CN102593458B - Recarburization negative electrode of metal hydride-nickel battery and method for improving power - Google Patents
Recarburization negative electrode of metal hydride-nickel battery and method for improving power Download PDFInfo
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- CN102593458B CN102593458B CN201210048023.0A CN201210048023A CN102593458B CN 102593458 B CN102593458 B CN 102593458B CN 201210048023 A CN201210048023 A CN 201210048023A CN 102593458 B CN102593458 B CN 102593458B
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- AMWRITDGCCNYAT-UHFFFAOYSA-L hydroxy(oxo)manganese;manganese Chemical compound [Mn].O[Mn]=O.O[Mn]=O AMWRITDGCCNYAT-UHFFFAOYSA-L 0.000 claims abstract description 86
- 239000000463 material Substances 0.000 claims abstract description 52
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims abstract description 46
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- 229930003268 Vitamin C Natural products 0.000 abstract description 3
- VMWYVTOHEQQZHQ-UHFFFAOYSA-N methylidynenickel Chemical compound [Ni]#[C] VMWYVTOHEQQZHQ-UHFFFAOYSA-N 0.000 abstract description 3
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- 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
- Y02E60/10—Energy storage using batteries
Abstract
The invention provides a recarburization negative electrode of a metal hydride-nickel battery and a method for improving power. The recarburization negative electrode is used for improving output power of the negative electrode and the battery and reducing charging and discharging temperature rise of the battery by replacing 15wt% of hydrogen storage alloy powder with manganese oxide doped activated carbon and graphite powder in the traditional negative electrode plate which takes foam nickel as a current collector for bearing the hydrogen storage alloy powder. Furthermore, the recarburization negative electrode lays a foundation for design and manufacture of an electrode plate of a self-transition power supply or a Faraday ultra-capacitor to be transited to an alkaline ultra-battery, a nickel-carbon capacitive battery, and a battery converting capacitor. Manganese oxide doped in-situ reaction is carried out by using oxidation-reduction reaction dual material consisting of sodium salts of vitamin C and potassium permanganate. The method is simple, convenient and easy to carry out; the industrial cost is low; and the effect is good. Therefore, the negative effects caused by the existence of graphite powder in the electrode plate can be effectively solved.
Description
Technical field
The present invention relates to a kind of method of metal hydride-nickel cell carburetting negative pole and bring to power.
Background technology
Nearly ten years, superbattery (Ultrabattery), is called for short by " super battery ", and it has powerful attraction to conventional batteries industry.This attraction, mainly come from the active demand such as cycle life, power output and cryogenic property that promotes conventional batteries.
Conventional batteries, cycle life is difficult breaks through 10
3the order of magnitude, power output is difficult to break through 30C (multiplying power) electric discharge, the difficult DEG C electric discharge high point, subzero-50 of breaking through, cryogenic property aspect.And for traditional electric capacity (capacity), the difficult index breaking through of these batteries, for it, reaches this index easy; The cycle life of electric capacity is at least 10
4the order of magnitude, 50 multiplying power dischargings and subzero-50 DEG C electric discharge are all easy to realize.Obvious, utilize the electric capacity that power density is high to make up the conventional batteries defect that power density is low, be that super battery is to the powerful attraction core of conventional batteries industry place.
A kind of viewpoint is thought, the super battery technology of current battery industry, be subject to a certain extent biological transgenic technology impact, be that the super battery of battery industry is in essence roughly the same in field of biology, " gene " of a certain amount of electric capacity (gene) transferred in battery by electric general character this " nucleic acid ", such as cycle life at least 10
4" gene " (genetic factor) of the order of magnitude, 50 multiplying power dischargings and subzero-50 DEG C these electric capacity of electric discharge can obtain " gene expression " (gene expression) to a certain degree in battery.
Relatively early carry out the development work that conventional batteries is converted into super battery, for CSIRO (COMMONWEALTH SCIENTIFIC AND INDUSTRIAL RESEARCH ORGANISATION), this industrial research tissue is built into the capacitance materials such as active carbon and carbon felt and pole plate in traditional lead acid accumulator, the super battery of structure taking lead acid accumulator as basis; This way, stands in the visual angle that battery material increases and decreases, and is equivalent to lead acid accumulator carburetting; Stand in the visual angle that battery and electric capacity hybridization or hydridization are manufactured, be equivalent to lead-acid battery internal parallel electric capacity; Stand in the visual angle of Faraday pseudo-capacitance, be equivalent to fake capacitance and cross over self limit or the infinitely-great fake capacitance of capacity.The O of CSIR later stage and battery Co., Ltd. of Furukawa Electronic (FURUKAWA BATTERY CO LTD) cooperation, the patent series of the super battery of lead-acid battery carburetting type of structure is in table 1.
Table 1 CSIRO builds patent group's abridged table of the super battery of lead-acid battery carburetting type
The 10th patent in table 1 patent group discloses, and after pole plate carburetting, preferably super battery discharge cut-ff voltage is defined in 1.5V, cycle life reaches left and right 100,000 times in this improvement.
After this, some companies or the group of China, Korea S and Japan also disclose the some patents that are similar to the super battery of Australia Commonwealth Scientific and Industrial Research Organisation's lead-acid battery carburetting type, such as: disclosed Shuangdeng Science & Technology Development Academy Co., Ltd., Nanjing City of Patent Office of the People's Republic of China application exercise question is the CN200910183503.6 patent of " a kind of method for manufacturing lead-carbon ultracapacitor battery cathode " etc.
Affected by this or influence each other, lithium ion chargeable battery manufacturing industry, apply active carbon as basis, at the collector back side etc. taking lithium ion battery, after pole plate carburetting, the super battery (also referred to as capacitor batteries) of structure taking lithium ion battery as basis, more corresponding patents disclose quite a few, such as in the disclosed CN201110101605.6 patent of Patent Office of the People's Republic of China and CN200810031490.6 patent etc.
From more than the invention of " the super battery of plumbic acid " and " the super battery of lithium ion " (capacitor batteries) be not difficult to return and state out: to shift the material support of electric capacity " gene " be mainly material with carbon element to super battery at present, this material with carbon element is mainly active carbon, conductive black, carbon nano-tube, carbon aerogels and graphite powder etc. only increase these material with carbon elements in battery; In super battery, " gene " of electric capacity could more or less give expression to multiplying power discharging, low temperature discharge and long circulation life.
Metal hydride-nickel cell, or the nickel-hydrogen cell being commonly called as, during the slurry negative pole taking nickel plated steel strip as collector was manufactured in the past, also will add a small amount of conductive black, and object is mainly to increase " deformability ".Battery cathode sheet rolls membrane process or battery charges, hydrogen storing alloy powder is inhaled hydrogen-expansion; In negative material, contain the material composition of this deformability, can avoid under draught pressure or hydrogen storing alloy powder is inhaled under hydrogen-expansion pressure, the lax or dry linting of active material and collector, causes that battery capacity declines, internal resistance increase.
During metal hydride-nickel cell negative pole taking nickel foam as collector is manufactured, especially during dry method negative pole is manufactured, add a small amount of conductive black to substitute expensive T210 carbonyl nickel powder or alternative T255 carbonyl nickel powder, the role of this conductive black in negative pole is " conductive agent ", and adding its main purpose is to reduce costs; Next is to increase deformability.
Taking wet method sintrered nickel anode, in anodal metal hydride-nickel cell is manufactured, the porous carbon skeleton before dipping nickel salt and alkali, itself is also material with carbon element.
Visible: metal hydride-nickel cell, in positive and negative electrode, self just contains the material with carbon element of super battery capacitor " gene ".Traditional metal hydride-nickel cell can not be called the super battery of nickel-hydrogen in Modern Significance, main cause may go out in carbon content insufficient, or self original carbon, to " gene " of multiplying power discharging, low temperature discharge and these electric capacity of long circulation life not " gene expression " fully.
Accordingly, traditional metal hydride-nickel cell is converted into the super battery of nickel-hydrogen in Modern Significance, and two-plate carburetting is basis.After carburetting, pole plate can carry out " gene expression " fully to electric capacity " gene ", and this battery just can change super battery into.This is that metal hydride-nickel cell is converted into the Fundamental Aspects that the super battery of nickel-hydrogen faces.
" carburetting " makes traditional metal hydride-nickel cell be converted into the super battery of nickel-hydrogen in Modern Significance, and " carburetting " limited amount running into is identical with the technology barriers that the super battery of plumbic acid runs into.
Before the carburetting result of study in lead-acid battery negative plate such as the CSIRO that addressed disclose, the limit of carburetting is the 15wt% that can not exceed negative plate cell active materials, desirable electric capacity carbon increment may be 7wt% left and right, and lithium ion battery is the super battery on basis or the carbon increasing amount ratio that is called capacitor batteries, in theory can be higher.It is volumetric specific energy that the carburetting of actual upper bound preparing lithium ion battery mainly restricts factor.
In battery, another common problem of carburetting is: active carbon is better than conductive black aspect the long-life, and its conductivity aspect is not as conductive black, so active carbon will follow a certain amount of graphite to add in battery simultaneously.
But graphite is very few, promote the scarce capacity of active carbon conductivity, the internal resistance of cell is not up to standard, bad pole piece, the temperature rise of heat conduction impels the internal resistance of cell further to increase, and internal resistance further increases, impel conversely pole piece temperature rise speed to increase, and forms thus vicious circle.
The too much negative effect of graphite is mainly manifested in: because " gene expression " contribution rate of " gene " of graphite to multiplying power discharging, low temperature discharge and these electric capacity of long circulation life is very little, too much cause self-discharge of battery or creepage along face in addition.Graphite is very little and cause self-discharge of battery or these creepage three kinds of negative effects of electrode to electric capacity " gene expression " contribution rate, becomes at present and makes metal hydride-nickel cell be converted into technology barriers or technical bottleneck that the super battery of nickel-hydrogen runs into.
Visible, introduce if do not abandon prior art the theory that the object of graphite is mainly assistance active carbon conduction; Graphite is just difficult to break through to the very little technical bottleneck creepage with causing self-discharge of battery or electrode of electric capacity " gene expression " contribution rate; This causes " carburetting ", is especially converted in the super cell process of nickel-hydrogen and increases active carbon operation at metal hydride-nickel cell, is difficult to reach the object that is converted into super battery.
Summary of the invention
The object of the present invention is to provide the method for metal hydride-nickel cell carburetting negative pole and bring to power.Particularly provide a kind of: on the basis of conventional metals hydride-nickel-based battery nickel foam dry method negative manufacturing technique, utilize a small amount of graphite powder to increase conduction, the thermal conductivity of active carbon, utilize doped with manganese oxide active carbon to reduce active carbon infringement to hydrogen bearing alloy because of its adsorb oxygen or oxygen, obtain thus the method for metal hydride-nickel cell carburetting negative pole and bring to power.
A kind of " method of metal hydride-nickel cell carburetting negative pole and bring to power " design principle:
(1), active carbon doped with manganese oxide design principle:
In metal hydride-nickel cell negative pole, add active carbon, it is compared with adding conductive black, and the defect of two aspects is more outstanding.First conductivity is not as conductive black, and this is mainly that active carbon does not pass through conductive processing as conductive black; It two is that charcoal absorption gas energy force rate conductive black is strong, once metal hydride-nickel cell decomposites hydrogen and oxygen, what after charcoal absorption hydrogen and oxygen, conductivity became is more weak, causes the increases such as the internal resistance of cell or amplitude beat and affect heavy-current discharge efficiency or charge efficiency.After active carbon doped with manganese oxide, reduce its surface to hydrogen and Oxygen Adsorption, produced " soil " thereby reduced " air bound " resistance after charcoal absorption gas; On the other hand, MnO
xalso be reasonable capacitance material, it contributes to charcoal absorption physical charge and improves the farad number that carburetting electrode shows with capacitive form.
(2), graphite powder doped with manganese oxide design principle:
Graphite powder is for capacitance material, and the ability that himself stores physical charge is little, and this is that it adds one of defect in metal hydride-nickel cell negative pole.Another defect is: once add quantity and method improper, the negative effect of himself satisfactory electrical conductivity is revealed as electrode surface and occurs " creepage along face ", thus loss electric capacity physical charge or reduce charge efficiency.More fearful: along with the double action that discharges and recharges electric charge and gas and move, the superfine graphite powder of granularity dissociates to barrier film from pole plate, seriously reduces the insulation property of barrier film, causes self-discharge of battery remarkable.And graphite powder granularity is excessive, although increase from the free resistance out of negative plate, but assist the design object of active carbon conduction to have a greatly reduced quality.
After graphite powder doped with manganese oxide, not only it increases from the free resistance out of negative plate, and can reasonable balance contradiction between " adding graphite to help active carbon conduction and graphite to add the generation creepage along face ".Be MnO
xreasonable capacitance material, graphite powder surface attachment MnO
xafter, can increase graphite and store the ability of physical charge, help active carbon conduction also to reduce the negative effect creepage along face simultaneously.
(3), doped with manganese oxide in-situ reaction designing principle:
MnO
xin material with carbon element doped with several different methods.And reaction in-situ of the present invention is designed to: " reaction " in " reaction in-situ " is: fierce oxidation-reduction reaction occurs after strong oxidizer and strong reductant meet; " original position " in " reaction in-situ " is embodied in: first strong reductant is adsorbed or is attached in aim carbon compound, again the drip washing of strong oxidizer potassium permanganate is being adsorbed or adhered in the aim carbon compound of strong reductant, on the aim carbon compound upper surface that adsorbs or adhere to strong reductant, vigorous reaction occurs, the Mn oxide of one of product is directly doped in carbide.
Sodium ascorbate (sodium ascorbate), formal name used at school is: L-(+)-threose type-2,3,4,5,6-penta hydroxy group-2-hexenoic acid-4-lactone sodium, its by ascorbic acid and reaction of sodium bicarbonate after refining forming, than the easy preservation of ascorbic acid, and approach with ascorbic acid reproducibility.And L-AA (Vitamin C) also claims vitamin C or tie up it to order C, it is the well-known strong reductant of region of chemistry.Equally, potassium permanganate is also the well-known strong oxidizer of region of chemistry.
Activated carbon adsorptive capacity is very strong, and after the sodium ascorbate in its absorption ascorbic acid sodium water solution, active carbon just becomes the carrier of sodium ascorbate.Obviously, the active carbon of carrying sodium ascorbate runs into potassium permanganate, one of reactant after its fierce chemical reaction---MnO or MnO
xbe retained on carrier active carbon.
Graphite powder is bad to most aqueous solution moistened surface effects, has entered superfine powder ranks although be ground to 600 object graphite powders, and specific surface has also increased a lot; But, find with the chemical reagent of 600 order graphite powder good wet or difficulty.Sodium ascorbate, this lactone compound, be few in number and one of chemical reagent graphite powder good wet.Although its specific surface is large less than active carbon, absorption sodium ascorbate intensity does not have active carbon firm yet, and than other reducing agent in chemical reagent, this lactone compound of sodium ascorbate is that graphite is one of best reaction in-situ material of carrier.
A method for metal hydride-nickel cell carburetting negative pole and bring to power, its manufacturing step, process conditions and bring to power method are as follows:
The preparation of the first step, doped with manganese oxide in-situ reaction reagent:
Potassium permanganate and distilled water be raw material, at 20 DEG C of room temperatures, be mixed with potassium permanganate saturated aqueous solution for subsequent use; Buy the sodium ascorbate powder of commercially available food additive grade, be mixed with the 20wt% aqueous solution for subsequent use with distilled water, this sodium ascorbate meets GB16313-1996 standard;
The preparation of second step, doped with manganese oxide graphite powder raw material:
Add the ratio of 100ml 20wt% ascorbic acid sodium water solution with 2 gram of 600 object graphite powder, the two is put in beaker, then this beaker is put into supersonic cleaning machine together with wine material, disperse 2 minutes, shifting this suspension-turbid liquid filters to glass funnel, be filtered to without filtrate and flow out afterwards, rapidly potassium permanganate saturated aqueous solution sprayed into material surface in glass funnel, make the graphite powder that contains sodium ascorbate by this liquor potassic permanganate drip washing, show redness, stop this liquor potassic permanganate drip washing operation until flow out glass funnel leacheate; Then use again the reactant in the reverse drip washing glass funnel of 20wt% ascorbic acid sodium water solution, disappear and be transformed into colourless until glass funnel shows red filtrate, stop the operation of the reactant in ascorbic acid sodium water solution drip washing glass funnel, then the reactant in glass funnel is put in baking oven to 85 DEG C and dries 12 hours, obtain doped with manganese oxide graphite powder raw material;
The preparation of the 3rd step, doped with manganese oxide active carbon raw material:
Adopt and second step---doped with manganese oxide graphite powder raw material is prepared essentially identical step, condition and method, unique different be by 600 object graphite powders in second step, with specific surface index be 190m
2/ g, order number are that 400 object active carbon powders are replaced, and obtain equally doped with manganese oxide active carbon raw material;
The carburetting negative pole preparation of the 4th step, bring to power:
The nickel foam commodity of selecting commercially available nickel-hydrogen power battery current collector to use, are that 1.0mm nickel foam collector is depressed into 0.8mm in advance by original thickness, then by carburetting negative pole blade coating on it, this carburetting negative pole spread coated paint formula is:
The AB that 275 order ± 25 orders and manufacturer's marked capacity are 285mAh/g
5type hydrogen storage alloy powder fixed proportion is 80wt%; Solid content is that the polytetrafluoro emulsion fixed proportion of 40wt% is 5wt%; The variation ratio 11.5wt%-13.5wt% of doped with manganese oxide activated carbon powder; The variation ratio 1.5wt%-3.5wt% of the graphite powder of doped with manganese oxide; The summation that these four kinds of materials are measured by weight percentage forms 100wt%;
In other words, the implication of this carburetting negative pole spread coated paint formula: this hydrogen storing alloy powder and this polytetrafluoro emulsion are fixed as respectively after the ratio of 80wt% and 5wt%; Remaining 15wt% is the activated carbon powder of doped with manganese oxide and the ratio of two kinds of material summations of graphite powder.
And the graphite powder of doped with manganese oxide activated carbon powder and doped with manganese oxide, be the implication of " carburetting thing " in the present invention;
Fixed proportion that the graphite powder summation of doped with manganese oxide activated carbon powder and doped with manganese oxide is 15wt%, implication in the present invention: " carburetting thing in negative pole spread coated paint shared ratio ";
If doped with manganese oxide activated carbon powder portion is (15-X) wt% in carburetting thing, so should " X " be decided to be the share that the graphite powder of doped with manganese oxide occupies in carburetting thing; Also the span that simultaneously means this " X " is 1.5wt%-3.5wt%; Be carburetting thing after shared ratio is fixed to 15wt% in negative pole spread coated paint, the graphite powder alternative dopings Mn oxide activated carbon powder scope of doped with manganese oxide is 1.5wt%-3.5wt%.
According to this formula, these four kinds of mixing of materials evenly construct carburetting negative pole spread coated paint, 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 after film, obtain the quantity that contains this spread coated paint in the thick and unit are of 0.35mm and meet 0.134g/cm
2the carburetting negative plate blank material of index;
The 5th step, structure promote the method for metal hydride-nickel cell power
Carburetting negative pole blank material is cut into bar shaped, in view of simulated experiment battery container 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, carburetting negative plate blank material negative pole blank material is cut out and is of a size of 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 welding the clear powder of lug width same size, after clear powder, by impulse spot welder lug for, according to AA cylinder nickel-hydrogen cell welding requirements firm welding, so far, the carburetting negative pole of acquisition bring to power;
Select commercially available nickel-hydrogen electrokinetic cell sintrered nickel anode, this sintrered nickel anode is wet method manufacture, is 30mAh/cm containing cobalt type, index
2; It is identical with negative pole that this positive plate is cut out size, 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 density of electrolyte is 1.31g/cm
3, this electrolyte solute consists of 70wt% potassium hydroxide, 28wt% NaOH and 2wt% lithium hydroxide, and three kinds of solute summations meet 100wt%; Water is the solvent of this electrolyte; Electrolyte is injected into after the housing with battery core, relend after encapsulating, encapsulate with AA cylinder nickel-hydrogen cell sealed in unit the nude simulated battery numbering obtaining under different condition, the operation of the metal hydride-nickel cell bring to power that so far, contains carburetting negative pole completes.
Metal hydride-nickel simulated battery the cell testers that again the present invention of acquisition contained to carburetting negative pole etc. are measured and are characterized.
Beneficial effect of the present invention:
1, a kind of taking nickel foam in collector metal hydride-nickel cell negative pole, do not changing under the prerequisite of metal hydride-nickel cell production craft step, complete the index of the maximum carbon increasing amount of in negative material carburetting 15wt%, and the production and processing of this carburetting negative pole, do not needed newly added equipment.The basis that can operate with rapid industrialization has been established in this exploitation that is capacitor batteries or the super battery of alkalescence and faraday's ultracapacitor for nickel-carbon.
2, selecting is carburetting source than the active carbon of the more difficult carburetting of conductive black, has fundamentally avoided conductive black in long-term charge and discharge cycles, because the degraded of organic conductive agent causes the hidden danger of the increase of pole piece internal resistance.For solid foundation has been established in the research and development that active carbon is capacitor batteries and faraday's ultracapacitor at the super battery of alkalescence, nickel-carbon.
3, be easy to get ascorbic sodium salt and potassium permanganate as reaction in-situ material taking raw material, and reaction in-situ method is convenient and easy, practicality and scientific strong, creativeness and novelty remarkable, fully demonstrate the design innovation of " main road is to letter ".The method of this novelty, has fundamentally solved the direct and indirect contradiction of activated carbon conduction between creepage with graphite, for electric capacity and the super battery carbon material manganese oxide that adulterates is opened up Liao Xin road.Also obtain simultaneously promote battery power output 4%-11%, reduce the good result such as battery discharge or charging temperature rise.
Brief description of the drawings
Fig. 1 is the representational charge and discharge curve chart of metal hydride-nickel simulated battery that the present invention contains carburetting negative pole and non-carburetting negative pole.
Curve in figure (1) is under room temperature, with the constant current of 100mA to contain non-carburetting negative pole the charging of metal hydride-nickel simulated battery time, shown go out the charging interval V-t curve mutual corresponding with charging voltage; And curve (2) for metal hydride-nickel simulated battery of containing carburetting negative pole and with V-t curve under the identical charging system of curve (1).From two curve comparisons: after charging mid-term, the simulated battery charging voltage that contains non-carburetting negative pole comes back significantly, simulated battery charging needs to consume more high-power and consumes more energy; And the simulated battery that contains carburetting negative pole is contrary, charging is energy-saving and cost-reducing; Curve in figure (3) is under room temperature, with the constant current of 1288mA to contain carburetting negative pole the electric discharge of metal hydride-nickel simulated battery time, shown go out the V-t curve mutual corresponding with discharge voltage discharge time; And curve (4) for metal hydride-nickel simulated battery of containing non-carburetting negative pole and with V-t curve under the identical discharge system of curve (3).Obvious from two curve comparisons: the simulated battery that contains non-carburetting negative pole, initial power, instantaneous power and the average power of its electric discharge, all can not show a candle to the simulated battery that contains carburetting negative pole.
Fig. 2 is the representational charging temperature rise of the metal hydride-nickel simulated battery recording curve figure that the present invention contains carburetting negative pole and non-carburetting negative pole.
Curve in figure (1) is under room temperature, with the constant current of 644mA to contain carburetting negative pole the charging of metal hydride-nickel simulated battery time, shown go out charging interval and the simulated battery temperature mutual corresponding T-t curve that raises; And curve (2) for metal hydride-nickel simulated battery of containing non-carburetting negative pole and with T-t curve under the identical charging system of curve (1).From two curve comparisons: no matter be before simulated battery is full of electricity, after being still full of electricity, the simulated battery charging temperature rise speed that contains non-carburetting negative pole, all will be faster than the simulated battery that contains carburetting negative pole.
Embodiment
Embodiment 1:
The preparation of the first step, doped with manganese oxide in-situ reaction reagent:
Taking chemical pure potassium permanganate and distilled water as raw material, at 20 DEG C of room temperatures, be mixed with potassium permanganate saturated aqueous solution for subsequent use; Buy the sodium ascorbate powder of commercially available food additive grade, be mixed with the 20wt% aqueous solution for subsequent use with distilled water, this sodium ascorbate meets GB16313-1996 standard;
The preparation of second step, doped with manganese oxide graphite powder raw material:
Add the ratio of 100ml 20wt% ascorbic acid sodium water solution with 2 gram of 600 object graphite powder, the two is put in beaker, then this beaker is put into supersonic cleaning machine together with wine material, disperse to obtain for 2 minutes suspension-turbid liquid, shifting this suspension-turbid liquid filters to glass funnel, be filtered to without filtrate and flow out afterwards, rapidly potassium permanganate saturated aqueous solution sprayed into material surface in glass funnel, make the graphite powder that contains sodium ascorbate by this liquor potassic permanganate drip washing, show redness, stop this liquor potassic permanganate drip washing operation until flow out glass funnel leacheate; Then use again the reactant in the reverse drip washing glass funnel of 20wt% ascorbic acid sodium water solution, disappear and be transformed into colourless until glass funnel shows red filtrate, stop the operation of the reactant in ascorbic acid sodium water solution drip washing glass funnel, then the reactant in glass funnel is put in baking oven to 85 DEG C and dries 12 hours, obtain doped with manganese oxide graphite powder raw material;
The preparation of the 3rd step, doped with manganese oxide active carbon raw material:
Adopt and second step---doped with manganese oxide graphite powder raw material is prepared essentially identical step, condition and method, unique different be by 600 object graphite powders in second step, with specific surface index be 190m
2/ g, order number are that 400 object active carbon powders are replaced, and obtain equally doped with manganese oxide active carbon raw material;
The carburetting negative pole preparation of the 4th step, bring to power:
The nickel foam commodity of selecting commercially available nickel-hydrogen power battery current collector to use, are that 1.0mm nickel foam collector is depressed into 0.8mm in advance by original thickness, then by carburetting negative pole blade coating on it, this carburetting negative pole spread coated paint formula is:
The AB that 275 order ± 25 orders and manufacturer's marked capacity are 285mAh/g
5type hydrogen storage alloy powder fixed proportion is 80wt%; Solid content is that the polytetrafluoro emulsion fixed proportion of 40wt% is 5wt%; The ratio 13.5wt% of doped with manganese oxide activated carbon powder; The variation ratio 1.5wt% of the graphite powder of doped with manganese oxide; The summation that these four kinds of materials are measured by weight percentage forms 100wt%.
According to this formula, evenly, these four kinds of mixing of materials construct carburetting negative pole spread coated paint, 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 after film, obtain the quantity that contains this spread coated paint in the thick and unit are of 0.35mm and meet 0.134g/cm
2the carburetting negative plate blank material of index;
The 5th step, structure promote the method for metal hydride-nickel cell power:
Carburetting negative pole blank material is cut into bar shaped, in view of simulated experiment battery container 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, carburetting negative plate blank material negative pole blank material is cut out and is of a size of 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 welding the clear powder of lug width same size, after clear powder, by impulse spot welder lug for, according to AA cylinder nickel-hydrogen cell welding requirements firm welding, so far, the carburetting negative pole of acquisition bring to power.
Select commercially available nickel-hydrogen electrokinetic cell sintrered nickel anode, this sintrered nickel anode is wet method manufacture, is 32mAh/cm containing cobalt type, index
2; It is identical with negative pole that this positive plate is cut out size, 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 density of electrolyte is 1.31g/cm
3, this electrolyte solute consists of 70wt% potassium hydroxide, 28wt% NaOH and 2wt% lithium hydroxide, and three kinds of solute summations meet 100wt%; Water is the solvent of this electrolyte; Electrolyte is injected into after the housing with battery core, relend after encapsulating, encapsulate with AA cylinder nickel-hydrogen cell sealed in unit the nude simulated battery numbering obtaining under different condition, the operation of the metal hydride-nickel cell bring to power that so far, contains carburetting negative pole completes;
The 6th step, construct the method that non-carburetting negative pole is contrast negative pole and corresponding simulated battery:
For control experiment, doped with manganese oxide activated carbon powder and graphite powder in carburetting negative pole spread coated paint are removed, with the hydrogen storing alloy powder replacement of 0.5g; Construct non-carburetting negative pole contrast negative pole.After replacement, contrast meets 0.145g/cm by the quantity that contains spread coated paint in negative pole unit are
2index.All the other conditions are identical with carburetting negative pole with method, and construct too metal hydride-nickel simulated battery of non-carburetting negative pole;
The characterizing method of the 7th step, metal hydride-nickel cell carburetting negative pole and bring to power negative pole:
Metal hydride-nickel simulated battery of metal hydride-nickel simulated battery that the present invention of acquisition is contained to carburetting negative pole and non-carburetting negative pole, change into according to conventional nickel-hydrogen cell chemical synthesizing method, after this constant current charge-discharge makes for 8 times its capacity tend towards stability, then with cell tester blank determination its to discharge power and the relevant index of charging;
At 18 DEG C of room temperatures, with constant-current discharge form, the electric discharge power output index of correlation of the simulated battery to carburetting negative pole and non-carburetting negative pole simulated battery is carried out comparative determination, and it the results are shown in table 2.
Constant-current discharge at 18 DEG C of table 2 room temperatures, the performance of carburetting negative pole power output
From table 2: in unit are, average power 0.029W/cm when carburetting negative discharge
2, but not average power 0.026W/cm when carburetting negative discharge
2.When carburetting negative discharge, in unit are, average power has promoted 11.5%[(0.029-0.026)/0.026].As everyone knows, the power output of battery (P) is the product (P=I × V) of its output current (I) and its output voltage; Obviously,, in carburetting negative pole constant-current discharge process, the power output promoting is mainly derived from the contribution that output voltage (discharge voltage intermediate value) increases 100mV.
At 18 DEG C of room temperatures, with the constant-current discharge form of the electric current of constant 1.288A, simulated battery is externally discharged, and use immobilization with adhesive tape at AA cylindrical battery cylinder medium position the temp probe of cell tester, for detection of the electric discharge temperature rise of larger discharge current density Imitating battery, the comparative determination of the electric discharge temperature rise of the simulated battery to carburetting negative pole and non-carburetting negative pole simulated battery, taking the cell tester record electric discharge end pulling temperature numerical value that temp probe was collected in last 1 second as index, simulated battery temperature rise blank determination the results are shown in table 3.
18 DEG C of table 3 room temperatures are with 1.288A constant-current discharge, the simulated battery temperature rise table of comparisons
From table 3: it is 28 DEG C that the electric discharge of carburetting negative pole simulated battery electric discharge finishes final moment temperature; It is 31 DEG C but not the electric discharge of carburetting negative pole simulated battery electric discharge finishes final moment temperature.While electric discharge under the larger discharge current density of carburetting negative pole, the electric discharge temperature rise of the simulated battery of the non-carburetting negative pole of its contrast of electric discharge temperature rise ratio of its simulated battery has reduced by 3 DEG C.
Industry peer is known, nickel-hydrogen cell electric discharge, and active material chemical reaction is the endothermic reaction.The manifested temperature rise of discharging under the large electric current of battery, the temperature rise that the net heat after Joule heat summation, the heat absorption of deduction active material chemical reaction producing for each interface contact resistance in battery produces battery.Carburetting negative pole, owing to sneaking into graphite powder conductive agent, effectively reduces the contact resistance between spread coated paint and nickel foam collector interface, thereby has reduced temperature rise.
Embodiment 2:
With embodiment 1 difference be:
In carburetting negative pole spread coated paint formula, the ratio 11.5wt% of doped with manganese oxide activated carbon powder; The variation ratio 3.5wt% of the graphite powder of doped with manganese oxide; The summation that these four kinds of materials are measured by weight percentage still forms 100wt%.
All the other conditions and step are with embodiment 1.
At 18 DEG C of room temperatures, with constant-current discharge form, the electric discharge power output of the simulated battery to carburetting negative pole and non-carburetting negative pole simulated battery is carried out the table 4 that the results are shown in of comparative determination.
Constant-current discharge at 18 DEG C of table 4 room temperatures, the performance of carburetting negative pole power output
From table 4: in unit are, average power when the non-carburetting negative discharge of average power ratio when carburetting negative discharge has promoted 5%.
At 18 DEG C of room temperatures, make the external constant-current discharge simulated battery of simulated battery temperature rise blank determination the results are shown in table 5 with the electric current of constant 1.93A.
18 DEG C of table 5 room temperatures are with 1.93A constant-current discharge, the simulated battery temperature rise table of comparisons
From table 5: the electric discharge of carburetting negative pole simulated battery electric discharge finishes final moment temperature, compared with it finishes final moment temperature with electric discharge of non-carburetting negative pole simulated battery electric discharge, its electric discharge temperature rise than the simulated battery of the non-carburetting negative pole of contrast has reduced by 6 DEG C.
Embodiment 3:
With embodiment 1 difference be:
In carburetting negative pole spread coated paint formula, the ratio 13wt% of doped with manganese oxide activated carbon powder; The variation ratio 2wt% of the graphite powder of doped with manganese oxide; The summation that these four kinds of materials are measured by weight percentage still forms 100wt%.
All the other conditions and step are with embodiment 1.
At 18 DEG C of room temperatures, with constant-current discharge form, the electric discharge power output of the simulated battery to carburetting negative pole and non-carburetting negative pole simulated battery is carried out the table 6 that the results are shown in of comparative determination.
Constant-current discharge at 18 DEG C of table 6 room temperatures, the performance of carburetting negative pole power output
From table 6: in unit are, average power when the non-carburetting negative discharge of average power ratio when carburetting negative discharge has promoted 4%.
At 18 DEG C of room temperatures, make the external constant-current discharge simulated battery of simulated battery temperature rise blank determination the results are shown in table 7 with the electric current of constant 0.322A.
18 DEG C of table 7 room temperatures are with 1.93A constant-current discharge, the simulated battery temperature rise table of comparisons
From table 7: the electric discharge of carburetting negative pole simulated battery electric discharge finishes final moment temperature, compared with it finishes final moment temperature with electric discharge of non-carburetting negative pole simulated battery electric discharge, the electric discharge temperature rise of the simulated battery of the non-carburetting negative pole of its contrast has reduced by 1 DEG C.
Embodiment 4:
With embodiment 1 difference be:
1. during carburetting negative pole spread coated paint is filled a prescription, the ratio 12wt% of doped with manganese oxide activated carbon powder; The variation ratio 3wt% of the graphite powder of doped with manganese oxide; The summation that these four kinds of materials are measured by weight percentage still forms 100wt%.
2. constant-current discharge form at 18 DEG C of room temperatures, replaces by constant-current discharge form at low temperature-35 DEG C; Wherein simulated battery is full of after electricity in room temperature, and the refrigerator and cooled that is put into subzero-35 DEG C was frozen after 8 hours, then in this refrigerator, discharged.
3. at 18 DEG C of room temperatures, with the electric discharge temperature rise of constant-current discharge blank determination simulated battery, replace in order to the charging temperature rise experiment of constant current charge, blank determination simulated battery.
4. increase self-discharge of battery test: at room temperature, with the electric current of 100mA to simulated battery constant current charge 10 hours, then simulated battery is put into temperature and is in the insulating box of 40 DEG C and place 7 days, after taking out under room temperature, with the electric current of 50mA to simulated battery constant-current discharge, discharge cut-off voltage is 1.0V, obtains the charged conservation rate of simulated battery.
5. increase battery cycle life test: at room temperature, the charge and discharge mode that " fills eight and put six " with the simulated battery of carburetting negative pole carries out the contrast test of cycle life, be under room temperature, with the electric current of 130mA, battery charged 1 hour, the carburetting negative pole simulated battery that makes to be charged to rated capacity 60% reaches the rated capacity of charging 80%, then with the electric current of 130mA to battery discharge 1 hour, the carburetting negative pole simulated battery that makes to be charged to rated capacity 80% reaches the rated capacity of electric discharge 60%, cycling; Every circulation 50 times, increases once the operation that discharges and recharges of " complete empty full up ", and this operation, by the whole emptying of electric weight (discharge cut-off voltage is 0.6V) of battery, is then full of, and then emptying.This kind is to battery cycle life test, and the usually said cycle life that charge and discharge mode was carried out with " fill eight and put six " is tested.All the other conditions and step are with embodiment 1.
At low temperature-35 DEG C, with constant-current discharge form, the electric discharge power output of the simulated battery to carburetting negative pole and non-carburetting negative pole simulated battery is carried out the table 8 that the results are shown in of comparative determination.
Constant-current discharge at table 8 low temperature-35 DEG C, the performance of carburetting negative pole power output
From table 8: at low temperature-35 DEG C, in unit are, average power when the non-carburetting negative discharge of average power ratio when carburetting negative discharge has promoted 6%.
At 18 DEG C of room temperatures, with the electric current of constant 1.16A to simulated battery constant current charge; Simulated battery temperature rise blank determination the results are shown in table 9.
18 DEG C of table 9 room temperatures are with 1.16A constant current charge, the simulated battery temperature rise table of comparisons
From table 9: the putting to fill of carburetting negative pole simulated battery electric discharge finished final moment temperature, and compared with it finishes final moment temperature with charging of non-carburetting negative pole simulated battery charging, its charging temperature rise than the simulated battery of the non-carburetting negative pole of contrast has reduced by 6 DEG C.
At 40 DEG C, battery, accelerate self discharge test result and list in table 10.
At table 1040 DEG C, accelerate self discharge, the charged conservation rate table of comparisons of simulated battery
From table 10: accelerate self discharge at 40 DEG C and show, carburetting negative pole simulated battery has reduced nine percentage points than the self discharge of non-carburetting negative pole simulated battery.
At 18 DEG C of room temperatures, the contrast test blank determination that carries out cycle life with the charge and discharge mode of " fill eight and put six " the results are shown in table 11.
At 18 DEG C of table 11 room temperatures, the simulated battery capacity attenuation rate table of comparisons
From table 11: under room temperature, carry out the contrast test of cycle life with the charge and discharge mode of " fill eight and put six ", the capacity attenuation rate that carburetting negative pole simulated battery and the circulation of non-carburetting negative pole simulated battery are 400 times is more approaching.
Claims (1)
1. a method for metal hydride-nickel cell bring to power, its manufacturing step, process conditions and bring to power method are as follows:
The preparation of the first step, doped with manganese oxide in-situ reaction reagent:
Taking chemical pure potassium permanganate and distilled water as raw material, at 20 DEG C, be mixed with potassium permanganate saturated aqueous solution for subsequent use; Buy the sodium ascorbate powder of commercially available food additive grade, be mixed with the 20wt% aqueous solution for subsequent use with distilled water, this sodium ascorbate meets GB16313-1996 standard;
The preparation of second step, doped with manganese oxide graphite powder raw material:
Add the ratio of 100 milliliters of 20wt% ascorbic acid sodium water solutions with 2 gram of 600 object graphite powder, the two is put in beaker, then this beaker is put into supersonic cleaning machine together with wine material, disperse to obtain for 2 minutes suspension-turbid liquid, shifting this suspension-turbid liquid filters to glass funnel, be filtered to without filtrate and flow out afterwards, rapidly potassium permanganate saturated aqueous solution sprayed into material surface in glass funnel, make the graphite powder that contains sodium ascorbate by this liquor potassic permanganate drip washing, show redness, stop this liquor potassic permanganate drip washing operation until flow out glass funnel leacheate; Then use again the reactant in the reverse drip washing glass funnel of 20wt% ascorbic acid sodium water solution, disappear and be transformed into colourless until glass funnel shows red filtrate, stop the operation of the reactant in ascorbic acid sodium water solution drip washing glass funnel, then the reactant in glass funnel is put in baking oven in 85 DEG C and dries 12 hours, obtain doped with manganese oxide graphite powder raw material;
The preparation of the 3rd step, doped with manganese oxide active carbon raw material:
Adopt and second step---doped with manganese oxide graphite powder raw material is prepared essentially identical step, condition and method, unique different be by 600 object graphite powders in second step, with specific surface index be 190m
2/ g, order number are that 400 object active carbon powders are replaced, and obtain equally doped with manganese oxide active carbon raw material;
The carburetting negative pole preparation of the 4th step, bring to power:
The nickel foam commodity of selecting commercially available nickel-hydrogen power battery current collector to use, are that 1.0mm nickel foam collector is depressed into 0.8mm in advance by original thickness, then by carburetting negative pole blade coating on it, this carburetting negative pole spread coated paint formula is:
The AB5 type hydrogen storage alloy powder fixed proportion that 275 order ± 25 orders and manufacturer's marked capacity are 285mAh/g is 80wt%; Solid content is that the polytetrafluoro emulsion fixed proportion of 40wt% is 5wt%; The variation ratio 11.5wt%-13.5wt% of doped with manganese oxide activated carbon powder; The variation ratio 1.5wt%-3.5wt% of the graphite powder of doped with manganese oxide; The summation that these four kinds of materials are measured by weight percentage forms 100wt%;
According to this formula, these four kinds of mixing of materials are even, construct carburetting negative pole spread coated paint, 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 0.134g/cm
2the carburetting negative plate blank material of index;
The 5th step, structure promote the method for metal hydride-nickel cell power:
Carburetting negative pole blank material is cut into bar shaped, simulated experiment battery container is used the housing of nickel-hydrogen cell AA type cylindrical battery in affixed merchandise and upper cover, sealing ring, be subject to this and use shell dimension restriction, carburetting negative plate blank material negative pole blank material is cut out and is of a size of 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 welding the clear powder of lug width same size, after clear powder by impulse spot welder lug for, according to AA cylinder nickel-hydrogen cell welding requirements firm welding, so far, the carburetting negative pole of acquisition bring to power;
Select commercially available nickel-hydrogen electrokinetic cell sintrered nickel anode, this sintrered nickel anode is wet method manufacture, is 30mAh/cm2 containing cobalt type, index; It is identical with negative pole that positive plate is cut out size, to in the middle of and negative pole anodal with lug bar shaped, be separated by with the sulfonated membranes in nickel-hydrogen cell barrier film commodity, after alignment, on battery winder, reel, after completing, coiling puts into housing, add 2.4 milliliters of electrolyte, this density of electrolyte is 1.31g/cm3, and this electrolyte solute consists of 70wt% potassium hydroxide, 28wt% NaOH and 2wt% lithium hydroxide, and three kinds of solute summations meet 100wt%; Water is the solvent of this electrolyte; Electrolyte is injected into after the housing with battery core, relend after encapsulating, encapsulate with AA cylinder nickel-hydrogen cell sealed in unit the nude simulated battery numbering obtaining under different condition, the operation of the metal hydride-nickel cell bring to power that so far, contains carburetting negative pole completes.
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| Publication number | Priority date | Publication date | Assignee | Title |
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| US5682592A (en) * | 1996-07-16 | 1997-10-28 | Korea Institute Of Science And Technology | Fabrication method for paste-type metal hydride electrode |
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| JP5182789B2 (en) * | 2007-05-28 | 2013-04-17 | 国立大学法人福井大学 | Hydrogen storage alloy-containing sheet, method for producing the same, and nickel metal hydride battery |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5682592A (en) * | 1996-07-16 | 1997-10-28 | Korea Institute Of Science And Technology | Fabrication method for paste-type metal hydride electrode |
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| JP特开2008-293915A 2008.12.04 |
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