CN1976114A - Charging control method for Ni-Cd accumulator - Google Patents

Charging control method for Ni-Cd accumulator Download PDF

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Publication number
CN1976114A
CN1976114A CNA2006101540534A CN200610154053A CN1976114A CN 1976114 A CN1976114 A CN 1976114A CN A2006101540534 A CNA2006101540534 A CN A2006101540534A CN 200610154053 A CN200610154053 A CN 200610154053A CN 1976114 A CN1976114 A CN 1976114A
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charging
cadmium
voltage
battery
cell
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CN100499249C (en
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江黒高志
阿部勲
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FUKUKAWA DENSHI Co Ltd
Furukawa Denshi Co Ltd
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FUKUKAWA DENSHI Co Ltd
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    • HELECTRICITY
    • H01ELECTRIC ELEMENTS
    • H01MPROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00Secondary cells; Manufacture thereof
    • H01M10/42Methods or arrangements for servicing or maintenance of secondary cells or secondary half-cells
    • H01M10/44Methods for charging or discharging
    • YGENERAL 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
    • Y02TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02EREDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/10Energy storage using batteries

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  • Engineering & Computer Science (AREA)
  • Manufacturing & Machinery (AREA)
  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Electrochemistry (AREA)
  • General Chemical & Material Sciences (AREA)
  • Battery Electrode And Active Subsutance (AREA)

Abstract

Provided a harging control method for simplifying the constitution of Ni-Cd accumulator, and on the other hand capable of detecting the chage rate of voltage of its part in the charging state and accumulator voltage. The method is charactered in that by adding indium and indium compound into the non-sintered cadmium cathode, and modulating the cooperating ratio of sodium hydroxide and potassium hydroxide as electrolyte ingredients of alkalescence electrolyte, the Ni-Cd accumulator is formed, and charging voltage action of the accumulator during the charging period are measured.

Description

The charge control method of cadmium-nickel storage cell
Technical field
The present invention relates to the charge control method of cadmium-nickel storage cell.
Background technology
In the past, as cadmium-nickel storage cell, known have a following storage battery, promptly, general as anodal sintered type or the non-sintering nickel positive pole of using, use sintered type or non-sintered type cadmium cathode as negative pole, use NaOH, KOH or LiOH as the electrolyte constituent as its alkaline electrolyte, and the electrolyte that their appropriate combination are modulated.This cell batteries combined as Battery pack separately or with a plurality of cell batteries be used for various uses.
During at every turn with the cell batteries of these cadmium-nickel storage cells or Battery pack quick charge or supper-fast charging, adopt 4 following modes as its charge control method.
(1) detects the voltage detecting mode that increases the rising of the battery tension that causes by the polarization of charging latter stage
(2) detect the battery tension that the heating of GAS ABSORPTION reaction enclosed cell, that follow charging latter stage causes decline-Δ V mode
(3) detect the dT/dt mode of the variation of the battery temp that the heating of GAS ABSORPTION reaction enclosed cell, that follow charging latter stage causes
(4) the calculation charge/discharge electricity amount is inferred the charged state (remaining capacity) of battery and the mode of the control of charging
The charge control method of described (1) to (3), it all is the method for having utilized the rapid variation of the cell voltage in charging latter stage and battery temperature, but under the situation of the Battery pack that constitutes by a plurality of cell batteries, in during the repetition charge and discharge cycles, exist the cell voltage between the cell batteries and the deviation of battery capacity to enlarge gradually, part cell batteries is overcharged, and causes the tendency that reduces of the cycle life of Battery pack.
With the charge control method of described (4),, therefore can not use separately owing to can not revise the error that the computing by the electric weight revenue and expenditure causes.
So, in order to prevent overcharging of cell batteries, expectation be not to detect the cell voltage in charging latter stage or the mode of variation of temperature, but the detection mode of the cell voltage under the part charged state (PSOC) in charging.But, under the situation of cadmium-nickel storage cell, because it is more stable that the cell voltage in the charging changes, so cell voltage under its part charged state, promptly, the polarization of charging movement is smooth, does not have to rise in charging, therefore detects its charging of charging the polarization movement with the voltage detection mode and controls difficulty.
On the other hand, the charging control mode that replaces above-mentioned (1)~(4), open to disclose in the clear 63-313474 communique the spy and be adapted to pass through voltage detecting charge hermetic type cadmium-nickel storage cell and its charging method of method of control of the charging of part charged state polarization movement.Promptly, the spy opens the invention that clear 63-313474 communique is put down in writing, the cadmium-nickel storage cell of the thickener formula that does not change into is disclosed, promptly, with non-sintered type cadmium cathode plate as its claim 1 is put down in writing, make the volume of the conductive material of removing core body be defined as 29.5% the thickener formula cadmium cathode plate that does not change into, with (イ) of its claim 1 specific nickel hydroxide positive plate combine, and with (ロ) that satisfy its claim 1 specific theoretical capacity be condition, thus, appearing at thickener formula cadmium cathode does not have the increase of the distinctive polarization of hydrogen generation under the state that reaches before overcharging, and, can realize the charging method of this storage battery of quick charge without detriment to seal ground by using it for charging control.If the increase of this distinctive polarization is described briefly, be exactly at first to make to participate in overcharging exoelectrical reaction more than or equal to the less cadmium hydroxide of polarization once, the charging reaction with once all not have to participate in overcharging the bigger cadmium hydroxide of polarization exoelectrical reaction, that charging is reacted and be present in the active material of thickener (non-sintering) formula cadmium cathode plate.Thus, in charging, the former charging that the reaction resistance in the time of will charging at first selectively is less, afterwards, the latter's that the reaction resistance during charging is bigger charging begins.Then, in the stage in the gap that the former charging finishes, concentrating of electric current being taken place, and the increase (crest voltage) of the distinctive polarization that hydrogen produces occurs not having.By detecting this crest voltage, and detect the charging and the control of charging by arriving at thickener (non-sintering) formula cadmium cathode plate under the part charged state before the charging fully, just can be without detriment to the realization quick charge of seal ground.
The charging method of above-mentioned patent documentation 1, as the charge control method under the PSOC charged state is method preferably, but its cadmium-nickel storage cell since as described above its positive and negative pole plate create conditions and the specified conditions of theoretical capacity very strict, therefore can not easily and stablize well and make, and, existence must make the part of the active material of thickener formula cadmium cathode carry out once the reaction that discharges and recharges at least, can't realize the shortcomings such as simplification of formation process.
Summary of the invention
The object of the present invention is to provide the undesirable condition of eliminating the charge control method that charges latter stage, and can carry out comparing with above-mentioned patent documentation 1 disclosed storage battery, structure is obviously simple and can stablize the charge control method of the control of the charging polarization movement of the cadmium-nickel storage cell of manufacturing well.
A first aspect of the present invention, it is a kind of charge control method of cadmium-nickel storage cell, it is characterized in that, by in the non-sintered type cadmium cathode, adding indium or indium compound, and modulation is as the NaOH of the electrolyte constituent of alkaline electrolyte and the cooperation ratio of potassium hydroxide, constitute cadmium-nickel storage cell, and detect the charging voltage movement that changes under the part charged state of this storage battery in charging.
And then the invention is characterized in that on the basis aspect the 1st, the addition of indium or indium compound or their mixture is 0.01 weight %~2.00 weight % with respect to the cadmium active material.
And then the invention is characterized in that on the basis aspect the 1st, the electrolyte of this alkaline electrolyte is formed, and is potassium hydroxide 0~40 weight %, and NaOH 0~30 weight %, and electrolytical total amount is 50 weight %.
And then the invention is characterized in that on the basis aspect the 1st, the detection method of described charging voltage movement is battery voltage detection method or cell voltage rate of change detection method.
Cadmium-nickel storage cell of the present invention, in its non-sintered type cadmium cathode, indium or indium compound have been added, in therefore charging, that is, the charging voltage movement under the part charged state, promptly, cell voltage or voltage change ratio rise, be non-flat forms, therefore can be in the variation of this cell voltage of required location detection or voltage change ratio, and the control of charging.Thereby, can not occur stablizing finishing charging well with overcharging.Promptly, finish or step charge by charging, charging such as constant current/constant current charging mode switching control, for example, in the Battery pack that constitutes by a plurality of cell batteries, even if because the carrying out of charge and discharge cycles over a long time, aspect the charged state between each cell batteries because of the built-in distinction of cell batteries or Temperature Distribution etc. deviation appears, also because the control of can under the part charged state, charging, therefore can reduce the possibility that each cell batteries is subjected to the damage that causes by overcharging, thereby, can further improve life performance as Battery pack.Particularly, in sealed type battery, produce owing to can suppress gas, therefore more effective.
In addition, owing to obtain following effect, promptly, the position of the charging voltage movement in the above-mentioned charging, can the electrolyte ingredient by suitable adjustment alkaline electrolyte form it is changed, therefore can obtain the storage battery of required charging capacity with the detected value of battery voltage value of suitably setting or voltage change ratio.
On the other hand, cadmium-nickel storage cell of the present invention constitutes simply as described above, therefore is easy to make.
Description of drawings
Fig. 1 is the figure of movement of cell voltage of the battery of expression embodiments of the invention.
Fig. 2 is the figure of battery and the movement corresponding cell voltage of charging capacity of expression comparative example.
Fig. 3 is the figure of the movement of the cell voltage of expression embodiments of the invention 1 and 2 battery and voltage change ratio.
Fig. 4 is the figure of the movement of the cell voltage of battery of expression comparative example and voltage change ratio.
Fig. 5 is the figure of cycle life separately of the Battery pack of expression Battery pack of the present invention and comparative example.
Embodiment
The present invention is developed into according to following idea.
That is, contain the non-sintered type cadmium pole plate of indium, changing in the processing in potassium hydroxide aqueous solution, the cadmium that is subjected to the influence of indium is varied to the cadmium hydroxide of the bigger β type of particle diameter, and the cadmium hydroxide that is not subjected to the influence of indium is varied to the cadmium hydroxide of less β type.Owing to there is cadmium hydroxide like this with 2 kinds of particle diameters, therefore when charging because bigger potential change appears in the difference of overcharging.That is, the cadmium hydroxide of the β type less, that particle diameter is less that overcharges is recharged earlier, and the cadmium hydroxide of the β type bigger, that particle diameter is bigger that then overcharges is recharged.At this moment can think appearance potential classification on the charging potential curve.
On the other hand, in sodium hydrate aqueous solution, whether no matter indium arranged, all produce the cadmium hydroxide of the uniform γ type of particle diameter, thereby can not think potential change in occurring charging.
And find,, can at random change the position of appearance potential classification by potassium hydroxide and NaOH are mixed.
Below, be described in detail execution mode more specifically of the present invention.
The positive pole of cadmium-nickel storage cell of the present invention, can be in the past sintered type or the nickel hydroxide positive plate of non-sintered type.The non-sintered type cadmium cathode, can use following negative pole: with cadmium oxide or cadmium hydroxide as the non-sintered type cadmium cathode of active material or based on this active material, and the mixed with little amount cadmium metal forms therein the non-sintered type cadmium cathode of material as active material in, adding mixing indium or indium compound or their mixture with the scope of 0.01 weight %~2.00 weight % forms, as indium compound, can use indium oxide, indium hydroxide etc.The interpolation of indium can be micro-, but for the voltage movement being occurred significantly and control easily, with respect to the cadmium active material, 0.01 weight %~2.00 weight % preferably, that good especially is 0.04 weight %~1.00 weight %.Add too much and only can cause expensive and the minimizing cadmium active material.
Usually, with the non-sintered type cadmium cathode plate of the interpolation indium of the above-mentioned nickel positive electrode plate of required number and required number or its compound across dividing plate and stacked, and as the pole plate group with in its battery case of packing into, sneak into the alkaline electrolyte of ormal weight therein, add a cover, airtight, make cadmium-nickel storage cell.
Alkaline electrolyte is with as the NaOH and these 2 kinds of the KOH of electrolyte ingredient or appended 3 kinds of electrolyte of combining of LiOH therein, is dissolved in liquid in the water with debita spissitudo, and its whole weight % is preferably smaller or equal to 50 weight %.Usually, preferably based on KOH, and cooperated the electrolyte of NaOH therein.These various electrolytical use levels are that KOH is 0~40 weight %, and NaOH is 0~30 weight %, and LiOH is 0~10 weight %.
Can think that in the scope of the above-mentioned addition of NaOH, its addition is many more, the rising of the charging polarization movement of the part charged state that occurs owing to the interpolation of indium or indium compound, that is, the rising of voltage change ratio is slow more, that is, appear at the more side of charging capacity; Its addition is few more, and is just fast more,, appears at the less side of charging capacity that is.
Be under 0 the situation at the addition of KOH, the rising of voltage change ratio with in the past do not have difference substantially.On the other hand, be that the rising of voltage change ratio is too fast, and is impracticable usually under 0 the situation at the addition of NaOH.Though LiOH impact can not for the electrode movement, as well-known, be use in order to improve anodal utilance etc.
Like this, cadmium-nickel storage cell of the present invention, by in the non-sintered type cadmium cathode, adding indium or indium compound or their mixture, the charging polarization movement of part charged state can be used as the variation of cell voltage and shows, therefore can detect the variation of charging this cell voltage in the past in latter stage, and the modulation by electrolyte is formed can detect its charging polarization movement with battery voltage detection method that is predetermined or voltage change ratio detection method at the position of regulation.Its result, the danger that can prevent cadmium-nickel storage cell of the present invention to be damaged owing to overcharging, thus can obtain long-life storage battery.
And, in storage battery of the present invention, the Battery pack that constitutes by a plurality of cell batteries, in quick charge or supper-fast charging, can detect above-mentioned charging polarization movement with cell voltage detection method or voltage change ratio detection method, prevent the deterioration of overcharging and being caused significantly by a part of cell batteries that brings because of the deviation of the repetition of the deviation of the built-in distinction of cell batteries or/and charge and discharge cycles, short life with the Battery pack that causes by it, can obtain long-life Battery pack, be suitable between a few minutes the supper-fast charging of short time between tens minutes, thereby, can obtain being applicable to storage battery drive-type industrial robot, electri forklift or the unmanned transfer cart of storage battery formula etc. repeat the storage battery of the purposes that discharges and recharges continually.
Secondly, more detailed embodiment of comparative descriptions and comparative example.
Embodiment 1
Will be across dividing plate and 21 positive plates and 22 alternately laminated pole plate groups that form of negative plate are packed in the metallic battery case, wherein use thick 0.65mm as positive plate, wide 70mm, high 157mm, the sintered nickel positive electrode of design capacity 2.6Ah, use thick 0.63mm as negative plate, wide 70mm, high 157mm, the non-sintered type cadmium cathode plate of design capacity 4.5Ah, it is a main active substances with cadmium oxide or cadmium hydroxide with respect to this cadmium metal that is equivalent to about 20% precharge amount, and add the indium of 0.05 weight % with respect to main active substances, use the polypropylene type nonwoven fabrics of thick 0.2mm as dividing plate, in this container, inject the alkaline electrolyte of 200cc, it is to use potassium hydroxide (KOH) 30.0 weight % as electrolyte, lithium hydroxide (LiOH) 2.0 weight % and NaOH (NaOH) 2.0 weight %, and they are dissolved in the water are modulated into, with airtight this metallic battery case of metallic lid, make the square closed cadmium-nickel storage cell (cell batteries) of nominal capacity 50Ah then afterwards with safety valve.
Embodiment 2
Making is except as alkaline electrolyte, use is with potassium hydroxide (KOH) 0 weight %, lithium hydroxide (LiOH) 2.0 weight % and NaOH (NaOH) 20 weight % are dissolved in the water and beyond the electrolyte that is modulated into, with the square closed cadmium-nickel storage cell of embodiment 1 identical main points, nominal capacity 50Ah.
Embodiment 3
Making is except as alkaline electrolyte, use is with potassium hydroxide (KOH) 20 weight %, lithium hydroxide (LiOH) 2.0 weight % and NaOH (NaOH) 10.0 weight % are dissolved in the water and beyond the electrolyte that is modulated into, with the square closed cadmium-nickel storage cell of embodiment 1 identical main points, nominal capacity 50Ah.
Secondly, the battery to the embodiment 1,2,3 that makes by this way carries out the fundamental characteristics test according to following step.
(1) activate discharges and recharges
Charge condition: carry out 150% constant current charge with the electric current of 0.1CA (5A)
Discharging condition: till being 1.0V with the current discharge of 0.2CA (10A) to voltage
Environment temperature: 25 ± 5 ℃
(2) capacity test
Charge condition: carry out 150% constant current charge with the electric current of 0.1CA (5A)
Discharging condition: till being 1.0V with the current discharge of 0.2CA (10A) to voltage
Environment temperature: 25 ± 5 ℃
(3) quick charge test
Charge condition: carry out 105% constant current charge with the electric current of 1.5CA (75A)
Discharging condition: till being 1.0V with the current discharge of 1.5CA (75A) to voltage
Environment temperature: 25 ± 5 ℃
And then, the battery (cell batteries) of 5 box embodiment 2 is connected in series, and in 25 ℃ air blast cooling environment, carries out accelerated life test according to following order.
(4) acceleration cycle test
1) finishes charging: the constant current charge that carries out 15Hr (150%) with the electric current of 0.1CA (5A)
2) circulation discharge: the electric current with 3.0CA (150A) carries out the discharge of 2 minutes (10%)
3) cycle charging: the electric current with 3.0CA (150A) charges, till the voltage of 5 cell batteries series connection is to detect voltage 8.0V
4) cycle-index: 2000 times
5) capacity discharge: till with the electric current of 0.2A (10A) each cell batteries being discharged into 1.0V
6) environment temperature: 25 ± 5 ℃ (air blast cooling)
Secondly, in order to compare test, make the square closed cadmium-nickel storage cell of comparative example 1~3 in such a way.
Comparative example 1
Preparation will be across dividing plate and battery case that the pole plate group that 21 positive plates and 22 negative plates are laminated is mutually packed into and forms in the metallic battery case, wherein use thick 0.65mm as positive plate, wide 70mm, high 157mm, the sintered nickel positive electrode of design capacity 2.6Ah, use thick 0.80mm as negative plate, wide 70mm, high 157mm, the sintered cadmium cathode of design capacity 4.5Ah, use the polypropylene type nonwoven fabrics as dividing plate, in this container, inject 200cc similarly to Example 1 and form the alkaline electrolyte that constitutes by the electrolyte identical with embodiment 1, cover airtight metallic battery case with metallic afterwards, make the square closed cadmium-nickel storage cell of nominal capacity 50Ah with safety valve.Moreover, on described sintered cadmium cathode, implement the precharge of 20% (following all use % to represent) of nominal capacity in advance with respect to nominal capacity.
Comparative example 2
Making is except as alkaline electrolyte, uses by the electrolyte identical with embodiment 2 and forms beyond the electrolyte that constitutes, with the square closed cadmium-nickel storage cell of comparative example 1 identical main points, nominal capacity 50Ah.
Comparative example 3
Making is except as alkaline electrolyte, uses by the electrolyte identical with embodiment 3 and forms beyond the electrolyte that constitutes, with the square closed cadmium-nickel storage cell of comparative example 1 identical main points, nominal capacity 50Ah.
Secondly, to the battery of the comparative example 1~3 made by this way,, that is, carry out (1) activate charging test, (2) capacity test, (3) quick charge test according to carrying out the fundamental characteristics test with the identical main points that battery to embodiment 1~3 carries out.
And then, the battery (cell batteries) of 5 comparative examples 2 is connected in series, according to the identical main points that storage battery to the foregoing description 3 carries out carry out accelerated life test " acceleration cycle test 1), 2), 3), 4), 5), 6) ".
The movement characteristic of the cell voltage when Fig. 1 represents the charging of battery of embodiment 1~3, the movement characteristic of the cell voltage when Fig. 2 represents the charging of battery of comparative example 1~3.
As comparison diagram 1 and Fig. 2 understood, because the rising of the charging voltage in the charging of embodiment 1~3 is very fast, so the cell voltage in the charging of cell voltage and comparative example 1~3 compares, and is totally higher.Promptly, cell voltage in the charging of comparative example 1~3 as can be known, when reaching the 50Ah of rated capacity, charging capacity reaches 1.6V, with respect to this, when the cell voltage in the charging of embodiment 1~3 reaches identical 1.6V, the charging capacity of battery is 40Ah, reaches 1.65V during for 50Ah in battery capacity.In addition, from the viewpoint that electrolyte is formed, the rising of the many more cell voltages of the amount of NaOH is slow more as can be known.
Thereby, with the battery voltage detection method that is predetermined of the battery of embodiment 1~3, can ground more than needed movement with the battery voltage detection charging voltage on required position there be in the past latter stage in charging.For example, embodiment 1~3, in the part charging in charging, can carry out battery voltage detection smaller or equal to about 80% place that is full of electricity (50Ah), therefore can prevent overcharging under the situation of carrying out voltage detecting latter stage of charging in the past, in addition, can also prevent to reduce by the rapid capacity that the minimizing of electrolyte or leakage cause.In addition, be made as at the detection voltage that will be predetermined under the situation of 1.6V for example,, also can keep bigger capacity even if the actual detection value is offset to 1.59V.
Cell voltage when Fig. 3 represents the charging of battery of embodiment 1 and 2 and the movement of voltage change ratio, the cell voltage when Fig. 4 represents the charging of battery of comparative example 1 and 2 and the movement of voltage change ratio.
As comparison diagram 3 and Fig. 4 understood, the voltage change ratio of comparative example 1 shown in Figure 4 and 2 battery, up to charging capacity reach be full of electricity (50Ah) about 80% till, its charging polarization does not change, be smooth, from beginning the variation of rising sharp, therefore can not detect the movement of the voltage change ratio in the charging, thereby can not charge control near the charging capacity that is full of electricity.In addition, comparative example 1 and 2 battery, the about 80% o'clock cell voltage of its charging capacity is about 1.51~1.54V.With respect to this, the voltage change ratio of the battery of embodiment 1 begins to rise from charging capacity about 10%, reaches peak value near about 50%, therefore can detect the movement of the voltage change ratio in the charging, thereby charge control.The voltage change ratio of the battery of embodiment 2, charging capacity be full of electricity about 6% to about 9% between charging polarization movement show the variation of rising, so can detect the movement of the voltage change ratio in the charging, thereby charge control.In addition, embodiment 1 and 2 battery, the about 80% o'clock voltage of its charging capacity is 1.6V and 1.57V, compares with the battery of comparative example 1 and 2, can obtain higher voltage.
Moreover, though following situation has been confirmed in not expression among Fig. 3, promptly, the movement of the cell voltage rate of change of embodiment 3 is the more close right side of peak value of centre of 20~30Ah of the cell voltage rate of change in the charging of embodiment 1, peak value occurs in the centre of 30~40Ah.
Moreover, by NaOH, the KOH that adjusts alkaline electrolyte, the use level of LiOH, can make cell voltage movement and the charging in, promptly, the change location of the movement of the cell voltage rate of change of part charging suitably is shifted, thereupon, change the set point of the detection cell voltage that is predetermined and the set point of detection cell voltage rate of change, the detection of the charging polarization movement in charging then.
As from Fig. 1 to Fig. 4 understood, used the cadmium-nickel storage cell of sintered cadmium cathode as negative pole, the cell voltage that is obtained by charging is totally lower, in addition, the charging polarization movement of part charged state is smooth, the detection of the voltage change ratio in therefore can not charging, but by on the non-sintered type cadmium cathode, adding indium or its compound, shown in embodiment 1~3, in the movement of the voltage change ratio of part charged state, form and change, therefore can detect the charging polarization movement in the charging.
Secondly, the result of the cycling life test of Battery pack (embodiment 2-1,2-2,2-3,2-4 and 2-5) that expression is connected in series the battery of 5 the foregoing descriptions 2 and Battery pack (comparative example 2-1,2-1,2-3,2-4 and 2-5) that the battery of 5 above-mentioned comparative examples 2 is connected in series.That is, be illustrated in residual discharge capacity/specified (%) of the capacity discharge result behind the cycle chargings of per 2000 circulations of each cell batteries of conduct of measuring in the acceleration cycle test that each Battery pack is carried out.As from Fig. 5 understood, 5 cell batteries of Battery pack of battery of the comparative example 2 of sintered cadmium cathode have been used as negative pole, owing to detect carrying out charging voltage when being full of electricity, therefore remaining capacity is more, but because the carrying out of circulation, the cell batteries of a part is overcharged because of deviation, and safety valve moves continually, thereby damages seal and cause the minimizing of electrolyte.Therefore,, cause the reduction of remaining capacity sharp when surpassing 30000 circulation times, also do not reach 40000 circulations during in, its capacity is just near 0.Its result confirms as the short situation of the cycle life of Battery pack.
With respect to this, used the Battery pack of battery of the embodiment 2 of non-sintered type negative pole, 5 cell batteries are at 60000 circulation times, and remaining capacity all also maintains more than 60%, has confirmed the extremely long situation of cycle life.This means the Battery pack of the battery of embodiment 2, when for example by carrying out voltage detecting, detect the variation of charging polarization of the part charging of non-sintered type negative pole of the present invention, and rated capacity 80% near when carrying out voltage control, even if in each cell batteries, there are some deviations of capacity, but because the capacity of each cell batteries all remains on more than 60% as described above, therefore it is lower that the cell batteries that is overcharged with electricity reaches the probability that overcharges, and can keep in long-term and stablize good cycle life.
Moreover, in an embodiment, being illustrated in the example that has added lithium hydroxide in the electrolyte, lithium hydroxide not necessarily must have, and is not having also have same effect under the situation of adding.

Claims (5)

1. the charge control method of a cadmium-nickel storage cell, it is characterized in that, by in the non-sintered type cadmium cathode, adding indium or indium compound, and modulation is as the NaOH of the electrolyte constituent of alkaline electrolyte and the cooperation ratio of potassium hydroxide, constitute cadmium-nickel storage cell, and detect the charging voltage movement that changes under the part charged state of this storage battery in charging.
2. the charge control method of cadmium-nickel storage cell as claimed in claim 1 is characterized in that, the addition of indium or indium compound or their mixture is 0.01 weight %~2.00 weight % with respect to the cadmium active material.
3. the charge control method of cadmium-nickel storage cell as claimed in claim 1 is characterized in that, in the electrolyte of this alkaline electrolyte is formed, potassium hydroxide is 0~40 weight %, NaOH is 0~30 weight %, and electrolytical total amount is smaller or equal to 50 weight %.
4. the charge control method of cadmium-nickel storage cell as claimed in claim 1 is characterized in that, the detection method of described charging voltage movement is the battery voltage detection method.
5. the charge control method of cadmium-nickel storage cell as claimed in claim 1 is characterized in that, the detection method of described charging voltage movement is a cell voltage rate of change detection method.
CNB2006101540534A 2005-12-02 2006-09-20 Charging control method for Ni-Cd accumulator Active CN100499249C (en)

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JP2005348891A JP2007157417A (en) 2005-12-02 2005-12-02 Charge control method of nickel cadmium storage battery

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CN104752778A (en) * 2013-12-25 2015-07-01 中国电子科技集团公司第十八研究所 Preparation method of controllable charging full sealed nickel-cadmium accumulator
CN104752778B (en) * 2013-12-25 2018-07-10 中国电子科技集团公司第十八研究所 The preparation method of the hermetically sealed nickel-cadmium storage battery of controllable charge type

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