CN102543458B - Alkali pseudo-capacitor alloplastic electrode and matching method therefor - Google Patents
Alkali pseudo-capacitor alloplastic electrode and matching method therefor Download PDFInfo
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- CN102543458B CN102543458B CN201210049903.XA CN201210049903A CN102543458B CN 102543458 B CN102543458 B CN 102543458B CN 201210049903 A CN201210049903 A CN 201210049903A CN 102543458 B CN102543458 B CN 102543458B
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- 238000000034 method Methods 0.000 title claims abstract description 53
- 239000003990 capacitor Substances 0.000 title claims abstract description 49
- 239000003513 alkali Substances 0.000 title abstract description 4
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims abstract description 69
- 239000000463 material Substances 0.000 claims abstract description 48
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 46
- 239000001257 hydrogen Substances 0.000 claims abstract description 46
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 37
- 229910052759 nickel Inorganic materials 0.000 claims abstract description 33
- 239000000843 powder Substances 0.000 claims abstract description 32
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims abstract description 22
- 239000012286 potassium permanganate Substances 0.000 claims abstract description 21
- 239000000956 alloy Substances 0.000 claims abstract description 19
- 229910045601 alloy Inorganic materials 0.000 claims abstract description 19
- 238000003860 storage Methods 0.000 claims abstract description 7
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 33
- 239000003792 electrolyte Substances 0.000 claims description 24
- 230000008569 process Effects 0.000 claims description 22
- 230000008859 change Effects 0.000 claims description 13
- 230000008878 coupling Effects 0.000 claims description 13
- 238000010168 coupling process Methods 0.000 claims description 13
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- 230000004888 barrier function Effects 0.000 claims description 7
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- 238000004519 manufacturing process Methods 0.000 claims description 7
- 239000011248 coating agent Substances 0.000 claims description 5
- 238000000576 coating method Methods 0.000 claims description 5
- 229910002804 graphite Inorganic materials 0.000 claims description 4
- 239000010439 graphite Substances 0.000 claims description 4
- 239000007787 solid Substances 0.000 claims description 4
- 241000209140 Triticum Species 0.000 claims description 3
- 235000021307 Triticum Nutrition 0.000 claims description 3
- 239000008199 coating composition Substances 0.000 claims description 3
- 229910017052 cobalt Inorganic materials 0.000 claims description 3
- 239000010941 cobalt Substances 0.000 claims description 3
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims description 3
- 230000000994 depressogenic effect Effects 0.000 claims description 3
- 235000013312 flour Nutrition 0.000 claims description 3
- 238000003780 insertion Methods 0.000 claims description 3
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- 239000000203 mixture Substances 0.000 claims description 3
- 239000002245 particle Substances 0.000 claims description 3
- 150000003109 potassium Chemical class 0.000 claims description 3
- 238000012545 processing Methods 0.000 claims description 3
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- 238000004088 simulation Methods 0.000 claims description 3
- 238000006243 chemical reaction Methods 0.000 abstract description 10
- 238000011065 in-situ storage Methods 0.000 abstract description 6
- 230000002349 favourable effect Effects 0.000 abstract description 2
- NUJOXMJBOLGQSY-UHFFFAOYSA-N manganese dioxide Chemical compound O=[Mn]=O NUJOXMJBOLGQSY-UHFFFAOYSA-N 0.000 abstract 2
- 230000002035 prolonged effect Effects 0.000 abstract 1
- 238000007790 scraping Methods 0.000 abstract 1
- 238000005245 sintering Methods 0.000 abstract 1
- 238000013461 design Methods 0.000 description 21
- 229910052799 carbon Inorganic materials 0.000 description 12
- 238000007599 discharging Methods 0.000 description 8
- 229910018663 Mn O Inorganic materials 0.000 description 6
- 239000007772 electrode material Substances 0.000 description 6
- 238000013459 approach Methods 0.000 description 5
- 238000012512 characterization method Methods 0.000 description 5
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 5
- VMWYVTOHEQQZHQ-UHFFFAOYSA-N methylidynenickel Chemical compound [Ni]#[C] VMWYVTOHEQQZHQ-UHFFFAOYSA-N 0.000 description 5
- 230000002441 reversible effect Effects 0.000 description 5
- 239000001996 bearing alloy Substances 0.000 description 4
- 238000011161 development Methods 0.000 description 4
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- 238000013519 translation Methods 0.000 description 4
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- 229910002640 NiOOH Inorganic materials 0.000 description 3
- WPBNNNQJVZRUHP-UHFFFAOYSA-L manganese(2+);methyl n-[[2-(methoxycarbonylcarbamothioylamino)phenyl]carbamothioyl]carbamate;n-[2-(sulfidocarbothioylamino)ethyl]carbamodithioate Chemical compound [Mn+2].[S-]C(=S)NCCNC([S-])=S.COC(=O)NC(=S)NC1=CC=CC=C1NC(=S)NC(=O)OC WPBNNNQJVZRUHP-UHFFFAOYSA-L 0.000 description 3
- 238000006479 redox reaction Methods 0.000 description 3
- 238000004758 underpotential deposition Methods 0.000 description 3
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 description 2
- 239000003638 chemical reducing agent Substances 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 230000004087 circulation Effects 0.000 description 2
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- 238000009402 cross-breeding Methods 0.000 description 2
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- 239000011263 electroactive material Substances 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 239000004615 ingredient Substances 0.000 description 2
- 229910052748 manganese Inorganic materials 0.000 description 2
- 239000011572 manganese Substances 0.000 description 2
- 230000013011 mating Effects 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 229920006395 saturated elastomer Polymers 0.000 description 2
- 229910052720 vanadium Inorganic materials 0.000 description 2
- 201000004569 Blindness Diseases 0.000 description 1
- 239000004966 Carbon aerogel Substances 0.000 description 1
- 229910010340 TiFe Inorganic materials 0.000 description 1
- 239000011149 active material Substances 0.000 description 1
- 239000012736 aqueous medium Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- OJIJEKBXJYRIBZ-UHFFFAOYSA-N cadmium nickel Chemical compound [Ni].[Cd] OJIJEKBXJYRIBZ-UHFFFAOYSA-N 0.000 description 1
- 150000001721 carbon Chemical class 0.000 description 1
- 239000003610 charcoal Substances 0.000 description 1
- 230000019771 cognition Effects 0.000 description 1
- 230000001427 coherent effect Effects 0.000 description 1
- 238000004891 communication Methods 0.000 description 1
- 238000012790 confirmation Methods 0.000 description 1
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- 230000007797 corrosion Effects 0.000 description 1
- 125000004122 cyclic group Chemical group 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 230000004069 differentiation Effects 0.000 description 1
- 230000005684 electric field Effects 0.000 description 1
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- 150000002500 ions Chemical class 0.000 description 1
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- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical class C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 1
- 238000013508 migration Methods 0.000 description 1
- 230000005012 migration Effects 0.000 description 1
- 238000000465 moulding Methods 0.000 description 1
- QELJHCBNGDEXLD-UHFFFAOYSA-N nickel zinc Chemical compound [Ni].[Zn] QELJHCBNGDEXLD-UHFFFAOYSA-N 0.000 description 1
- 239000007800 oxidant agent Substances 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 238000002161 passivation Methods 0.000 description 1
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- 238000007634 remodeling Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 230000000630 rising effect Effects 0.000 description 1
- 229910001925 ruthenium oxide Inorganic materials 0.000 description 1
- WOCIAKWEIIZHES-UHFFFAOYSA-N ruthenium(iv) oxide Chemical compound O=[Ru]=O WOCIAKWEIIZHES-UHFFFAOYSA-N 0.000 description 1
- 230000000638 stimulation Effects 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 230000032258 transport Effects 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
- 230000003313 weakening effect Effects 0.000 description 1
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
- H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
- H01G11/54—Electrolytes
- H01G11/58—Liquid electrolytes
-
- 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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- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- Engineering & Computer Science (AREA)
- Power Engineering (AREA)
- Microelectronics & Electronic Packaging (AREA)
- Battery Electrode And Active Subsutance (AREA)
Abstract
The invention relates to an alkali pseudo-capacitor alloplastic electrode and a matching method therefor. The pseudo-capacitor positive pole is a sintering nickel anode of a traditional battery, and the negative pole is a capacitor pole piece mainly formed by activated charcoal. The matching method capable of balancing the capacitance characteristics of the two alloplastic electrodes comprises the following steps: in potassium permanganate solution, a certain amount of MnO2 is added in the positive pole and negative pole through in-situ reaction; and hydrogen storage alloy powder no more than 5 percent is mixed in negative pole scraping material. The method obtaining the positive and the negative pole pieces of the pseudo-capacitor is easy to operate, the matching between the energy of the alkali pseudo-capacitor alloplastic electrodes and the power density is obtained, and the advantages of high-power density, prolonged service life, favorable low-temperature performance, and high energy density are achieved.
Description
Technical field
The present invention relates to the heterogeneous electrode of a kind of alkaline fake capacitance and matching process.Particularly relating to a kind of nickel-carbon is in fake capacitance, in nickel-carbon positive plate and activated carbon negative electrode plate after artificial doped with manganese, two kinds of heterogeneous pole plates are forming among fake capacitance process, each other and with electrolyte or conductive agent or hold and mating design and practical method between hydrogen agent.
Background technology
Nearly 20 years, electrode material development, the especially development of the electrode material under energy problem promotes, by past electric capacity clearly demarcated physical concept relative to battery, electrode material is selected and device classification, thickened and complicated.Make the giddy new term of people, such as: ultracapacitor, super battery, capacitor batteries, super capacitance cell, and some new mechanism, the device that stores physical charge laying particular stress on physical change in the past classifies as electric capacity, take chemical change as main body and by the device that chemical change outwards transports electric charge classify as battery, exist microchemistry to change or chemical substance is made substantive contribution device to storing physical charge to classify as the appearance that the traditional classification of chemical capacitor impacts all non-.Form trend or the trend of one " electric capacity and battery crossbreeding ".
Fake capacitance or pseudo-capacitance, the Chinese translation of source Psedocapacitance mono-word; Its full name is Faraday pseudocapacitance; Chinese is translated as " faraday fake capacitance " or " faraday pseudo-capacitance ".Different translations are looked at flowers in a fog beginner, and " counterfeit " with to pass judgement on justice in " standard " Chinese different, and this different translation, if if the also viewpoint to this electric capacity science essence hidden aobvious expression difference scientists.
English pseudo prefix " puppet " and " vacation " original meaning are focused in " fake capacitance " word translation, seeming expressing is not real electric capacity, also revealing " real electric capacity; along with charging voltage continues to raise; capacitance is linear to be increased; as long as dielectric voltage withstand class is enough, charging hectovolt or kilovolt can; And fakement electric capacity, such as the chemical capacitor of common interpolation aqueous medium, the electrochemical window of water decomposition is in 2V left and right, when charging voltage is 1.8V-2.5V, this fakement electric capacity recharges impossible, real electric capacity, along with charging voltage continues rising characteristic, has not existed ".By " counterfeit " word, setting forth this problem in science simultaneously, implying for solving the thinking of technology barriers among this problem in science and a kind of of the natural law being revered.
And in " pseudo-capacitance " " standard ", by " approaching ", " similar " and " between " commendation, reveal out this part scientific worker to a kind of expectation of this class electric capacity and long for.
Fake capacitance has stepped into a member (fake capacitance type ultracapacitor) in ultracapacitor ranks, and alkaline fake capacitance is (newly to be claimed) at present " accurate faraday's super capacitor " basis by people, also by insider (such as U.S. EEStor company), thought there will be the basis of development " faraday's super capacitor " future most.
Using ultracapacitor and jumbo battery pack, separately as separate component, by IGBT etc. as electronic switch, the combined circuit module forming or electric energy regulation and control module has very high commercial value, such as more disclosed patents of Patent Office of the People's Republic of China (application number, as follows):
CN200810048988.3 patent discloses, and " Wu Gaosuo " is for solving the use of national grid voltage dip, raising grid supply quality;
CN200910062455.5 patent discloses, and contains double loop commercial power rich and influential family and can be used for solving power supply in the grid switching operation process use of disconnected problem temporarily;
CN201010128989.6 patent discloses: active in parallel mixing of this storage battery and ultracapacitor, can be used as the use of the energy-storage system of balance electrical network peak-valley electric energy problem;
CN200810094406.5 patent discloses: the assembly of this lithium-ion-power cell and ultracapacitor, can be used as communication and command shelter vehicle, solves the use of the problems such as power supply disguise and continuation.
The application of the commercial value that these are very high, is constantly promoting the industrialized development of ultracapacitor with commercial affairs stimulation form.
With NiO
x, MnO
2, V
2o
5to such an extent as to expensive these metal oxides of ruthenium-oxide are as positive electrode, using active carbon as negative material, and the ultracapacitor that this class is constructed by heterogeneous electrode material is for to be thought having one of the ultracapacitor of applicable prospect developing direction most by industry peer at present.Also be considered in the trend of " electric capacity and battery crossbreeding ", easily obtain one of approach of super battery.
Yet, thisly take the heterogeneous electrode ultracapacitor of being constructed that fake capacitance is basis, electrode " heterogeneousization " brings all mismatch, wherein the condensed difficulty of problem in science surpasses the ability of current human knowledge's nature and nature remodeling, makes design of material and Engineering Design in the blindness stage.
Electrode " heterogeneousization " mismatch of bringing, objectively alkaline fake capacitance designer is proposed: the conductivity how in balanced asymmetric the two poles of the earth, capacity is coordinated, output electronics requires is coordinated, electrolyte basicity and material store the coordination between amount of charge etc., obviously, the basic goal of " coordination " is: guaranteeing that under fake capacitance certain power density prerequisite, acquisition is compared with the fake capacitance of macro-energy density.In other words, in " fake capacitance " three words, guaranteeing, under " electric capacity " characteristic prerequisite, to make " counterfeit " word table reveal optimum capacity density.Thisly take " coordination " as means, impel the two poles of the earth of fake capacitance to be tending towards " coupling " and close to " symmetry " can operation measure, the novelty that more particularly possesses skills can operation measure, at alkaline fake capacitance, especially alkaline nickel-carbon is in fake capacitance system, rarely has article report or patent open.
Summary of the invention
The object of the present invention is to provide the heterogeneous electrode of alkaline fake capacitance and matching process.It is in fake capacitance that a kind of nickel-carbon is particularly provided, in nickel-carbon positive plate and activated carbon negative electrode plate after artificial doped with manganese, two kinds of heterogeneous pole plates are forming among fake capacitance process each other and with electrolyte or conductive agent or hold and mating design and practical method between hydrogen agent.
A kind of " the heterogeneous electrode of alkaline fake capacitance and matching process " design principle and principle:
(1) in fake capacitance, the design of " counterfeit " word is followed principle and principle:
The present invention is in can be used as the multiple material and structure thereof of capacitor plate, choose sintrered nickel anode conventional in alkaline battery industry, and after artificial doped with manganese as the positive plate of fake capacitance of the present invention, mentality of designing is: impregnated Ni (OH) in sintrered nickel anode
2, established NiOOH and NiO
xcontinuous reversible oxidation-reduction reaction basis can occur, and this point has been tested and facts have proved; MnO
2can be used as equally the highly active matter of reversible oxidation-reduction reaction, this point is also tested and be facts have proved.Wet method sintrered nickel anode is one of " optimum carrier of electric double layer capacitance carrying electric charge " not accommodating doubting as the porous carbon of carrying cell active materials carrier, and what is more important: the potassium permanganate that the oxidizability of take is very high is raw material, at artificial doped with Mn O
2time, to a certain extent passivation the sudden change of phase in the continuous change procedure of redox state.Accordingly, should all be fulfilled with " height reversible reaction occurs " by " counterfeit " word " underpotential deposition ".Last point wherein---representativeness that " potassium permanganate that the oxidizability of usining is very high is directly processed sintrered nickel anode at 80 ℃ " is the present invention's " three property " (creativeness, novelty and practicality) as one of.
The above-mentioned design of the present invention, follow the cognition that is different from following main 2 scientific meanings of electric double layer capacitance to " counterfeit " word:
1. in the two dimension or accurate two-dimensional space of electrode surface, electroactive material carries out underpotential deposition, and height reversible reaction occurs, and produces the physics electric weight relevant with electrode charge voltage and easily transforms out the active points of physics electric weight.
2. not only at electrode surface, and can whole electrode interior or body mutually in, electroactive material carries out underpotential deposition, and height reversible reaction occurs, and produces the physics electric weight relevant with electrode charge voltage and easily transforms out the active points of physics electric weight.
(2) in fake capacitance, the design of " electricity " word is followed principle and principle:
Fake capacitance of the present invention externally discharges: the active points positive terminal that easily transforms out physics electric weight is mainly NiOOH or NiO
xand MnO
2, the active points that negative pole end easily transforms out physics electric weight is mainly the hydrogen in hydrogen bearing alloy; This part easily transforms out physics electric weight, and can be rough or approximate think derives from the electric weight of emitting in conventional batteries, remaining active carbon and MnO
2physical charge electric weight derives from the electric weight that electric capacity is emitted.The former, derive from the electric weight of emitting in conventional batteries, is obviously the main contributions source of " counterfeit " word in fake capacitance, is also the main source that fake capacitance of the present invention approaches " accurate faraday's super capacitor " index electric weight.
Follow this design concept, the present invention is in activated carbon negative electrode plate after artificial doped with manganese, and also doping has the hydrogen storing alloy powder that stores up hydrogen function simultaneously.Doped with manganese simultaneously in both positive and negative polarity, in fake capacitance positive and negative electrode of the present invention, around coordination and the coupling measure of capacitive properties in fake capacitance; And the hydrogen storing alloy powder that adulterates in negative pole is coordination and the coupling measure around (in positive pole existing NiOOH) battery character.
(3) in fake capacitance, the design of " appearance " word is followed principle and principle:
Fake capacitance in the present invention, establishing " electric capacity " characteristic is primary goal, first must solve the characterizing method of heterogeneous the two poles of the earth capacity, the capacitance parameter being obtained by suitable characterizing method, as the Capacity design basic data of fake capacitance positive pole and negative pole.
The characterizing method of the heterogeneous the two poles of the earth of fake capacitance of the present invention capacity is defined as: by two, with sintrered nickel positive plate, be configured to double electric layer capacitor (dividing plate or barrier film and electrolyte are put in centre) in advance, determine its capacity; Utilize same method of operation, by two, take active carbon in advance and be that main pole plate is configured to double electric layer capacitor, also determine its capacity, as Main Basis, on the capacity basis of fixing positive plate.By adjusting the blade coating amount of negative plate, its capacity and positive plate capacity are progressively approached, finally realize the capacity matching on two-plate capacitive properties; For example:
Commercially available nickel-hydrogen electrokinetic cell sintrered nickel positive plate, the battery index that it symbolizes for the manufacture of battery is 31mAh/cm
2.Through artificial doped with Mn O
2after, cut out, obtain being of a size of long 119mm, the sign materials of wide 41mm; Two sintrered nickel positive plates that characterize materials are configured to double electric layer capacitor, put barrier film in the middle of characterizing materials for two, be immersed in the KOH aqueous solution of 2M, it is 0.2V that discharge cut-off voltage is set, and the capacitance that mAh expresses of take determining is 0.072mAh/cm
2; This 0.072mAh/cm
2the capacity revealing with " electric capacity " property list for fake capacitance positive plate of the present invention.
Utilize same method of operation, by two, take active carbon and be that main pole plate is configured to double electric layer capacitor, measure its capacity, adjust for three times of the blade coating amount by negative plate and formula, obtaining fake capacitance minus plate of the present invention, to take the capacity that " electric capacity " property list reveals be 0.071mAh/cm
2; So far, confirm that capacity and positive plate capacity that minus plate reveals with " electric capacity " property list approach, the capacity matching operation task on two-plate capacitive properties completes.
(4) principle that the design of " alkali " word is followed in alkaline fake capacitance:
The colleague of alkaline battery industry is known, alkaline batteries such as nickel-hydrogen, nickel-cadmium and nickel-zinc, in battery, conventionally adopting " KOH of 6M-9M " is the alkaline electrolyte design of foundational system, and this meets the actual demand of the overall targets such as conductivity, operation temperature area and power performance of alkaline charging battery.
And fake capacitance of the present invention is not battery, but take electric capacity as main, its good power density derives from electric capacity contribution rate, the excessive concentration of alkaline electrolyte KOH, be easy to cause lean solution fake capacitance of the present invention because leaking electricity along face is creepage, thereby the concentration of alkaline electrolyte KOH of the present invention is controlled at 0.5M-2M scope and is advisable.And guarantee fake capacitance operation temperature area low temperature discharge effect to be mainly derived from pole plate physical charge, this design that guarantees ion migration from low-freezing in battery dependence " KOH of 6M-9M " is completely different aspect internal principle.
This electrolyte low concentration design, is also following novel fake capacitance dividing plate or the barrier film that may occur, aspect carrying corrosion pressure, is reducing burden.
(5) " coupling " in exercise question of the present invention and corresponding operated matching process design principle:
1. the coupling of positive and negative electrode capacity: for both positive and negative polarity homogeneity electrode material, such as both positive and negative polarity, be all active carbon, as long as make uniform battery lead plate, the two poles of the earth capacity natural equilibrium.
Obviously, heterogeneous electrode is realized capacitance balance and limited by material, and is subject in battery core under polar plate area symmetry, electric field balance, gravitational field the many factors restrictions such as electric core construct is reasonable; Although the present invention, by structure double electric layer capacitor method, approaches the capacity on heterogeneous two-plate capacitive properties, complete the capacity matching revealing with " electric capacity " property list.Yet the capacity difference showing with battery behavior also must be controlled at zone of reasonableness.The hydrogen storing alloy powder that the present invention selects, it has taken on the key player of coupling both positive and negative polarity battery capacity.In the negative pole spread coated paint that hydrogen storing alloy powder of the present invention is major ingredient at active carbon, addition is 1wt%-5wt%, surpass 5wt%, by weakening the capacitance characteristic of fake capacitance of the present invention, add quantity lower than 1wt%, widen positive and negative electrode battery capacity gap, caused battery unreasonable.
2. positive and negative electrode MnO
2the coupling of doping: a certain amount of MnO adulterates in carbon aerogels, porous carbon and activated carbon fiber
2to improving the life-span of super capacitor and reducing self discharge effect, be all favourable, this has all obtained confirmation in much research.
Yet, in numerous doping methods, MnO
2doping process loaded down with trivial details, and for rigid and mechanical " for doping is adulterated ", stiff and inapplicable in fake capacitance manufacture; Reaction in-situ doping method of the present invention, flexible and let nature take its course; Aspect operability, short process and economy combine, enriched " three property " of the present invention.Wherein: sintrered nickel anode is inserted in 80 ± 5 ℃ of saturated liquor potassic permanganates and the short stay several seconds, and chemical reaction basic principle is: the very strong potassium permanganate of oxidizability is as oxidant, the Ni of sintrered nickel anode (OH)
2deng as reducing agent, the two meets, and oxidation-reduction reaction is being adsorbed Ni (OH)
2ni in carbon hole (OH)
2original position is occurred, and potassium permanganate is reduced into MnO
2, and this MnO
2be embedded in this carbon hole simultaneously.Doped with Mn O in porous carbon
2, by this easy reaction in-situ, be achieved.
And be major ingredient, the negative pole of lift-launch in nickel foam by containing a certain amount of hydrogen storing alloy powder isoreactivity charcoal, by identical technique, inserting in saturated liquor potassic permanganate, hydrogen storing alloy powder and nickel foam collector can be born the role of reducing agent, doped with Mn O
2reaction in-situ is realized equally very easily.
Obviously, doped with Mn O
2main purpose is to guarantee that fake capacitance of the present invention has good capacitance characteristic.Positive pole and the equal doped with Mn O of negative pole
2, enriching the diversification of positive and negative electrode capacitance material simultaneously, also realized " in enemy, having me, in me, having enemy " in the heterogeneous the two poles of the earth of the present invention and (in positive pole, had MnO
2; With the anti-electrical counter electrode of positive pole in also have MnO
2; MnO in the two poles of the earth
2, after charging, assist respectively the contrary electrical electric charge of self electrode carrying) strategy design, the MnO in the two poles of the earth
2, for the tactical design of the aspect couplings such as fake capacitance of the present invention life-span lays the foundation.
The heterogeneous electrode of alkaline fake capacitance and a matching process, the manufacturing step of its heterogeneous positive and negative electrode, process conditions, formula, structure and matching process are as follows:
The structure of the first step, the anodal blank material of fake capacitance:
Select commercially available nickel-hydrogen electrokinetic cell sintrered nickel anode, this sintrered nickel anode is wet method manufacture, containing cobalt type, index, is 31mAh/cm
2.The saturated potassium permanganate solution of room temperature is heated to 75 ℃-85 ℃, and continue to add chemical pure potassium permanganate particles, be mixed with the supersaturated solution of this warm area, again sintrered nickel anode strip is inserted in the potassium permanganate saturated solution of these 75 ℃-85 ℃, 2 seconds-5 seconds residence time, rapidly this pole piece is shifted out from solution, room temperature is dried standby, constructs the anodal blank material of fake capacitance; This positive pole blank material characterizes through being configured to double electric layer capacitor characterizing method, and it take the capacity that " electric capacity " property list reveals is 0.072mAh/cm
2;
The structure of second step, fake capacitance negative pole blank material:
Select commercially available nickel-hydrogen power battery current-collecting body nickel foam commodity, by original thickness, be that 1.0mm nickel foam collector is depressed into 0.8mm in advance, by fake capacitance negative pole material blade coating on it, this fake capacitance negative pole material blade coating formula is: the polytetrafluoro emulsion that the AB5 type hydrogen storage alloy powder that 600 object activated carbon powders, 600 object graphite powders, 275 order ± 25 orders and its manufacturer's marked capacity are 285mAh/g and solid content are 52wt% again; Four according to the ratio of (100-7-X-3) wt%, fix four percentage by weight summations while being 100wt%, graphite powder accounts for 7wt% definite value ratio, polytetrafluoro emulsion accounts for 3wt% definite value ratio, hydrogen storing alloy powder accounts for X wt% change value ratio, all the other are activated carbon powder, and four percentage by weight summations form 100wt%; X=1wt%-5wt% wherein; Four mix and construct fake capacitance negative pole material spread coated paint according to this formula, then by the 0.8mm foam nickel strap containing this spread coated paint, put into and regulate the roll squeezer that gap is 0.35mm to roll film processing; Roll and obtain the quantity that contains this spread coated paint in the thick and unit are of 0.35mm after film and meet 0.075g/cm
2blank in the middle of the fake capacitance negative plate of index; In the potassium permanganate saturated solution that this centre blank insertion is 50 ℃-70 ℃, 2 seconds-5 seconds residence time, shift out rapidly this saturated solution, room temperature is dried standby, constructs fake capacitance negative pole blank material; This negative pole blank material characterizes through being configured to double electric layer capacitor characterizing method, and it take the capacity that " electric capacity " property list reveals is 0.072mAh/cm
2± 0.001mAh/cm
2;
Structure and the matching process of the 3rd step, fake capacitance positive pole, negative pole:
Fake capacitance positive pole and negative pole blank material are cut into bar shaped, in view of fake capacitance housing of the present invention is used in affixed merchandise, the spare and accessory parts such as the housing of nickel-hydrogen cell AA type cylindrical battery and upper cover, sealing ring, be subject to this and use shell dimension restriction, fake capacitance positive pole and negative pole blank material are cut out size and are long 119mm, wide 41mm, by the bar shaped blank material of this 119mm * 41mm size, on soft machine, soft treatment three times; Be transferred to again ultrasonic wave wheat flour purifier, on long limit of bar shaped blank material pole piece according to the clear powder of lug width same size with welding, after clear powder, by impulse spot welder for lug, according to AA cylinder nickel-hydrogen cell welding requirements firm welding; To be separated by with the sulfonated membranes in nickel-hydrogen cell barrier film commodity with negative pole is middle with lug bar shaped is anodal, after alignment, on battery winder, reel, after coiling completes, put into housing, add 2.4ml electrolyte, this electrolyte is the potassium hydroxide aqueous solution of concentration 0.5M-2M; Electrolyte is noted as after the housing with battery core, is relended after encapsulating, encapsulate with AA cylinder nickel-hydrogen cell sealed in unit the nude simulation fake capacitance obtaining under different condition is numbered, and so far, fake capacitance is anodal, structure and the matching task of negative pole complete.
The nude of the present invention of acquisition being simulated to alkaline fake capacitance measures and characterizes with DC-5 type cell tester and internal resistance instrument etc. again.Computing formula, measuring condition and characterizing method in measuring and characterizing have:
1. discharge current density computing formula is: current density=I/S， current density unit is milliampere/square centimeter; With symbol mA/cm
2represent.
Wherein: I is artificial capacitor discharging current, unit is mA; S is the area of two electrode slices that in capacitance core, size equates, unit is cm
2.
2. artificial capacitor energy density computing formula is: energy density=C/m， energy density unit is: farad/kilogram, with symbol, F/Kg represents.
Wherein: the capacity that C is artificial capacitor, unit is F; Its computing formula is: artificial capacitor C=(I * t)/Δ V, and in its computing formula: I is discharging current, unit is ampere; T is discharge time, and unit is second; Δ V is for take initial voltage and the cut-ff voltage difference that volt is unit; M be artificial capacitor weight ，Qi unit for kilogram.
3. artificial capacitor cycle life condition determination is: front 300 circulations discharge and recharge form for " entirely fill entirely and put ", according to the chargeable maximum farad number of the artificial capacitor of this numbering and the maximum farad number that can discharge, discharges and recharges; Wherein the highest cut-ff voltage of charging is 1.6V, and discharge cut-off voltage is 0.8V.At front 300 circulating cycle numbers " complete empty full up ", discharge and recharge on basis, then according to the form that discharges and recharges of " fill eight and put six ", then circulate 500 weeks (301 weeks---800 weeks), 60% of the farad number that can discharge according to artificial capacitor maximum is depth of discharge (putting six); In the charge node of working to the last minute for charging at the maximum chargeable maximum farad several 80% of artificial capacitor, after front once electric discharge, after once according to " capacity limit " form be after its supplementary electric weight discharging, again then circulate 500 weeks.
The characterizing method of the actual maximum power density of the gravimetric specific power of 4. take metering is actual maximum power density=P
max/ m.In this formula: P
maxfor maximum discharge current and discharge initiation voltage product; M is that AA type simulated capacitor quality ，Qi unit is Kg.
The characterizing method of the actual maximum power density of the volumetric specific power of 5. take metering is actual maximum power density=P
max/ V; P wherein
maxfor maximum discharge current and discharge initiation voltage product, the unit after product is watt; V is that AA type simulated electric capacity volume ，Qi unit is liter.
Beneficial effect of the present invention
1, in the heterogeneous electrode of alkaline fake capacitance, utilize reaction in-situ pattern, the MnO simultaneously adulterating in positive pole and negative pole
2; Its doped pathway is determined after pole piece moulding, the clear and coherent nature of doping pattern, creativeness, novelty, practicality and workable.The MnO that heterogeneous the two poles of the earth are doped
2homogeneity and the nearlyer step of symmetry direction to capacitance characteristic.The hight coordinate in this reaction in-situ region, time and space, is the aspects such as heterogeneous the two poles of the earth capacitance characteristic coupling and anticorrosive coupling, in the aspect of design, started that doping method is made and treatment process is simple, is easy to realization, practical new tool.
2, alkaline fake capacitance negative plate of the present invention a small amount of AB that adulterates
5type hydrogen storage alloy, this kind of bold design, has broken through this battery of hydrogen bearing alloy and has selected materials, can not, for the Traditional Thinking restriction of electric capacity, be ZrMn
2, the AB such as TiFe
2, AB, AB
3alternative approach has been opened up in all kinds of hydrogen bearing alloys of type, the tentative application in faraday's electric capacity.Negative pole and anodal characteristic aspect battery should " exploration application " further; Through this matching process, can make the differentiation of heterogeneous electrode reduce.
Accompanying drawing explanation
Fig. 1 is that the present invention simulates the representational multiplying power discharging curve of fake capacitance.Its discharge temp is 18 ℃; Its negative pole raw material ratio is the AB that 600 object activated carbon powders, 600 object graphite powders, 275 order ± 25 orders and its manufacturer's marked capacity are 285mAh/g
5type hydrogen storage alloy powder and solid content are the polytetrafluoro emulsion of 52wt%; Four according to the ratio of (100-7-5-3) wt%; The electrolyte that adds 2.4ml 2M.
Fig. 2 is that the present invention simulates the representational cyclic curve of fake capacitance.It discharges and recharges temperature is 18 ℃; Its charging and discharging currents density of relatively mixing negative pole is 4.1A/cm
2; This curve discloses: alkaline fake capacitance meets the feature of ultracapacitor stable cycle performance.
Embodiment
Embodiment 1:
The structure of the first step, the anodal blank material of fake capacitance:
Select commercially available nickel-hydrogen electrokinetic cell sintrered nickel anode, this sintrered nickel anode is wet method manufacture, containing cobalt type, index, is 31mAh/cm
2.The saturated potassium permanganate solution of room temperature is heated to 85 ℃, and continue to add chemical pure potassium permanganate particles, be mixed with the saturated solution of this warm area, again sintrered nickel anode strip is inserted in this potassium permanganate saturated solution of 85 ℃, 5 seconds residence times, shift out rapidly this solution, room temperature is dried standby, constructs the anodal blank material of fake capacitance;
The structure of second step, fake capacitance negative pole blank material:
Select commercially available nickel-hydrogen power battery current-collecting body nickel foam commodity, by original thickness, be that 1.0mm nickel foam collector is depressed into 0.8mm in advance, by fake capacitance negative pole material blade coating on it, this fake capacitance negative pole material blade coating formula is: the AB that 600 object activated carbon powders, 600 object graphite powders, 275 order ± 25 orders and its manufacturer's marked capacity are 285mAh/g again
5type hydrogen storage alloy powder and solid content are the polytetrafluoro emulsion of 52wt%; Four according to the ratio of (100-7-X-3) wt%, fix four percentage by weight summations while being 100wt%, graphite powder accounts for 7wt% definite value ratio, polytetrafluoro emulsion accounts for 3wt% definite value ratio, hydrogen storing alloy powder accounts for Xwt% change value ratio, all the other are activated carbon powder, and four percentage by weight summations form 100wt%; X=5wt% wherein; Four mix and construct fake capacitance negative pole material spread coated paint according to this formula, then by the 0.8mm foam nickel strap containing this spread coated paint, put into and regulate the roll squeezer that gap is 0.35mm to roll film processing; Roll and obtain the quantity that contains this spread coated paint in the thick and unit are of 0.35mm after film and meet 0.075g/cm
2blank in the middle of the fake capacitance negative plate of index; In the potassium permanganate saturated solution that this centre blank insertion is 70 ℃, 2 seconds-5 seconds residence time, shift out rapidly this saturated solution, room temperature is dried standby, constructs fake capacitance negative pole blank material;
Structure and the matching process of the 3rd step, fake capacitance positive pole, negative pole:
Fake capacitance positive pole and negative pole blank material are cut into bar shaped, in view of fake capacitance housing of the present invention is used in affixed merchandise, the spare and accessory parts such as the housing of nickel-hydrogen cell AA type cylindrical battery and upper cover, sealing ring, be subject to this and use shell dimension restriction, fake capacitance positive pole and negative pole blank material are cut out size and are long 119mm, wide 41mm, by the bar shaped blank material of this 119mm * 41mm size, on soft machine, soft treatment three times; Be transferred to again ultrasonic wave wheat flour purifier, on long limit of bar shaped blank material pole piece according to the clear powder of lug width same size with welding, after clear powder, by impulse spot welder for lug, according to AA cylinder nickel-hydrogen cell welding requirements firm welding; By being separated by with the sulfonated membranes in nickel-hydrogen cell barrier film commodity with negative pole is middle with lug bar shaped is anodal, after alignment, on battery winder, reel, after having reeled, put into housing, add 2.4ml electrolyte, this electrolyte is the potassium hydroxide aqueous solution of concentration 2M; Electrolyte, such as after the housing with battery core, relends after encapsulating, encapsulate with AA cylinder nickel-hydrogen cell sealed in unit the nude simulation fake capacitance obtaining under different condition is numbered, and so far, fake capacitance is anodal, structure and the matching task of negative pole complete.
Dependence test and the characterizing method of the artificial capacitor of the 4th step, alkaline fake capacitance:
1. discharge current density computing formula is: current density=I/S， current density unit is milliampere/square centimeter; With symbol mA/cm
2represent.
Wherein: I is artificial capacitor discharging current, unit is mA; S is the area of two electrode slices that in capacitance core, size equates, unit is cm
2.
2. artificial capacitor energy density computing formula is: energy density=C/m， energy density unit is: farad/kilogram, with symbol, F/Kg represents.
Wherein: the capacity that C is artificial capacitor, unit is F; Its computing formula is: artificial capacitor C=(I * t)/Δ V, and in its computing formula: I is discharging current, unit is ampere; T is discharge time, and unit is second; Δ V is for take initial voltage and the cut-ff voltage difference that volt is unit; M be artificial capacitor weight ，Qi unit for kilogram.
3. artificial capacitor cycle life condition determination is: front 300 circulations discharge and recharge form for " entirely fill entirely and put ", according to the chargeable maximum farad number of the artificial capacitor of this numbering and the maximum farad number that can discharge, discharges and recharges; Wherein the highest cut-ff voltage of charging is 1.6V, and discharge cut-off voltage is 0.8V.At front 300 circulating cycle numbers " complete empty full up ", discharge and recharge on basis, then according to the form that discharges and recharges of " fill eight and put six ", then circulate 500 weeks (301 weeks---800 weeks), 60% of the farad number that can discharge according to artificial capacitor maximum is depth of discharge (putting six); In the charge node of working to the last minute for charging at the maximum chargeable maximum farad several 80% of artificial capacitor, after front once electric discharge, after once according to " capacity limit " form be after its supplementary electric weight discharging, again then circulate 500 weeks.
The characterizing method of the actual maximum power density of the gravimetric specific power of 4. take metering is actual maximum power density=P
max/ m.In this formula: P
maxfor maximum discharge current and discharge initiation voltage product, the unit after this product is defined as watt; M is that AA type simulated capacitor quality ，Qi unit is Kg.Thereby the unit of actual maximum power density is watt/kilogram, with symbol, W/Kg represents.
The characterizing method of the actual maximum power density of the volumetric specific power of 5. take metering is actual maximum power density=P
max/ V; P wherein
maxfor maximum discharge current and discharge initiation voltage product, the unit after product is watt; V is that AA type simulated electric capacity volume ，Qi unit is liter.The unit of actual maximum power density is watt/liter that W/L represents with symbol.
Around power density and energy density balance optimizing and take into account the life-span and cryogenic property, process is that main negative pole, sintrered nickel anode is main positive pole to active carbon, the coupling design of these two kinds of heterogeneous electrode materials, the artificial capacitor of the alkaline fake capacitance of the heterogeneous electrode of the present invention after coupling, they are under different discharge current densities, and the energy density that room temperature electric discharge shows is listed in table 1; The energy density showing at low temperature-40 ℃ is listed in table 2; The power density that room temperature and low temperature discharge show is listed in table 3; Under room temperature, the characterization result of cycle life is listed in table 4.
At 18 ℃ of table 1 room temperatures, the different current density (mA/cm of heterogeneous electrode slice
2)
The energy density that Imitating capacitance meter reveals (F/kg)
At table 2 low temperature-40 ℃, the different current density (mA/cm of heterogeneous electrode slice
2) energy density (F/kg) that reveals of Imitating capacitance meter
Power density (W/kg or W/L) at 18 ℃ of table 3 room temperatures and low temperature-40 ℃
Cycle life at 18 ℃ of table 4 room temperatures characterizes
Embodiment 2:
With embodiment 1 difference be:
1. sintrered nickel anode strip inserts in the potassium permanganate saturated solution of 75 ℃;
2. hydrogen storing alloy powder accounts for 1wt% change value ratio;
3. blank inserts in the potassium permanganate saturated solution of 50 ℃ in the middle of fake capacitance negative plate;
4. add 2.4ml electrolyte, this electrolyte is the potassium hydroxide aqueous solution of concentration 0.5M;
The artificial capacitor of the alkaline fake capacitance of the heterogeneous electrode of the present embodiment, they are under different discharge current densities, and the energy density that room temperature electric discharge shows is listed in table 5; The energy density showing at low temperature-40 ℃ is listed in table 6; The power density that room temperature and low temperature discharge show is listed in table 7; Under room temperature, the characterization result of cycle life is listed in table 8.
All the other are with embodiment 1.
At 18 ℃ of table 5 room temperatures, the different current density (mA/cm of heterogeneous electrode slice
2)
The energy density that Imitating capacitance meter reveals (F/kg)
At table 6 low temperature-40 ℃, the different current density (mA/cm of heterogeneous electrode slice
2) energy density (F/kg) that reveals of Imitating capacitance meter
Power density (W/kg or W/L) at 18 ℃ of table 7 room temperatures and low temperature-40 ℃
Cycle life at 18 ℃ of table 8 room temperatures characterizes
Embodiment 3:
With embodiment 1 difference be:
1. hydrogen storing alloy powder accounts for 2wt% change value ratio;
2. add 2.4ml electrolyte, this electrolyte is the potassium hydroxide aqueous solution of concentration 1M;
The artificial capacitor of the alkaline fake capacitance of the heterogeneous electrode of the present embodiment, they are under different discharge current densities, and the energy density that room temperature electric discharge shows is listed in table 9; The energy density showing at low temperature-40 ℃ is listed in table 10; The power density that room temperature and low temperature discharge show is listed in table 11; Under room temperature, the characterization result of cycle life is listed in table 12.
All the other are with embodiment 1.
At 18 ℃ of table 9 room temperatures, the different current density (mA/cm of heterogeneous electrode slice
2)
The energy density that Imitating capacitance meter reveals (F/kg)
At table 10 low temperature-40 ℃, the different current density (mA/cm of heterogeneous electrode slice
2) energy density (F/kg) that reveals of Imitating capacitance meter
Power density (W/kg or W/L) at 18 ℃ of table 11 room temperatures and low temperature-40 ℃
Cycle life at 18 ℃ of table 12 room temperatures characterizes
Embodiment 4:
With embodiment 1 difference be:
1. sintrered nickel anode strip inserts in the potassium permanganate saturated solution of 75 ℃;
2. blank inserts in the potassium permanganate saturated solution of 50 ℃ in the middle of fake capacitance negative plate;
3. hydrogen storing alloy powder accounts for 3wt% change value ratio;
The artificial capacitor of the alkaline fake capacitance of the heterogeneous electrode of the present embodiment, they are under different discharge current densities, and the energy density that room temperature electric discharge shows is listed in table 13; The energy density showing at low temperature-40 ℃ is listed in table 14; The power density that room temperature and low temperature discharge show is listed in table 15; Under room temperature, the characterization result of cycle life is listed in table 16.
All the other are with embodiment 1.
At 18 ℃ of table 13 room temperatures, the different current density (mA/cm of heterogeneous electrode slice
2)
The energy density that Imitating capacitance meter reveals (F/kg)
At table 14 low temperature-40 ℃, the different current density (mA/cm of heterogeneous electrode slice
2) energy density (F/kg) that reveals of Imitating capacitance meter
Power density (W/kg or W/L) at 18 ℃ of table 15 room temperatures and low temperature-40 ℃
Cycle life at 18 ℃ of table 16 room temperatures characterizes
Embodiment 5:
With embodiment 1 difference be:
1. hydrogen storing alloy powder accounts for 4wt% change value ratio;
2. add 2.4ml electrolyte, this electrolyte is the potassium hydroxide aqueous solution of concentration 1.5M;
The artificial capacitor of the alkaline fake capacitance of the heterogeneous electrode of the present embodiment, they are under different discharge current densities, and the energy density that room temperature electric discharge shows is listed in table 17; The energy density showing at low temperature-40 ℃ is listed in table 18; The power density that room temperature and low temperature discharge show is listed in table 19; Under room temperature, the characterization result of cycle life is listed in table 20.
All the other are with embodiment 1.
At 18 ℃ of table 17 room temperatures, the different electric currents of heterogeneous electrode slice are close
Degree (mA/cm
2) energy density (F/kg) that reveals of Imitating capacitance meter
At table 18 low temperature-40 ℃, the different current density (mA/cm of heterogeneous electrode slice
2) energy density (F/kg) that reveals of Imitating capacitance meter
Power density (W/kg or W/L) at table 19 room temperature 18 and low temperature-40 ℃
Cycle life at 18 ℃ of table 20 room temperatures characterizes
Claims (1)
1. a matching process for the heterogeneous electrode of alkaline fake capacitance, is characterized in that, the manufacturing step of its heterogeneous positive and negative electrode, process conditions, formula, structure and matching process are as follows:
The structure of the first step, the anodal blank material of fake capacitance:
Select commercially available nickel-hydrogen electrokinetic cell sintrered nickel anode, this sintrered nickel anode is wet method manufacture, and containing cobalt type, index is 31mAh/cm
2the saturated potassium permanganate solution of room temperature is heated to 75 ℃-85 ℃, and continue to add chemical pure potassium permanganate particles, be mixed with the supersaturated solution of this warm area, again sintrered nickel anode strip is inserted in the potassium permanganate supersaturated solution of these 75 ℃-85 ℃, 2 seconds-5 seconds residence time, rapidly this pole piece is shifted out from solution, room temperature is dried standby, constructs the anodal blank material of fake capacitance; This positive pole blank material characterizes through being configured to double electric layer capacitor characterizing method, and it take the capacity that capacitance characteristic shows is 0.072mAh/cm
2;
The structure of second step, fake capacitance negative pole blank material:
Select commercially available nickel-hydrogen power battery current-collecting body nickel foam commodity, by original thickness, be that 1.0mm nickel foam collector is depressed into 0.8mm in advance, by fake capacitance negative pole material blade coating on it, this fake capacitance negative pole material blade coating formula is: the AB that 600 object activated carbon powders, 600 object graphite powders, 275 order ± 25 orders and its manufacturer's marked capacity are 285mAh/g again
5type hydrogen storage alloy powder and solid content are the polytetrafluoro emulsion of 52wt%; Fix four percentage by weight summations while being 100wt%, graphite powder accounts for 7wt% definite value ratio, and polytetrafluoro emulsion accounts for 3wt% definite value ratio, and hydrogen storing alloy powder accounts for Xwt% change value ratio, and all the other are activated carbon powder, and four percentage by weight summations form 100wt%; X=1wt%-5wt% wherein; Four mix and construct fake capacitance negative pole material spread coated paint according to this formula, then by the 0.8mm foam nickel strap containing this spread coated paint, put into and regulate the roll squeezer that gap is 0.35mm to roll film processing; Roll and obtain the quantity that contains this spread coated paint in the thick and unit are of 0.35mm after film and meet 0.075g/cm
2blank in the middle of the fake capacitance negative plate of index; In the potassium permanganate saturated solution that this centre blank insertion is 50 ℃-70 ℃, 2 seconds-5 seconds residence time, shift out rapidly this saturated solution, room temperature is dried standby, constructs fake capacitance negative pole blank material; This negative pole blank material characterizes through being configured to double electric layer capacitor characterizing method, and it take the capacity that capacitance characteristic shows is 0.072mAh/cm
2± 0.001mAh/cm
2;
Structure and the matching process of the 3rd step, fake capacitance positive pole, negative pole:
Fake capacitance positive pole and negative pole blank material are cut into bar shaped, in view of fake capacitance housing of the present invention is used in affixed merchandise, housing, upper cover and the sealing ring spare and accessory parts of nickel-hydrogen cell AA type cylindrical battery, be subject to this and use shell dimension restriction, fake capacitance positive pole and negative pole blank material are cut out size and are long 119mm, wide 41mm, by the bar shaped blank material of this 119mm * 41mm size, on soft machine, soft treatment is three times; Be transferred to again ultrasonic wave wheat flour purifier, on long limit of bar shaped blank material pole piece according to the clear powder of lug width same size with welding, after clear powder, by impulse spot welder for lug, according to AA cylinder nickel-hydrogen cell welding requirements firm welding; To be separated by with the sulfonated membranes in nickel-hydrogen cell barrier film commodity with negative pole is middle with lug bar shaped is anodal, after alignment, on battery winder, reel, after coiling completes, put into housing, add 2.4ml electrolyte, this electrolyte is the potassium hydroxide aqueous solution of concentration 0.5M-2M; Electrolyte is injected into after the housing with battery core, relends after encapsulating, encapsulate with AA cylinder nickel-hydrogen cell sealed in unit the nude simulation fake capacitance obtaining under different condition is numbered, and so far, completes the coupling of the heterogeneous electrode of alkaline fake capacitance.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201210049903.XA CN102543458B (en) | 2012-02-29 | 2012-02-29 | Alkali pseudo-capacitor alloplastic electrode and matching method therefor |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201210049903.XA CN102543458B (en) | 2012-02-29 | 2012-02-29 | Alkali pseudo-capacitor alloplastic electrode and matching method therefor |
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Family Cites Families (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH0547380A (en) * | 1991-08-19 | 1993-02-26 | Furukawa Battery Co Ltd:The | Nickel hydroxide electrode for alkaline secondary battery |
| RU2140681C1 (en) * | 1998-11-27 | 1999-10-27 | Разумов Сергей Николаевич | Asymmetric electrochemical capacitor |
| US6222723B1 (en) * | 1998-12-07 | 2001-04-24 | Joint Stock Company “Elton” | Asymmetric electrochemical capacitor and method of making |
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