CN1242612A - Alkaline storage battery - Google Patents
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- CN1242612A CN1242612A CN99110506A CN99110506A CN1242612A CN 1242612 A CN1242612 A CN 1242612A CN 99110506 A CN99110506 A CN 99110506A CN 99110506 A CN99110506 A CN 99110506A CN 1242612 A CN1242612 A CN 1242612A
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
Abstract
The present invention relates to improvements of clapboards in alkaline storage battery. According to the present invention, a nonwoven cloth clapboard is utilized, which has higher perforation intensity than a clapboard of existing technology with same weight and thickness per square. Then, leakage limitation percentage during battery manufacturing is depressed and batteries with desired characteristics can be obtained effectively. Said battery comprises a positive electrode, a negative electrode, a clapboard which is composed of nonwoven cloth containing polyolefin resin fiber and can generate hydrophilic groups, and an alkaline electrolyte. Said clapboard comprises at least two polyolefin fibers with different intensities, wherein the weight of the high module polyolefin fiber with the highest intensity is 5-50% of the total weight of fibres in the clapboard.
Description
The present invention relates to a kind of improvement of alkaline battery, especially wherein used dividing plate.
The alkaline battery that is widely used now as various power supplys has desired high reliability, and is easy to obtain small size, light weight.So they have obtained extensive use in practice, can be used as the power supply of various light instruments during small size, large-sized industrial power that can be used as.
In this alkaline battery, the general just very nickel electrode of Cai Yonging.As for the type of battery lead plate, to develop into slug type and foam metal type from shell mould, make final properties that raising arranged, the development of simultaneous hermetic type electrode, its application scenario has further expanded.
On the other hand, the negative pole material therefor comprises cadmium, zinc, iron, hydrogen adsorbing alloy etc.So far, mainly adopt cadmium electrode so that nickel-cadmium cell to be provided.Yet, in order to obtain high energy density, adopt the nickel metal hydride batteries of hydrogen adsorbing alloy to receive publicity, because of this battery has reached the practicability stage, a lot of schemes about its preparation method and related fields have been proposed.
In general, in the alkaline battery of hermetic type, characteristics such as similar high power capacity, rapid charge rate, long-life, long-term reliability wish to obtain very much.In order to address that need, a lot of work are used for improving storage performance, the utilance of electrode active material, the ability of negative pole adsorbed gas and the hydrophily of dividing plate.
The dividing plate of alkaline battery requires to have the function of separating positive and negative electrode and keeping electrolyte.Because the defective that produces in the cell preparation process mainly is because physics fine (interior) short circuit between positive pole and negative pole caused (being referred to as hereinafter to leak), improves dividing plate and separate anodal function (this function is referred to as " the anti-leaks of dividing plate " hereinafter) and make that the occurrence rate of substandard products becomes possibility in the preparation process that reduces battery with negative pole.
For example, by increasing the content of the fiber in the dividing plate, and then increase dividing plate per unit area weight (hereinafter being referred to as " weight per unit area "), or, can reach the purpose of improving the anti-leaks of dividing plate by increasing block board thickness to strengthen method anodal and the negative pole spacing.
Yet in order to ensure desirable cell high-capacity and long cycle life characteristics, the positive and negative electrode material and the electrolyte of various predetermined quantities must be filled in the battery.So, be embedded into the restriction that dividing plate in the battery is subjected to weight per unit area and thickness.
Thereby, how under the situation of quantity that does not increase the dividing plate fiber material and thickness thereof, improve the anti-leaks of dividing plate, and then the leakage defect that reduces in the cell preparation process becomes an important problem.
The alkaline battery that the purpose of this invention is to provide less appearance electric leakage defective in a kind of preparation process, its method are by improving the used dividing plate of alkaline battery, and then improve that the anti-leaks of dividing plate realizes.
In order to achieve the above object, the invention provides a kind of alkaline battery, comprise positive electrode, negative electrode, that constitute by the nonwoven fabrics that comprises polyolefin resin fiber and dividing plate and alkaline electrolyte that given hydrophilic group.Its median septum comprises at least two kinds of polyolefine fibers that intensity is different, the polyolefine fiber that in described polyolefine fiber, has the highest intensity, be a kind of polyolefine fiber of high-modulus, its shared percentage by weight in all fibres that constitutes dividing plate is 5-50%.
Preferably a kind of high modulus polypropylene fiber of high modulus polyolefin fibersand, preferably a kind of dividing plate of dividing plate among the present invention, the perforation strength that it adopts blade to measure, compare with the dividing plate of not selecting the high modulus polypropylene fiber for use and having same units area weight and a same thickness, improved at least 10%.
Fig. 1 is the figure of used high modulus polypropylene fiber x x ray diffraction analysis x result in the expression an example of the present invention.
Fig. 2 is expression plain polypropylene fiber (non-high-modulus) x x ray diffraction analysis x result's figure.
Fig. 3 is the schematic diagram of the incident direction of an x ray perpendicular to high modulus polypropylene machine direction used in the example of the present invention.
Fig. 4 is the schematic diagram that the incident direction of an x ray is parallel to this high modulus polypropylene machine direction.
Fig. 5 is the figure that the differential scanning calorimetry method of a this high modulus polypropylene fiber of expression records the result.
Fig. 6 is the figure that the differential scanning calorimetry method of an a kind of plain polypropylene fiber of expression (non-high-modulus) records the result.
Fig. 7 is the figure that the differential scanning calorimetry method of an a kind of polypropylene, polyethylene skin-core composite fibre of expression records the result.
Fig. 8 is the figure of the measurement result of the perforation strength of used dividing plate E and displacement (extension) in the expression example 2 of the present invention.
Fig. 9 is the figure of the measurement result of an expression perforation strength and displacement (extension), is that example 2 used dividing plate F record among employing the present invention.
Figure 10 is the figure of the measurement result of an expression perforation strength and displacement (extension), is that used dividing plate G records in the employing comparison example.
Detailed Description Of The Invention
A first aspect of the present invention relates to a kind of alkaline storage battery, and this battery comprises positive electrode, negative electrode, dividing plate and alkaline electrolyte that be made of the nonwoven that comprises polyolefin resin fiber and that given hydrophilic group. Its median septum comprises at least two kinds of polyolefine fibers that intensity is different, the polyolefine fiber that in described polyolefine fiber, has the highest intensity, it is a kind of polyolefine fiber of high-modulus, its shared percentage by weight in all fibres that consists of dividing plate is 5-50%, preferred 10-40% percentage by weights, more preferably 25-35% percentage by weight.
By means of said structure, improved the anti-leaks of dividing plate, and the incidence of the leakage defect between positive pole and the negative pole has reduced obviously in the battery preparation process.
" high modulus polyolefin fibersand " in this specification is meant to have the polyolefine fiber of fiber modulus value at least 6 gram/daniers (determining according to JIS L1015).
This high modulus polyolefin fibersand is a kind of polypropylene fibre of high-modulus preferably.
This high modulus polypropylene fiber is a kind of polypropylene fibre of high-modulus preferably, when the incident direction of x ray in the x x ray diffraction analysis x is vertical with the direction of this fiber, in the 10-20 scope, present three diffraction maximums, i.e. first peak, second peak, the 3rd peak.In this fiber, preferably observed peak to first peak is strong when the x directions of rays is vertical with machine direction, is observed strong at least 7 times in peak that arrive on the same position when the x directions of rays is parallel with machine direction.
Preferably, the polypropylene fibre of this high-modulus the temperature of endothermic peak occurs than plain polypropylene fiber height at least 5 degree in the differential scanning calorimetry analysis.
The dividing plate of above-mentioned alkaline battery preferably uses a kind of nonwoven fabrics, and the perforation strength of dividing plate that adopts this nonwoven fabrics is than adopting the perforation strength high at least 10% of dividing plate do not comprise the high modulus polypropylene fiber and to have the nonwoven fabrics of same units area weight and thickness.
Aforementioned barriers preferably is made of a kind of nonwoven fabrics, and this nonwoven fabrics comprises through giving the polyolefin resin fiber of hydrophilic processing.By adopting sulfuric acid or oleum sulfonation to handle ethene constituent element in the polyolefin resin fiber of hydrophily deficiency, used this resin fibre sulfonic group modified, this sulfonic group is a kind of hydrophilic group, and has given this cloth long-acting hydrophily thus, can be used as dividing plate.Yet, in this sulfonation is handled, when producing hydrophilic group and handling because strong acid may cause the serious embrittlement of fiber, so, when fibre weight after a little while, the anti-leaks of cloth and form the necessary intensity of battery and predispose to damage.And then for avoiding this shortcoming, it is effective introducing a kind of high modulus fibre in this cloth.In addition, the introducing of high modulus fibre makes and to reduce that the weight per unit area of sulfonation dividing plate and the sulfonic group content that increases in the dividing plate become possibility.
The surface of the fiber that used dividing plate also can be by the modified hydrophilic deficiency among the present invention obtains, and can adopt the carboxyl as a kind of hydrophilic group, makes fiber produce long-acting hydrophily.This hydrophilic group can also produce by acrylic acid glycerol polymerization.
A second aspect of the present invention relates to a kind of alkaline battery, and this storage battery comprises positive electrode, negative electrode, constituted and given the dividing plate and the alkaline electrolyte of its hydrophilic group by the nonwoven fabrics that comprises polyolefin resin fiber.The 1g/m of its median septum
2The perforation strength index (gf/mm) of per unit area weight (herein the perforation strength index be meant when the perforation strength (gf) of dividing plate is penetrated divided by dividing plate displacement (extension) (mm)) be 6gf/m at least, preferred 7gf/mm at least.
The top dividing plate of introducing has the advantage of leakage defect occurrence rate in the obvious minimizing cell preparation process, these defectives are because the cutting section of positive plate and negative plate causes, or because the small prominent point that causes of battery lead plate bending causes that this buckling phenomenon may occur in and anodally twine with the negative pole spiral, when dividing plate inserts the electrode plate assembly that forms therebetween.
Example
Below with reference to example in detail the present invention is described in detail.Example 1
In this example 1, introduce a kind of nickel metal hydride batteries as an example, its dividing plate adopts a kind of polyolefin nonwoven fabrics, and high modulus polyolefin fibersand wherein adopts a kind of high modulus polypropylene fiber of handling through oversulfonate.[dividing plate preparation]
Polyolefin nonwoven fabrics (the hereinafter referred sulfonation dividing plate) preparation process of handling through oversulfonate is as follows: with percentage by weight is that (fiber diameter is about 13 μ m for 80% polypropylene, polyethylene skin-core composite fibre, average fiber length is about 50mm) and percentage by weight be that (fiber diameter is about 19 μ m for 20% high modulus polypropylene fiber, average fiber length is about 50mm) mix, and to form weight per unit area by dry method be 52 ± 6g/m
2Nonwoven fabrics, after this nonwoven fabrics is immersed in temperature is that 35 ℃, concentration are in 20% the oleum about 20 minutes, obtain the dividing plate A in this example again after washing, drying and calender are handled, its sulfonation degree (sulphur atom compares with the quantity of carbon atom) is 2.5 * 10
-3, thickness is 120 ± 20 μ m.
Then, be that 70% polypropylene, polyethylene skin-core composite fibre and percentage by weight are 30% high modulus polypropylene fiber with percentage by weight, these fibers are identical with fiber among the dividing plate A, and mixing the back, to form weight per unit area by wet method be 59 ± 3g/m
2Nonwoven fabrics, this nonwoven fabrics is handled through the sulfonation identical with dividing plate A, obtains the dividing plate B in this example, its sulfonation degree (quantity of sulphur atom and carbon atom than) is 2.5 * 10
-3, thickness is 120 ± 20 μ m.
As a comparison case, wherein do not adopt the preparation process of dividing plate of high modulus polypropylene fiber as follows:
Adopt method preparation sulfonation dividing plate identical with dividing plate A, be called dividing plate C, different is does not comprise with percentage by weight being that 80% polypropylene, polyethylene skin-core composite fibre and percentage by weight are that 20% plain polypropylene fiber (fiber diameter is about 19 μ m, and average fiber length is about 50mm) mixes.The fiber modulus of plain polypropylene fiber is 5 gram/daniers.In addition, adopt method preparation sulfonation dividing plate identical with dividing plate B, be called dividing plate D, do not comprise with percentage by weight being that 70% polypropylene, polyethylene skin-core composite fibre and percentage by weight are 30% plain polypropylene fiber mixing but different is, used identical among this plain polypropylene fiber and the dividing plate C.
Adopt these 4 kinds of dividing plate A, B, C and the D obtain above to prepare nickel metal hydride batteries respectively, and examined or check physics in the cell preparation process and leak the percentage of defects that causes and the cycle life of battery.[dividing plate analysis]
The x x ray diffraction analysis x result of the high modulus polypropylene fiber that example median septum A and B are used as shown in Figure 1.The x x ray diffraction analysis x result of the plain polypropylene fiber that Comparative Examples median septum C and D are used as shown in Figure 2.
X-ray diffraction analysis is to adopt RINT2500 (trade (brand) name, Rigaku Denki K.K. makes) to carry out, and experiment condition is as follows: pipe: copper, tube voltage: 50kV, tube current: 150mA.X-ray diffraction analysis adopts two kinds of methods to carry out, the incident direction that promptly a kind of situation is the x ray perpendicular to machine direction as shown in Figure 3, another kind of situation is that the incident direction of x ray is parallel to machine direction as shown in Figure 4.
As shown in Figure 1, used high modulus polypropylene fiber among dividing plate A and the B promptly when x ray incident direction during perpendicular to machine direction, presents three peak values, i.e. first peak value, second peak value and the 3rd peak value in 10-20 degree scope in situation (1); In situation (2), promptly when x ray incident direction is parallel to machine direction, in 10-20 degree scope, do not present peak value.It is observed strong 10.2 times on the same position when peak under the vertical incidence situation on viewed first position, peak is parallel incident by force to the peak.
On the other hand, as shown in Figure 2, the plain polypropylene fiber that Comparative Examples median septum C and D are used promptly when x ray incident direction during perpendicular to machine direction, presents three peak values in 10-20 degree scope in situation (1); In situation (2), promptly when x ray incident direction is parallel to machine direction, in 10-20 degree scope, present a diffraction peak, and the position during with vertical incidence viewed first position, peak identical.It is observed strong 4.6 times on the same position when peak under the vertical incidence situation on viewed first position, peak is parallel incident by force to the peak.
Thereby this high modulus polypropylene fiber is compared with the plain polypropylene fiber as can be known, has the obvious fibre orientation of having improved.
In addition, also the high modulus polypropylene fiber has been carried out differential scanning calorimetry analysis (hereinafter referred DSC) repeatedly, a resulting typical DSC curve as shown in Figure 5.Used DSC equipment is Shimadzu hot-fluid speed differential scanning calorimetry instrument DSC-50 (trade (brand) name, Shimadzu company makes).Measurement be with 10 the degree/minute heating rate carry out, peak temperature is 171.0 ℃.
For the purpose of contrast, under the same measuring condition of as above being introduced, the DSC curve of plain polypropylene fiber has been carried out repeatedly measuring, typical experimental results as shown in Figure 6, peak temperature is 161.9 ℃.
DSC curve to polypropylene, polyethylene skin-core composite fibre used in above-mentioned four kinds of dividing plates is also measured respectively, and method is same as above, and resulting typical consequence as shown in Figure 7.The peak temperature of polyethylene constituent element observes at 108 ℃, and the peak temperature of polypropylene constituent element is 160 ℃ and 166 ℃.
The DSC result who introduces from above as can be known, the temperature that the high modulus polypropylene fiber presents endothermic peak is higher 5 ℃ or higher than plain polypropylene fiber, thus the high modulus polypropylene fiber has high thermal stability.So, can know by inference of the present invention by high modulus fibre add wherein dividing plate not only its anti-leaks in the cell preparation process improve, and the temperature that use is followed for battery raises and has higher stability.
Perforation strength to C in the A in the example and B dividing plate and the Comparative Examples and D dividing plate is examined or check, and the measurement of perforation strength adopts KES-G5 pin type perforation strength testing equipment (KATO TECHCO.LTD. manufacturings) to carry out, use be that a blade type is popped one's head in.The speed of probe perforation is 0.2mm/ second, and direction is perpendicular to the thickness direction of dividing plate.Intensity when penetrating is decided to be perforation strength.
Form the supposition that burr cause internal short-circuit when the use of the probe of this blade type is based on the cutting electrode plate, and make the dividing plate fiber be cut off to cause the supposition of physics leakage because electrode end surface contacts with dividing plate.Because measured perforation strength value is vulnerable to the influence of blade abrasion degree, so four kinds of dividing plate examinations simultaneously under similarity condition.When the perforation strength index of Comparative Examples median septum C is taken as 100, the perforation strength index of example median septum A and when the perforation strength index of Comparative Examples median septum D is taken as 100, the perforation strength index of example median septum B is all as shown in table 1.Table 1
| Dividing plate | Weight per unit area (g/m 2) | The preparation method of base cloth | The shared mixture ratio of high modulus polypropylene fiber | Perforation strength (index) |
| ??A | ??????52 | Dry method | ??????20 | ????115 |
| ??C | ??????0 | ????100 | ||
| ??B | ??????62 | Wet method | ??????30 | ????121 |
| ??D | ??????0 | ????100 |
Clearly visible from table 1, comprise the intensity that does not comprise the dividing plate C of high modulus polypropylene fiber in intensity that 20% percentage by weight high modulus polypropylene fiber adds dividing plate A wherein and the Comparative Examples in the example and compare, exceed 15%.Equally, dividing plate B in the example compares with dividing plate D in the Comparative Examples, two kinds of dividing plates have all adopted nonwoven fabrics, and their weight per unit area is bigger than the weight per unit area of dividing plate A in the example and the dividing plate C in the Comparative Examples, comprise the intensity that does not comprise the dividing plate D of high modulus polypropylene fiber in intensity and the Comparative Examples of dividing plate B of 30% percentage by weight high modulus polypropylene fiber in the example and compare, exceed 21%.
As mentioned above, the dividing plate of used fiber with the strong ratio of higher x ray diffraction peaks shows higher perforation strength.When the orientation of fiber was higher, the intensity of fiber also can improve.In the present invention under the situation of the weight per unit area of dividing plate and thickness, when the diffraction maximum of fiber strong than being 7 or when higher, the effect of raising perforation strength can clearly show.
The quantity preferred value of the high modulus polypropylene fiber that adds in the dividing plate is the 5-50% that accounts for whole separator.When the quantity that is added was positioned at scope above-mentioned, the anti-leaks in the cell preparation process can effectively be improved, and by means of the fiber adhesiveness, the shape of nonwoven fabrics is easy to be kept.
Though in the method for mentioning in the above for preparing dividing plate, example median septum A and Comparative Examples median septum C adopt dry method, and example median septum B and Comparative Examples median septum D adopt wet method, the intensity that adopts the blade perforation to record, high in than dividing plate C that does not adopt the high modulus polypropylene fiber and D in dividing plate A that adopts the high modulus polypropylene fiber and B, is dry method or wet method no matter the dividing plate preparation adopts.[cell preparation]
Adopt dividing plate A in the example and the dividing plate C in the Comparative Examples to prepare the hermetic type nickel metal hydride batteries respectively, size is HR17/67, and each nominal capacity is 3800mAh.The gained battery is called battery A and battery C.
Adopt dividing plate B in the example and the dividing plate D in the Comparative Examples to prepare the hermetic type nickel metal hydride batteries respectively, size is SUM-4, and each nominal capacity is 650mAh.The gained battery is called battery B and battery D.
It is as follows to prepare the required material except dividing plate of battery:
The preparation process of used pulpous state nickel positive electrode, comprise in the nickel hydroxide powder of the active material that cobalt hydroxide powder and water with 7 parts of weight add 100 parts of weight to, wherein add zinc, cobalt or the like in the active material and formed the co-precipitation state, the gained mixture is stirred into pulpous state, this paste mixture is filled in the spongy nickel porous plate again, drying, pressurization subsequently, porous plate is immersed in the fluororesin suspension again, through super-dry, at last desciccate is cut to required size again.
The hydrogen adsorbing alloy preparation process that negative pole is used comprises that with composition formula be MmNi
3.55Mn
0.4Al
0.3Co
0.75(Mm represents the mixture of rare earth element), crystal structure is CaCu
5The hydrogen adsorbing alloy of type ball milling in ball mill, to form particle diameter is the fine powder of 25 μ m, again these powder are immersed in 80 ℃ potassium hydroxide aqueous solution, through washing, powder with above-mentioned processing mixes with the suspension of butadiene-styrene rubber, carboxymethyl cellulose, carbon and water again, to form slurry, it is coated onto on the iron plate of nickel plating of punching press again, back drying, pressurization are with the sheets thus obtained required size that is cut into.
And then, with pulpous state positive electrode above-mentioned, length is the dividing plate that the twice of positive electrode adds 40mm, and theoretical capacity is 1.4-1.5 a times of positive electrode theoretical capacity, and length is combined for the negative electrode that positive electrode length adds 35mm, and spiral is wound in an enclosed-type battery.The preparation process of used electrolyte comprises LiOHH
2It is in 1.30 the potassium hydroxide aqueous solution, to be 40g/l until concentration that O is dissolved into proportion.
Battery A, B, C and the D for preparing above is under 20 ℃ of situations in ambient temperature all, passed through the charge and discharge in advance in 3 cycles, carries out the cycle life test subsequently.Leaked the percent defective cause calculates with the ratio of total cell number of substandard products cell number and preparation by physics in the cell preparation process.It is as shown in table 2 to leak the percent defective and the cycle life characteristics that cause by the physics between positive pole and the negative pole in battery A, B, C and the D preparation process.Table 2
| Battery | Percent defective in the cell preparation process | Life-span (60% cycle that keeps) |
| ??A | ???????????0.8％ | 300 cycles |
| ??C | ???????????1.2％ | |
| ??B | ???????????0.3％ | 500 cycles |
| ??D | ???????????0.6％ |
As shown in table 2, owing to leaking the percent defective that causes, the physics between positive pole and the negative pole in battery A, the C preparation process is respectively 0.8%, 1.2%.
Cycle life characteristics shown in the table 2 is by under 20 ℃ of situations of ambient temperature, charges the battery, discharges and test with the electric current of 1CmA, and charging is adjusted by-Δ V (Δ V=10mV), and the terminal voltage of discharging until battery reaches 1.0V.
Table 2 reflect battery A in the example and the battery C in the Comparative Examples until 300 cycles can both keep nominal capacity 60% or more, so battery A and battery C are not having difference aspect the cycle life characteristics of battery.
As shown in table 2 equally, owing to leaking the percent defective that causes, the physics between positive pole and the negative pole in battery B and the D preparation process is respectively 0.3%, 0.6%.In the cycle life identical test of carrying out with above-mentioned condition, reflect battery B and battery D until 500 cycles can both keep nominal capacity 60% or more, battery B and battery D are not having difference aspect the cycle life characteristics of battery thus.
As shown in table 2, because the level that the physics between positive pole and the negative pole leaks the percent defective that causes in the cell preparation process is different between battery A, B and battery C, D, this is that the difference of the weight per unit area shown in the table 1 causes.Yet, when the battery of the dividing plate formation with same units area weight is compared, be that battery A compares with battery C, when battery B compares with battery D, in both cases, adopt the battery A and the B of the dividing plate that adds the high modulus polypropylene fiber in the example, show lower leakage defect percentage and better battery performance than battery C in the Comparative Examples and D respectively.
In the example of above the weight per unit area of dividing plate and thickness lay respectively at, introducing of the present invention during employed scope, and when the amount of the high modulus polypropylene fiber that adds is the 5-50% percentage by weight, can obtain with described example in approximately uniform effect.The amount of the high modulus polypropylene fiber that adds is preferably 10-40% percentage by weight, more preferably 25-35%.
The effect of high modulus polypropylene fiber above-mentioned is not only being observed to produce in the hydrophilic dividing plate by sulfonation, and can also observe producing in the hydrophilic dividing plate by acrylic acid-grafted polymerization.
Acrylic acid-grafted polymerization is carried out as follows:
Polypropylene non-woven fabric is immersed in a kind of solution, this solution comprises the acrylic acid, 76.7% percentage by weight distilled water, 0.2% percentage by weight benzophenone, the ferrous sulfate of 0.1% percentage by weight, the non-ionic surface active agent of 3.0% percentage by weight of 20% percentage by weight, and the immersion time is 10 minutes.Used solution passes through deoxidation treatment in advance, to eliminate the influence of oxygen in the aggregation processing of back as far as possible.Nonwoven fabrics through above-mentioned processing is got rid of redundant solution, again in deoxidation atmosphere, under the about 90 ℃ temperature, be 200mW/cm with intensity with metal halide lamp
2Its two sides of UV-irradiation carrying out acrylic acid glycerol polymerization, this cloth obtains dividing plate through washing, dry, calendering again, the weight per unit area of this dividing plate is 59 ± 5g/m
2, thickness is 120 ± 20 μ m, the acrylic acid-grafted degree of polymerization is 9 ± 2%.And the perforation strength of this dividing plate examined or check.Prepared the battery that adopts this dividing plate, is of a size of SUM-4, and its percent defective and cycle life characteristics have been examined or check.The gained result show obtained with example in B dividing plate and adopt good effect like the battery category-B of this dividing plate.
High modulus polyolefin fibersand also can be a kind of high-modulus polyethylene fibres or the composite fibre of a kind of high modulus polypropylene and high modulus polyethylene.
The generation hydrophily of dividing plate is handled also can obtain similar effects by the coating surface activating agent or by corona discharge.
The effect of high modulus polypropylene fiber above-mentioned can also obtain in alkaline battery except being embodied in nickel metal hydride batteries.Alkaline battery comprises nickel-cadmium accumulator, nickel-zinc battery and manganese dioxide-Ni/metal hydride secondary cell.Example 2
In example 2, introduce a kind of nickel metal hydride batteries as an example, its dividing plate adopts a kind of polyolefinic nonwoven fabrics that comprises, and this polyolefine fiber oversulfonate is handled.[dividing plate preparation]
The preparation process of sulfonation dividing plate is as follows: adopting polypropylene, polyethylene skin-core composite fibre (fiber diameter is about 13 μ m, and average fiber length is about 10mm) to prepare weight per unit area by wet method is 59 ± 4g/m
2Nonwoven fabrics.Then this nonwoven fabrics was immersed in temperature and is 35 ℃, concentration and be in 20% the oleum about 20 minutes, obtain the dividing plate E in the example 2 of the present invention again after washing, drying and calender are handled, its sulfonation degree (sulphur atom compares with the quantity of carbon atom) is 2.5 * 10
-3, thickness is 120 ± 20 μ m.
Then, with percentage by weight is that used polypropylene, polyethylene skin-core composite fibre of 70% dividing plate E and percentage by weight are that (fiber diameter is about 19 μ m for 30% high modulus polypropylene fiber, average fiber length is about 10mm), the fibre strength value of this high modulus polypropylene fiber is 7～9 gram/daniers (according to JIS L1015: the method for measurement of chemical fibre material is measured), and mixing and forming weight per unit area by wet method is 59 ± 4g/m
2Nonwoven fabrics, this nonwoven fabrics is handled through the sulfonation identical with dividing plate E, obtains the dividing plate F in this example, its sulfonation degree (quantity of sulphur atom and carbon atom than) is 2.5 * 10
-3, thickness is 120 ± 20 μ m.
In addition, adopting polypropylene, polyethylene skin-core composite fibre (fiber diameter is about 13 μ m, and average fiber length is about 50mm) is 62 ± 6g/m by dry method (currying method) preparation weight per unit area
2Nonwoven fabrics.This nonwoven fabrics is handled through the sulfonation identical with dividing plate E, obtains the dividing plate G in the Comparative Examples, and its sulfonation degree is 2.5 * 10
-3, thickness is 120 ± 20 μ m.
Measured the perforation strength of three kinds of dividing plate E, F and G respectively.Adopt these 3 kinds of dividing plates to prepare nickel metal hydride batteries respectively, i.e. battery E, F and G, and examined or check physics in the cell preparation process and leak the percent defective that causes and the cycle life characteristics of battery.[dividing plate examination]
Respectively dividing plate E, F and G are cut into 400cm
2Size is measured the weight of each sample of gained by electronic balance.Adopt the perforation strength of identical each dividing plate of sample in measurement again.Measure and adopt KES-G5 pin type perforation strength measuring equipment (manufacturing of KATO TECH company) to carry out.The diameter of the pin of perforation probe is 1mm, and pointed shape is spherical (0.5R), and punching rate is 0.2mm/ second.Each dividing plate carries out 5 times at optional point and measures.The perforation strength index of dividing plate is determined by following formula: the displacement (mm) of the perforation strength (gf) of dividing plate perforation strength index (gf/mm)=dividing plate/when dividing plate is penetrated.
Details are as follows for the example of mensuration dividing plate E, F and G perforation strength index:
In Fig. 8, the displacement of popping one's head in when x axle representative perforation probe is pushed dividing plate, Y-axis representative probe is applied to the pressure of dividing plate when pushing dividing plate.The ductility of dividing plate is being represented in the displacement of perforation probe, and the pressure during partition ruptures is being represented perforation strength (withstand voltage).
As shown in Figure 8, when the pressure that is applied to dividing plate E reaches 1015gf, dividing plate distortion 2.60mm also breaks.The weight per unit area of dividing plate E is 56.1g/m
2, the perforation strength index of dividing plate E is 390.38gf/mm, the 1g/m of dividing plate E
2Per unit area weight strength Index for Calculation value is 6.96gf/mm.
The perforation strength determination data of example median septum F as shown in Figure 9, measurement be with the used identical measuring condition of dividing plate A under carry out.As shown in Figure 9, when the pressure that is applied to dividing plate F reaches 1060gf, dividing plate distortion 2.45mm also breaks.The weight per unit area of dividing plate F is 60.3g/m
2, the perforation strength index of dividing plate F is 432.65gf/mm, the 1g/m of dividing plate F
2Per unit area weight strength Index for Calculation value is 7.18gf/mm.
The perforation strength determination data of Comparative Examples median septum G as shown in figure 10, measurement be with the used identical measuring condition of dividing plate E under carry out.As shown in figure 10, when the pressure that is applied to dividing plate G reaches 760gf, dividing plate distortion 2.75mm also breaks.The weight per unit area of dividing plate G is 63.3g/m
2, the perforation strength index of dividing plate G is 276.36gf/mm, the 1g/m of dividing plate F
2Per unit area weight strength Index for Calculation value is 4.37gf/mm.
From The above results, can reflect dividing plate E and F in the example of wet method preparation, extend pressure littler and that ability is higher than the dividing plate G in the Comparative Examples of dry process.When the pin type ridge of the used perforation probe in being similar to above-mentioned measurement of deducibility from then on appears in anodal and the negative pole, compare, use the dividing plate E of wet method preparation and the anti-leaks of F obviously to improve with the dividing plate G of dry process.
Though extending pressure littler and that ability is higher, the dividing plate why wet method prepares also imperfectly understands now, but can consider in the wet method in order to impel the even dispersion of fiber in water, adopted than fiber shorter in the dry method, and then make bounding point between fiber mutually in the wet method than bigger in the dry method, thereby the dividing plate that wet method obtains extends little and anti-more high pressure.
As for fibre length, can not provide blanket explanation, because the intensity of dividing plate also is subjected to the weight per unit area of dividing plate, the shape of perforation probe and the influence of other factor.Yet,, under the condition of this example, when fibre length is not more than 30mm, can access desirable perforation strength among the present invention by discovering in a large number.
The dividing plate F of the employing high modulus polypropylene fiber in the example extends still less and anti-more high pressure than the dividing plate E in the example that does not adopt the high modulus polypropylene fiber.The high rigidity that this is attributable to the high crystal orientation of high modulus polypropylene fiber and produces therefrom.
From the perforation strength that measures for above-mentioned 5 times, get maximum and deduct minimum value as " undulating value ", the undulating value of the perforation strength of each dividing plate etc. has been carried out calculating and comparing.The perforation strength undulating value of example median septum E is 215gf, and the displacement fluctuation value is 0.28mm, 1g/m
2The undulating value of the perforation strength index of per unit area weight is 1.07gf/mm; Three respective value of example median septum F are respectively 125gf, 0.23mm, 0.71gf/mm.Three respective value of Comparative Examples median septum F are respectively 425gf, 0.75mm, 1.83gf/mm.The result is as shown in table 3.Table 3
| Dividing plate | Strength fluctuation value (gf) | Displacement fluctuation value (mm) | Intensity index undulating value (gf/mm) |
| ??E | ????215 | ????0.28 | ????????1.07 |
| ??F | ????125 | ????0.23 | ????????0.71 |
| ??G | ????425 | ????0.75 | ????????1.83 |
Dividing plate G is all showing bigger fluctuation than dividing plate E and F aspect intensity, displacement and the intensity index.Dividing plate E and F in the example of wet method preparation also imperfectly understand than the reason that dividing plate G has shown less strength fluctuation, but in general, the dividing plate of wet method preparation shows less weight per unit area undulating value (wet method be about dry method 1/2) than the dividing plate of dry process.These results can infer and are explained as follows: wet method cloth is big unlike dry method cloth difference aspect the local density of fiber, and texture is more even, and then the intensity difference between each point of measuring is less.In addition, when the fiber that adopts same diameter adopts wet method and dry process respectively, and when obtaining the dividing plate of same units area weight and thickness, hole in the wet method dividing plate is littler and be more evenly distributed than the yardstick of hole in the dry method dividing plate, that is to say that the fibre gap of wet method dividing plate is little and do not have a big hole.And then cause the strength difference between the difference little.
From top description as seen, the wet method dividing plate is compared with the dry method dividing plate, suppressing owing to be effectively aspect the leakage that pin type protrusion anodal and negative pole causes, expecting also that in addition it arrives aspect the relative pole plate at the hole of the active material that prevents to come off from positive pole and negative pole by dividing plate is effectively.Thereby the wet method dividing plate has better anti-leaks.[cell preparation]
Adopt dividing plate E in the example and the dividing plate G in F and the Comparative Examples to prepare the hermetic type nickel metal hydride batteries respectively, size is SUM-4, and each nominal capacity is 650mAh.The gained battery is called example battery E and F and Comparative Examples battery G.
Battery E, F are all identical with G material therefor except dividing plate, and the structure of battery is as follows:
The preparation process of used positive electrode pole plate, comprise in the nickel hydroxide powder of the active material that cobalt hydroxide powder and water with 7 parts of weight add 100 parts of weight to, wherein add zinc, cobalt or the like in the active material and formed the co-precipitation state, the gained mixture is stirred into pulpous state, this jelly is filled in the spongy nickel porous plate, drying, pressurization subsequently is immersed in porous plate in the fluororesin suspension more again, through super-dry, at last drying sample is cut to required size again.
The preparation process of used negative electrode pole plate comprises that with composition formula be MmNi
3.55Mn
0.4Al
0.3Co
0.75(Mm represents the mixture of rare earth element), crystal structure is CaCu
5The hydrogen adsorbing alloy ball milling of type is levigate, to form average grain diameter is the fine powder of 25 μ m, again these powder are immersed in 80 ℃ potassium hydroxide aqueous solution, through washing, powder with above-mentioned processing mixes with the suspension of butadiene-styrene rubber, carboxymethyl cellulose, carbon and water again, to form slurry, it is coated onto on the iron plate of nickel plating of punching press again, back drying, pressurization are cut into required size with the gained sheet.The negative electrode theoretical capacity is 1.4-1.5 a times of positive electrode theoretical capacity, and negative electrode pole plate length is than the long 35mm of positive electrode pole plate.
The length of used dividing plate is than the also long 40mm of twice of the length of positive electrode pole plate.
The preparation process of used alkaline electrolyte comprises LiOHH
2It is in 1.30 the potassium hydroxide aqueous solution, to be 40g/l until concentration that O is dissolved into proportion.
Positive electrode pole plate for preparing above and negative electrode pole plate and dividing plate E spiral twine, and dividing plate E inserts in two battery lead plates, form the electrode pad assembly.This electrode pad assembly is placed metal battery case, alkaline electrolyte is poured in this battery case again, sealing plate sealing is adopted on the top of battery case, and then forms the nickel metal hydride batteries E in the example of the present invention.Except used dividing plate is F, other all identical with battery E battery is referred to as nickel metal hydride batteries F of the present invention, and the just dividing plate of same preparation adopts is the nickel metal hydride batteries G that the battery of dividing plate G is referred to as Comparative Examples.
Battery E, F for preparing above and G are under 20 ℃ of situations in ambient temperature all, have passed through the charge and discharge in advance in 3 cycles, carry out the cycle life test subsequently.Leaked the percent defective cause calculates with the ratio of total cell number of substandard products cell number and preparation by physics in the cell preparation process.
Because it is as shown in table 4 that the physics in battery E, F and the G preparation process between positive pole and the negative pole leaks the percent defective and the cycle life characteristics that cause.
Characteristic value about the intensity of used dividing plate E, F and G among battery E, F and the G is also as shown in table 4.Table 4
| Battery | E | F | G |
| Weight per unit area (the g/m of dividing plate 2) | 56.1 | 60.3 | 63.3 |
| The mean value of dividing plate perforation strength (gf) | 983 | 1114 | 620 |
| Displacement during baffle-plate penetrating (mm) | 2.48 | 2.32 | 2.23 |
| Per unit area weight 1g/m 2The mean value (gf/mm) of diaphragm strength index | 7.07 | 7.96 | 4.39 |
| Per unit area weight 1g/m 2The undulating value (gf/mm) of diaphragm strength index | 1.07 | 0.71 | 1.83 |
| The leakage defect percentage (%) of cell preparation process | 0.6 | 0.4 | 1.2 |
| Life characteristic (cycle) | ≥500 | ≥500 | ≥500 |
As shown in table 4, to have shown minimum leakage defect percentage be 0.4% to battery F in the example, and to have shown deputy result preferably be 0.6% to battery E in the example, and battery G has then shown relatively poor result 1.2% in the Comparative Examples.
As seen, battery E and F have adopted per unit area weight 1g/m respectively
2The perforation strength index is 7.0gf/mm or higher dividing plate, and their leakage defect percentage obviously is less than battery G.
Measuring as follows of life characteristic shown in the table 4.Employing-Δ V (Δ V=10mV) control is charged to mesuring battary with the electric current of 0.65A (1CA), then with the current discharge of 0.65A (1CA), reaches 1.0V until the terminal voltage of battery.Said process is as the one-period of charge and discharge.Charge and discharge repeat, when discharge capacity is reduced to 60% or the time point still less time of battery nominal capacity 650mA, as the end point of battery life.The cycle-index of charge and discharge is defined as life characteristic when arriving end point.
Can find out obviously that from table 4 battery E and the battery G in F and the Comparative Examples in the example can both keep at least 60% of nominal capacity until 500 cycles, so battery E and F and battery G are not having difference aspect the life characteristic of battery.
Then, adopt polypropylene, polyethylene skin-core composite fibre that the influence of fibre diameter is studied.Except operating weight percentage be 20% with the used identical polypropylene, polyethylene skin-core composite fibre of dividing plate E, and the another kind of percentage by weight 80% (fiber diameter is about 19 μ m than the former thicker polypropylene, polyethylene skin-core composite fibre, average fiber length is about 10mm) outside, other all adopts the condition identical with dividing plate E, prepare a dividing plate, be referred to as example dividing plate H of the present invention.
In addition, a kind of (fiber diameter is about 16 μ m than the thicker polypropylene, polyethylene skin-core composite fibre of the used polypropylene, polyethylene skin-core of dividing plate E composite fibre except using, average fiber length is about 10mm) outside, other all adopts the condition identical with dividing plate E, prepare a dividing plate, be referred to as example dividing plate I.Adopt and with top identical method dividing plate H and I are tested, the gained result is as shown in table 5.Table 5
| Battery | H | I |
| Weight per unit area (the g/m of dividing plate 2) | 61.1 | 61.5 |
| The mean value of dividing plate perforation strength (gf) | 906 | 1028 |
| Displacement during baffle-plate penetrating (mm) | 2.39 | 2.38 |
| Per unit area weight 1g/m 2The mean value (gf/mm) of diaphragm strength index | 6.20 | 7.02 |
| Per unit area weight 1g/m 2The undulating value (gf/mm) of diaphragm strength index | 0.65 | 1.11 |
| The leakage defect percentage (%) of cell preparation process | 0.7 | 0.6 |
| Life characteristic (cycle) | ≥500 | ≥500 |
By result shown in the table 5 as seen, every 1g/m of dividing plate H and I
2Weight per unit area perforation strength index is 6gf/mm or higher, and this is than the respective value height of Comparative Examples median septum G.And battery H and I have shown promptly lower preferably leakage defect percentage than the battery G in the Comparative Examples in the preparation process of battery.
Dividing plate among the battery H has shown lower intensity index, and the dividing plate among the relative battery E has provided slightly poor leakage defect percentage.This may be because the dividing plate of battery H has used a kind of ratio used thicker fiber in the dividing plate of battery E, interfibrous bonding counting reduces to make perforation strength to reduce, again since between fiber the diameter of hole become big, make to stop the effect of the material arrival comparative electrode that comes off from anodal and negative pole to weaken.
Though used thicker fiber in the dividing plate than battery E in the dividing plate of battery I, the perforation strength index of the battery that the former provides and leakage defect percentage are identical with the latter basically.This may be because the weight per unit area value of the dividing plate of battery I is bigger than the dividing plate of battery E, and then has bigger perforation strength.This has just offseted and has adopted crude fibre to cause in conjunction with the negative factor of counting and reducing, and makes the former anti-leaks and battery E median septum substantially the same.
From The above results as can be known, a dividing plate will have good anti-leaks, the preferred per unit area weight of the intensity index value 1g/m of dividing plate
2Be 6gf/mm or higher, more preferably 7gf/mm or higher.
This effect is not only being observed to produce in the hydrophilic dividing plate by sulfonation, and can also observe in the dividing plate of the acrylic acid-grafted polymerization of experience.
Acrylic acid-grafted polymerization is carried out as follows: the polyolefin nonwoven fabrics is immersed in a kind of solution, this solution comprises the acrylic acid, 76.7% percentage by weight distilled water, 0.2% percentage by weight benzophenone, the ferrous sulfate of 0.1% percentage by weight, the non-ionic surface active agent of 3.0% percentage by weight of 20% percentage by weight, and the immersion time is 10 minutes.Used solution passes through deoxidation treatment in advance, to eliminate the influence of oxygen in the aggregation processing of back as far as possible.
Nonwoven fabrics through above-mentioned processing is got rid of redundant solution, again in deoxidation atmosphere, under the about 90 ℃ temperature, be 200mW/cm with intensity with metal halide lamp
2Its two sides of UV-irradiation carrying out acrylic acid glycerol polymerization, this cloth obtains dividing plate through washing, dry, calendering again, the weight per unit area of this dividing plate is 59g/m
2, thickness is 120 ± 20 μ m, the acrylic acid-grafted degree of polymerization is 9 ± 2%.And the perforation strength of this dividing plate examined or check.Prepared the battery that adopts this dividing plate, is of a size of SUM-4, and its percent defective and cycle life characteristics have been examined or check.The gained result is similar with the result of the dividing plate that adopts sulfonation to handle.
The generation hydrophily of dividing plate is handled also can obtain similar effects by the coating surface activating agent or by corona discharge.
Undoubtedly, similar above-mentioned effect can also obtain in alkaline battery except accomplished in nickel metal hydride batteries.Alkaline battery comprises nickel-cadmium accumulator, nickel-zinc battery and manganese dioxide-Ni/metal hydride secondary cell.
As mentioned above,, provide a kind of alkaline battery, dividing plate and alkaline electrolyte that this storage battery comprises positive electrode, negative electrode, is made of the nonwoven fabrics that comprises the polyolefin resin fiber of having given hydrophilic group according to the present invention.Its median septum comprises at least two kinds of polyolefine fibers that intensity is different, the polyolefine fiber that in described polyolefine fiber, has the highest intensity, it is a kind of polyolefine fiber of high-modulus, its shared percentage by weight in all fibres that constitutes dividing plate is 5-50%, preferably a kind of high modulus polypropylene fiber of this high modulus polyolefin fibersand.The perforation strength that the employing blade of this dividing plate is measured and is not selected the high modulus polypropylene fiber for use and is compared with the dividing plate that median septum of the present invention has same units area weight and a same thickness, has improved at least 10%.So, a kind of alkaline battery is provided, its anti-leaks is improved, and the possibility that the physics leakage takes place between positive pole and negative pole when assemble has reduced, and has good life characteristic.
In addition, provide a kind of alkaline battery, dividing plate and alkaline electrolyte that this storage battery comprises positive electrode, negative electrode, is made of the nonwoven fabrics that comprises the polyolefin resin fiber of having given hydrophilic group.Its median septum 1g/m
2The perforation strength index (gf/mm) (the perforation strength index here is meant the displacement (mm) the when perforation strength (gf) of dividing plate is penetrated divided by dividing plate) of per unit area weight be 6gf/m at least.So, a kind of alkaline battery is provided, its anti-leaks is improved, and the possibility that the physics leakage takes place between positive pole and negative pole when assemble has reduced, and has good life characteristic.
Claims (13)
1. alkaline battery, comprise positive electrode, negative electrode, that constitute by the nonwoven fabrics that comprises polyolefin resin fiber and dividing plate and alkaline electrolyte that given hydrophilic group, its median septum comprises at least two kinds of polyolefine fibers that intensity is different, the polyolefine fiber that in described polyolefine fiber, has the highest intensity, be a kind of polyolefine fiber of high-modulus, its shared percentage by weight in all fibres that constitutes dividing plate is 5-50%.
2. according to the alkaline battery of claim 1, its median septum adopts a kind of nonwoven fabrics, its perforation strength and is not selected high modulus polyolefin fibersand for use and is compared with the nonwoven fabrics that above-mentioned nonwoven fabrics has same units area weight and a same thickness, has improved at least 10%.
3. according to the alkaline battery of claim 1, the hydrophilic group of its median septum is a sulfonic group.
4. according to the alkaline battery of claim 1, the hydrophilic group of its median septum is a glycerol polymerization acrylic acid.
5. according to the alkaline battery of claim 1, wherein the polyolefine fiber that has the highest intensity in described polyolefine fiber is a kind of polypropylene fibre of high-modulus.
6. according to the alkaline battery of claim 5, wherein the high modulus polypropylene fiber is a kind of like this polypropylene fibre, when the incident direction of x ray in the x x ray diffraction analysis x is vertical with the direction of this fiber, in 10-20 degree scope, present three diffraction peaks, be first peak, second peak, the 3rd peak, and observed peak to first peak is strong, is observed strong at least 7 times in peak that arrive on the same position when the x directions of rays is parallel with machine direction.
7. according to the alkaline battery of claim 5, the polypropylene fibre of wherein said high-modulus the temperature of endothermic peak occurs than polypropylene fibre height at least 5 degree in the differential scanning calorimetry analysis.
8. according to the alkaline battery of claim 5, its median septum adopts a kind of nonwoven fabrics, its perforation strength and is not selected the high modulus polypropylene fiber for use and is compared with the nonwoven fabrics that above-mentioned nonwoven fabrics has same units area weight and a same thickness, has improved at least 10%.
9. according to the alkaline battery of claim 5, the hydrophilic group of its median septum is a sulfonic group.
10. according to the alkaline battery of claim 5, the hydrophilic group of its median septum is the acrylic acid of glycerol polymerization.
11. an alkaline battery comprises positive electrode, negative electrode, that be made of the nonwoven fabrics that comprises polyolefin resin fiber and dividing plate and alkaline electrolyte that given hydrophilic group, the per unit area weight 1g/m of its median septum
2Perforation strength index (gf/mm) be 6gf/mm at least, the perforation strength index here is meant the displacement (mm) the when perforation strength (gf) of dividing plate is penetrated divided by dividing plate.
12. according to the alkaline battery of claim 11, the hydrophilic group of its median septum is a sulfonic group.
13. according to the alkaline battery of claim 11, the hydrophilic group of its median septum is the acrylic acid of glycerol polymerization.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN99110506A CN1242612A (en) | 1998-07-21 | 1999-07-21 | Alkaline storage battery |
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP204659/98 | 1998-07-21 | ||
| JP303576/98 | 1998-10-26 | ||
| CN99110506A CN1242612A (en) | 1998-07-21 | 1999-07-21 | Alkaline storage battery |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN1242612A true CN1242612A (en) | 2000-01-26 |
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ID=5274576
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN99110506A Pending CN1242612A (en) | 1998-07-21 | 1999-07-21 | Alkaline storage battery |
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|---|---|
| CN (1) | CN1242612A (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1305144C (en) * | 2001-04-06 | 2007-03-14 | 松本功 | Cell separator manufacturing method, cell separator and alkaline storage battery using said separator |
| CN106887557A (en) * | 2015-09-28 | 2017-06-23 | 日本高度纸工业株式会社 | Battery separator and the secondary cell with the dividing plate |
-
1999
- 1999-07-21 CN CN99110506A patent/CN1242612A/en active Pending
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1305144C (en) * | 2001-04-06 | 2007-03-14 | 松本功 | Cell separator manufacturing method, cell separator and alkaline storage battery using said separator |
| CN106887557A (en) * | 2015-09-28 | 2017-06-23 | 日本高度纸工业株式会社 | Battery separator and the secondary cell with the dividing plate |
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