CN106298263B - A kind of bismuth/charcoal super capacitance cell and preparation method thereof - Google Patents
A kind of bismuth/charcoal super capacitance cell and preparation method thereof Download PDFInfo
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- CN106298263B CN106298263B CN201610967583.4A CN201610967583A CN106298263B CN 106298263 B CN106298263 B CN 106298263B CN 201610967583 A CN201610967583 A CN 201610967583A CN 106298263 B CN106298263 B CN 106298263B
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- bismuth
- capacitance
- pole
- capacitance cell
- super capacitance
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- JCXGWMGPZLAOME-UHFFFAOYSA-N bismuth atom Chemical compound [Bi] JCXGWMGPZLAOME-UHFFFAOYSA-N 0.000 title claims abstract description 150
- 229910052797 bismuth Inorganic materials 0.000 title claims abstract description 143
- 239000003610 charcoal Substances 0.000 title claims abstract description 32
- 238000002360 preparation method Methods 0.000 title claims abstract description 22
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- 239000000463 material Substances 0.000 claims abstract description 44
- 229910052799 carbon Inorganic materials 0.000 claims abstract description 30
- 239000003638 chemical reducing agent Substances 0.000 claims abstract description 17
- 229910001451 bismuth ion Inorganic materials 0.000 claims abstract description 14
- 239000003792 electrolyte Substances 0.000 claims abstract description 10
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- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 17
- 239000011230 binding agent Substances 0.000 claims description 16
- 239000003575 carbonaceous material Substances 0.000 claims description 15
- 238000003756 stirring Methods 0.000 claims description 14
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- 239000002904 solvent Substances 0.000 claims description 13
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- NWZSZGALRFJKBT-KNIFDHDWSA-N (2s)-2,6-diaminohexanoic acid;(2s)-2-hydroxybutanedioic acid Chemical compound OC(=O)[C@@H](O)CC(O)=O.NCCCC[C@H](N)C(O)=O NWZSZGALRFJKBT-KNIFDHDWSA-N 0.000 claims description 10
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- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 claims description 6
- RXPAJWPEYBDXOG-UHFFFAOYSA-N hydron;methyl 4-methoxypyridine-2-carboxylate;chloride Chemical compound Cl.COC(=O)C1=CC(OC)=CC=N1 RXPAJWPEYBDXOG-UHFFFAOYSA-N 0.000 claims description 6
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- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 4
- LZZYPRNAOMGNLH-UHFFFAOYSA-M Cetrimonium bromide Chemical compound [Br-].CCCCCCCCCCCCCCCC[N+](C)(C)C LZZYPRNAOMGNLH-UHFFFAOYSA-M 0.000 claims description 4
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- GSEJCLTVZPLZKY-UHFFFAOYSA-N Triethanolamine Chemical compound OCCN(CCO)CCO GSEJCLTVZPLZKY-UHFFFAOYSA-N 0.000 claims description 4
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- GMZOPRQQINFLPQ-UHFFFAOYSA-H dibismuth;tricarbonate Chemical compound [Bi+3].[Bi+3].[O-]C([O-])=O.[O-]C([O-])=O.[O-]C([O-])=O GMZOPRQQINFLPQ-UHFFFAOYSA-H 0.000 claims description 4
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- QYIGOGBGVKONDY-UHFFFAOYSA-N 1-(2-bromo-5-chlorophenyl)-3-methylpyrazole Chemical compound N1=C(C)C=CN1C1=CC(Cl)=CC=C1Br QYIGOGBGVKONDY-UHFFFAOYSA-N 0.000 claims description 3
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 3
- 239000002202 Polyethylene glycol Substances 0.000 claims description 3
- UWHCKJMYHZGTIT-UHFFFAOYSA-N Tetraethylene glycol, Natural products OCCOCCOCCOCCO UWHCKJMYHZGTIT-UHFFFAOYSA-N 0.000 claims description 3
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- KKMOSYLWYLMHAL-UHFFFAOYSA-N 2-bromo-6-nitroaniline Chemical compound NC1=C(Br)C=CC=C1[N+]([O-])=O KKMOSYLWYLMHAL-UHFFFAOYSA-N 0.000 claims description 2
- LQJBNNIYVWPHFW-UHFFFAOYSA-N 20:1omega9c fatty acid Natural products CCCCCCCCCCC=CCCCCCCCC(O)=O LQJBNNIYVWPHFW-UHFFFAOYSA-N 0.000 claims description 2
- KWSLGOVYXMQPPX-UHFFFAOYSA-N 5-[3-(trifluoromethyl)phenyl]-2h-tetrazole Chemical compound FC(F)(F)C1=CC=CC(C2=NNN=N2)=C1 KWSLGOVYXMQPPX-UHFFFAOYSA-N 0.000 claims description 2
- QSBYPNXLFMSGKH-UHFFFAOYSA-N 9-Heptadecensaeure Natural products CCCCCCCC=CCCCCCCCC(O)=O QSBYPNXLFMSGKH-UHFFFAOYSA-N 0.000 claims description 2
- FEWJPZIEWOKRBE-JCYAYHJZSA-N Dextrotartaric acid Chemical compound OC(=O)[C@H](O)[C@@H](O)C(O)=O FEWJPZIEWOKRBE-JCYAYHJZSA-N 0.000 claims description 2
- 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 description 2
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- 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 2
- 150000008044 alkali metal hydroxides Chemical class 0.000 claims description 2
- 150000003973 alkyl amines Chemical class 0.000 claims description 2
- 150000003934 aromatic aldehydes Chemical class 0.000 claims description 2
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- 229940049676 bismuth hydroxide Drugs 0.000 claims description 2
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- TZSXPYWRDWEXHG-UHFFFAOYSA-K bismuth;trihydroxide Chemical compound [OH-].[OH-].[OH-].[Bi+3] TZSXPYWRDWEXHG-UHFFFAOYSA-K 0.000 claims description 2
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- TYIXMATWDRGMPF-UHFFFAOYSA-N dibismuth;oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[Bi+3].[Bi+3] TYIXMATWDRGMPF-UHFFFAOYSA-N 0.000 claims description 2
- BEQZMQXCOWIHRY-UHFFFAOYSA-H dibismuth;trisulfate Chemical compound [Bi+3].[Bi+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O BEQZMQXCOWIHRY-UHFFFAOYSA-H 0.000 claims description 2
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- QGWDKKHSDXWPET-UHFFFAOYSA-E pentabismuth;oxygen(2-);nonahydroxide;tetranitrate Chemical compound [OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[O-2].[Bi+3].[Bi+3].[Bi+3].[Bi+3].[Bi+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O QGWDKKHSDXWPET-UHFFFAOYSA-E 0.000 claims description 2
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- 150000002500 ions Chemical class 0.000 description 1
- 239000007791 liquid phase Substances 0.000 description 1
- 239000000314 lubricant Substances 0.000 description 1
- 239000010687 lubricating oil Substances 0.000 description 1
- 229910001425 magnesium ion Inorganic materials 0.000 description 1
- 230000014759 maintenance of location Effects 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- JKQOBWVOAYFWKG-UHFFFAOYSA-N molybdenum trioxide Chemical compound O=[Mo](=O)=O JKQOBWVOAYFWKG-UHFFFAOYSA-N 0.000 description 1
- 239000002086 nanomaterial Substances 0.000 description 1
- 239000002077 nanosphere Substances 0.000 description 1
- 239000002070 nanowire Substances 0.000 description 1
- OQCDKBAXFALNLD-UHFFFAOYSA-N octadecanoic acid Natural products CCCCCCCC(C)CCCCCCCCC(O)=O OQCDKBAXFALNLD-UHFFFAOYSA-N 0.000 description 1
- 150000007524 organic acids Chemical class 0.000 description 1
- 239000012074 organic phase Substances 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- CJJMLLCUQDSZIZ-UHFFFAOYSA-N oxobismuth Chemical compound [Bi]=O CJJMLLCUQDSZIZ-UHFFFAOYSA-N 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 239000011941 photocatalyst Substances 0.000 description 1
- 229920005862 polyol Polymers 0.000 description 1
- 150000003077 polyols Chemical class 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 239000003380 propellant Substances 0.000 description 1
- 238000004080 punching Methods 0.000 description 1
- 239000012429 reaction media Substances 0.000 description 1
- 238000006479 redox reaction Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 230000004044 response Effects 0.000 description 1
- 230000002441 reversible effect Effects 0.000 description 1
- PYWVYCXTNDRMGF-UHFFFAOYSA-N rhodamine B Chemical compound [Cl-].C=12C=CC(=[N+](CC)CC)C=C2OC2=CC(N(CC)CC)=CC=C2C=1C1=CC=CC=C1C(O)=O PYWVYCXTNDRMGF-UHFFFAOYSA-N 0.000 description 1
- 235000011121 sodium hydroxide Nutrition 0.000 description 1
- KKCBUQHMOMHUOY-UHFFFAOYSA-N sodium oxide Chemical compound [O-2].[Na+].[Na+] KKCBUQHMOMHUOY-UHFFFAOYSA-N 0.000 description 1
- 229910001948 sodium oxide Inorganic materials 0.000 description 1
- 241000894007 species Species 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 239000008117 stearic acid Substances 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 150000005846 sugar alcohols Polymers 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 238000005979 thermal decomposition reaction Methods 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- 238000001075 voltammogram Methods 0.000 description 1
- 239000003643 water by type Substances 0.000 description 1
- 239000002759 woven fabric Substances 0.000 description 1
Classifications
-
- 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
Landscapes
- Engineering & Computer Science (AREA)
- Power Engineering (AREA)
- Microelectronics & Electronic Packaging (AREA)
- Chemical & Material Sciences (AREA)
- Materials Engineering (AREA)
- Carbon And Carbon Compounds (AREA)
- Manufacturing & Machinery (AREA)
- Battery Electrode And Active Subsutance (AREA)
Abstract
The invention discloses a kind of bismuth/charcoal super capacitance cell and preparation method thereof.The super capacitance cell of the present invention provides faraday's capacitance with bismuth pole, and carbon resistance rod provides electric double layer capacitance, and aqueous slkali is electrolyte.The bismuth is the bismuth metal powder of 0.005~5 μm of particle diameter, specific surface area is 5~500m2/ g, its preparation method are：The auxiliary agent of appropriate molar ratio and certain density bismuth ion are made into mixed solution, reducing agent then, which is added dropwise, to it is reacted, and prepares bismuth metal dusty material.Electrode is limited by capacitance of bismuth pole when constructing the battery, the capacitance of carbon resistance rod is than bismuth pole capacitance surplus 0~30%.The operating voltage of super capacitance cell of the present invention is 0~1V, and the specific capacitance when current density is 0.5A/g is 258mAh/g.The battery has good chemical property, environmental-friendly, is a kind of mechanism of new electrochemical power sources with broad prospect of application.
Description
Technical field
The present invention relates to a kind of bismuth/charcoal super capacitance cell and preparation method thereof, belong to electrochemical energy storage technical field.
Background technology
With the development of the society, people are skyrocketed through the demand of the energy.Current most common energy storage device includes battery
With two kinds of ultracapacitor, and in many fields, both cannot meet application demand well.It is higher in order to obtain at the same time
Energy density and power density, people start to design new super capacitance cell, and a pole of super capacitance cell is double electricity
Layer capacitance electrode, another pole are faraday's capacitance electrodes.Super capacitance cell combines the advantages of double layer capacitor and battery,
It has the energy density than Conventional electrochemical capacitor bigger, the power density than secondary cell higher, and can quickly fill
Electric discharge, service life length, is a kind of energy storing device of highly effective, is with a wide range of applications.
Electrode active material is the key factor for determining electrochmical power source performance, and the power supply active material usually selected is metal
And metal oxide, Carbon Materials etc..China possesses the bismuth resource of very abundant, is the country of bismuth reserves maximum in the world, at present
Explored bismuth reserves account for more than the 70% of world's gross reserves.Bismuth, No. 83 elements, are a kind of typical half gold with covalent bond
Belonging to element, bismuth metal has the layer structure of approximate graphite, and fusing point is relatively low, only 271 DEG C, and boiling point is 1580 DEG C higher than fusing point,
Nano metal bismuth meal suitably is prepared with the method for solution dispersion, and bismuth metal is a kind of green metal, therefore bismuth is in medicine, ring
The fields such as guarantor, cosmetics, ceramics, dyestuff, lubricating oil, functional material show potential application value.
Wang Yanmin etc. [Shandong Jiaotong University's journal 4 (2012) 67-74.] using bismuth nitrate as raw material, ethylene glycol for solvent and
Reducing agent, PVP are stabilizer, and monocrystalline bismuth nanobelt is prepared for using solvent-thermal method.[the Chinese Journal of Inorganic Chemistry 9 such as Zhao Yanbao
(2003) 997-1000.] using bismuth granule as starting material, atoleine is solvent, and stearic acid is dressing agent, is prepared using dispersion method
Go out Stearate Modified Bi nanoparticle, and its reaction mechanism is studied.[Yanbian University's journal such as Wang Yi:Natural science
3 (2011) 245-248. of version] using bismuth chloride as raw material, hydrazine hydrate is reducing agent, and enuatrol is surfactant, using water phase one
Stage reduction method prepare high-purity, particle diameter for 20nm almost sphericals superfine metal bismuth nanoparticle, and explore reaction temperature,
Influence of the reductant concentration to bismuth nanoparticle.Tang Chunjuan etc. [investigation of materials journal 3 (2011) 273-277.] is with five water nitric acid
Bismuth is raw material, and hydrazine hydrate is reducing agent, and CTAB is covering, and water and ethylenediamine are solvent, has studied in detail water and ethylenediamine
Change of component further provides ethylenediamine template effect and is caused by ethylenediamine to the pattern of product and the influence of structure
Slave dynamics to thermodynamic conversion control crystal growth growth mechanism.[the Chemical Physics Letters such as Dai
591 (2014) 126-129.] by varying the species of surfactant, bismuth nanoparticle of different-shape is prepared, wherein adopting
It is surfactant with P123, the bismuth nano flower being made of hexagon nanoprisms can be prepared.[the Materials such as Kim
153 (2015) 316-322. of Chemistry and Physics] basic bismuth carbonate is used as raw material, using tetraethylene glycol to be molten
In agent, the solution that PVP is covering, direct basic bismuth carbonate is reduced by two steps annealing method by globulate bismuth nanoparticle.C J
Tang etc. [113 (2009) 5422-5427. of J Phys Chem C] passes through solvent respectively using ethylene glycol and ethylenediamine as solvent
Thermal response prepares bismuth nano-wire and bismuth nano flower.Wang etc. [110 (2006) 25702-25706. of J Phys Chem B] is logical
The molar ratio for changing PVP and bismuth raw material is crossed, using polyol reduction method, prepares monocrystalline bismuth nanoparticle of different-shape, and
And under identical synthesis condition, by the Fe for introducing trace3+, bismuth nanocube can be converted into bismuth nanobelt.Wang
Deng [109 (2005) 7067-7072. of J Phys Chem B] at room temperature using DMF as solvent, bismuth chloride is bismuth source, hydroboration
Sodium is reducing agent, and PVP is end-capping reagent, prepares bismuth nanoparticle；And explore experiment condition to the size of bismuth nanoparticle and
The influence of monodispersity.[the Colloids and Surfaces A such as Ma:Physicochem Eng Aspects 395(2012)
276-283.] using bismuth nitrate as bismuth source, tartaric acid is complexing agent, NaH2PO2·H2O is reducing agent, by adjusting tartaric acid and hydrogen
The amount of sodium oxide molybdena, it is about 10 μm wide to prepare the bismuth nanoparticle of diameter 10-50nm and length using liquid phase surface modification reduction method
Degree is about the bismuth nanobelt of 100nm.Cheng etc. [Materials Letters 63 (2009) 2239-2242.] uses ethylene glycol
For solvent, using the hot method of polyalcohol, when reflux 2 is small at 198 DEG C, bismuth microballoon or nanosphere are prepared, and further study
Its possible growth mechanism.Zeng etc. [Advanced Materials 304 (2016) 1-8.] is prepared using electrochemical deposition method
Go out stable monocrystalline state bismuth simple substance, and using bismuth as cathode, NiCo2O4For anode, 1mol/L KOH are electrolyte, prepare alkalescence
Secondary cell, and capacity is substantially undamped after 10000 circulations.[Nanomaterials 4 (2015) 1756- such as Zuo
1765] using Ti as substrate, bismuth simple substance is made to be dispersed in Ti matrix using simple hydro-thermal method, in 1mol/L KOH electrolyte
Bismuth pole specific capacitance is 170mAh/g in solution and under 0.5A/g current densities.Timothy S.Arthur etc.
[Electrochemistry Communications 16 (2012) 103-06.] prepares simple substance Bi, Sb using electrodeposition process
And Bi1-xSbxAlloy, and it is applied to the positive electrode of Mg ion batteries.
Patent of invention [application publication number CN101569934A] discloses " a kind of preparation method of metal bismuth nanoparticle ", leads to
Mixing soluble bismuth salt aqueous solution and dressing agent organic solution are crossed, adds reducing agent, agitating and heating reflux, prepares particle diameter distribution
Than more uniform metal bismuth nanoparticle.Patent of invention [application publication number CN102212880A] discloses a kind of " Bi simple substance nanometer
Structural material and preparation method and application ", is dissolved in water by surfactant, hydrazine hydrate and bismuth salt and is prepared into suspension；By institute
Suspension is stated when reaction 18~30 is small under the conditions of 80~120 DEG C, it is construction unit to prepare by sheet hexagonal phase Bi simple substance
The nano particle with flower shape pattern of composition, and bismuth modified electrode is prepared into, applied to the heavy metal in aqueous solution
Ion detection.Patent of invention [application publication number CN102717095A] discloses a kind of " preparation side of monodisperse bismuth nano particle
Method ", the present invention uses bismuth acetate as bismuth source, oleyl amine or oleic acid as coating agent and surfactant stabilizer, in organic phase body
Bismuth nano particle is synthesized in system, obtained bismuth nano particle has higher yield, good stability.Patent of invention [Shen
Please publication number CN102989507A] " a kind of preparation of bismuthino photochemical catalyst and method for testing performance " is disclosed, the invention is first
By Bi (NO3)3·5H2O is dissolved in acetic acid, using ethylene glycol as reaction medium, stirs and evenly mixs, and adds the dimethyl methyl of certain volume
After acid amides, flow back obtained solution is heated and stirs and obtain product Bi-DMF bouquets.The Bi-DMF bouquets of preparation are existed
Photocatalysis performance test is carried out under visible light conditions, rhodamine is taken off to be colourless by purple in 2h, and degraded is complete.Show that this is spherical
Bismuth-based catalysts have good photocatalysis performance in visible-range.Patent of invention [application publication number
CN105312086A] " a kind of pomegranate shape carbon coating bismuth nanocomposite and its preparation method " is disclosed, the invention is closed
In container, water-soluble saccharides, bismuth nitrate and polyvinylpyrrolidone are dissolved in water, add organic acid, it is anti-at 160~260 DEG C
Should, it is washed, be dried to obtain pomegranate shape carbon coating bismuth nanocomposite.And thermal decomposition of the material to hexogen has substantially
Catalytic action, can be applied to propellant combustion catalysis.Patent of invention [application publication number CN104475133A] discloses
" a kind of preparation method of Bi/BiOCl photochemical catalysts ", the present invention uses a step combustion method, with bismuth nitrate, ammonium chloride and citric acid
For raw material, by the redox reaction between nitrate and citric acid, Bi/BiOCl composite photo-catalysts are prepared.
It is existing much on report of the bismuth metal as application aspects such as photochemical catalysts and lubricant, but exist on bismuth at present
Research in terms of super capacitance cell yet there are no relevant report with application.
The content of the invention
It is an object of the invention to provide a kind of new bismuth/charcoal super capacitance cell and preparation method thereof.The present invention adopts
Faraday's capacitance is provided with bismuth pole, electric double layer capacitance amount is provided using carbon resistance rod, is assembled into super capacitance cell, there is provided compared with
The electrochmical power source of high-specific capacitance super.
The technical scheme is that：
A kind of bismuth/charcoal super capacitance cell, it is characterised in that including bismuth pole and carbon resistance rod, bismuth pole provides faraday
Capacitance, carbon resistance rod provide electric double layer capacitance, and aqueous slkali is as electrolyte, when constructing the super capacitance cell, use bismuth pole for
Capacitance limits electrode, the capacitance surplus 0~30% of the capacitance of carbon resistance rod than bismuth pole.
The carbon resistance rod, for the Carbon Materials used for activated carbon, graphitized carbon or grapheme material, it presses element group
Into mass percent be calculated as：Carbon 60~95%, oxygen element 0.01~25%, protium 0.05~5%, nitrogen 0~
15%；The particle diameter of Carbon Materials is 0.05~3 μm, specific surface area is 500~3000m2/g。
Bismuth pole material is that 0.005~5 μm of bismuth metal dusty material is formed by particle diameter, its specific surface area for 5~
500m2/g。
The preparation method of bismuth pole material includes the following steps:
(1) soluble bismuth raw material is dissolved in solvent, it is the molten of 0.01~5mol/L to be configured to bismuth concentration
Liquid；Or insoluble bismuth raw material is dissolved in acid, it is configured to the solution that bismuth concentration is 0.01~5mol/L；
(2) it is 0.1~16mol/L reducing agent solutions reducing agent to be dissolved in solvent and be configured to concentration；
(3) by auxiliary agent (end-capping reagent) and bismuth ion (0~10):1 molar ratio, auxiliary agent is added in bismuth ion solution,
It is sufficiently mixed；
(4) it is (1~100) by the molar ratio of reducing agent and bismuth ion in the case where temperature is 0~100 DEG C and stirring condition:1
Reducing agent solution is added drop-wise in the bismuth ion solution containing auxiliary agent, after continuing 1~360min of stirring reaction after being added dropwise to complete, will be produced
Thing is washed with water and ethanol respectively, and carries out separation of solid and liquid, solids dried in 30~100 DEG C of vacuum drying chamber to 6~
36h prepares bismuth meal end, i.e. bismuth pole material to constant weight.
Further, the solvent is water, methanol, ethanol, propyl alcohol, isopropanol, butanol, ethylene glycol, glycerine, poly- second
It is more than one or both of glycol, triethanolamine, tetraethylene glycol, DMF.
Further, the bismuth raw material, including bismuth metal, bismuth oxide, bismuth hydroxide, waltherite, basic bismuth carbonate, sulphur
It is more than one or both of sour oxygen bismuth, novismuth, bismuth sulfate, bismuth nitrate, halogenation bismuth, bismuth acetate, bismuth citrate.
Further, the acid solution is hydrochloric acid, sulfuric acid, acetic acid or nitric acid, its concentration is 0.1~5mol/L.
Further, the reducing agent is sodium borohydride, potassium borohydride, sodium hypophosphite, alkyl amine borine, hydration
It is more than one or both of hydrazine, fatty aldehyde, aromatic aldehyde.
Further, the auxiliary agent for polyethylene glycol, ethylene glycol, glycerine, triethanolamine, citric acid, ascorbic acid,
It is more than one or both of tartaric acid, enuatrol, CTAB, PVP.
The preparation method of above-mentioned bismuth/charcoal super capacitance cell, includes the following steps：
(1) preparation of bismuth pole and carbon resistance rod
Binding agent is dissolved in 1-methyl-2-pyrrolidinone, is made into the solution of 0.02~1g/ml, then by bismuth or Carbon Materials, lead
Electric agent is added in binder solution, is evenly stirred until paste, coating on a current collector, then by its drying at 80~150 DEG C
Dry 5~36h, electrode slice is cut into after roll-in, that is, obtains bismuth pole or carbon resistance rod, the bismuth or Carbon Materials, conductive agent in case
And binding agent meets following mass percent：Bismuth or Carbon Materials 70~95%, conductive agent 3~15%, binding agent 2~15%；
(2) assembling of bismuth/charcoal super capacitance cell
The electrode slice obtained in step (1) is sequentially placed into super capacitance cell mould by bismuth pole piece, membrane, carbon resistance rod piece
It is configured to the sandwich structure of two electrodes in tool, is added dropwise super capacitance cell mould fit sealing after electrolyte, that is, is configured to
The super capacitance cell.
Further, the conductive agent is more than one or both of conductive black, acetylene black, graphite, graphene.
Further, the binding agent is polytetrafluoroethylene (PTFE), Kynoar, sodium carboxymethylcellulose or butadiene-styrene rubber
One or both of more than.
Further, the collector is the high electronic conductivity material of holey, foil-like or textile-like, is related to
Nickel foam, nickel foil or nickel screen, copper mesh or copper foil, stainless (steel) wire, stainless steel Punching steel strip or stainless steel foil, titanium foil or titanium net, lead
It is more than one or both of paper tinsel or lead cloth, graphitization carbon cloth or graphene cloth material；
Further, when constructing the super capacitance cell, bismuth pole is used to limit electrode, the capacitance of carbon resistance rod for capacitance
Measure the capacitance surplus 0~30% than bismuth pole.
Further, the electrolyte is the aqueous solution of one or more kinds of alkali metal hydroxides, its concentration is 1
~8mol/L.
Further, the membrane for graft polypropylene non-woven fabrics, graft PP microporous barrier, all-glass paper, nylon without
It is more than one or both of woven fabric, polyvinyl alcohol film, asbestos paper.
The structure and electrochemical property test of material prepared
The test of microscopic appearance and size is carried out to material prepared using JEOLJEM-3010 types scanning electron microscope；
The test of crystal phase structure is carried out to prepared material using D/MAX-3C types Powder X-ray Diffractometer.
Using the CHI660A electrochemical workstations of Shanghai Chen Hua company production, the new Weir Electronics Co., Ltd. life in Shenzhen
The BTS-3000 cell testers of production the super capacitance cell that is constructed is carried out cyclic voltammetric, constant current charge-discharge, cycle life,
High rate performance is tested.
The beneficial effects of the present invention are：
The present invention provides faraday's capacitance with bismuth pole, and carbon resistance rod provides electric double layer capacitance, constructs new super electricity
The advantages of holding battery, making it have ultracapacitor and secondary cell, the operating voltage of the super capacitance cell of present invention gained
Window is 0~1V, and specific capacitance during 0.5A/g is 258mAh/g, and specific capacitance during 5A/g is 213mAh/g.With coulombic efficiency
It is high, have extended cycle life, the advantages that capacitance is big, environmentally friendly, be a kind of mechanism of new electrochemical power sources with broad prospect of application.
Brief description of the drawings
Fig. 1 is the scanning electron microscope diagram of the bismuth meal powder material prepared by embodiment 1.
Fig. 2 is the scanning electron microscope diagram of the bismuth meal powder material prepared by embodiment 2.
Fig. 3 is the X-ray diffractogram of the bismuth meal powder material prepared by embodiment 1.
Fig. 4 is constant current charge-discharge test chart of the bismuth/charcoal super capacitance cell under different current densities in embodiment 1.
Fig. 5 is cyclic voltammetry figure of the bismuth/charcoal super capacitance cell under different scanning rates in embodiment 3.
Fig. 6 is the circulation of bismuth/charcoal super capacitance cell different cycles under 20mV/s sweep speeds prepared by embodiment 4
Voltammogram.
Fig. 7 is constant current charge-discharge test of the bismuth/charcoal super capacitance cell under 0.5A/g current densities in embodiment 5
Figure.
Fig. 8 is the current ratio performance map of bismuth/charcoal super capacitance cell in embodiment 5.
Fig. 9 is the cycle life figure of bismuth/charcoal super capacitance cell in embodiment 5.
Embodiment
The present invention is further illustrated with specific embodiment below, but the present invention is not limited thereto.
Embodiment 1
(1) certain mass Bi (NO are weighed3)3·5H2O, is dissolved in 10ml concentrated nitric acid solutions, after being diluted with water, is configured to
Bi (the NO of 0.5mol/L3)3Solution, it is spare.
(2) by 2.22gPVP, the Bi (NO of 20mL 0.5mol/L3)3Solution is sequentially added in 100mL round-bottomed flasks, mixing
After uniformly, 30min is stirred at room temperature.
(3) it is 3 by sodium borohydride and bismuth ion molar ratio:1, the sodium borohydride for weighing certain mass is dissolved in 20ml deionizations
Sodium borohydride solution is made into water, at room temperature, is stirred while sodium borohydride solution is added dropwise to step (2) solution
In, after being added dropwise to complete, continue to stir 5min, gains washs with distilled water and ethanol be respectively to pH value repeatedly with suction filtration
Property, dry 12h is put into vacuum drying chamber at 90 DEG C, bismuth material is made.
(4) the bismuth meal powder material prepared by embodiment 1 is surveyed using JEOLJEM-3010 types scanning electron microscope
Examination, as shown in Figure 1, the material forms cauliflower pattern by the nanoparticle that particle diameter is about 20-50nm.
(5) the bismuth meal powder material prepared by embodiment 1 is tested using XRD-6000 types x-ray diffractometer, such as schemed
Shown in 3, sample has obvious spy in 2 θ=22 °, the positions such as 24 °, 27 °, 38 °, 40 °, 45 °, 46 °, 49 °, 56 ° and 59 °
Levy peak, it is consistent with standard card (JCPDS No.44-1246), the crystal face corresponding to it is respectively 003,101,012,104,
110th, 015,113,202,024 and 107.
(6) preparation of bismuth pole and carbon resistance rod：According to bismuth or Carbon Materials 80%, binding agent PVDF12% and conductive agent second
Binding agent, is dissolved in 1-methyl-2-pyrrolidinone by the mass percent of acetylene black 8% first, is made into the solution of 0.02g/ml, then will
Bismuth or Carbon Materials, conductive agent are added in binder solution, are evenly stirred until paste, coated in foamed nickel current collector, then
It is dried into 12h in 100 DEG C of vacuum drying chamber, electrode slice is cut into after roll-in, that is, obtains bismuth material electrodes piece or charcoal
Material electrodes piece.
(7) bismuth pole prepared piece/membrane/carbon resistance rod piece is sequentially placed into special battery mould and is configured to two electricity
The sandwich structure of pole, then be added dropwise after 6mol/LKOH electrolyte and by battery mould fit sealing, that is, be assembled into the bismuth/charcoal
Super capacitance cell.
(8) using the CHI660A electrochemical workstations of Shanghai Chen Hua company production, to the bismuth/charcoal super capacitor constructed
Battery carries out constant current charge-discharge test at room temperature, and voltage window is 0~1V.As shown in Figure 4, the capacitor batteries are 0.5A/g's
Specific capacitance reaches 258mAh/g under current density, and the specific capacitance when current density is 1,2 and 5A/g is respectively 254,242 and
213mAh/g。
Embodiment 2
(1) 1.99g bismuth citrates are weighed to be dissolved in 20ml ethylene glycol solutions.
(2) 0.5g tartaric acid, 2.0g sodium hydroxides are sequentially added and are added in step (1) solution, after mixing,
30min is stirred at room temperature.
(3) NaH is pressed2PO2It is 80 with bismuth ion molar ratio:1, weigh the NaH of certain mass2PO2It is dissolved in 40ml deionized waters
In be made into NaH2PO2Solution, at 90 DEG C, is stirred while by NaH2PO2Liquid is added dropwise in step (2) solution, is added dropwise
After the completion of, continue to stir 300min, until solution is changed into black from clarifying, gains are washed with distilled water and ethanol respectively and
It is repeatedly neutrality to pH value to filter, and is put into vacuum drying chamber at 80 DEG C dry 18h, bismuth material is made.
(4) the bismuth meal powder material prepared by embodiment 2 is surveyed using JEOLJEM-3010 types scanning electron microscope
Examination, as shown in Fig. 2, the material is made of the particle that particle diameter is about 0.5-5 μm
Embodiment 3
(1) certain mass Bi is weighed2(SO4)3, it is dissolved in 10mL concentrated sulfuric acid solutions, is configured to the Bi of 0.5mol/L2
(SO4)3Solution, it is spare.
(2) 0.05g enuatrols are added in step (1) solution, after mixing, 30min are stirred at room temperature.
(3) it is 80 by hydrazine hydrate and bismuth ion molar ratio:1, measure 80wt% hydrazine hydrate be diluted to it is certain density molten
Liquid, at 90 DEG C, stirs while hydrazine hydrate solution is added dropwise in step (2) solution, after being added dropwise to complete, continues to stir
120min is mixed, until solution is changed into black from clarifying, gains are washed with filtering repeatedly to pH with distilled water and ethanol respectively
It is worth for neutrality, is put into vacuum drying chamber at 70 DEG C dry 24h, bismuth material is made.
(4) preparation of bismuth pole and carbon resistance rod：According to bismuth or Carbon Materials 80%, binding agent PVDF10% and conductive agent second
Binding agent, is dissolved in 1-methyl-2-pyrrolidinone by the mass percent of acetylene black 10% first, is made into the solution of 0.02g/ml, then will
Bismuth or Carbon Materials, conductive agent are added in binder solution, are evenly stirred until paste, coated in foamed nickel current collector, then
It is dried into 12h in 100 DEG C of drying box, electrode slice is cut into after roll-in, that is, obtains bismuth material electrodes piece or Carbon Materials
Electrode slice.
(5) carbon resistance rod prepared piece/membrane/bismuth pole piece is sequentially placed into special battery mould and is configured to two electricity
The sandwich structure of pole, then be added dropwise battery mould fit sealing after the mixed electrolytic solution of 5mol/L KOH and 1mol/L LiOH,
It is assembled into the bismuth/charcoal super capacitance cell.
(6) using the CHI660A electrochemical workstations of Shanghai Chen Hua company production, to the bismuth/charcoal super capacitor constructed
Battery carries out cyclic voltammetry at room temperature, and voltage window is 0~1V.As shown in figure 5, prepared bismuth pole is in different scanning
Under speed (5,10,20,50mV/s) cyclic voltammetry curve, obvious faraday's reaction feature is shown, even in higher
Sweep under speed, redox reversible is good.
Embodiment 4
(1) certain mass Bi (CH are weighed3COO)3, it is dissolved in 20ml acetic acid solutions, after being diluted with water, is configured to
Bi (the CH of 0.5mol/L3COO)3Solution, it is spare.
(2) 0.01g citric acids and 0.025g CTAB are added in step (1) solution, after mixing, at room temperature
Stir 30min.
(3) it is 100 by hydrazine hydrate and bismuth ion molar ratio:1, measure 80wt% hydrazine hydrate be diluted to it is certain density molten
Liquid, at 90 DEG C, stirs while hydrazine hydrate solution is added dropwise in step (2) solution, after being added dropwise to complete, continues to stir
90min is mixed, until solution is changed into black from clarifying, gains are washed with filtering repeatedly to pH value with distilled water and ethanol respectively
For neutrality, dry 10h is put into vacuum drying chamber at 100 DEG C, bismuth material is made.
Step (4), (5) are respectively the same as the step (6) in embodiment 1, (7).
(6) using the CHI660A electrochemical workstations of Shanghai Chen Hua company production, to the bismuth/charcoal super capacitor constructed
Battery carries out cyclic voltammetry at room temperature, and voltage window is 0~1V.It is as shown in fig. 6, different under 20mV/s sweep speeds
The cyclic voltammetry curve of cycle period (the 1st time and the 20th time circulation), oxidation peak and reduction peak are respectively 0.78V and 0.47V, it
Essentially coincide, illustrate this electrode stablize invertibity it is good.
Embodiment 5
(1) certain mass BiCl is weighed3, it is dissolved in 10ml concentrated hydrochloric acid solutions, after being diluted with water, is configured to 0.5mol/L
BiCl3Solution, it is spare.
(2) by 2.22gPVP, the BiCl of 20mL 0.5mol/L3Solution is sequentially added in 100mL round-bottomed flasks, and mixing is equal
After even, 30min is stirred at room temperature.
(3) it is 4 by potassium borohydride and bismuth ion molar ratio:1, the potassium borohydride for weighing certain mass is dissolved in 20ml deionizations
Solution of potassium borohydride is made into water, at room temperature, is stirred while solution of potassium borohydride is added dropwise to step (2) solution
In, after being added dropwise to complete, continue to stir 5min, gains washs with distilled water and ethanol be respectively to pH value repeatedly with suction filtration
Property, dry 30h is put into vacuum drying chamber at 60 DEG C, bismuth material is made.
Step (4), (5) are respectively the same as the step (6) in embodiment 1, (7).
(6) using the CHI660A electrochemical workstations of Shanghai Chen Hua company production, to the bismuth/charcoal super capacitor constructed
Battery carries out constant current charge-discharge test at room temperature, and voltage window is 0~1V.As shown in Figure 7, under the current density of 0.5A/g
Specific capacitance reaches 215mAh/g.
(7) using the BTS-3000 cell testers of new Weir Electronics Co., Ltd. of Shenzhen production, to constructed bismuth/
Charcoal super capacitance cell carries out high rate performance and cycle life test at room temperature, and voltage window is 0~1V.As seen from Figure 8, exist
Specific capacitance when current density is 0.5A/g reaches 215mAh/g, and the specific capacitance when current density is 5A/g reaches 196mAh/
G, capacity retention ratio illustrate there is superior current ratio performance up to 91.2%.Cycle life test is carried out to it, can by Fig. 9
See, under the current density of 5A/g, the 73.8% of initial specific capacitance can also be kept after afterwards by 1000 charge and discharge cycles,
This illustrates it with good stable circulation performance.
Claims (8)
1. a kind of bismuth/charcoal super capacitance cell, it is characterised in that bismuth pole provides faraday's capacitance, and carbon resistance rod provides electric double layer
Capacitance, aqueous slkali when constructing the super capacitance cell, use bismuth pole to limit electrode, carbon resistance rod for capacitance as electrolyte
Capacitance than bismuth pole capacitance surplus 0 ~ 30%；
Bismuth pole material is made of the bismuth metal dusty material that particle diameter is 0.005 ~ 5 μm, its specific surface area is 5 ~ 500m2/g。
2. bismuth according to claim 1/charcoal super capacitance cell, it is characterised in that：The carbon resistance rod, used charcoal
Material is activated carbon, graphitized carbon or grapheme material, its element composition is by mass percentage：Carbon 60 ~ 95%,
Oxygen element 0.01 ~ 25%, protium 0.05 ~ 5%, nitrogen 0 ~ 15%；The particle diameter of Carbon Materials is 0.05 ~ 3 μm, specific surface area 500
~3000m²/g。
3. bismuth according to claim 1 or 2/charcoal super capacitance cell, it is characterised in that the preparation method of bismuth pole material
Include the following steps:
(1) soluble bismuth raw material is dissolved in solvent, is configured to the solution that bismuth concentration is 0.01 ~ 5mol/L；Or
Insoluble bismuth raw material is dissolved in acid by person, is configured to the solution that bismuth concentration is 0.01 ~ 5mol/L；
(2) it is 0.1 ~ 16mol/L reducing agent solutions reducing agent to be dissolved in solvent and be configured to concentration；
(3) by auxiliary agent and bismuth ion (0 ~ 10):1 molar ratio, auxiliary agent is added in bismuth ion solution, is sufficiently mixed；
(4) it is (1 ~ 100) by the molar ratio of reducing agent and bismuth ion in the case where temperature is 0 ~ 100 DEG C and stirring condition:1 will reduction
Agent solution is added drop-wise in the bismuth ion solution containing auxiliary agent, and after continuing 1 ~ 360min of stirring reaction after being added dropwise to complete, product is distinguished
Washed with water and ethanol, and carry out separation of solid and liquid, solids is dried into 6 ~ 36h to constant weight in 30 ~ 100 DEG C of vacuum drying chamber
Prepare bismuth meal end, i.e. bismuth pole material；
The auxiliary agent is polyethylene glycol, ethylene glycol, glycerine, triethanolamine, citric acid, ascorbic acid, tartaric acid, oleic acid
It is more than one or both of sodium, cetyl trimethylammonium bromide, polyvinylpyrrolidone.
4. bismuth according to claim 3/charcoal super capacitance cell, it is characterised in that the solvent is water, methanol, second
It is a kind of in alcohol, propyl alcohol, isopropanol, butanol, ethylene glycol, glycerine, polyethylene glycol, triethanolamine, tetraethylene glycol, dimethylformamide
It is or two or more；The acid solution is hydrochloric acid, sulfuric acid, acetic acid or nitric acid, its concentration is 0.1 ~ 5mol/L.
5. bismuth according to claim 3/charcoal super capacitance cell, it is characterised in that the bismuth raw material, including metal
Bismuth, bismuth oxide, bismuth hydroxide, waltherite, basic bismuth carbonate, sulfuric acid oxygen bismuth, novismuth, bismuth sulfate, bismuth nitrate, halogenation bismuth,
It is more than one or both of bismuth acetate, bismuth citrate.
6. bismuth according to claim 3/charcoal super capacitance cell, it is characterised in that the reducing agent for sodium borohydride,
It is more than one or both of potassium borohydride, sodium hypophosphite, alkyl amine borine, hydrazine hydrate, fatty aldehyde, aromatic aldehyde.
7. the preparation method of claim 1 to 6 any one of them bismuth/charcoal super capacitance cell, it is characterised in that including as follows
Step：
(1) preparation of bismuth pole and carbon resistance rod
Binding agent is dissolved in 1-methyl-2-pyrrolidinone, is made into the solution of 0.02 ~ 1g/ml, then by bismuth pole material or Carbon Materials,
Conductive agent is added in binder solution, is evenly stirred until paste, coating on a current collector, then by its drying at 80 ~ 150 DEG C
5 ~ 36h is dried in case, electrode slice is cut into after roll-in, that is, obtains bismuth pole or carbon resistance rod, the bismuth pole material or Carbon Materials,
Conductive agent and binding agent meet following mass percent：Bismuth pole material or Carbon Materials 70 ~ 95%, conductive agent 3 ~ 15%, binding agent 2
~15%；
(2) assembling of bismuth/charcoal super capacitance cell
The electrode slice obtained in step (1) is sequentially placed into super capacitance cell mould by bismuth pole piece, membrane, carbon resistance rod piece
It is configured to the sandwich structure of two electrodes, is added dropwise super capacitance cell mould fit sealing after electrolyte, that is, is assembled into super
Capacitor batteries；When constructing the super capacitance cell, the capacitance surplus 0 ~ 30% of the capacitance of carbon resistance rod than bismuth pole.
8. the preparation method of bismuth according to claim 7/charcoal super capacitance cell, it is characterised in that the conductive agent
More than one or both of conductive black, acetylene black, graphite, graphene；The binding agent is polytetrafluoroethylene (PTFE), gathers partially
It is more than one or both of vinyl fluoride, sodium carboxymethylcellulose or butadiene-styrene rubber；The collector is holey, foil-like
Or the high electronic conductivity material of textile-like；The electrolyte is the water-soluble of one or more kinds of alkali metal hydroxides
Liquid, its concentration are 1 ~ 8mol/L；The membrane is graft polypropylene non-woven fabrics, graft PP microporous barrier, all-glass paper, nylon
It is more than one or both of non-woven fabrics, polyvinyl alcohol film, asbestos paper.
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| CN108866353B (en) * | 2017-05-15 | 2020-11-17 | 中南大学 | Method for recovering bismuth from bismuth methanesulfonate solution |
| KR102364364B1 (en) | 2017-11-24 | 2022-02-16 | 주식회사 엘지에너지솔루션 | Process for preparing anode active material for pseudocapacitor |
| CN108400292B (en) * | 2018-01-24 | 2020-06-02 | 东北电力大学 | Preparation method and application of bismuth elementary substance nanosheet composite electrode |
| CN108493501B (en) * | 2018-03-30 | 2020-08-18 | 华南师范大学 | Preparation method of sodium fluoride dual-ion battery and application of sodium fluoride dual-ion battery in electrochemical fluorine removal |
| CN111250076B (en) * | 2020-03-25 | 2022-08-02 | 电子科技大学 | Nano bismuth catalyst and preparation method and application thereof |
| CN112599361B (en) * | 2020-12-14 | 2023-06-23 | 湖南大学 | Bismuth-based electrode-based wide-temperature-zone high-performance electrochemical energy storage device |
| CN114744223B (en) * | 2022-05-06 | 2024-01-26 | 湖北理工学院 | Iron-chromium redox flow battery electrode material and preparation method thereof |
| CN116375032A (en) * | 2023-04-10 | 2023-07-04 | 南京信息工程大学 | Preparation method of lithium ion battery anode material |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101763949A (en) * | 2009-11-09 | 2010-06-30 | 南京双登科技发展研究院有限公司 | Manufacturing method for increasing specific capacity of electrochemical capacitor |
| CN103050293A (en) * | 2012-12-20 | 2013-04-17 | 上海奥威科技开发有限公司 | Hard-carbon-based chemical power supply with long service life |
| CN105190810A (en) * | 2013-03-19 | 2015-12-23 | 住友电气工业株式会社 | Lithium ion capacitor and method for charging and discharging same |
| CN105244184A (en) * | 2015-09-24 | 2016-01-13 | 宁波南车新能源科技有限公司 | Preparation method for hybrid capacitor battery |
Family Cites Families (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2008294314A (en) * | 2007-05-28 | 2008-12-04 | Sanyo Electric Co Ltd | Capacitor |
| JP6047342B2 (en) * | 2011-08-31 | 2016-12-21 | 株式会社半導体エネルギー研究所 | Negative electrode for power storage device |
-
2016
- 2016-10-31 CN CN201610967583.4A patent/CN106298263B/en not_active Expired - Fee Related
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101763949A (en) * | 2009-11-09 | 2010-06-30 | 南京双登科技发展研究院有限公司 | Manufacturing method for increasing specific capacity of electrochemical capacitor |
| CN103050293A (en) * | 2012-12-20 | 2013-04-17 | 上海奥威科技开发有限公司 | Hard-carbon-based chemical power supply with long service life |
| CN105190810A (en) * | 2013-03-19 | 2015-12-23 | 住友电气工业株式会社 | Lithium ion capacitor and method for charging and discharging same |
| CN105244184A (en) * | 2015-09-24 | 2016-01-13 | 宁波南车新能源科技有限公司 | Preparation method for hybrid capacitor battery |
Non-Patent Citations (5)
| Title |
|---|
| Direct Growth of Bismuth Film as Anode for Aqueous Rechargeable Batteries in LiOH, NaOH and KOH Electrolytes;Wenhua Zuo 等;《Nanomaterials》;20151022;第5卷;第1756-1765页论文摘要、结果与讨论部分 * |
| Electrodeposited Bi, Sb and Bi1-xSbx alloys as anodes for Mg-ion batteries;Timothy S. Arthur 等;《Electrochemistry Communications》;20111220;第16卷;第103-106页 * |
| Fabrication of Bi2O3-AC asymmetric supercapacitor with redox additive aqueous electrolyte and its improved electrochemical performances;S.T. Senthilkumar 等;《Electrochimica Acta》;20131112;第518-524页 * |
| LiNi1/3Co1/3Mn1/3O2/AC混合超级电容器正负极容量配比研究;吴明霞 等;《电子元件与材料》;20110131;第30卷(第1期);第34-37页 * |
| New anode systems for lithium ion cells;O. Crosnier 等;《Journal of Power Sources》;20010223;第94卷;第169-174页 * |
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