CN1243386C - Alkaline accumulator - Google Patents
Alkaline accumulator Download PDFInfo
- Publication number
- CN1243386C CN1243386C CNB001354272A CN00135427A CN1243386C CN 1243386 C CN1243386 C CN 1243386C CN B001354272 A CNB001354272 A CN B001354272A CN 00135427 A CN00135427 A CN 00135427A CN 1243386 C CN1243386 C CN 1243386C
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- CN
- China
- Prior art keywords
- battery
- negative
- area
- negative pole
- positive
- Prior art date
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- Expired - Fee Related
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- 238000003860 storage Methods 0.000 claims description 5
- 125000006850 spacer group Chemical group 0.000 claims description 3
- 239000013543 active substance Substances 0.000 abstract 1
- 239000007789 gas Substances 0.000 description 18
- 238000000034 method Methods 0.000 description 18
- 238000006243 chemical reaction Methods 0.000 description 13
- 238000005215 recombination Methods 0.000 description 10
- 230000006798 recombination Effects 0.000 description 9
- 239000011149 active material Substances 0.000 description 8
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 7
- 229910052739 hydrogen Inorganic materials 0.000 description 7
- 239000001257 hydrogen Substances 0.000 description 7
- 150000001875 compounds Chemical class 0.000 description 6
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 5
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 5
- 238000013461 design Methods 0.000 description 5
- 229910052760 oxygen Inorganic materials 0.000 description 5
- 239000001301 oxygen Substances 0.000 description 5
- 239000000956 alloy Substances 0.000 description 4
- 229910045601 alloy Inorganic materials 0.000 description 4
- 239000012071 phase Substances 0.000 description 4
- 229910017704 MH-Ni Inorganic materials 0.000 description 3
- 229910017739 MH—Ni Inorganic materials 0.000 description 3
- 239000000654 additive Substances 0.000 description 3
- 230000004888 barrier function Effects 0.000 description 3
- 238000009826 distribution Methods 0.000 description 3
- 239000008151 electrolyte solution Substances 0.000 description 3
- 239000007788 liquid Substances 0.000 description 3
- 229910052759 nickel Inorganic materials 0.000 description 3
- 238000003825 pressing Methods 0.000 description 3
- WMFOQBRAJBCJND-UHFFFAOYSA-M Lithium hydroxide Chemical compound [Li+].[OH-] WMFOQBRAJBCJND-UHFFFAOYSA-M 0.000 description 2
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 2
- 230000000996 additive effect Effects 0.000 description 2
- 238000013459 approach Methods 0.000 description 2
- 239000011230 binding agent Substances 0.000 description 2
- 238000006555 catalytic reaction Methods 0.000 description 2
- 239000006258 conductive agent Substances 0.000 description 2
- 125000004122 cyclic group Chemical group 0.000 description 2
- 239000007772 electrode material Substances 0.000 description 2
- 239000003792 electrolyte Substances 0.000 description 2
- 239000006260 foam Substances 0.000 description 2
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 2
- 239000007791 liquid phase Substances 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 2
- 239000002002 slurry Substances 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- 239000007790 solid phase Substances 0.000 description 2
- 206010011906 Death Diseases 0.000 description 1
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 239000001996 bearing alloy Substances 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 238000003795 desorption Methods 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- 238000007599 discharging Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 230000005518 electrochemistry Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 238000001125 extrusion Methods 0.000 description 1
- 150000002431 hydrogen Chemical class 0.000 description 1
- 230000002209 hydrophobic effect Effects 0.000 description 1
- 229910000480 nickel oxide Inorganic materials 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- GNRSAWUEBMWBQH-UHFFFAOYSA-N oxonickel Chemical compound [Ni]=O GNRSAWUEBMWBQH-UHFFFAOYSA-N 0.000 description 1
- 229910052763 palladium Inorganic materials 0.000 description 1
- 230000002093 peripheral effect Effects 0.000 description 1
- 230000005501 phase interface Effects 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- 239000010970 precious metal Substances 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 230000000630 rising effect Effects 0.000 description 1
- 239000004065 semiconductor Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 238000003466 welding Methods 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
- 239000011701 zinc Substances 0.000 description 1
Images
Classifications
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
Landscapes
- Secondary Cells (AREA)
- Battery Electrode And Active Subsutance (AREA)
Abstract
The present invention relates to an alkaline accumulator which mainly comprises a positive pole, a negative pole, a separator and an accumulator casing. A negative pole area is larger than a positive pole area. The upper terminal of the negative pole is above the upper terminal of the positive pole, or a naked area on the upper terminal of the negative pole is larger than a naked area on the upper terminal of the positive pole. A relationship of the areas of the negative pole and the positive pole is that S<positive> is equal to S<negative>, wherein the a is more than 0 and is less than 1.0. The alkaline accumulator can effectively reduce accumulator internal pressure, enhance the utilization rate of an electrode active substance and reduce the short circuit incidence rate of the alkaline accumulator.
Description
Technical field
The present invention relates to a kind of alkaline battery.
Background technology
In the size of pressing and whether can to reach balance be the key factor that influences the alkaline battery life-span, pressing the design of MH-Ni battery, generally is just to limit principle, both the capacity of negative plates surplus, the capacity of entire cell is determined that by positive electrode capacity desirable MH-Ni battery charge and discharge process is followed following reaction
Anodal:
(1)
Overall reaction:
(3)
Negative pole:
(4)
Overall reaction:
(6)
But in the charge and discharge process of reality, have a reaction and reaction (1) competition on the positive pole, promptly OH-is in the oxidation of positive pole
(7)
Also there are a reaction and reaction (5) competition, the i.e. absorption of H atom, combination, desorption process simultaneously on the negative pole
Battery just becomes the complex system that contains the solid, liquid, gas three phase boundary like this, and different being reflected on the different interfaces carried out.Because the design of battery is just to limit principle, reaction (7) generally takes place when over-charging of battery, all might take place in whole charging process and react (8), and oxygen, hydrogen partial pressure form inner pressure of battery together.
But oxygen can be by being diffused in the negative terminal surface reduction, and hydrogen can be by diffusing into negative pole alloy inside.
The recombination process of oxygen:
The recombination process of hydrogen:
At O
2Recombination process in, chemically composited accounting for more than 70%, electrochemistry is compound to be no more than 30%, so the degree of carrying out of reaction (9) and reaction (11) is the key factor of the big or small and interior pressure of decision inner pressure of battery with circulation change trend.
Generally speaking, gas compound by 2 approach: one is diffused into compound on electrode (solid, liquid, gas) three phase boundary by barrier film, electrode surface liquid film layer, and it two enters air chamber and carry out compound.Last approach so diffusion rate is little, makes gas recombination speed also little because the resistance to mass tranfer of gas in liquid phase is very big, presses effect limited in reducing.There is experiment to show that the speed constant of gas in gas phase is 10 of its speed constant in liquid phase
7Doubly, this that is to say that gas directly is diffused into negative pole, directly carries out compoundly on the solid phase interface of negative pole, just can accelerate gas recombination speed, has both just improved the chemical reaction velocity of equation (9) and (11), makes the big reduction of inner pressure of battery.In the battery structure of routine, the method for pressing in solving generally has:
(1) reduces O
2Growing amount.The charge volume of limit battery (CN1166007) or in positive pole, add some additives for example to improve O
2Deposition potential, gas production is reduced.
(2) improve the ability of negative pole composite oxygen and the suction hydrogen and the hydrogen storage property of hydrogen-storage alloy.For example anticathode carries out that hydrophobic is handled or makes alloy surface form the catalytic center of rich nickel dam by precious metal (WO95/27315) such as interpolation palladium, platinum or by processing.
(3) enlarge air chamber, space (USP5744259) the space to provide gas temporarily store of pole piece upper end to battery cap both had been provided, make inside battery keep lower interior pressure.
But these methods do not break away from anodal and negative pole has scope of the same area, often or cause cell active materials not make full use of, and then have influence on discharge capacity, perhaps improve the battery cost greatly or make electrode manufacturing process process complications, and adopt the said method inner pressure of battery still higher, in the charge and discharge cycles process, the safety valve overfrequency is opened, cause electrolyte solution loss, make the battery hermetization variation, cycle life descends.
Summary of the invention
The purpose of this invention is to provide a kind of interior pressure that can reduce battery effectively, improve the electrode active material utilance, reduce the alkaline battery of battery short circuit incidence.
For achieving the above object, the present invention mainly comprises positive pole, negative pole, spacer, battery container, and the negative pole area is greater than anodal area, and the area that the negative pole upper end exposes is greater than the exposed area in anodal upper end, and the pass of both positive and negative polarity area is S
Just=aS
Negative, 0.6＜a＜1.0 wherein.
Each periphery of storage battery positive and negative electrode of the present invention superimposed arrangement of all staggering.
Adopt structural design of the present invention, the area of negative pole is higher than anodal upper end greater than the area and the negative pole upper end of positive pole, make that gas is unnecessary to be transmitted with electrolyte mutually by barrier film, and can directly be diffused into negative pole, being higher than anodal solid phase surface at negative pole directly carries out compound, enough gas recombination spaces so both were provided, increased the particle number of gas phase compound (catalysis) reaction again greatly, thereby improved the gas recombination ability, quickened gas recombination speed, inner pressure of battery is reduced greatly, avoided causing the overfrequency of safety valve to open because interior pressure is excessive in the conventional structure, cause the phenomenon of electrolyte solution loss, improved the cycle life of battery.
Adopt the present invention, because positive and negative electrode size difference, the negative pole area is greater than anodal area, the positive and negative electrode placement that overlaps mutually, be the electrode perimeter formula structure that staggers, just can avoid zone overlapped that peripheral two Da Yi around lug Welding Area and the electrode bring out short circuit, so not only reduced the probability of battery in the living short circuit of initial loading timing, and also reduced battery and in charge and discharge cycles, penetrated the probability of the micro-short circuit that barrier film causes, originally studies have shown that and adopt battery structure of the present invention can eliminate short circuit phenomenon substantially because of electrode expansion mutual extrusion causes burr.Table four is comparisons of short circuit probability in initial assembling of battery and the cyclic process.The present invention's short circuit probability that circulates in 200 processes reduces to 1 ‰ than conventional structure by 2%.
Adopt the size form design of electrode of the present invention, because change has taken place in electrode length and width ratio, especially anodal, because of its active material belongs to semi-conducting material, so just improved electric current along the degree that pole plate reduces gradually from top to bottom, made the electric current distribution on the pole plate more be tending towards evenly having improved charge efficiency, electrode active material is fully used, and has improved the utilance of active material.Table three is to the present invention and traditional structure storage battery, at normal temperature battery capacity contrast test, relatively active material utilization.Use battery of the present invention, because improved the degree that electric current reduces gradually along pole plate from top to bottom, make the electric current distribution on the pole plate more be tending towards even, improved and discharged and recharged dear money, improved the battery high-rate charge-discharge capability, greatly reduce the speed of battery capacity decay, the utilance of active material has improved about 8% than the battery of conventional structure.
Because the electric current distribution on the electrode is more even, the charge efficiency height, not only available buffer gas precipitation rate but also can accelerate gas recombination speed reduced hydrogen, partial pressure of oxygen simultaneously, thereby reached the purpose that reduces inner pressure of battery.The battery of conventional structure, Yin Qinei presses higher, cause electrolyte solution loss bigger, battery charges and discharge only 300 cycles with 1C, because of capacity attenuation makes end-of-life, improves battery structure and adopt, battery the circulation 180 times after capacity still in rising trend, pressure still is stabilized in about 5 atmospheric pressure in when cycle life proceeds to 300 times, and this cycle life that just might guarantee battery reaches practical requirement greater than 500 times.And utilize form design of the present invention can improve the utilance of active material, reduce the generation of battery short circuit in initial assembling and the cyclic process, improved rate of finished products.
The present invention will be described in detail below in conjunction with the drawings and specific embodiments.
Description of drawings
Fig. 1 is a kind of both positive and negative polarity closed state figure of a kind of alkaline battery of the present invention
Fig. 2 is the another kind of both positive and negative polarity closed state figure of a kind of alkaline battery of the present invention
Fig. 3 reveals both positive and negative polarity closed state figure for a kind of anodal right side of a kind of alkaline battery of the present invention is right
Fig. 4 reveals both positive and negative polarity closed state figure down for a kind of anodal lower end of a kind of alkaline battery of the present invention
Embodiment
Nickel oxide electrode just very during the invention process, negative pole can be hydrogen-occlussion alloy electrode, every electrode, the zinc electrode or the ferroelectric utmost point, existing is that the basis is elaborated with ni-mh (MH-Ni) battery:
Embodiment one: the anodal making: be with Ni (OH)
2, conductive agent, additive, binding agent form slurry by a certain percentage, be coated on the nickel foam collector, with oven dry, roll and make electrode.
Negative pole is made: be that hydrogen bearing alloy, conductive agent, additive, binding agent are formed slurry by a certain percentage, be coated on the nickel foam collector, to dry, to roll and make electrode.
The making of battery: be that the utmost point in the above-mentioned made positive/negative plate is wrapped up with spacer, the positive and negative electrode placement that overlaps mutually, can adopt the form of Fig. 1, Fig. 2, Fig. 3 or Fig. 4 during the superimposed placement of anodal and negative pole, anodal 1 each limit of Fig. 1 does not exceed negative pole 2 each limit, only reveal on the positive pole ear 3, negative lug 4 in negative lug 4 in negative pole 2 upper right corner.Fig. 2 and Fig. 1 difference only reveal on the neck shape for anodal 1 top is; Fig. 3 exposes on anodal right side; Fig. 4 exposes anodal bottom, is assembled into battery together with pole, safety valve, seal cover, housing etc. then, injects the electrolyte of d=1.28g/ml KOH+10g LiOH/L, and the back surveys its performance and the conventional structure battery compares.Inner pressure ratio when table 1 is different structure battery difference cycle-index value, a value is the coefficient value of both positive and negative polarity area relationship.Structure A is anodal and negative pole homalographic conventional structure, has bigger air chamber.Structure B is anodal and negative pole homalographic conventional structure, has enough catalytic reaction particle numbers.Structure C had both had enough big air chamber for the structure of negative pole area of the present invention greater than anodal area, had abundant reaction substance again and counted.
Embodiment two: the making of both positive and negative polarity and battery is identical with embodiment 1, according to shown in the table 2, when b value one regularly, get different c values, be assembled into battery and circulate after 100 times inner pressure ratio.Wherein the b value is the described both positive and negative polarity the right and left of claims length factor value.
Adopt structure of the present invention, negative terminal surface is long-pending greater than anodal surface area, and the negative pole upper end is higher than anodal upper end, inner pressure of battery is reduced more than 60%, and show that the coefficient value of both positive and negative polarity area and the right and left length relation is big more, and internal drop is low not obvious more.The a value is more little as can be known by table 1, table 2, drops is remarkable more in the battery charging and discharging circulation, but the volume of battery specific energy can be more little, the a value is big more, though help the raising of battery volumetric specific energy, but it is not obvious that inner pressure of battery descends, and the y value is little to the inner pressure of battery influence, and it mainly influences volume of battery specific energy and active material and utilance.
Table one
| Cycle-index (inferior) | Structure A | Structure B | Structure C | |||
| a＝1 | a＝1 | a＝0.6 | a＝0.7 | a＝0.8 | a＝0.9 | |
| Interior press (psi) | Interior press (psi) | Interior press (psi) | Interior press (psi) | Interior press (psi) | Interior press (psi) | |
| 100 | 70 | 70 | 22 | 28 | 37 | 52 |
| 200 | 130 | 130 | 30 | 43 | 55 | 89 |
| 300 | 200 | 200 | 35 | 60 | 96 | 138 |
Table two
| The b value | The c value | Press in corresponding (psi) |
| 0.60 | 0.68 | 26 |
| 0.60 | 0.80 | 37 |
| 0.60 | 0.93 | 55 |
| 0.80 | 0.68 | 28 |
| 0.80 | 0.80 | 37 |
| 0.80 | 0.93 | 52 |
| 1.00 | 0.68 | 28 |
| 1.00 | 0.80 | 38 |
| 1.00 | 0.93 | 55 |
Table three
| Battery structure | Initial assembling short circuit probability | Short circuit probability 200 times the time circulates |
| The | 2％ | 2％ |
| Seven invention battery structures | / | 1‰ |
Table four
| Battery structure | Battery capacity (Ah) | Active material utilization |
| The conventional batteries structure | 21 | 85％ |
| Battery structure of the present invention | 22 | 93％ |
Claims (2)
1, a kind of alkaline battery mainly comprises positive pole, negative pole, spacer, battery container, it is characterized in that the negative pole area greater than anodal area, the area that the exposed area in negative pole upper end exposes greater than anodal upper end, and the pass of both positive and negative polarity area is S
Just=aS
Negative, 0.6＜a＜1.0 wherein.
2, storage battery according to claim 1 is characterized in that the superimposed arrangement of all staggering of each periphery of positive and negative electrode.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB001354272A CN1243386C (en) | 2000-12-22 | 2000-12-22 | Alkaline accumulator |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB001354272A CN1243386C (en) | 2000-12-22 | 2000-12-22 | Alkaline accumulator |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1360355A CN1360355A (en) | 2002-07-24 |
| CN1243386C true CN1243386C (en) | 2006-02-22 |
Family
ID=4596700
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CNB001354272A Expired - Fee Related CN1243386C (en) | 2000-12-22 | 2000-12-22 | Alkaline accumulator |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN1243386C (en) |
-
2000
- 2000-12-22 CN CNB001354272A patent/CN1243386C/en not_active Expired - Fee Related
Also Published As
| Publication number | Publication date |
|---|---|
| CN1360355A (en) | 2002-07-24 |
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