CN101593834A - The nickel positive pole that a kind of zinc-nickel cell is used - Google Patents
The nickel positive pole that a kind of zinc-nickel cell is used Download PDFInfo
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- CN101593834A CN101593834A CNA2009100994251A CN200910099425A CN101593834A CN 101593834 A CN101593834 A CN 101593834A CN A2009100994251 A CNA2009100994251 A CN A2009100994251A CN 200910099425 A CN200910099425 A CN 200910099425A CN 101593834 A CN101593834 A CN 101593834A
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- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
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Abstract
The nickel positive pole that a kind of zinc-nickel cell is used, it mainly includes one and adopts nickel foam substrate that active material is filled wherein positive plate with dry method or wet processing, and the part that the positive plate edge is not covered by material is formed with a function admirable, can reduce the electron motion distance and can reduce the flow collection band of impedance; Wherein side at positive plate is welded the shockproof band that connects of conduction of extending out with nickel foil and pole plate; Add the nickel anode additive have the mixture by the oxide of metal or hydroxide and rare earth oxide to constitute in the described positive plate; But characteristics such as described nickel is just having simple, with low cost, the safe and reliable long term storage of technology, has extended cycle life, good heavy current.
Description
Technical field
What the present invention relates to is the nickel positive pole that a kind of zinc-nickel cell is used, and especially a kind of adding has the zinc-nickel cell positive pole of additive.
Background technology
At present, because increasingly serious environmental protection situation forces national governments to put into effect the environmental regulation of increasingly stringent, and international oil price is high and the prosperity of Internet and electronic product, bring new quick growth to Battery Market, such as hybrid vehicle, electric automobile, chargeable energy storage system, uninterruptible power system of data center or the like, along with hybrid vehicle (HEV), plug type hybrid vehicle (PHEV), and the prosperity and development of electric automobile (EV), press on the market a kind of can satisfy following for high power, high energy storage, high reliability and fail safe, the battery product of environmental protection more.And topmost battery technology of past, lead-acid battery and nickel-cadmium cell (NiCd), can't catch up with the demand of market development, they do not possess environmental protection requirement yet simultaneously, though lithium ion battery is succeedd in portable electric appts, but because underpower, cost an arm and a leg, security hidden trouble, can't satisfy the requirement of large scale system.Emerging zinc-nickel cell technology can satisfy above all requirements; Zinc-nickel cell is the rechargeable battery of power height, energy foot (up to 4 times of lead-acid battery), non-environmental-pollution (not leaded, do not contain cadmium, not mercurous), high reliability and fail safe good (nonflammable), with low cost, long service life.
Zinc-nickel cell comprises battery container, electrode group and electrolyte, and described electrode group and electrolyte are accommodated in the battery case, described electrode group comprises the nickel positive pole, zinc negative pole and barrier film, barrier film are between nickel positive pole and zinc negative pole, and described zinc negative pole comprises negative material and is loaded with the negative current collector of this material.
In zinc-nickel cell, on greatly the research of part all concentrates on preventing of zinc negative pole dendrite and is out of shape, less to the research of positive pole.General way is, the nickel positive pole in ni-mh or the nickel-cadmium cell indiscriminately imitated fully be used for zinc-nickel cell.Battery is made as a whole, anodal performance and is tended to have influence on the quality of entire cell in fact.
In original technology, anodal wet method or the dry process of adopting of zinc-nickel cell, positive active material is coated with the surface that invests matrix or wherein makes flexible foils formula electrode as matrix with nickel foil, nickel foam, Punching steel strip, with one or more lugs as anodal channelizing line (being commonly called as lug).Because electric current must arrive each position of pole plate via lug, the electron motion approach is very long, impedance is bigger, so active material utilization is not high, charge efficiency is lower, the battery ohmic internal resistance big, the battery heating is serious, can not realize heavy-current discharge, and the product range of application is restricted.
In original technology, the zinc-nickel cell positive pole is in order to improve charge efficiency, improve the oxygen oxygen evolution potential, to extend depth of discharge, and the general practice is to add Co or cobalt/cobalt oxide, hydroxide.Metallic cobalt is insoluble to alkali in theory, but inevitable material top layer is oxidized in actual production and the use, and the oxide of cobalt and other cobalts, hydroxide all have the characteristic that is dissolved in alkali lye without exception in fact.The cobalt that is dissolved in the alkali will cause the micro cell evolving hydrogen reaction with zincode, and battery will have bigger potential safety hazard, can't reach the product application requirements.Therefore, in zinc-nickel cell, the additive of cobalt will be avoided.
Patent content
The objective of the invention is to overcome the deficiency that prior art exists, but and simple, with low cost, the safe and reliable long term storage of a kind of technology be provided, have extended cycle life, nickel positive pole that the zinc-nickel cell of good heavy current is used.
The objective of the invention is to finish by following technical solution, it mainly includes one and adopts nickel foam substrate that active material is filled wherein positive plate with dry method or wet processing, and the part that the positive plate edge is not covered by material is formed with a function admirable, can reduce the electron motion distance and can reduce the flow collection band of impedance; Wherein side at positive plate is welded the shockproof band that connects of conduction of extending out with nickel foil and pole plate; Add the nickel anode additive have the mixture by the oxide of metal or hydroxide and rare earth oxide to constitute in the described positive plate.
Described nickel anode additive is a magnesium oxide, magnesium hydroxide, zirconia, zirconium hydroxide, calcium oxide, calcium hydroxide, strontium oxide strontia, at least a in the strontium hydroxide, and the mixture of at least a rare earth oxide in the yittrium oxide (Y2O3), ytterbium oxide (Yb2O3), luteium oxide (Lu2O3).
The invention belongs to a kind of improvement to prior art, but it have simple, with low cost, the safe and reliable long term storage of technology, have extended cycle life, characteristics such as good heavy current.
Description of drawings
Fig. 1 is a structural representation of the present invention.
Fig. 2 of the present inventionly has/non-additive battery circulation comparison diagram.
Embodiment
The present invention will be described in detail below in conjunction with accompanying drawing: as shown in Figure 1, positive plate adopts nickel foam substrate that active material is filled wherein with dry method or wet processing, the flow collection band 1 that the part that anodal edge 1 is not covered by material forms a function admirable has reduced the electron motion distance, reduce impedance, reach the high current charge-discharge job requirement.Weld the conduction of extending out in a wherein side of positive pole with nickel foil and pole plate and shockproof the connection be with 2, this will greatly improve battery anti-vibration resistance in use.Attached charge level 4 of positive plate and alkaline-resisting insulating tape 3 in addition shown in Fig. 1.
In the prior art, for improving nickel electrode charging oxygen evolution potential and depth of discharge, abandoning adding Co is additive, add calcium system as calcirm-fluoride, calcium oxide, calcium hydroxide and use instead, addition scope 0.2-5% adds rare earth luteium oxide, yittrium oxide simultaneously, addition scope 0.01-3%, add Zinc oxide additive such as zinc oxide, zinc hydroxide simultaneously, add scope 0.5-5%.Experiment showed, that by a series of these additives are can bigger raising positive active material gram volume about 4%, improve oxygen evolution potential, improve battery charge efficient, particularly especially remarkable under high-temperature condition.
This additive can improve the cycle life of nickel electrode, the decline that slows down capacity effectively.Use the zinc-nickel cell of this additive, the life-span obviously improves.
Oxide or hydroxide that described nickel anode additive is a kind of metal, comprising, but be not limited to, magnesium oxide, magnesium hydroxide, zirconia, zirconium hydroxide, calcium oxide, calcium hydroxide, strontium oxide strontia, at least a and a kind of rare earth oxide in the strontium hydroxide etc., comprising, but be not limited at least a mixture in yittrium oxide (Y2O3), ytterbium oxide (Yb2O3), the luteium oxide (Lu2O3).
We are at another discovery under study for action: in order to reach best effect, the additive in the described nickel positive pole must be the mixture of two kinds of materials, and a kind of is the oxide or the hydroxide of metal, and another kind is a rare earth oxide.
Nickel electrode makes charge efficiency not high owing to analysing oxygen in charging process, thereby add calcium compound and can improve separating out of overpotential for oxygen evolution inhibition oxygen, add cobalt can increase active material in discharge process conductivity and help the conversion reaction of active material, add utilance and discharge potential that cobalt and calcium can significantly improve active material simultaneously.But described before combining, cobalt compound is easy to be dissolved in the electrolyte solution in alkaline solution, and has influence on the zinc negative pole, makes the zinc negative pole be easy to liberation of hydrogen, thereby makes inner pressure of battery too high, causes battery leakage.Therefore, in zinc-nickel cell, the additive of cobalt will be avoided.
Nickel electrode makes charge efficiency not high owing to analysing oxygen in the high-temperature charging process, can improve separating out of overpotential for oxygen evolution inhibition oxygen thereby add rare earth compound, can significantly improve the active material high-temperature behavior.Select for use rare earth oxide yittrium oxide (Y2O3), ytterbium oxide (Yb2O3), luteium oxide (Lu2O3) as additive, study its influence, and interpolation Y2O3 is carried out high-temperature behavior with the battery that does not add rare earth addition make comparisons the nickel electrode high-temperature behavior.Experiment is found: rare earth addition can suppress separating out of oxygen in the nickel electrode charging process, improves high-temperature charging efficient; Reduce activity cycle simultaneously, reduce the battery manufacturing cost; In addition, the anodal high temperature active material specific capacity of adding Lu2O3 is the highest, and the anodal high-temperature charging that adds yittrium oxide is most effective, and cost is minimum, tool market potential.
The anodal battery that adds CaF2 and Ca (OH) 2 of the present invention has than height ratio capacity and higher Ni (OH) 2 utilances, because after adding the Ca compound of CaF2 and Ca (OH) 2 among β-Ni (OH) 2, anodal charging later stage overpotential for oxygen evolution significantly increases, thereby the charge efficiency of nickel electrode and the active material utilization of Ni (OH) 2 are improved greatly.
Add the refinement that the Ca compound can suppress crystal grain, with comparing of not adding, average grain size increases, and wherein to add the most obvious of Ca (OH) 2, calcium compound has promoted the transformation of growth fault, but the variation of total fault probability is little.Calcium compound has also changed because the microstrain that reversible transition causes, variation Ca (OH) 2 of contrast properties and microstructure parameters and the influence of CaF2 are the most remarkable, the influence of CaCo3 is less, this is relevant with the solubility of three kinds of compounds in alkali lye, and the meltage of three kinds of compounds in the KOH of 9ml electrolyte is respectively 0.0056g/l, 0.0132g/l, 0.0067g/l.
Adding Ca (OH) 2, Y2O3, Lu2O3, two yuan of Co or multi-element doping in the nickel positive pole simultaneously will greatly improve the charge efficiency of nickel electrode and suppress oxygen and separate out, improve Ni (OH) 2 material utilizations, reduce nickel electrode expansion shedding situation and take place, zinc-nickel cell stability is improved, as shown in Figure 2.
Another consideration of the present invention is, in order to improve the conductivity of nickel electrode, in zinc-nickel cell, we are by adding metal powder, and as nickel powder, or other conductive agent improves anodal electrical conductance.The material that is added not only requires can not have influence on the performance of negative pole, and the nickel powder that also requires simultaneously to be added has ultra-fine and homogeneous granules, high porosity, low-apparent-density and high specific area.High specific surface and porosity and special ultra-fine grain structure make it produce good conductive network in application, improve the utilance of active material greatly, further improve simultaneously the battery high rate during charging-discharging significantly, reduce the internal resistance of cell and improve battery life.Low apparent density also makes it in the use as the conductive agent of the secondary cell of any form specification or additive, uses less consumption and can obtain good effect simultaneously.
Instantiation: an example of specific implementation method is, will be selected from Cologne, the Henan trade mark and be 5# and cover and estimate ball nickel (OH)
2, be selected from the permanent auspicious Lu in Chengdu
2O
3, middle golden south of the Five Ridges Y
2O
3, be selected from Shanghai west Gansu Province CaF2, be selected from the T210 nickel powder, be selected from and three like rich 60%PTFE, be selected from Shanghai import packing AH-26PVA (bathe heat with H2O and be hybridly prepared into concentration 7% adhesive), these materials were by 63.8: 1: 0.2: 0.8: 6: 1.2: 27 are mixed with cream, be coated on then in the anodal matrix, through 90 ℃ of baking 1.5h, again through grinding forming.
With the earlier clear powder in lug position, put an antidetonation water conservancy diversion lead-out tablet again, clear powder and spot welding parts cover fully with alkaline-resisting insulating tape 3 two sides.Both positive and negative polarity, is loaded in the container of sealing through reeling by corresponding dimension and weight collocation.Through changing into 0.1C charging 13h, 0.2C is discharged to 1.4V, discharges and recharges through three times repeatedly again, makes the battery charge activation fill a part utilization to reach material.
SC battery key property such as following table by this explained hereafter:
| 0.2C discharge capacity | The 1C discharge capacity | The 5C discharge capacity | The 10C discharge capacity | The 20C discharge capacity | Exchange internal resistance |
| 2200mAh | 2150mAh | 1970mAh | 1855mAh | 1763mAh | 3.7 milliohm |
Claims (2)
1, the nickel positive pole used of a kind of zinc-nickel cell, it mainly includes one and adopts nickel foam substrate that active material is filled wherein positive plate with dry method or wet processing, and the part that the positive plate edge is not covered by material is formed with a function admirable, can reduce the electron motion distance and can reduce the flow collection band of impedance; Wherein side at positive plate is welded the shockproof band (2) that connects of conduction of extending out with nickel foil and pole plate; Add the nickel anode additive have the mixture by the oxide of metal or hydroxide and rare earth oxide to constitute in the described positive plate.
2, the nickel positive pole used of zinc-nickel cell according to claim 1, it is characterized in that described nickel anode additive is a magnesium oxide, magnesium hydroxide, zirconia, zirconium hydroxide, calcium oxide, calcium hydroxide, strontium oxide strontia, the mixture of at least a rare earth oxide at least a and yittrium oxide in the strontium hydroxide, ytterbium oxide, the luteium oxide.
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| Application Number | Priority Date | Filing Date | Title |
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| CNA2009100994251A CN101593834A (en) | 2009-06-15 | 2009-06-15 | The nickel positive pole that a kind of zinc-nickel cell is used |
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| CNA2009100994251A CN101593834A (en) | 2009-06-15 | 2009-06-15 | The nickel positive pole that a kind of zinc-nickel cell is used |
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| CN101593834A true CN101593834A (en) | 2009-12-02 |
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102263298A (en) * | 2011-06-22 | 2011-11-30 | 广东博特动力能源有限公司 | Nickel-zinc secondary battery and preparation method thereof |
| CN102263266A (en) * | 2011-06-22 | 2011-11-30 | 广东博特动力能源有限公司 | Cathode material for zinc-nickel secondary battery, cathode and preparation method for cathode |
| EP2472652A1 (en) * | 2010-12-31 | 2012-07-04 | Fuyuan Ma | Additive for nickel-zinc battery |
| CN102800869A (en) * | 2012-08-30 | 2012-11-28 | 上海锦众信息科技有限公司 | Anode preparing method of nickel based alkali secondary cell |
| CN103000861A (en) * | 2011-09-14 | 2013-03-27 | 比亚迪股份有限公司 | Anode of alkali-manganese battery and alkali-manganese battery |
-
2009
- 2009-06-15 CN CNA2009100994251A patent/CN101593834A/en active Pending
Cited By (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP2472652A1 (en) * | 2010-12-31 | 2012-07-04 | Fuyuan Ma | Additive for nickel-zinc battery |
| CN102544503A (en) * | 2010-12-31 | 2012-07-04 | 杭州新研动力能源有限公司 | Additive for nickel-zinc battery |
| CN102544503B (en) * | 2010-12-31 | 2015-04-15 | 杭州新研动力能源有限公司 | Additive for nickel-zinc battery |
| CN102263298A (en) * | 2011-06-22 | 2011-11-30 | 广东博特动力能源有限公司 | Nickel-zinc secondary battery and preparation method thereof |
| CN102263266A (en) * | 2011-06-22 | 2011-11-30 | 广东博特动力能源有限公司 | Cathode material for zinc-nickel secondary battery, cathode and preparation method for cathode |
| WO2012175000A1 (en) * | 2011-06-22 | 2012-12-27 | Guangdong Powerlink Energy Co., Ltd | Positive electrode material and positive electrode for nickel-zinc secondary battery and method for manufacturing positive electrode |
| CN102263298B (en) * | 2011-06-22 | 2014-09-24 | 广东博特动力能源有限公司 | Nickel-zinc secondary battery and preparation method thereof |
| US9356285B2 (en) | 2011-06-22 | 2016-05-31 | Guangdong Powerlink Energy Co., Ltd | Positive electrode material and positive electrode for nickel—zinc secondary battery and method for manufacturing positive electrode |
| US9614217B2 (en) | 2011-06-22 | 2017-04-04 | Guangdong Powerlink Energy Co., Ltd | Nickel-zinc secondary battery and method for preparing the same |
| CN103000861A (en) * | 2011-09-14 | 2013-03-27 | 比亚迪股份有限公司 | Anode of alkali-manganese battery and alkali-manganese battery |
| CN102800869A (en) * | 2012-08-30 | 2012-11-28 | 上海锦众信息科技有限公司 | Anode preparing method of nickel based alkali secondary cell |
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Effective date of registration: 20100609 Address after: 526060, B Industrial Park, Hin Gang 127 area, science and Technology Industrial Park, Duanzhou District, Zhaoqing, Guangdong Applicant after: Guangdong Powerlink Energy Co., Ltd. Address before: Hangzhou City, Zhejiang province 311501 Tonglu Economic Development Zone baiyunyuan Road No. 117 Applicant before: Hangzhou Fuchi Power Engergy Co., Ltd. |
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Application publication date: 20091202 |