CN1007855B - Metal-hydrogen alkaline accumulator - Google Patents

Metal-hydrogen alkaline accumulator

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Publication number
CN1007855B
CN1007855B CN85103500A CN85103500A CN1007855B CN 1007855 B CN1007855 B CN 1007855B CN 85103500 A CN85103500 A CN 85103500A CN 85103500 A CN85103500 A CN 85103500A CN 1007855 B CN1007855 B CN 1007855B
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China
Prior art keywords
hydrogen
negative pole
battery
pressure
metal
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CN85103500A
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CN85103500A (en
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山野大
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Sanyo Electric Co Ltd
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Sanyo Electric Co Ltd
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Priority to CN85103500A priority Critical patent/CN1007855B/en
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Publication of CN1007855B publication Critical patent/CN1007855B/en
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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
    • 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
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P70/00—Climate change mitigation technologies in the production process for final industrial or consumer products
    • Y02P70/50—Manufacturing or production processes characterised by the final manufactured product

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Abstract

The present invention relates to a metal-hydrogen alkaline accumulator with a positive electrode containing metal oxide, a negative pole containing hydrogen absorption alloy, and a partition body submerged in an electrolyte. The positive electrode, the negative pole and the partition body are accommodated in a sealed battery casing, and the casing has a means for keeping the internal pressure of the accumulator at a range of higher than the hydrogen absorption balance pressure of the negative pole but lower than 20 kg/cm<2>.

Description

Metal-hydrogen alkaline accumulator
The background of invention
FIELD OF THE INVENTION
The invention relates to storage battery, more particularly, is about comprising negative pole with hydrogen adsorbing alloy and the metal-hydrogen alkaline accumulator with positive pole of metal oxide.
Prior art
Used in the past storage battery has excide battery and nickel-cadmium cell,, and in recent years, owing to may produce than the light and capacious battery of these batteries, so the metal-hydrogen battery just has been subjected to gazing at.In the metal-hydrogen battery, have nickel hydroxide etc. metal oxide positive pole and can be the negative pole of absorption of reversible hydrogen ground and the hydrogen adsorbing alloy of emitting, this suction hydrogen electrode that has the metal hydride of hydrogen adsorbing alloy, usually, as the clear 58-46827 of patent disclosure number advise, employing will be inhaled the hydrogen metal dust and be made porous body with the conducting material powder sintering, then this porous body is made the method for electrode, perhaps as the clear 53-103541 of patent disclosure number propose, adopt with binding agent and interosculate and make the method for inhaling hydrogen electrode inhaling hydrogen metal dust and conducting material powder.
The suction hydrogen electrode that makes like this is because the pole plate capacity is decided by the uptake of active material hydrogen, so the uptake of hydrogen is The more the better, this uptake of inhaling the hydrogen of hydrogen electrode has the characteristic that depends on temperature and pressure consumingly, usually, when temperature raise, its pressure that absorbs hydrogen also will increase., some is used for the alloy of the absorption hydrogen of negative pole, even when low temperature, if pressure is not high, can not absorb hydrogen fully, when making battery using such hydrogen adsorbing alloy to make negative pole yet, if the battery that is constituted is opening, owing to can not get enough pressure, so negative pole can not absorb hydrogen, also have, even hermetic type absorbs hydrogen in order to make negative pole, must improve the pressure of inside battery certainly, and like this, be breakneck as the battery of general use.
Also have, the hydrogen adsorbing alloy that is used for above-mentioned battery is when alkaline electrolyte repeats to discharge and recharge, because absorption and releasing hydrogen gas and reexpansion and contraction, make the distortion of alloy grid, carry out micronizing, the micronizing of this metal dust comes off metal dust and causes capacity and descend, and mechanical strength of electrodes and conductivity also can significantly descend simultaneously, and the electric property that wants to keep chronically it is very difficult.
The general introduction of invention
The objective of the invention is to provide metal-hydrogen alkaline accumulator, and the negative pole of the suction hydrogen electrode of this battery can absorb the hydrogen of q.s, and stable capacity of negative plates is arranged.
Another object of the present invention is to suppress that the hydrogen adsorbing alloy that produces is micronized comes off owing to repeating to discharge and recharge, thereby suppress the deterioration of battery capacity and the decline of mechanical strength of electrodes and conductivity, be provided at the long-term metal-hydrogen alkaline accumulator of keeping high power capacity in the cycle that discharges and recharges.
Another object of the present invention is that a kind of metal-hydrogen alkaline accumulator will be provided, this storage battery can by make the hydrogen adsorbing alloy negative pole near keep minimal alkaline electrolyte, determine electrolyte content from the balance of battery life and flash-over characteristic, and suppress the micronizing of hydrogen adsorbing alloy.
Further purpose of the present invention is will be by the concentration of control electrolyte, so that big capacity and durable metal-hydrogen alkaline accumulator to be provided.
Another purpose of the present invention is that a kind of metal-hydrogen alkaline accumulator will be provided, this storage battery is by allowing hydrogen-absorbing alloy electrode heat release successfully, makes it also can absorb hydrogen fully when charging latter stage or high temperature start, keep and roughly the same battery capacity during in the room temperature start.
Metal-hydrogen alkaline accumulator of the present invention has the positive pole of metal oxide, the negative pole of hydrogen adsorbing alloy, and the spacer body that is dipped in the alkaline electrolyte is arranged between above-mentioned positive pole and negative pole and hold the enclosed-type battery shell of above-mentioned positive pole, negative pole and spacer body, above-mentioned battery case has and the pressure of inside battery is remained on negative pole inhales and be lower than 20kg/cm more than the equilibrium pressure of hydrogen 2Scope in means.
The suction hydrogen electrode of negative pole is emitted hydrogen when hydrogen adsorbing alloy absorbs hydrogen, discharge when charging.Inhale kind different have nothing in common with each other of the hydrogen of hydrogen electrode according to hydrogen adsorbing alloy, but usually, no matter use any hydrogen adsorbing alloy, when pressure on every side increases, the hydrogen of inhaling hydrogen electrode just increases, when increasing to a certain pressure, when promptly reaching the suction hydrogen balance pressure of inhaling hydrogen electrode, almost no longer increase even continue the uptake of increase pressure, hydrogen.In addition, in metal-hydrogen alkaline accumulator, when pressure is higher than 20kg/cm 2The time, being kept at moving of the interior electrolyte of battery, the difficulty that can become reduces capacity of negative plates, when temperature is higher than 70 ℃, in high-temperature alkaline electrolyte, chemical reaction will take place in hydrogen adsorbing alloy, cause the variation of material, increased oneself discharging of negative pole simultaneously, preservation characteristics is degenerated.Therefore, with above-mentioned structure, can prevent that the voltage of inside battery is increased to the 20kg/cm that capacity of negative plates is reduced 2More than, the hydrogen adsorbing alloy that is used in negative pole simultaneously absorbs unchangeably and emits protium.
In preferred embodiment of the present invention, above-mentioned hydrogen adsorbing alloy is at the temperature below 70 ℃, 20kg/cm 2Can absorb hydrogen under the following pressure condition.The alloy that forms with other metal replacements of the 1st composition of handlebar lanthanum-nickel series, calcium-nickel series and Ti-Ni row or the 2nd composition for example.In this case, above-mentioned means preferably make negative pole inhale hydrogen balance press more than and be lower than 20kg/cm 2Scope in the valve of start.
Above-mentioned negative pole is by alkali resistance araldite (preferably constituting fibrous not sintering polyfurolresin in conjunction with net) and sticky agent (preferably polyethylene oxide) keeps hydrogen adsorbing alloy and formation.Also have, in preferred embodiment, above-mentioned positive pole and negative pole are that Jie is rolled into helical form and constitutes electrode body in spacer body, and the backrush of this helix electrode body formation pressure is 1.0～5.0kg/cm 2In addition as electrolyte, comparatively desirable with the potassium hydroxide aqueous solution of 15% weight～35% weight, and every 1AH that its amount can the negative pole theoretical capacity is a standard with 0.50～2.10ml.In other embodiments of the invention, battery case is metal, the negative pole that is positioned at the electrode body most peripheral directly or the inboard by sebaceous heat conductivity material and battery case join.
The schematic illustration of accompanying drawing
Fig. 1 represents that working as the hydrogen adsorbing alloy that is used for negative pole is LaNi 5Or CaNi 5Or LaNi 4.6Al 0.4The time separately temperature and the relation of hydrogen absorption pressure;
Fig. 2 represents to adopt battery A, B, the C of 3 kinds of hydrogen adsorbing alloys shown in Figure 1 to be under the room temperature condition, the result when keeping the internal pressure of each battery to measure capacity of negative plates, be respectively a), b), c);
Fig. 3 is 7 kinds of cyclophysis figure of nickel-hydrogen alkaline accumulator of nominal capacity 1.5AH;
Fig. 4 represents that the backrush of electrode constitutes the relation of the cycle lie of pressure and battery;
Fig. 5 represents the internal pressure of nickel-hydrogen alkaline accumulator and the relation of discharge capacity of the cell;
The comparison diagram that discharges and recharges cyclophysis of nickel-hydrogen alkaline battery when Fig. 6 is the situation of adding sticky agent in inhaling hydrogen electrode and the situation that does not add sticky agent;
What Fig. 7 and Fig. 8 represented to change various batteries behind the electrolyte content respectively discharges and recharges cyclophysis and 5 hours charge-discharge characteristics thereof;
Fig. 9 and Figure 10 represent to change between the resting period of battery behind the concentration of electrolyte relation with capacity of negative plates respectively, and the relation with discharge capacity of discharging and recharging of battery;
Figure 11 and Figure 12 are the sectional view according to battery structure of the present invention.
Being described in detail of preferred embodiment
Be illustrated with regard to preferred embodiment of the present invention hereinafter with reference to accompanying drawing.
Embodiment 1
Make negative pole in order to hydrogen adsorbing alloy, metal oxide is made anodal representative battery, and promptly nickel-hydrogen cell explains.
LaNi with hydrogen-absorbing ability 5Mechanically micronizing is at this LaNi 5In the powder, with for LaNi 5The ratio of powder weight 1～5%, adding just can be with the powder of the polytetrafluoroethylene (PTFE) of its particle fibrillatable and plastic deformation with very little shear strength, mixed equably with mixer, make polytetrafluoroethylene fibreization simultaneously, divide then and get this material with 1ton/cm 2The exert pressure moulding, cause diameter 30mm, the suction hydrogen electrode of thick 2mm.
With the suction hydrogen electrode that makes and theoretical capacity is that the sintered nickel positive electrode of 500mAH combines, and injects alkaline electrolyte, makes the nickel-hydrogen alkaline accumulator A of hermetic type.Moreover, in the battery A of present embodiment, for the pressure that makes inside battery can not be increased to 20kg/cm 2More than, in battery case, be provided with at 15kg/cm 2Pressure the time start safety valve (with reference to Figure 11).Also have, with CaNi 5Replace above-mentioned LaNi 5, other programs are then identical with A and make same battery B, similarly, and with LaNi 4.6Al 0.4Replace LaNi 5Other programs are then constant, thereby make same battery C.
The negative pole that Fig. 1 is illustrated in above-mentioned battery A to C has used LaNi respectively 5, CaNi 5And LaNi 4.6Al 0.4The time temperature and the relation of inhaling hydrogen pressure, when the temperature below 70 ℃, the suction hydrogen pressure of various situations is all less than 20kg/cm 2Also having, in Fig. 2, respectively with a) to c) expression battery A to C at room temperature keeps the internal pressure of each battery and measures the result of capacity of negative plates, and above-mentioned safety valve is set in 15kg/cm do dynamic pressure 2Battery A, B, C have respectively with an A, B, the shown cell internal pressure of C and capacity of negative plates.
Can know from Fig. 1 and Fig. 2 and to know that as long as pressure is more than the equilibrium pressure of hydrogen adsorbing alloy, capacity of negative plates just can obtain enough capacity, but at 20kg/cm 2The time, capacity will reduce.Like this, be increased to 20kg/cm at cell internal pressure 2When above, why capacity of negative plates reduces, be because after the cell internal pressure increase, electrolyte is distributed produce the cause of significant uneven homogenize, particularly in this metal-hydrogen battery, by water in addition negative electrodeization absorb hydrogen, and this of negative pole to inhale H-H reaction be exothermic reaction, near the hydrone negative plate inside and the negative plate is reduced.At this moment, in the battery with the low pressure start, because interior pressure lowers, electrolyte can successfully be shifted to the reaction of charging of negative pole peripheral part from positive pole or spacer body, is increased to 20kg/cm but work as inner pressure of battery 2When above, remain on the moving of electrolyte that constitutes the position in the battery difficulty just takes place, thereby make the charging reaction be difficult to carry out.Also have, this battery is when overcharge, and resistance increases, and causes discharge failure even causes that discharging and recharging of later cycle is bad because gas is put aside, and that yes is bad for this.Therefore, in order to obtain sufficient capacity of negative plates, cell internal pressure is being remained on 20kg/cm 2In the time of following, being used for that the hydrogen adsorbing alloy of negative pole is also essential can be at 20kg/cm 2Absorb under the following pressure and emit protium.
The hydrogen of hydrogen adsorbing alloy is subjected to the influence of temperature and pressure consumingly, when constituting enclosed-type battery, as described above, must be pressure limit at 20kg/cm 2Below, as for temperature, when in the temperature more than 70 ℃, following problem will take place:
(1) usually, chemical reaction takes place in hydrogen adsorbing alloy in high-temperature alkaline electrolyte, cause that material changes, and the absorption of protium, the reversible reaction of emitting can not be kept, along with the process in cycle, capacity reduces gradually.
(2) anodal and oneself discharging of suction hydrogen electrode increases, and preservation characteristics degenerates.Particularly, in high temperature, just promoted oneself discharging of it because the discharge (emitting protium) of hydrogen adsorbing alloy is the endothermic reaction.
(3) owing to the creep phenomenon of alkaline electrolyte, easily leakage takes place.Therefore, be difficult to sealing, and must have vacuum-packed special tectonic with Ka Shimifa.
(4) increase, metal-hydrogen alkaline accumulator is produced the bad influence that charge efficiency descends in positive pole, for example nickel utmost point, oxygen reaction of formation, make negative pole so will be used in the hydrogen adsorbing alloy that can absorb and emit hydrogen below 70 ℃.
Can know that from above thing the hydrogen adsorbing alloy of the negative pole that is used for metal-hydrogen alkaline accumulator must be at the temperature below 70 ℃, 20kg/cm 2Following pressure can absorb and emit the material of hydrogen down.In fact, when constituting storage battery, the serviceability temperature of matching battery, from above-mentioned hydrogen adsorbing alloy suitably is chosen in that temperature and 20kg/cm 2Alloy that following pressure can absorb and emit hydrogen down just because at 70 ℃, 20kg/cm 2Following pressure can absorb and emit the alloy of hydrogen down, usually, low along with temperature, the hydrogen absorption pressure also can descend, so this battery can use in the broad range below 70 ℃.
Like this, because the suction hydrogen electrode of negative pole can absorb and emit the hydrogen of q.s, so can reach metal-hydrogen alkaline accumulator with safe capacity of negative plates.
Embodiment 2
The mixture that will contain hydrogen storage alloy powder is bonded in the suction hydrogen electrode that the two sides of collector body forms, by the spacer body made by nylon and discharge capacity is that the general sintered nickel positive electrode of 1.5AH combines, backrush formation shown in the following table pushes back volume, most peripheral is fixed with belt, make helix electrode body, behind this helix electrode body insertion battery case, inject electrolyte and also seal, just obtaining nominal capacity is nickel-hydrogen alkaline battery D, E, F, G, H, I, the J of 1.5AH.
Table 1
Battery D E F G H I J
Backrush constitutes 0.5 1.0 2.0 3.0 4.0 5.0 6.0
Press (kg/cm 2)
Fig. 3 is the cyclophysis figure of above-mentioned battery D to J, after in 10 hours, doing nominal capacity 150% charging with the rate electric current, final voltage is set at 1.0V fully discharges with the periodic condition that 5 hour rate currents discharge, the initial capacity of battery E to I is 100.Fig. 4 represents that discharge capacity reaches cycle of 60% of initial capacity of battery E to I and the backrush of electrode body constitutes the relation of pressing.Can understand the battery that backrush constitutes the high initial capacity of pressing minimum battery D from this figure, its cycle deterioration is very remarkable, also has, and the backrush of electrode body constitutes presses maximum battery J, its initial capacity step-down.For this, the initial capacity height of battery E to I and the cycle deterioration is few.In order to infer its reason, be over the back when battery dismantle when the cycle, the negative pole distortion of battery D is the most remarkable, has only 0.5kg/cm though the backrush of battery D constitutes pressure 2So low, and the electrolyte maintenance dose of electrode body is many, cell reaction carries out sleekly and makes the initial capacity height, but carrying out along with the cycle of discharging and recharging, during the hydrogen adsorbing alloy micronizing of negative pole, force down because the backrush of electrode body constitutes, make micronizing hydrogen adsorbing alloy come off and accelerated the decline of capacity.On the other hand, the backrush of electrode body formation is pressed and is 6kg/cm 2The highest such battery J, because constituting, its backrush presses height, electrolyte can not be impregnated in the electrode body carefully, make the electrolyte maintenance dose of electrode body few, thus the reaction table area of electrode be restricted, simultaneously because the generation of hydrogen makes charge efficiency decline and owing to the savings of gas makes internal resistance increase etc., cell reaction is subjected to serious obstruction, make capacity just low since the initial stage, and along with the carrying out in the cycle of discharging and recharging, charging is not enough more and cycle lie is shortened.Also have, the backrush formation of electrode body is pressed in 1.0～5.0kg/cm 2Battery E～I in the scope, even the hydrogen adsorbing alloy generation micronizing of negative pole, but since the backrush of electrode body constitute the pressure handle micronizing hydrogen adsorbing alloy remain on the electrode body, suppress it and come off, so the deterioration of capacity of negative plates and mechanical strength of electrodes and conductivity lowly be subjected to inhibition, simultaneously, because it is can guarantee that at one electrode body has the numerical value of enough electrolyte maintenance doses that backrush constitute to be pressed, and cell reaction is carried out smoothly, thereby keep high power capacity in can be between long-term.
In the above-described embodiment, be 1.0～5.0kg/cm owing to having backrush formation pressure 2Helix electrode body, so when repeating to discharge and recharge, even the hydrogen adsorbing alloy generation micronizing of negative pole, above-mentioned backrush constitute press make micronizing hydrogen adsorbing alloy remain on and suppress it on the electrode body and come off, simultaneously, can make electrode body keep enough electrolyte contents, battery performance is kept in long-time for the battery reaction.
Embodiment 3
Form the suction hydrogen electrode of long 4cm, wide 5cm, thick 1mm with the method identical with the foregoing description 2, with sintered nickel positive electrode with 2000mAH capacity, with spacer body between negative pole and positive pole and constitute electrode body, this electrode body is inserted in the battery case, inject alkaline electrolyte then, seal, make the hermetic type nickel-hydrogen cell.
Fig. 5 demonstration places 20 ℃, 40 ℃ and 60 ℃ of each temperature with above-mentioned battery, and cell internal pressure is changed and the charge/discharge capacity of negative pole when discharging and recharging, under each temperature, along with increasing of cell internal pressure, capacity of negative plates also increases, but has arrived certain pressure, when promptly inhaling the suction hydrogen balance pressure of hydrogen electrode, even continue to increase cell internal pressure, it is certain that capacity of negative plates but keeps basically, arrived pressure greater than 20kg/cm 2The time, capacity then reduces.
Secondly, above-mentioned battery respectively by having 3kg/cm 2, 15kg/cm 2And 22kg/cm 2The seal closure of safety valve seal, discharge and recharge to measure capacity of negative plates at 40 ℃.The result is as shown in the table.
Table 2
Valve is made the dynamic pressure capacity of negative plates
3kg/cm 2600mAH
15kg/cm 21100mAH
22kg/cm 2900mAH
Can know that from table 2 valve is 15kg/cm do dynamic pressure 2The capacity of negative plates of battery be 3kg/cm than valve do dynamic pressure 2And 22kg/cm 2The capacity of negative plates of battery all bigger.Here, valve is 3kg/cm do dynamic pressure 2The low reason of capacity of negative plates of battery be because internal pressure is pressed the early gate breakdown bringing up to the suction hydrogen balance of inhaling hydrogen electrode so that can not obtain sufficient pressure.In addition, valve is 22kg/cm do dynamic pressure 2The capacity of negative plates of battery low, its reason is described as embodiment 1, when cell internal pressure surpasses 20kg/cm 2The time, the distribution of electrolyte produces tangible unequal phenomenon.For this, valve is 15kg/cm do dynamic pressure 2Battery, arrive to inhale before hydrogen electrode absorbs the equilibrium pressure of hydrogen, valve does not have start, and cell internal pressure does not rise to and making the charging reaction be difficult to the 20kg/cm that carries out 2More than, can absorb fully on the pressure of hydrogen so can remain on the suction hydrogen electrode to cell internal pressure, thereby capacity of negative plates is increased.Also having, is to inhale more than the hydrogen electrode suction hydrogen balance pressure in order to make the suction hydrogen electrode absorb hydrogen, valve fully do dynamic pressure, and 20kg/cm 2In the following scope, do dynamic pressure by setting valve in this scope and just can increase capacity of negative plates effectively.
Also have, can know from Fig. 5 and to find out, the different temperature that discharge and recharge according to battery, cell internal pressure is different when reaching heap(ed) capacity, it is consistent that this pressure is pressed in the hydrogen absorption equilibrium of the suction hydrogen electrode of each temperature, and along with temperature rises and increases, therefore, the valve start has been set just according to service condition at all, but because the upper limit that valve is made the setting range of dynamic pressure is the same, lower limit then increases with the temperature rising, so the valve in the time of should being pressed on above-mentioned the highest anticipation serviceability temperature to the valve start is done in the dynamic pressure scope, like this, even use, also can obtain maximum capacity of negative plates in lower temperature.
Embodiment 4
As described in top embodiment 2, in order to suppress, adopted the electrode that hydrogen storage alloy powder is being kept with alkali-proof araldite and sticky agent as inhaling hydrogen electrode owing to the coming off of the micro mist that repeats to discharge and recharge the hydrogen adsorbing alloy that generates.Can use polytetrafluoroethylene (PTFE) as binding agent, hexafluoropropylene (HFP)/tetrafluoroethylene (TFE) copolymer (FEP), the fluoride resin of tetrafluoroethene and hexafluoropropylene etc., chloroprene-based, the resin of nitrile rubber system and ethylene rubber system, polystyrene, nylon is polyamide etc., also have, as sticky agent, can use hydrogenation polypropylene fibre (HPC), polyethylene oxide (PEO), unsaturated polyester resin, methylcellulose (MC), carbon gathers methylcellulose (CMC), polyvinyl alcohol (PVA), polyvinylpyrrolidone (polyvinyl pyrrolidone), polyacrylic acid, polypropylene amino, bridge formation starch, PAA, acetylenic acid sodium, sodium metasilicate etc.
About specific embodiment just like following narration.The LaNi that will have hydrogen-absorbing ability 5Mechanically micronizing is at this LaNi 5Powder in, in order to very little shear strength just can be easily the polytetrafluoroethylene (PTFE) powder of its particle fibrillatable and plastic deformation as binding agent, with for LaNi 5 Weight 5% and be sticky agent, LaNi with polyethylene oxide (PEO) 51% weight add LaNi respectively 5Powder in, mixed equably and make polytetrafluoroethylene fibreization.Mixture after this fibrillatable prolonged be press-fitted cloth and compress, just obtain inhaling hydrogen electrode on the two sides of collector body.
Then, be that the general sintered nickel positive electrode of 2.0AH combines with this electrode and discharge capacity, inject alkaline electrolyte, just obtaining nominal capacity is the nickel-hydrogen cell K of 2.0AH.To also have, in order comparing, in inhaling hydrogen electrode, not add the polyethylene oxide (PEO) as sticky agent, then the practice with the foregoing description is the same for all the other, just can make comparison battery L simultaneously.
Fig. 6 be battery K and L discharge and recharge cyclophysis figure, after 150% charging of 10 hour rate currents, final voltage is set at 1.0V, discharge with 5 hour rate currents, result when discharging and recharging under such periodic condition is 100 to show with the initial capacity of each battery.Can understand from Fig. 6, when battery K compared with comparison battery L, the deterioration of battery that takes place along with the process of discharge cycle was suppressed in Min., thereby better performances.After periodic test, when the battery dismounting is observed, relatively the distortion of the suction hydrogen electrode of battery L is remarkable, and this explanation is owing to repeat to discharge and recharge when making hydrogen adsorbing alloy generation micronizing, the binding agent of depending fiberized polytetrafluoroethylene alone be can not suppress micronizing fully the coming off of hydrogen adsorbing alloy.For this, and the distortion of the suction hydrogen electrode of battery K is suppressed in lesser extent.This is because battery K as above-mentioned, except the binding agent part also is added with sticky agent, by these materials, firmly remains on hydrogen storage alloy powder on the electrode.
Embodiment 5
Embodiment 5 is in order to suppress the micronizing of hydrogen adsorbing alloy, and the research of carrying out that is different from the various embodiments described above.Promptly be by this research, known the electrolyte content that suitably adds inside battery, very effective to suppressing above-mentioned micronizing.Below will narrate specific embodiment.
The same with the above embodiments 2, the suction hydrogen electrode of having made is combined with the general sintered nickel positive electrode with 2.0AH discharge capacity, just obtain the nickel-hydrogen cell that nominal capacity is 2.0AH.Moreover the theoretical capacity of negative pole is adjusted to anodal 3 times.As for electrolyte, then use the potassium hydroxide aqueous solution of about 15～35% weight (, describing in detail more below) about this scope, liquid measure is as shown in table 3, injects electrolyte with the every 1AH of the theoretical capacity of negative pole with the ratio of 0.40～2.30ml and studies.
Table 3
Battery M N O P Q R S
Liquid measure 0.40 0.50 0.90 1.30 1.70 2.10 2.30
（ml/AH）
Fig. 7 shows that various batteries are 100 o'clock the cyclophysis that discharges and recharges with the initial capacity of battery S.Also have, periodic condition is with 10 hour rate currents charging 150%, and with discharge in 5 hours, and final voltage was 1.0V.Can know that from Fig. 7 the minimum battery M of liquid measure is owing to the inhomogeneous initial performance that causes of the distribution of electrolyte is bad.Here it is, inhales being hindered of hydrogen electrode with discharging and recharging significant reaction, the internal resistance of battery increased, thereby encouraged undercharge, makes shorter battery life.On the other hand, in the maximum battery S of liquid measure, along with the carrying out in cycle micronizing coming off of hydrogen adsorbing alloy be subjected to facilitation, also make the lost of life of battery.Moreover, because increasing of interior pressure also can make liquid measure significantly reduce.For this, N～R it seems with regard to battery, has that to reach for 200 cycles above its life-span, and this is because above-mentioned unfavorable factor has obtained the cause that relaxes.
Fig. 8 shows 5 hours charge-discharge characteristics.The deterioration that is appreciated that its flash-over characteristic of battery M of liquid measure deficiency from figure is significant.Also have, then do not have much difference basically as for battery N～S.Just be only limited to flash-over characteristic and it seems, how liquid measure does not bring any obstacle.
Know from the above fact, can be by keeping suitable electrolyte content using the performance of inhaling the hydrogen electrode battery to improve.That is exactly, and the alkaline electrolysis liquid measure is limited in the scope of every 1AH negative pole theoretical capacity with 0.50～2.10ml, just can improve the flash-over characteristic and the charge characteristic of battery.
In the above embodiments 5, be 15～35% weight as for the ideal concentration of the potassium hydroxide aqueous solution of electrolyte, it be the reasons are as follows:
That is exactly, between the resting period of the battery that shows different electrolytes concentration with Fig. 9 of the relation of capacity of negative plates in, when concentration of electrolyte had surpassed 40% weight, along with the growth between resting period, the top layer part of hydrogen adsorbing alloy was corroded, and becomes La(OH) 3And Ni(OH) 2, hydrogen-absorbing ability is reduced significantly, the result has caused the low of battery capacity.Because this causes owing to segregation or hydroxide epithelium, so even repeatedly discharge and recharge, also can not return original hydrogen adsorbing alloy composition (LaNi 5), promptly capacity can not restore.Therefore, change for fear of the composition of hydrogen adsorbing alloy, concentration of electrolyte must be below 35% weight.
Secondly, in Figure 10 of the charge volume of the battery that shows different electrolytes concentration and discharge capacity relation, when concentration of electrolyte was lower than 15% weight, charge efficiency just reduced significantly.Also have, the growing amount of hydrogen increases, and inner pressure of battery rises, and these all are undesirable phenomenons.Therefore, in order to improve charge efficiency, concentration of electrolyte must be more than 15% weight.Moreover, though the hydrogen adsorbing alloy of above-mentioned example is to adopt LaNi 5, but for CaNi 5Wait other alloys also to obtain same result (diagram is not come out) with hydrogen-absorbing ability.
Embodiment 6
The suction hydrogen of hydrogen adsorbing alloy is exothermic reaction, and its hydrogen-absorbing ability will significantly descend during high temperature.In order to handle this situation, preferably between the negative pole and metal battery shell of hydrogen adsorbing alloy, load conduction material, make hydrogen-absorbing alloy electrode heat release successfully.For example, use to inhale hydrogen electrode and general nickel positive pole and spacer body and form electrode body, at this moment, should be installed in negative pole the outermost wall of electrode body, simultaneously electrode body is closely contacted with battery case, so that the heat that takes place at negative pole passes to shell as soon as possible.Figure 11 shows the battery with this structure.
As shown in figure 11, the electrode body that negative pole of being made by hydrogen adsorbing alloy 1 and positive electrode collector 2 and positive active material 3 and spacer body 4 constitute is incorporated in the battery case 5, and as shown in figure 11, negative pole is installed in the inboard of battery case 5 or the outermost wall of electrode body.Such formation is successfully carried out the heat release of negative pole, thereby reduces the temperature of negative pole, and charging is normally carried out, and its result particularly when the high temperature start, can increase battery capacity.Moreover, in Figure 11, numeral 6 expression positive terminals, numeral 7 is the expression safety valve then.This safety valve is no more than 20kg/cm in order to make battery pressure 2, for example, be designed at 15kg/cm 2Pressure under start (with reference to previous embodiment 3).
As for other embodiment, Figure 12 is presented between the both positive and negative polarity 1,3 and gets involved spacer body, and the battery that is rolled into spiral helicine electrode body is arranged.It is 1.0～5.0kg/cm that the backrush of wound electrode body constitutes pressure 2, suitable electrolyte is the potassium hydroxide aqueous solution of 15～35% weight, its amount for the every 1AH of theoretical capacity of negative pole 1 with 0.50～2.10ml.As shown in figure 12, the inner face of metal battery shell, by sebaceous conduction material 8 be in the outermost negative pole 1 of electrode body and contact.
More than, be illustrated with regard to preferred embodiment of the present invention, but the present invention is not limited to cited embodiment, in the scope of in patent of the present invention requires, being put down in writing, can do all changes.

Claims (8)

1, a kind of metal-hydrogen alkaline accumulator comprises:
Anodal ... have metal oxide;
Negative pole ... have hydrogen adsorbing alloy;
Spacer body ... Jie is dipped in the alkaline electrolyte between said positive pole and negative pole;
The enclosed-type battery shell ... accommodate said positive pole, negative pole and spacer body, have pressure maintenance device, cell internal pressure is maintained be higher than negative pole inhale hydrogen equilibrium pressure and less than 20kg/cm 2Scope in;
It is characterized in that: said hydrogen adsorbing alloy is at temperature below 70 ℃ and 20kg/cm 2Can absorb the material of hydrogen under the condition of following pressure;
Said pressure maintenance device is less than 20kg/cm inhale the hydrogen balance pressure greater than negative pole 2Scope in the valve of start;
The gauge of said electrolyte is decided to be the negative pole theoretical capacity 0.50-2.10ml for every 1AH, and its concentration is 15-35Wt%.
2, the described metal-hydrogen alkaline accumulator of claim 1 is characterized in that, said negative pole is hydrogen adsorbing alloy is kept and to be constituted by alkali resistance araldite and sticky agent.
3, the described metal-hydrogen alkaline accumulator of claim 2 is characterized in that, said alkali resistance araldite is to constitute fibrous not sintering polyfurolresin in conjunction with net.
4, the described metal-hydrogen alkaline accumulator of claim 2 is characterized in that, said sticky agent is a polyethylene oxide.
5, the described metal-hydrogen alkaline accumulator of claim 1 is characterized in that, said positive pole and negative pole are rolled into helical form, forms electrode body together with the spacer body between them, and the backrush of this wound electrode body constitutes pressure and is 1.0-5.0kg/cm 2
6, the described metal-hydrogen alkaline accumulator of claim 1 is characterized in that, said electrolyte is potassium hydroxide aqueous solution.
7, the described metal-hydrogen alkaline accumulator of claim 1 is characterized in that, said battery case is metal, and the inner face of this battery case is contacting the said negative pole that is in the electrode body most peripheral.
8, the described metal-hydrogen alkaline accumulator of claim 1 is characterized in that, said battery case is metal, and the inner face of this battery case and exist fatty heat conductivity material between the said negative pole of electrode body most peripheral.
CN85103500A 1985-05-03 1985-05-03 Metal-hydrogen alkaline accumulator Expired CN1007855B (en)

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CN85103500A CN1007855B (en) 1985-05-03 1985-05-03 Metal-hydrogen alkaline accumulator

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Application Number Priority Date Filing Date Title
CN85103500A CN1007855B (en) 1985-05-03 1985-05-03 Metal-hydrogen alkaline accumulator

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CN85103500A CN85103500A (en) 1986-10-29
CN1007855B true CN1007855B (en) 1990-05-02

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JP3615699B2 (en) * 2000-09-26 2005-02-02 Ｎｅｃトーキン栃木株式会社 Sealed battery and method for manufacturing the same
JP6112822B2 (en) * 2012-10-30 2017-04-12 Fdk株式会社 Nickel metal hydride secondary battery

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