CN105609330A - Glue-containing composite carbon powder and preparation method therefor, and electrochemical capacitor manufactured from carbon powder - Google Patents
Glue-containing composite carbon powder and preparation method therefor, and electrochemical capacitor manufactured from carbon powder Download PDFInfo
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- CN105609330A CN105609330A CN201610117743.6A CN201610117743A CN105609330A CN 105609330 A CN105609330 A CN 105609330A CN 201610117743 A CN201610117743 A CN 201610117743A CN 105609330 A CN105609330 A CN 105609330A
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- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 169
- 239000003990 capacitor Substances 0.000 title claims abstract description 52
- 239000003292 glue Substances 0.000 title claims abstract description 44
- 239000002131 composite material Substances 0.000 title claims abstract description 23
- 238000002360 preparation method Methods 0.000 title claims abstract description 23
- 229910052799 carbon Inorganic materials 0.000 claims abstract description 60
- 239000006258 conductive agent Substances 0.000 claims abstract description 29
- 239000000203 mixture Substances 0.000 claims abstract description 29
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 claims abstract description 14
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 13
- 238000000034 method Methods 0.000 claims abstract description 8
- 239000002245 particle Substances 0.000 claims description 45
- 239000000463 material Substances 0.000 claims description 30
- 150000001875 compounds Chemical class 0.000 claims description 27
- 239000000853 adhesive Substances 0.000 claims description 26
- 230000001070 adhesive effect Effects 0.000 claims description 26
- 238000003756 stirring Methods 0.000 claims description 17
- 239000000843 powder Substances 0.000 claims description 13
- 239000000839 emulsion Substances 0.000 claims description 12
- 239000000428 dust Substances 0.000 claims description 11
- 229910002804 graphite Inorganic materials 0.000 claims description 9
- 239000010439 graphite Substances 0.000 claims description 9
- 239000010985 leather Substances 0.000 claims description 9
- 229920001343 polytetrafluoroethylene Polymers 0.000 claims description 9
- 229910002114 biscuit porcelain Inorganic materials 0.000 claims description 8
- 150000001721 carbon Chemical class 0.000 claims description 8
- 239000006229 carbon black Substances 0.000 claims description 6
- 239000003610 charcoal Substances 0.000 claims description 6
- 230000005611 electricity Effects 0.000 claims description 6
- 239000003822 epoxy resin Substances 0.000 claims description 6
- 229920000647 polyepoxide Polymers 0.000 claims description 6
- LLYXJBROWQDVMI-UHFFFAOYSA-N 2-chloro-4-nitrotoluene Chemical compound CC1=CC=C([N+]([O-])=O)C=C1Cl LLYXJBROWQDVMI-UHFFFAOYSA-N 0.000 claims description 4
- 239000000443 aerosol Substances 0.000 claims description 4
- 239000002134 carbon nanofiber Substances 0.000 claims description 4
- 239000012467 final product Substances 0.000 claims description 4
- 239000008187 granular material Substances 0.000 claims description 4
- 229910021389 graphene Inorganic materials 0.000 claims description 4
- 238000010438 heat treatment Methods 0.000 claims description 4
- 230000004048 modification Effects 0.000 claims description 4
- 238000012986 modification Methods 0.000 claims description 4
- 229920000049 Carbon (fiber) Polymers 0.000 claims description 3
- 239000004917 carbon fiber Substances 0.000 claims description 3
- 229920002134 Carboxymethyl cellulose Polymers 0.000 claims description 2
- 239000003575 carbonaceous material Substances 0.000 claims description 2
- 238000003475 lamination Methods 0.000 claims description 2
- 239000004816 latex Substances 0.000 claims description 2
- 229920000126 latex Polymers 0.000 claims description 2
- 238000002156 mixing Methods 0.000 claims description 2
- 229920001084 poly(chloroprene) Polymers 0.000 claims description 2
- 239000004814 polyurethane Substances 0.000 claims description 2
- 229920002635 polyurethane Polymers 0.000 claims description 2
- 238000003828 vacuum filtration Methods 0.000 claims description 2
- 239000001768 carboxy methyl cellulose Substances 0.000 claims 1
- 235000010948 carboxy methyl cellulose Nutrition 0.000 claims 1
- 239000008112 carboxymethyl-cellulose Substances 0.000 claims 1
- 238000011049 filling Methods 0.000 claims 1
- 230000008569 process Effects 0.000 abstract description 4
- 239000011230 binding agent Substances 0.000 abstract 3
- 239000002994 raw material Substances 0.000 abstract 2
- 238000005303 weighing Methods 0.000 abstract 2
- 230000008021 deposition Effects 0.000 abstract 1
- 229910000464 lead oxide Inorganic materials 0.000 description 12
- YEXPOXQUZXUXJW-UHFFFAOYSA-N oxolead Chemical compound [Pb]=O YEXPOXQUZXUXJW-UHFFFAOYSA-N 0.000 description 12
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 8
- 239000004810 polytetrafluoroethylene Substances 0.000 description 8
- 239000006230 acetylene black Substances 0.000 description 7
- YADSGOSSYOOKMP-UHFFFAOYSA-N lead dioxide Inorganic materials O=[Pb]=O YADSGOSSYOOKMP-UHFFFAOYSA-N 0.000 description 7
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 6
- 239000003792 electrolyte Substances 0.000 description 6
- 239000007772 electrode material Substances 0.000 description 5
- 239000002002 slurry Substances 0.000 description 5
- 238000007599 discharging Methods 0.000 description 4
- 238000004146 energy storage Methods 0.000 description 4
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- 239000000243 solution Substances 0.000 description 3
- 238000000967 suction filtration Methods 0.000 description 3
- 239000010936 titanium Substances 0.000 description 3
- 229910052719 titanium Inorganic materials 0.000 description 3
- 239000004593 Epoxy Substances 0.000 description 2
- HSFWRNGVRCDJHI-UHFFFAOYSA-N alpha-acetylene Natural products C#C HSFWRNGVRCDJHI-UHFFFAOYSA-N 0.000 description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- OCKPCBLVNKHBMX-UHFFFAOYSA-N butylbenzene Chemical compound CCCCC1=CC=CC=C1 OCKPCBLVNKHBMX-UHFFFAOYSA-N 0.000 description 2
- 235000013339 cereals Nutrition 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 238000004070 electrodeposition Methods 0.000 description 2
- 125000002534 ethynyl group Chemical group [H]C#C* 0.000 description 2
- 238000005469 granulation Methods 0.000 description 2
- 230000003179 granulation Effects 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 229910044991 metal oxide Inorganic materials 0.000 description 2
- 230000003647 oxidation Effects 0.000 description 2
- 238000007254 oxidation reaction Methods 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
- -1 polytetrafluoroethylene Polymers 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- 238000003860 storage Methods 0.000 description 2
- KEQXNNJHMWSZHK-UHFFFAOYSA-L 1,3,2,4$l^{2}-dioxathiaplumbetane 2,2-dioxide Chemical compound [Pb+2].[O-]S([O-])(=O)=O KEQXNNJHMWSZHK-UHFFFAOYSA-L 0.000 description 1
- 239000006245 Carbon black Super-P Substances 0.000 description 1
- 240000007594 Oryza sativa Species 0.000 description 1
- 235000007164 Oryza sativa Nutrition 0.000 description 1
- 239000002033 PVDF binder Substances 0.000 description 1
- 229910000831 Steel Inorganic materials 0.000 description 1
- 239000002250 absorbent Substances 0.000 description 1
- 230000002745 absorbent Effects 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 238000007605 air drying Methods 0.000 description 1
- 229910052924 anglesite Inorganic materials 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 230000008901 benefit Effects 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 239000002322 conducting polymer Substances 0.000 description 1
- 229920001940 conductive polymer Polymers 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 230000008878 coupling Effects 0.000 description 1
- 238000010168 coupling process Methods 0.000 description 1
- 238000005859 coupling reaction Methods 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 238000003795 desorption Methods 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 230000005518 electrochemistry Effects 0.000 description 1
- 239000004744 fabric Substances 0.000 description 1
- 238000005087 graphitization Methods 0.000 description 1
- 239000010903 husk Substances 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 239000005414 inactive ingredient Substances 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- HTUMBQDCCIXGCV-UHFFFAOYSA-N lead oxide Chemical compound [O-2].[Pb+2] HTUMBQDCCIXGCV-UHFFFAOYSA-N 0.000 description 1
- 230000035800 maturation Effects 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- 230000010412 perfusion Effects 0.000 description 1
- 229920002981 polyvinylidene fluoride Polymers 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 238000004080 punching Methods 0.000 description 1
- 238000006479 redox reaction Methods 0.000 description 1
- 238000006722 reduction reaction Methods 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 230000002441 reversible effect Effects 0.000 description 1
- 235000009566 rice Nutrition 0.000 description 1
- 238000007493 shaping process Methods 0.000 description 1
- 239000010959 steel Substances 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 238000004758 underpotential deposition Methods 0.000 description 1
- 230000010148 water-pollination Effects 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
- H01G11/84—Processes for the manufacture of hybrid or EDL capacitors, or components thereof
- H01G11/86—Processes for the manufacture of hybrid or EDL capacitors, or components thereof specially adapted for electrodes
-
- 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
- H01G11/22—Electrodes
- H01G11/30—Electrodes characterised by their material
- H01G11/32—Carbon-based
- H01G11/42—Powders or particles, e.g. composition 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)
- Microelectronics & Electronic Packaging (AREA)
- Chemical & Material Sciences (AREA)
- Materials Engineering (AREA)
- Electric Double-Layer Capacitors Or The Like (AREA)
- Battery Electrode And Active Subsutance (AREA)
- Manufacturing & Machinery (AREA)
Abstract
The invention discloses glue-containing composite carbon powder and a preparation method therefor, and an electrochemical capacitor manufactured from the carbon powder. The glue-containing composite carbon powder comprises 70-90wt% of modified active carbon granules, 5-20wt% of conductive agent and 5-10wt% of binder; the preparation method comprises the following steps of weighing a proper amount of the modified active carbon granules and conductive agent, then enabling the weighed modified active carbon granules and conductive agent to be mixed in a dry manner, then adding water to mix uniformly to obtain a raw material mixture; then weighing a proper amount of binder, and adding the weighed binder to the raw material mixture to be uniformly mixed to obtain the glue-containing composite carbon powder. According to an active carbon negative electrode plate of the capacitor, due to the combined action of the microstructural three-dimensional conductive network in the modified active carbon granules and the three-dimensional conductive network in the electrode, the equivalent series resistance of the electrode is lowered, and the capacity is obviously improved; meanwhile, the lead deposition problem existing in the electrode in the charge-discharge process of the active carbon negative electrode plate is restrained; and furthermore, the electrochemical capacitor has the features of high capacity and long service life.
Description
Technical field
The invention belongs to technical field of electrochemistry, be specifically related to a kind of containing glue compound carbon powder and system thereofThe electrochemical capacitor that Preparation Method and this carbon dust are made.
Background technology
Along with economic development, the energy, resource and environment etc. becomes social focus and asksTopic, finds the energy clean, renewable and resource-conserving and is human society very urgently andVery difficult task.
At present, mainly contain the energy storage device of three types at energy field: battery, physics electricityContainer and electrochemical capacitor (also claiming ultracapacitor). Electrochemical capacitor is in recent yearsA kind of novel green between traditional physical capacitor and battery behavior growing upEnergy storage device, has fast charging and discharging characteristic, and power density (is tens of common batteries greatlyDoubly), have extended cycle life (cycle-index can reach more than 100,000 times), serviceability temperature modelEnclose wide (between-40 DEG C～75 DEG C). Based on these special performances, electrochemical capacitor has non-Normal good application prospect.
According to the difference of energy storage mechanism, electrochemical capacitor can be divided into double layer capacitor and methodDraw the large class of pseudo-capacitance device two. Double layer capacitor is to utilize between electrode and electrolyte to formInterfacial electric double layer electric capacity carry out stored energy, its electrode conventionally adopts has high-specific surface areaPorous carbon material. Pseudo capacitance capacitor refers to the two dimension in mutually at electrode surface or bodyOr on accurate two-dimensional space, electrode active material carries out underpotential deposition, make its occur fast,Reversible chemisorbed/desorption or oxidation/reduction reaction, thus produce than double layer capacitor moreHigh specific capacity, its electrode material is mainly metal oxide and conducting polymer.
In order to obtain higher energy density and power density simultaneously, development in recent years gets up onePlant Novel asymmetric type electrochemical capacitor (also claiming hybrid electrochemical capacitor), i.e. capacitorA utmost point be double layer electrodes, another is pseudo capacitance electrode very. Asymmetric electrificationLearn the advantage that ultracapacitor combines two class electrochemical capacitors, can meet better actualThe energy density of load to power-supply system and the overall requirement of power density in application.
In the asymmetric electrochemical capacitor of each quasi-metal oxides/carbon, PbO2/ C system,Because material price is low and PbO2Electrode manufacturing technology maturation is applicable to manufacturing large capacity version very muchEnergy storage device.
The PbO mentioning in previous literature2The asymmetric electrochemical capacitor of/C, its anodal employingThe positive electrode of slim lead-acid battery, utilizes PbSO4/PbO2The redox reaction that electricity is right,Negative pole adopts Coated Activated Carbon or active carbon fiber fabrics, H2SO4The aqueous solution is made electrolyte. ByIn the problem such as equivalent series resistance and electrolyte ion mobile route of carbon electrode, it is generally acknowledgedThe thickness of carbon electrode is preferably no more than 0.3mm, even slim positive electrode is also difficult to itCoupling. Consequently the capacitance of activated carbon negative electrode, much smaller than lead oxide positive pole, is discharging and rechargingIn process, most of positive electrodes are not utilized, and the energy density of capacitor is low, Wu FachaoCross 20Wh/kg, be less than 1/3rd of battery. In addition, slim positive electrode is also not suitable forManufacture large scale pole plate.
Brown lead oxide/active carbon ultracapacitor that patent 200910115958.4 is announced, positive poleFor pulse electrodeposition brown lead oxide film on dull and stereotyped titanium electrode, negative pole is with active carbon, leadsThe slurry of electricity agent and adhesive configuration, in the online direct tablet compressing preparation of titanium. Patent201210330660.7 the water system of three-dimensional porous ti-supported lead dioxide electric/active carbon of announcing is non-rightClaim ultracapacitor, just very at three-dimensional porous titanium base electro-deposition brown lead oxide, negative pole is for usingThe slurry of rice husk Quito mesoporous activated carbon, conductive agent and adhesive configuration is straight on stainless (steel) wireConnect compressing tablet preparation. These are all typical power type super capacitor design pattern, slimAnodal and slim negative pole combination, the coupling of capacity is very good, and power density is large but energy is closeSpend little, this be due to the inactive ingredients that forms capacitor (collector, bus-bar, pole,Dividing plate and shell etc.) will account for the greater part of gross mass, therefore, its energy density is only electricity/ 10th left and right in pond.
The hybrid electrochemical capacitor that patent 200910221793.9 is announced, adopts multilayer slimCarbon powder electrodes and negative pole dividing plate alternately arrange combination form prepare negative pole, preferably solveThe plumbous anodal capacity matching problem of negative pole and conventional oxidation, energy density has also obtained significantlyImprove. But the accounting of negative current collector in negative pole gross mass is still very high, energy is closeWhat degree improved is limited in scope, and the shortcoming of complicated process of preparation also clearly simultaneously.
Existing PbO2The asymmetric electrochemical capacitor of/C, power density is high, cycle lifeLong, but its energy density is significantly lower than battery, does not also reach electric motor car and hybrid power vapourThe requirement of car electrokinetic cell and solar energy and wind energy power plant energy-storage battery, widely restrictionThe range of application of such capacitor.
Summary of the invention
For solving the problems of the technologies described above, the object of the present invention is to provide a kind of containing glue compound carbon powderAnd preparation method thereof the electrochemical capacitor made with this carbon dust, thereby the mixing electric capacity of preparationDevice, can not only metric density high, power density is high, and have extended cycle life, can meet electronicBicycle, battery-operated motor cycle, fork truck, touring car, old scooter, electric automobile and mixRequirement and the sun of requirement, automobile and the motor vehicle start and stop battery of the electrokinetic cells such as power vehicleCan with the requirement of wind energy power plant energy storage device.
For achieving the above object, technical scheme of the present invention is as follows:
On the one hand, the invention provides a kind of modified activated carbon particle, comprise following percentage by weightEach component: capacitive character material with carbon element 60～80%, conductive agent 15～25% and adhesive 5～15%.
Preferably, described modified activated carbon particle comprises each component of following percentage by weight: electricityCapacitive material with carbon element 70%, conductive agent 25% and adhesive 5%.
Preferably, described capacitive character material with carbon element be selected from active carbon, CNT, carbon nano-fiber,At least one in carbon/Carbon composites, graphitization active carbon and carbon aerosol.
Preferably, described conductive agent is selected from carbon black, acetylene black, graphite, expanded graphite, conductionAt least one in carbon black (Super-P), carbon fiber, CNT and Graphene.
More preferably, described adhesive is selected from polytetrafluoroethylene (PTFE) (PTFE) emulsion, butylbenzene rubberGlue (SBR) emulsion, epoxy resin latex, Kynoar (PVDF), fluorubber,At least one in polyurethane, carboxymethyl cellulose (CMC) and neoprene.
Modified activated carbon particle of the present invention, adopt active carbon, conductive agent and adhesive granulation andBecome, by material and the material mixture ratio combination of different-grain diameter, make active carbon be dispersed in large grainAround, the material with carbon element of nominal particle size is (as acetylene for the material with carbon element (as graphite, expanded graphite) in footpathBlack, Graphene) be filled in space, form thus the three-dimensional conductive network of micro-structural, significantlyThe electric conductivity of having improved absorbent charcoal material, has reduced equivalent series resistance.
On the other hand, the present invention also provides a kind of preparation method of above-mentioned modified activated carbon particle,Comprise the following steps:
1) take appropriate capacitive character material with carbon element and conductive agent, then by the capacitive character carbon takingMaterial and conductive agent are first dry mixed, then add water and mix, and obtain paste mixture; Preferably, willThe capacitive character material with carbon element and the conductive agent that take are first dry mixed 5 minutes, then add water to stir 7～8 hoursMix;
2) again by after described paste mixture vacuum filtration, add described adhesive, stir mixedEven, obtain mixed material; Preferably, stir and mix for 1～2 hour;
3) be finally processed into powder by dry described mixed material, obtain final product.
Preferably, in step 3) in, by the method comprising the following steps, by described mixingRaw material drying is processed into powder: at 50～75 DEG C, described mixed material is dried to 2～10 hoursTo leather hard, repeatedly composite material is carried out to pair roller and roll, simultaneously infrared heating composite materialMaterial, until composite material in the form of sheets, graininess, last 120 DEG C dry 2 hours, to obtain final product.
Preferably, at 50 DEG C, described mixed material is dried to 8～10 hours to leather hard,Or;
Preferably, at 75 DEG C, described mixed material is dried to 2～3 hours to leather hard.
The preparation method of the modified activated carbon particle in the present invention, is soaked and is fitted by the pre-of materialAmount is added adhesive, and composite material is held to pair roller and roll, solidify and dry processing, formsStable local bonded structure, in having improved the bulk density of material with carbon element, has guaranteed to changePorosity and the hydrophily of property activated carbon granule, thus effective electricity of activated carbon negative electrode plate improvedCapacity.
Again on the one hand, it is a kind of containing glue compound carbon powder that the present invention also provides, and comprises that above-mentioned modification is aliveProperty charcoal particle 70～90 % by weight, also comprise conductive agent 5～20 % by weight, adhesive 5～10 weightsAmount %.
Preferably, the described glue compound carbon powder that contains comprises above-mentioned modified activated carbon particle 90 weightsAmount %, also comprises conductive agent 5 % by weight, adhesive 5 % by weight.
Also on the one hand, the present invention also provides a kind of above-mentioned preparation method containing glue compound carbon powder, bagDraw together following steps:
(1) first take appropriate modified activated carbon particle and conductive agent, then by the modification takingActivated carbon granule and conductive agent are first dry mixed, then add water and mix, and obtain raw mixture; PreferablyGround, is first dry mixed 5 minutes by the modified activated carbon particle taking and conductive agent, then adds water to stirWithin 15 minutes, mix; More preferably, add 40 % by weight containing glue compound carbon powder gross weight of preparationWater mix;
(2) take again suitable amount of adhesive, and the adhesive taking is added to described raw mixtureIn, mix, after curing being dried, obtain, containing glue compound carbon powder, preferably, stirring 10～20 pointsClock mixes.
Another aspect, the present invention also provides a kind of hybrid electrochemical capacitor negative plate, comprises leadCollector, the positive and negative of described plumbous collector is equipped with containing glue composite carbon bisque, described containing glue carbonBisque is by the above-mentioned tow sides built in described plumbous collector containing glue compound carbon powder lamination, preferablyGround, the described thickness containing glue composite carbon bisque is 1.1～1.2mm, density is 0.75g/cm3。
Preferably, the described glue carbon dust layer that contains is compressed on described lead by the method comprising the following stepsThe tow sides of collector:
Annotate at the positive and negative of collector containing glue carbon dust described, through compressing, then existUnder vacuum, solidify 12～24 hours in 45 DEG C, then at 50～70 DEG C, dry 24 hours,Obtain tow sides and be provided with the capacitor anode plate containing glue composite carbon bisque.
Activated carbon negative electrode plate of the present invention is because the micro-structural 3 D in modified activated carbon particle is ledThe acting in conjunction of the three-dimensional conductive network in electric network and electrode, greatly reduces the equivalence of electrodeSeries resistance, capacity significantly improves, owing to adopting high density modified activated carbon particle, conductive agentCompressing containing glue compound carbon powder with the composition such as adhesive, carbon electrode also has highdensity spyProperty, effectively suppress the lead deposit of electrode interior in charge and discharge process of activated carbon negative electrode plate and askedTopic, electrode has high power capacity and long-life feature.
On the one hand, the present invention also provides a kind of hybrid electrochemical capacitor, comprises at least one againAbove-mentioned hybrid electrochemical capacitor negative plate.
Preferably, described hybrid electrochemical capacitor also comprises brown lead oxide positive plate, described twoBetween lead oxide positive plate and described negative plate, be provided with AGM dividing plate and dilute sulfuric acid electrolyte.
More preferably, described negative plate be flat, takeup type or tubular type highly carry in powder amount, thickShape activated carbon electrodes, this electrode is the powder electrode with three-dimensional conductive network structure, by containingGlue compound carbon powder is in the compressing preparation in plumbous collector two sides, and positive plate is 1.1～1.9mm preferably,Negative plate is 0.9～1.5mm preferably.
Hybrid electrochemical capacitor of the present invention is designed to rich solution type, valve-regulated sealed, and it overchargesThe oxygen producing when electricity is absorbed by the lead that is deposited on activated carbon negative electrode surface, realizes oxygen cycle.
Electrochemical capacitor of the present invention, due to activated carbon negative electrode adopt modified activated carbon particle,Conductive agent and compressed with adhesive are shaped and prepare, and conductive agent and adhesive are in modified activated carbon particle weekEnclose and form three-dimensional conductive network structure, be convenient to prepare large capacity carbon electrode medium-sized, thick size,The corrosion resistance to sulfuric acid that conductive agent and adhesive are good, makes the three-dimensional conductive mesh of carbon electrode insideNetwork has fabulous stability and durability, has greatly improved the service life of capacitor.
Brief description of the drawings
Fig. 1 is the structural representation of the negative plate in the present invention;
Fig. 2 is the principal section figure of the hybrid electrochemical capacitor in the present invention;
Fig. 3 is the both positive and negative polarity syndeton schematic diagram of the hybrid electrochemical capacitor in the present invention;
Fig. 4 is modified activated carbon grain structure schematic diagram in the present invention;
Fig. 5 is the discharging and recharging of capacitor of the negative plate composition prepared of the embodiment of the present invention 2Curve;
Fig. 6 is the cycle life curve that charge and discharge mode was obtained with Fig. 5;
Wherein:
1. positive plate, 2. negative plate, 21. plumbous collectors, 22. Powder electrode layer 3.AGM everyPlate, 4. active carbon, 5. positive bus bar, 6. negative bus bar, 7. shell, 8. positive terminal,9, negative terminal, 10. graphite, 11. adhesives, 12. acetylene blacks.
Detailed description of the invention
Describe the preferred embodiment of the present invention in detail below in conjunction with accompanying drawing.
Unless specialized, the reagent in following examples all can be from regular distributorPurchase acquisition.
In order to reach object of the present invention, as shown in Figure 1, hybrid electrochemical electric capacity of the present inventionDevice negative plate 2, comprises negative electrode lead collector 21, and the positive and negative of plumbous collector is equipped with containing glue multipleClose carbon dust layer 22, containing glue carbon dust layer 22 by containing glue compound carbon powder (following embodiment containing of preparingGlue compound carbon powder) compacting forms, and preferably, the described thickness containing glue composite carbon bisque is1.1～1.2mm, density is 0.75g/cm3。
In order to reach object of the present invention, as shown in Fig. 2 to 3, hybrid electrochemical of the present inventionCapacitor, comprises the hybrid electrochemical capacitor negative plate 2 that at least one is above-mentioned.
In order to optimize further implementation result of the present invention, hybrid electrochemical capacitor also comprisesBrown lead oxide positive plate 1, between brown lead oxide positive plate 1 and negative plate 2, be provided with AGM everyPlate 3 and dilute sulfuric acid electrolyte.
In order to optimize further implementation result of the present invention, negative plate 2 is flat, coilingFormula or tubular type height carry in powder amount, thick shape activated carbon electrodes, and this electrode is for having three-dimensional conductive networkThe powder electrode of structure, by containing glue compound carbon powder in the plumbous collector 21 compressing systems in two sidesStandby, preferably 1.1～1.9mm of brown lead oxide positive plate 1, preferably 0.9～1.5mm of negative plate 2.
In order to optimize further implementation result of the present invention, hybrid electrochemical capacitor also wrapsDraw together shell, in its shell 7, be packaged with five brown lead oxide positive plates that are intervally arranged1 and six negative plates 2, brown lead oxide positive plate 1 is of a size of long 68mm, wide38mm, thick 1.40mm are common lead battery PbO2Anodal; Negative pole sizeFor 68mm length and width 44mm, thick 2.95mm.
In order to optimize further implementation result of the present invention, the thickness of AGM dividing plate is1.2mm/10KPa; And the electrolyte of perfusion is dilute sulfuric acid (density 1.26g/cm3).
In order to optimize further implementation result of the present invention, the top of brown lead oxide positive plate 1Portion is connected by positive bus bar 5, and converge by negative pole at the top of negative plate 2Stream bar 6 is connected.
The preparation of embodiment 1 modified activated carbon particle
In conjunction with shown in Fig. 4, modified activated carbon particle is by active carbon 4, graphite powder again10, acetylene black 11, fluorubber granulation 12 form, and each components by weight is as follows:Active carbon 70%, graphite powder 20%, acetylene black 5%, fluorubber 5%, wherein liveProperty charcoal adopt specific area 1500m2/ g, mesoporous are greater than 40%, particle mean sizeThe commercialization active carbon of 5-10 μ m; The 800 object commercializations of graphite powder average grain diameterProduct; Acetylene black adopts specific area 70m2/ g, particle mean size 35nm, powderThe commercially produced product of resistance 0.19 Ω cm.
First active carbon, graphite powder and acetylene black are dry mixed to 5 minutes, add water furnishingThin pulp shape, stirs 7 hours, fully mixes. Then slurry is carried out to suction filtration, removeRemove apparent moisture, then add the ethyl acetate solution of fluorubber, stir 2 hours,Fully mix. Under 75 DEG C of environment, dry 3 hours, to leather hard, anti-Again composite material is carried out to pair roller and roll, infrared heating composite material is simultaneously straightTo powder in the form of sheets, graininess, last 120 DEG C dry 2 hours, obtain modificationActivated carbon granule.
The preparation of embodiment 2 negative plates
Each material component weight ratio containing glue compound carbon powder is as follows: prepared by embodiment 1Modified activated carbon particle 90%, graphite powder 5%, epoxy resin 5% (emulsion),Wherein modified activated carbon particle is pulverized and is ground through appropriateness, gets 40 mesh sieves, not mistakeThe part of 100 mesh sieves, jolt ramming bulk density is 0.65g/cm3; Graphite powder is for flatAll particle diameter 800 object commercially produced products.
First modified activated carbon particle, graphite powder are dry mixed to 5 minutes, use modified activeThe water-wet of 40 % by weight of charcoal particle weight, then continue to mix 15 minutes, soAfter add through premixed bicomponent epoxy resin (emulsion) (claiming again AB glue),Stir 10 minutes, fully mix, make containing glue compound carbon powder. Contain described againGlue compound carbon powder is annotated successively at the positive and negative of collector, is pressed into through hydraulic pressShape; Then under 45 DEG C of vacuum environments, solidify 12 hours, under 50 DEG C of environment,Dry 24 hours. Every lateral capacitance electrode material control thickness is on a 1.1-1.2mm left sideThe right side, density is controlled at 0.75g/cm3Left and right, obtains negative plate 2.
Negative electrode lead collector 21: adopt pure flat lead, thickness is 7mm left and right,Then punching and shaping.
Fig. 5 is by the cycle charge discharge electrical measurement of Zhangjiagang Jin Fan Electrosource, Inc.Test instrument (μ C-XCF08) is measured the capacitor of the made negative plate composition of this exampleCharging and discharging curve, the capacitor making by this example is by two five positive platesForm with the tandem compound of six negative plate capacitor cells, appearance and size is:102.2 × 44.2 × 96.2mm × mm × mm (length × wide × height), quality 912g; MarkClaim voltage 4.0V, electrochemical window 4.8-2.0V; Energy density 20.24Wh/Kg,44.46Wh/L, and the energy density of capacitor of the prior art is generally 7～8Wh/Kg, the energy density of the application's capacitor is far away higher than in prior artThe energy density of capacitor.
Fig. 6 is the cycle life curve that charge and discharge mode was obtained with Fig. 5, fromThis curve can see, the application's the capacitor deep discharge life-span can reach 8000More than inferior, thus the deep discharge life-span of known this capacitor can reach traditional plumbic acidThe more than 15 times of battery.
The preparation of embodiment 3 modified activated carbon particles
The adhesive of modified activated carbon particle is PTFE (content 70%) emulsion;Each components by weight is as follows: carbon nano-fiber 60%, acetylene black 20%, Graphene5%, PTFE (content 70%) emulsion 15%.
First carbon nano-fiber, Graphene and acetylene black are dry mixed to 5 minutes, add waterFurnishing thin pulp shape, stirs 8 hours, fully mixes. Then slurry is carried out to suction filtration,Remove apparent moisture, then add PTFE (polytetrafluoroethylene (PTFE)) (content 70%) breastLiquid, stirs 1 hour, fully mixes. Under 75 DEG C of environment, dry 2 hours,To leather hard, repeatedly composite material is carried out to pair roller and roll, infrared ray adds simultaneouslyHot composite material, until powder in the form of sheets, graininess, last 120 DEG C dry 2Hour, obtain modified activated carbon particle.
All the other are identical with embodiment 2.
The preparation of embodiment 4 negative plates
Modified activated carbon particle 70%, carbon black 20%, epoxy prepared by embodiment 3Resin emulsion 10%.
First modified activated carbon particle, carbon black are dry mixed to 5 minutes, use modified activated carbonThe water-wet of particle weight 40 % by weight, then continue to mix 15 minutes, then addEnter through premixed bicomponent epoxy resin (emulsion), stir 20 minutes, fullyMix, make containing glue compound carbon powder. Annotate successively containing glue compound carbon powder described againAt the positive and negative of collector, compressing through hydraulic press; Then true at 45 DEG CUnder Altitude, solidify 24 hours, under 50 DEG C of environment, dry 24 hours.Every lateral capacitance electrode material control thickness is in 1.1-1.2mm left and right, and density is controlled at0.75g/cm3Left and right, obtains negative plate 2.
All the other are identical with embodiment 2.
The preparation of embodiment 5 modified activated carbon particles
The each components by weight of modified activated carbon particle is as follows: carbon aerosol 80%, swollenSwollen graphite 5%, fluorubber 15%.
First carbon aerosol, expanded graphite are dry mixed to 5 minutes, add water furnishing thin pulpShape, stirs 7.5 hours, fully mixes. Then slurry is carried out to suction filtration, removeApparent moisture, then add the ethyl acetate solution of fluorubber, stir 1.5 hours,Fully mix. Under 50 DEG C of environment, forced air drying (can be dried 8-10 in 8 hoursHour), to leather hard, repeatedly composite material is carried out to pair roller and roll, simultaneouslyInfrared heating composite material, until powder in the form of sheets, graininess, last 120 DEG CDry 2 hours, obtain modified activated carbon particle.
All the other are identical with embodiment 1.
The preparation of embodiment 6 negative plates
Modified activated carbon particle 80%, carbon black 5%, epoxy prepared by embodiment 5Resin emulsion 15%.
First modified activated carbon particle, carbon black are dry mixed to 5 minutes, use modified activated carbonThe water-wet of particle weight 40 % by weight, then continue to mix 15 minutes, then addEnter through premixed bicomponent epoxy resin (emulsion) (claiming again AB glue), stir15 minutes, fully mix, make containing glue compound carbon powder. Again by described multiple containing glueClose carbon dust and annotate successively at the positive and negative of collector, compressing through hydraulic press;Then under 45 DEG C of vacuum environments, solidify 18 hours, under 50 DEG C of environment, dryDry 24 hours. Every lateral capacitance electrode material control thickness is in about 1.1-1.2mm,Density is controlled at 0.75g/cm3Left and right, obtains negative plate 2.
Above-described is only the preferred embodiment of the present invention, it should be pointed out that for this areaThose of ordinary skill, without departing from the concept of the premise of the invention, can also doGo out some distortion and improvement, these all belong to protection scope of the present invention.
Claims (10)
1. a modified activated carbon particle, comprises each component of following percentage by weight: capacitive character carbonMaterial 60～80%, conductive agent 15～25% and adhesive 5～15%.
2. modified activated carbon particle according to claim 1, is characterized in that, described modificationActivated carbon granule comprises each component of following percentage by weight: capacitive character material with carbon element 70%, conductive agent25% and adhesive 5%.
3. modified activated carbon particle according to claim 1 and 2, is characterized in that, described inCapacitive character material with carbon element is selected from active carbon, CNT, carbon nano-fiber, carbon/Carbon composites, graphiteChange at least one in active carbon and carbon aerosol; Preferably, described conductive agent is selected from carbon black, secondAlkynes is black, in graphite, expanded graphite, conductive carbon black, carbon fiber, CNT and Graphene extremelyFew a kind of; More preferably, described adhesive be selected from ptfe emulsion, SBR emulsion,Epoxy resin latex, Kynoar, fluorubber, polyurethane, carboxymethyl cellulose and neoprene rubberAt least one in glue.
4. according to the preparation method of the modified activated carbon particle described in any one in claims 1 to 3,Comprise the following steps:
1) take appropriate capacitive character material with carbon element and conductive agent, then by the capacitive character material with carbon element takingFirst be dry mixed with conductive agent, then add water and mix, obtain paste mixture; Preferably, will takeCapacitive character material with carbon element and conductive agent are first dry mixed 5 minutes, then add water stirring to mix for 7～8 hours;
2) again by after described paste mixture vacuum filtration, add described adhesive to stir and evenly mix,To mixed material; Preferably, stir and mix for 1～2 hour;
3) be finally processed into powder by dry described mixed material, obtain final product.
5. the preparation method of modified activated carbon particle according to claim 4, is characterized in that,In step 3) in, by the method comprising the following steps, by the dry described mixed material powder that is processed intoEnd: at 50～75 DEG C, described mixed material is dried to 2～10 hours to leather hard, more repeatedlyComposite material is carried out to pair roller and roll, infrared heating composite material simultaneously, until described composite materialMaterial in the form of sheets, graininess, last 120 DEG C dry 2 hours, to obtain final product;
Preferably, at 50 DEG C, described mixed material is dried to 8～10 hours to leather hard, or;
Preferably, at 75 DEG C, described mixed material is dried to 2～3 hours to leather hard.
6. containing a glue compound carbon powder, comprise that in claims 1 to 3, the modification described in any one is livedProperty charcoal particle 70～90 % by weight, also comprise conductive agent 5～20 % by weight and adhesive 5～10 % by weight.
7. the glue compound carbon powder that contains according to claim 6, is characterized in that, described multiple containing glueClose carbon dust and comprise modified activated carbon particle 90 % by weight described in any one in claims 1 to 3,Also comprise conductive agent 5 % by weight and adhesive 5 % by weight.
8. according to the preparation method containing glue compound carbon powder described in claim 6 or 7, comprise followingStep:
(1) first take appropriate modified activated carbon particle and conductive agent, then the modification taking is livedProperty charcoal particle and conductive agent are first dry mixed, then add water and mix, and obtain raw mixture; Preferably,The modified activated carbon particle taking and conductive agent are first dry mixed to 5 minutes, then add water to stir 15 minutesMix; More preferably, add the water of 40 % by weight containing glue compound carbon powder gross weight of preparation to mix;
(2) take again suitable amount of adhesive, and the adhesive taking added in described raw mixture,Mix, obtain containing glue compound carbon powder; Preferably, stir and mix for 10～20 minutes.
9. a hybrid electrochemical capacitor negative plate, comprises plumbous collector, described plumbous collectorPositive and negative is equipped with containing glue composite carbon bisque, and the described glue carbon dust layer that contains is by described in claim 6 or 7Containing glue compound carbon powder lamination built in the tow sides of described plumbous collector; Preferably, described containing glueComposite carbon bisque is compressed on the tow sides of described plumbous collector by the method comprising the following steps:
By described containing glue carbon dust filling the positive and negative at collector, through compressing, then veryUnder sky, solidify 12～24 hours in 45 DEG C, then at 50～70 DEG C, dry 24 hours, just obtainAnti-two sides is provided with the negative plate containing glue composite carbon bisque;
More preferably, the described thickness containing glue composite carbon bisque is 1.1～1.2mm, and density is 0.75g/cm3。
10. a hybrid electrochemical capacitor, comprises at least one mixing electricity claimed in claim 9Chemical capacitor negative plate.
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