 ~ 50%.
8. according to the sodium ion capacitor described in claim 1, it is characterized in that: sodium auxiliary electrode passes through sodium compacting and is filled in copper mesh, titanium net or stainless (steel) wire collector, is drawn by lug.
9. according to the sodium ion capacitor described in claim 1, it is characterized in that: described sodium ion capacitor internal structural form is sodium auxiliary electrode/barrier film/negative pole/barrier film/positive pole/barrier film/negative pole/barrier film/positive pole/barrier film/negative pole ... and negative pole always encases positive pole, capacitor unit structure both can be stacked, also can be takeup type.
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| CN108242543A (en) * | 2016-12-26 | 2018-07-03 | 福建新峰二维材料科技有限公司 | A kind of soft carbon makees the preparation method of the sodium Dual-ion cell of negative material |
| CN111261422A (en) * | 2020-01-20 | 2020-06-09 | 宁波瞬能科技有限公司 | Sodium ion capacitor and preparation method thereof |
| CN111681884A (en) * | 2020-06-18 | 2020-09-18 | 厦门大学 | Full-carbon-based mixed alkali metal ion capacitor and manufacturing method thereof |
| CN111919272A (en) * | 2018-03-29 | 2020-11-10 | 日本高度纸工业株式会社 | Diaphragm for aluminum electrolytic capacitor and aluminum electrolytic capacitor |
| CN112614704A (en) * | 2020-11-26 | 2021-04-06 | 中国电子科技集团公司第十八研究所 | Electrochemical preparation method of ultrathin metal sodium foil |
| CN114121499A (en) * | 2020-08-25 | 2022-03-01 | 厦门大学 | Electrolyte for high-voltage super capacitor and high-voltage super capacitor |
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Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108242543A (en) * | 2016-12-26 | 2018-07-03 | 福建新峰二维材料科技有限公司 | A kind of soft carbon makees the preparation method of the sodium Dual-ion cell of negative material |
| CN111919272A (en) * | 2018-03-29 | 2020-11-10 | 日本高度纸工业株式会社 | Diaphragm for aluminum electrolytic capacitor and aluminum electrolytic capacitor |
| CN111261422A (en) * | 2020-01-20 | 2020-06-09 | 宁波瞬能科技有限公司 | Sodium ion capacitor and preparation method thereof |
| CN111681884A (en) * | 2020-06-18 | 2020-09-18 | 厦门大学 | Full-carbon-based mixed alkali metal ion capacitor and manufacturing method thereof |
| CN114121499A (en) * | 2020-08-25 | 2022-03-01 | 厦门大学 | Electrolyte for high-voltage super capacitor and high-voltage super capacitor |
| CN114121499B (en) * | 2020-08-25 | 2023-11-10 | 厦门大学 | Electrolyte for high-voltage supercapacitor and high-voltage supercapacitor |
| CN112614704A (en) * | 2020-11-26 | 2021-04-06 | 中国电子科技集团公司第十八研究所 | Electrochemical preparation method of ultrathin metal sodium foil |
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