CN108538634A - A kind of water system compounding electrolyte and its preparation method and application - Google Patents
A kind of water system compounding electrolyte and its preparation method and application Download PDFInfo
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- CN108538634A CN108538634A CN201810515376.4A CN201810515376A CN108538634A CN 108538634 A CN108538634 A CN 108538634A CN 201810515376 A CN201810515376 A CN 201810515376A CN 108538634 A CN108538634 A CN 108538634A
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- electrolyte
- water system
- compounding
- salt solution
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- 239000003792 electrolyte Substances 0.000 title claims abstract description 53
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 title claims abstract description 25
- 238000002360 preparation method Methods 0.000 title claims abstract description 15
- 238000013329 compounding Methods 0.000 title claims description 28
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 claims abstract description 39
- 229910052938 sodium sulfate Inorganic materials 0.000 claims abstract description 22
- 235000011152 sodium sulphate Nutrition 0.000 claims abstract description 17
- 239000004094 surface-active agent Substances 0.000 claims abstract description 13
- JRMUNVKIHCOMHV-UHFFFAOYSA-M tetrabutylammonium bromide Chemical compound [Br-].CCCC[N+](CCCC)(CCCC)CCCC JRMUNVKIHCOMHV-UHFFFAOYSA-M 0.000 claims abstract description 12
- 150000001875 compounds Chemical class 0.000 claims abstract description 10
- MPTQRFCYZCXJFQ-UHFFFAOYSA-L copper(II) chloride dihydrate Chemical compound O.O.[Cl-].[Cl-].[Cu+2] MPTQRFCYZCXJFQ-UHFFFAOYSA-L 0.000 claims abstract description 10
- 239000003990 capacitor Substances 0.000 claims abstract description 7
- 229910021645 metal ion Inorganic materials 0.000 claims abstract description 6
- 239000000654 additive Substances 0.000 claims abstract description 5
- 238000005868 electrolysis reaction Methods 0.000 claims abstract description 5
- 230000000996 additive effect Effects 0.000 claims abstract description 4
- 230000007935 neutral effect Effects 0.000 claims description 22
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 20
- 239000012266 salt solution Substances 0.000 claims description 20
- 238000003756 stirring Methods 0.000 claims description 19
- 229910052751 metal Inorganic materials 0.000 claims description 18
- 239000002184 metal Substances 0.000 claims description 18
- 238000003760 magnetic stirring Methods 0.000 claims description 16
- 238000002156 mixing Methods 0.000 claims description 12
- 239000008367 deionised water Substances 0.000 claims description 7
- 229910021641 deionized water Inorganic materials 0.000 claims description 7
- 238000000034 method Methods 0.000 claims description 6
- 239000007787 solid Substances 0.000 claims description 6
- 239000002904 solvent Substances 0.000 claims description 6
- 238000006243 chemical reaction Methods 0.000 claims description 5
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical class C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 claims description 5
- 150000003839 salts Chemical class 0.000 claims description 5
- 238000012360 testing method Methods 0.000 claims description 5
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 4
- 239000002250 absorbent Substances 0.000 claims description 4
- 230000002745 absorbent Effects 0.000 claims description 4
- 239000003610 charcoal Substances 0.000 claims description 4
- 239000000463 material Substances 0.000 claims description 4
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 claims description 4
- 239000000843 powder Substances 0.000 claims description 4
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 claims description 3
- 239000010949 copper Substances 0.000 claims description 3
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 2
- 229910052802 copper Inorganic materials 0.000 claims description 2
- 229910052697 platinum Inorganic materials 0.000 claims description 2
- 239000011734 sodium Substances 0.000 claims description 2
- 238000010998 test method Methods 0.000 claims description 2
- 238000001291 vacuum drying Methods 0.000 claims description 2
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 claims 1
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 claims 1
- 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 1
- 239000000460 chlorine Substances 0.000 claims 1
- 229910052801 chlorine Inorganic materials 0.000 claims 1
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 claims 1
- 239000010931 gold Substances 0.000 claims 1
- 229910052737 gold Inorganic materials 0.000 claims 1
- 230000036571 hydration Effects 0.000 claims 1
- 238000006703 hydration reaction Methods 0.000 claims 1
- 229910052708 sodium Inorganic materials 0.000 claims 1
- RKHXQBLJXBGEKF-UHFFFAOYSA-M tetrabutylphosphanium;bromide Chemical compound [Br-].CCCC[P+](CCCC)(CCCC)CCCC RKHXQBLJXBGEKF-UHFFFAOYSA-M 0.000 claims 1
- 239000002131 composite material Substances 0.000 abstract 1
- 239000000243 solution Substances 0.000 description 13
- 239000007772 electrode material Substances 0.000 description 10
- 238000004146 energy storage Methods 0.000 description 9
- 239000007788 liquid Substances 0.000 description 7
- 239000007832 Na2SO4 Substances 0.000 description 5
- 230000005611 electricity Effects 0.000 description 4
- 238000011160 research Methods 0.000 description 4
- JPVYNHNXODAKFH-UHFFFAOYSA-N Cu2+ Chemical compound [Cu+2] JPVYNHNXODAKFH-UHFFFAOYSA-N 0.000 description 3
- 230000008901 benefit Effects 0.000 description 3
- ORTQZVOHEJQUHG-UHFFFAOYSA-L copper(II) chloride Chemical compound Cl[Cu]Cl ORTQZVOHEJQUHG-UHFFFAOYSA-L 0.000 description 3
- 230000005518 electrochemistry Effects 0.000 description 3
- 229910021592 Copper(II) chloride Inorganic materials 0.000 description 2
- 239000003575 carbonaceous material Substances 0.000 description 2
- 229910001431 copper ion Inorganic materials 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 239000008151 electrolyte solution Substances 0.000 description 2
- LCPVQAHEFVXVKT-UHFFFAOYSA-N 2-(2,4-difluorophenoxy)pyridin-3-amine Chemical compound NC1=CC=CN=C1OC1=CC=C(F)C=C1F LCPVQAHEFVXVKT-UHFFFAOYSA-N 0.000 description 1
- 206010013786 Dry skin Diseases 0.000 description 1
- PXGOKWXKJXAPGV-UHFFFAOYSA-N Fluorine Chemical compound FF PXGOKWXKJXAPGV-UHFFFAOYSA-N 0.000 description 1
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 1
- 229910015667 MoO4 Inorganic materials 0.000 description 1
- 229910004619 Na2MoO4 Inorganic materials 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- 239000005864 Sulphur Substances 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 230000004913 activation Effects 0.000 description 1
- 238000013019 agitation Methods 0.000 description 1
- 238000013459 approach Methods 0.000 description 1
- 125000004429 atom Chemical group 0.000 description 1
- 238000004891 communication Methods 0.000 description 1
- 239000002322 conducting polymer Substances 0.000 description 1
- 229920001940 conductive polymer Polymers 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 238000000151 deposition Methods 0.000 description 1
- 230000008021 deposition Effects 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 230000009977 dual effect Effects 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- QSVBKISKLFLGCJ-UHFFFAOYSA-N ethene 1-methylpyrrolidin-2-one Chemical group C=C.CN1C(CCC1)=O QSVBKISKLFLGCJ-UHFFFAOYSA-N 0.000 description 1
- 229910052731 fluorine Inorganic materials 0.000 description 1
- 239000011737 fluorine Substances 0.000 description 1
- 125000005842 heteroatom Chemical group 0.000 description 1
- 229920000831 ionic polymer Polymers 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 229910052744 lithium Inorganic materials 0.000 description 1
- INHCSSUBVCNVSK-UHFFFAOYSA-L lithium sulfate Inorganic materials [Li+].[Li+].[O-]S([O-])(=O)=O INHCSSUBVCNVSK-UHFFFAOYSA-L 0.000 description 1
- 239000002905 metal composite material Substances 0.000 description 1
- 230000005012 migration Effects 0.000 description 1
- 238000013508 migration Methods 0.000 description 1
- 231100000252 nontoxic Toxicity 0.000 description 1
- 230000003000 nontoxic effect Effects 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 239000011684 sodium molybdate Substances 0.000 description 1
- TVXXNOYZHKPKGW-UHFFFAOYSA-N sodium molybdate (anhydrous) Chemical compound [Na+].[Na+].[O-][Mo]([O-])(=O)=O TVXXNOYZHKPKGW-UHFFFAOYSA-N 0.000 description 1
- CHQMHPLRPQMAMX-UHFFFAOYSA-L sodium persulfate Substances [Na+].[Na+].[O-]S(=O)(=O)OOS([O-])(=O)=O CHQMHPLRPQMAMX-UHFFFAOYSA-L 0.000 description 1
- 230000006641 stabilisation Effects 0.000 description 1
- 238000011105 stabilization Methods 0.000 description 1
- 230000002195 synergetic effect Effects 0.000 description 1
- 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 description 1
Classifications
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
- H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
- H01G11/54—Electrolytes
- H01G11/58—Liquid electrolytes
- H01G11/64—Liquid electrolytes characterised by additives
-
- 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
- H01G11/34—Carbon-based characterised by carbonisation or activation of carbon
-
- 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
-
- 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
- H01G11/62—Liquid electrolytes characterised by the solute, e.g. salts, anions or cations 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
-
- 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)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- Microelectronics & Electronic Packaging (AREA)
- Materials Engineering (AREA)
- Manufacturing & Machinery (AREA)
- Electric Double-Layer Capacitors Or The Like (AREA)
Abstract
The present invention relates to a kind of water systems to compound electrolyte and its preparation method and application, which solve the low density technical problems of existing super capacitor energy, it is basic electrolyte with sodium sulphate, and the Copper dichloride dihydrate to provide metal ion compounds complex compound obtained as electrolysis additive with surfactant tetrabutylammonium bromide.Invention also provides preparation methods and application.It the composite can be widely applied to electrochemical field.
Description
Technical field
The present invention relates to electrolytic solution for super capacitor field, specifically a kind of water system compounding electrolyte and its preparation side
Method and application.
Background technology
Ultracapacitor is called electrochemical capacitor, there are two types of energy storage mode, respectively electric double layer capacitance energy storage and counterfeit
Capacitive energy storage.Different from traditional lithium battery, ultracapacitor has the advantages that safety, long circulating performance stabilization, power density is high,
And it therefore receives more and more attention.
The advantage of ultracapacitor promotes it in electric power, communications and transportation, consumer electronic product etc. to have to answer well
With, but the deficiency present in it is also non-negligible.The energy storage mode of aqueous super capacitor is electric double layer energy storage at present, with more
Hole carbon material is electrode material, using sulfuric acid as electrolyte, however, the capacitance that double electric layers supercapacitor is provided is 150F g-1
Left and right, energy density is substantially in 5-10Wh kg-1.Its relatively low energy density all limits its application at many aspects.So
Nowadays the research for being directed to ultracapacitor is that how to improve in its energy density.Currently used method is modified in research
On electrode material, including atom doped and metal composite oxide and conducting polymer, very by way of fake capacitance energy storage
Energy density is increased in big degree, but hoist capacity is limited by way of Heteroatom doping, and prepared by modified electrode material
Complex process, coulombic efficiency have a certain distance for traditional carbon material.
Based on problem above, we are focused on by changing existing thinking in the research of aqueous electrolyte, water system electricity
Solution liquid includes solvent and solute two parts, and with ionic conductivity height, non-toxic and safe, interface impedance is low and in two electrodes
On snap action and electronic compensation property.Aqueous electrolyte preparation process is simple, with obvious effects, but its at present there is also
Problem, voltage window is relatively low, and general water-based decomposition window is 1V or so, therefore energy density is also limited in hoisting depth
System, nowadays people improve defect problem existing for aqueous electrolyte by two methods, one is addition neutral electrolyte, according to
Fic K,Lota G,Meller M,et al.Novel insight into neutral medium as electrolyte
for high-voltage supercapacitors[J].Energy&Environmental Science,2012, 5(2):
5842-5850 is reported, using lithium sulfate as neutral electrolyte, electrochemical window expands to 2.2V, and another kind is that redox is added
Additive provides fake capacitance, according to Xu D, Hu W, Sun X N, et al.Redox additives of Na2MoO4,and
KI:Synergistic effect and the improved capacitive performances for carbon-
based supercapacitors[J].Journal of Power Sources,2017,341:448-456. report, with sulphur
Acid is electrolyte, wherein Na is added2MoO4Electrolyte is compounded with KI, increases by 17.4 times compared to traditional system specific capacity, and gather around
There is good cyclical stability, therefore the research of aqueous electrolyte has very important significance to ultracapacitor.
Invention content
The present invention is exactly to provide a kind of easy energy storage, height to solve the low density defect of existing super capacitor energy
Energy density, the water system of high coulombic efficiency compounding electrolyte and preparation method thereof and the application in ultracapacitor.
Be basic electrolyte with sodium sulphate for this purpose, the present invention provides a kind of water systems to compound electrolyte, with provide metal from
The Copper dichloride dihydrate of son is electrolysis additive with surfactant tetrabutylammonium bromide compounding complex compound obtained.
Present invention simultaneously provides the preparation methods that a kind of water system compounds electrolyte, specifically comprise the following steps：
(1) sodium sulphate neutral salt solution is prepared：Sodium sulphate is added in deionized water, is made a concentration of 0.5-5mol/L's
Sodium sulphate neutral salt solution, the beaker equipped with sodium sulphate neutral salt solution is placed on magnetic stirring apparatus, and mixing speed is
400r/min, mixing time are 1~3h；(2) metal salt solution is prepared：Into sodium sulphate neutral salt solution made from step (1)
Metal salt solid powder is added, the metal salt solution of a concentration of 0.005-5mol/L is made, by the beaker equipped with metal salt solution
It is placed on magnetic stirring apparatus, mixing speed 400r/min, mixing time is 1~3h；(3) compounding electrolyte is prepared：Xiang Bu
Suddenly surfactant tetrabutylammonium bromide is added in metal salt solution made from (2), it is 0.005- that surfactant concentration, which is made,
Beaker equipped with compounding electrolyte is placed on magnetic stirring apparatus, mixing speed 400r/ by the compounding electrolyte of 5mol/L
Min, mixing time are 1~3h.
Preferably, metal salt solid powder is Copper dichloride dihydrate.
Preferably, reaction environment temperature is 25 DEG C.
Preferably, reaction environment humidity is 26RH%.
Invention also provides a kind of application of water system compounding electrolyte in ultracapacitor, include specifically following step
Suddenly：
A. the poly- inclined fluorine that absorbent charcoal material will be commercialized and be 3.5% as solvent, mass fraction using N-Methyl pyrrolidone
Ethylene stirs into a paste, and using platinized platinum as collector, activated carbon active mass is controlled in 1.5mg, by activated carbon electrodes piece
The dry 12h in 120 DEG C of vacuum drying ovens；B. the activated carbon electrodes piece after step a dryings is steeped in the compounding electrolyte of preparation
As diaphragm symmetric form ultracapacitor is made, the two poles of the earth of symmetrical ultracapacitor are activated carbon electricity in 8h, cellulosic separator
Pole；C. two electrode test methods are used, under constant voltage, current condition, symmetrical ultracapacitor made from step b is carried out
Loop test, and calculate the unit capacitance values under corresponding current density.
Preferably, in step a, commercialization absorbent charcoal material is with by solvent, mass fraction of N-Methyl pyrrolidone
The mass fraction ratio of 3.5% Kynoar is 9:1.
Preferably, voltage range is 0.0~2V, and current range is 0.2~20A/g.
The present invention has the following advantages：
(1) it adds surfactant in electrolytic solution for super capacitor and metal ion, surfactant plays dual work
With on the one hand can reducing the surface tension of solid liquid interface, reduce interface impedance and promote more polyion to interfacial migration, another party
Face can fetter more metal ions, so that metal ion is dispersed on interface and promote reactivity, and complex compound quilt
Activation also can further energy storage, the energy density of ultracapacitor can be greatly improved in this, and functional.
(2) it uses commercialization activated carbon as electrode material, using aqueous sodium persulfate solution as solvent, copper chloride two is added and is hydrated
Object and surfactant tetrabutylammonium bromide are as compounding electrolyte.Coordination between metal ion and surfactant produces
Excellent influence, surfactant can both reduce surface tension in activated carbon and electrolyte interface, can also by with metal
The coordination of ion makes more copper ions be fixed on interface, and complex compound is activated acceptable further energy storage.Based on this
One new approaches, it is intended to pass through Cu2+/Cu+The fake capacitance reactions of/Cu in liquid-solid boundary, improves the energy of ultracapacitor
Density, while system being made to have very high coulombic efficiency.In addition, with neutral electrolyte 1M Na2SO4(63.1F g-1) compare, it is novel
Electrolyte is in 1A g-1Current density under capacity reach 657.2F g-1Specific capacity, and the presence of surfactant contributes to surely
Determine univalent copper ion, effectively prevents a large amount of copper depositions to a certain extent.
(3) preparation is simple, of low cost by the present invention, is easy to apply, and the present invention has a wide range of application, for
Different electrode materials has very high practicability.
Description of the drawings
The electrolyte of Fig. 1 present invention is respectively Na2SO4,Na2SO4+TBAB,Na2SO4+CuCl2, Na2SO4+CuCl2+
The high rate performance figure of TBAB solution.
Specific implementation mode
According to following embodiments, the present invention may be better understood.However, as it will be easily appreciated by one skilled in the art that real
It applies content described in example and is merely to illustrate the present invention, without this hair described in claims should will not be limited
It is bright.
Embodiment 1
Sodium sulphate is added in deionized water, the neutral electrolyte of a concentration of 0.5mol/L is configured to, is placed on magnetic force and stirs
It mixes on device, speed 400r/min, stirs 1h.
Copper dichloride dihydrate solution is added into neutral electrolyte, the metal salt for being configured to a concentration of 0.005mol/L is molten
Liquid is placed on magnetic stirring apparatus, speed 400r/min, stirs 1h.
Continue to add tetrabutylammonium bromide into the solution configured, is configured to the compounding electricity of a concentration of 0.005mol/L
Liquid is solved, is placed on magnetic stirring apparatus, speed 400r/min, 1h is stirred.Then electrification is carried out by electrode material of activated carbon
Learn test.
Embodiment 2
Sodium sulphate is added in deionized water, the neutral electrolyte of a concentration of 0.5mol/L is configured to, is placed on magnetic force and stirs
It mixes on device, speed 400r/min, stirs 1h.
Copper dichloride dihydrate solution is added into neutral electrolyte, is configured to the metal salt solution of a concentration of 0.5mol/L,
It is placed on magnetic stirring apparatus, speed 400r/min, stirs 1h.
Continue to add tetrabutylammonium bromide into the solution configured, is configured to the compounding electricity of a concentration of 0.025mol/L
Liquid is solved, is placed on magnetic stirring apparatus, speed 400r/min, 1h is stirred.Then electrification is carried out by electrode material of activated carbon
Learn test.
Embodiment 3
Sodium sulphate is added in deionized water, the neutral electrolyte of a concentration of 0.5mol/L is configured to, is placed on magnetic force and stirs
It mixes on device, speed 400r/min, stirs 2h.
Copper dichloride dihydrate solution is added into neutral electrolyte, is configured to the metal salt solution of a concentration of 0.5mol/L,
It is placed on magnetic stirring apparatus, speed 400r/min, stirs 2h.
Continue to add tetrabutylammonium bromide into the solution configured, is configured to the compounding electrolysis of a concentration of 0.1mol/L
Liquid is placed on magnetic stirring apparatus, speed 400r/min, stirs 2h.Then electrochemistry is carried out by electrode material of activated carbon
Test.
Embodiment 4
Sodium sulphate is added in deionized water, the neutral electrolyte of a concentration of 2.5mol/L is configured to, is placed on magnetic force and stirs
It mixes on device, speed 400r/min, stirs 2h.
Copper dichloride dihydrate solution is added into neutral electrolyte, is configured to the metal salt solution of a concentration of 2.5mol/L,
It is placed on magnetic stirring apparatus, speed 400r/min, stirs 2h.
Continue to add tetrabutylammonium bromide into the solution configured, is configured to the compounding electrolysis of a concentration of 2.5mol/L
Liquid is placed on magnetic stirring apparatus, and speed 400r/min stirs 2h.Then electrochemistry survey is carried out by electrode material of activated carbon
Examination.
Embodiment 5
Sodium sulphate is added in deionized water, the neutral electrolyte of a concentration of 5mol/L is configured to, is placed on magnetic agitation
On device, speed 400r/min stirs 3h.
Copper dichloride dihydrate solution is added into neutral electrolyte, is configured to the metal salt solution of a concentration of 5mol/L, puts
It sets on magnetic stirring apparatus, speed 400r/min, stirs 3h.
Continue to add tetrabutylammonium bromide into the solution configured, be configured to the compounding electrolyte of a concentration of 5mol/L,
It is placed on magnetic stirring apparatus, speed 400r/min, stirs 3h.Then electrochemistry survey is carried out by electrode material of activated carbon
Examination.
Claims (8)
1. a kind of water system compounds electrolyte, it is characterized in that being basic electrolyte with sodium sulphate, to provide two hydrations of metal ion
Copper chloride is electrolysis additive with surfactant tetrabutylammonium bromide compounding complex compound obtained.
2. the preparation method of water system compounding electrolyte as described in claim 1, it is characterised in that comprise the following steps：
(1) sodium sulphate neutral salt solution is prepared：Sodium sulphate is added in deionized water, the sulfuric acid of a concentration of 0.5-5mol/L is made
Beaker equipped with the sodium sulphate neutral salt solution is placed on magnetic stirring apparatus by sodium neutral salt solution, and mixing speed is
400r/min, mixing time are 1~3h；
(2) metal salt solution is prepared：Metal salt two is added into sodium sulphate neutral salt solution made from the step (1) and is hydrated chlorine
Change copper solid powder, the metal salt solution of a concentration of 0.005-5mol/L is made, the beaker equipped with the metal salt solution is put
It sets on magnetic stirring apparatus, mixing speed 400r/min, mixing time is 1~3h；
(3) compounding electrolyte is prepared：Surfactant tetrabutyl phosphonium bromide is added into metal salt solution made from the step (2)
The compounding electrolyte that surfactant concentration is 0.005-5mol/L is made in ammonium, by the beaker equipped with the compounding electrolyte
It is placed on magnetic stirring apparatus, mixing speed 400r/min, mixing time is 1~3h.
3. the preparation method of water system compounding electrolyte according to claim 2, which is characterized in that in the step (2), gold
Category salt solid powder is Copper dichloride dihydrate.
4. the preparation method of water system compounding electrolyte according to claim 2, which is characterized in that the reaction ring of the method
Border temperature is 25 DEG C.
5. the preparation method of water system compounding electrolyte according to claim 2, which is characterized in that the reaction ring of the method
Border humidity is 26RH%.
6. application of the water system compounding electrolyte as described in claim 1 in ultracapacitor, which is characterized in that comprising following
Step：
A. the Kynoar that absorbent charcoal material will be commercialized and be 3.5% as solvent, mass fraction using N-Methyl pyrrolidone
It stirs into a paste, using platinized platinum as collector, activated carbon active mass is controlled in 1.5mg, by the activated carbon electrodes
Piece dry 12h in 120 DEG C of vacuum drying ovens；
B. the activated carbon electrodes piece after the step a being dried steeps 8h, cellulosic separator conduct in the compounding electrolyte of preparation
Symmetric form ultracapacitor is made in diaphragm, and the two poles of the earth of the symmetrical ultracapacitor are activated carbon electrodes；
C. two electrode test methods are used, under constant voltage, current condition, to symmetrical super capacitor made from the step b
Device carries out loop test, and calculates the unit capacitance values under corresponding current density.
7. application of the water system compounding electrolyte according to claim 6 in ultracapacitor, which is characterized in that the step
In rapid a, commercialization absorbent charcoal material and the Kynoar for being 3.5% as solvent, mass fraction using N-Methyl pyrrolidone
Mass fraction ratio is 9:1.
8. application of the water system compounding electrolyte according to claim 6 in ultracapacitor, which is characterized in that voltage model
It encloses for 0.0~2V, current range is 0.2~20A/g.
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN113948318A (en) * | 2021-09-27 | 2022-01-18 | 西安交通大学 | High-voltage water system electrolyte, preparation method thereof and application thereof in super capacitor |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1767101A (en) * | 2005-09-08 | 2006-05-03 | 中国科学院山西煤炭化学研究所 | A kind of electrolyte that is used for electrochemical capacitor and preparation method thereof |
| CN101546652A (en) * | 2009-05-06 | 2009-09-30 | 北京科技大学 | Method for improving electric capacity of anode of electrochemical capacitor of organic system |
| CN104335405A (en) * | 2012-08-22 | 2015-02-04 | 日新电机株式会社 | Energy storage battery |
| US20150062777A1 (en) * | 2013-09-04 | 2015-03-05 | The Regents Of The University Of California | High Energy Capacitors Boosted by both Catholyte and Anolyte |
| CN106981371A (en) * | 2016-01-15 | 2017-07-25 | 黄潮 | A kind of water system electrolyte super capacitance cell |
-
2018
- 2018-05-25 CN CN201810515376.4A patent/CN108538634B/en active Active
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1767101A (en) * | 2005-09-08 | 2006-05-03 | 中国科学院山西煤炭化学研究所 | A kind of electrolyte that is used for electrochemical capacitor and preparation method thereof |
| CN101546652A (en) * | 2009-05-06 | 2009-09-30 | 北京科技大学 | Method for improving electric capacity of anode of electrochemical capacitor of organic system |
| CN104335405A (en) * | 2012-08-22 | 2015-02-04 | 日新电机株式会社 | Energy storage battery |
| US20150062777A1 (en) * | 2013-09-04 | 2015-03-05 | The Regents Of The University Of California | High Energy Capacitors Boosted by both Catholyte and Anolyte |
| CN106981371A (en) * | 2016-01-15 | 2017-07-25 | 黄潮 | A kind of water system electrolyte super capacitance cell |
Non-Patent Citations (2)
| Title |
|---|
| GRZEGORZ LOTA等: "Striking capacitance of carbon/iodide interface", 《ELECTROCHEMISTRY COMMUNICATIONS》 * |
| KRZYSZTOF FIC等: "Novel insight into neutral medium as electrolyte for high-voltage supercapacitors", 《ENERGY & ENVIRONMENTAL SCIENCE》 * |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113948318A (en) * | 2021-09-27 | 2022-01-18 | 西安交通大学 | High-voltage water system electrolyte, preparation method thereof and application thereof in super capacitor |
| CN113948318B (en) * | 2021-09-27 | 2022-12-09 | 西安交通大学 | High-pressure water system electrolyte and preparation method and application thereof |
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