CN102891272B - Lead accumulator - Google Patents
Lead accumulator Download PDFInfo
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- CN102891272B CN102891272B CN201210369447.7A CN201210369447A CN102891272B CN 102891272 B CN102891272 B CN 102891272B CN 201210369447 A CN201210369447 A CN 201210369447A CN 102891272 B CN102891272 B CN 102891272B
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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 provides a kind of lead accumulator, it has multiple cells, the cell has pole plate group, electrolyte and cell room, the pole plate group is accommodated in the cell room with impregnated in the state of electrolyte, the pole plate group is to be alternately arranged to form across dividing plate by multi-disc positive plate and multi-disc negative plate, wherein, the dividing plate is made up of multiple glass layers, spacing in the pole plate group between adjacent positive plate and negative plate is 0.8~1.2mm, and the electrolyte is with sulfuric acid as main component and density is 1.32~1.36g/cm3Wherein the multiple glass layer is formed by being laminated glass outer fibrage respectively on two surfaces of inner layer glass fibrage, wherein described inner layer glass fibrage be made up of the raw glass fiber that avarage fiber diameter is 4.3~4.9 μm and average pore size be 11.0~14.0 μm, the glass outer fibrage be made up of the thin glass fiber that avarage fiber diameter is 3.6~4.2 μm and average pore size be 7.0~10.0 μm.
Description
Technical field
The present invention relates to lead accumulator, specifically, relating to provide has good high rate discharging characteristic and can have
Effect ground suppresses the lead accumulator that short circuit occurs.
Background technology
Lead accumulator except for start vehicle power supply and for back-up source in addition to, be also widely used in main power source use
On the way, i.e., as independent charging/discharging apparatus power supply such as electric automobile, electric bicycle, battery-operated motor cycle, Segway Human Transporter, small
The electrical source of power of type Moped Scooter, golf cart etc., solar energy battery etc..In these purposes, the work of lead accumulator
It is as feature：Electric current is big during startup, and discharge current is smaller during driving, and discharge time is long.At the same time, reduction lead electric power storage is also required that
The maintaining in pond, particularly requires that it has cycle life more long.In terms of the long lifetime of battery, common practice
It is：Positive active material is pushed down by the pressure that is added in pole plate group of raising and with dividing plate, so as to suppress positive active material
Expansion, prevent coming off for positive active material.But, with the maximization of battery, material or increasing are changed for the electric groove of enhancing
Power-up cell wall is thick, even if so, it is also difficult to apply and maintain appropriate pressure in pole plate group.Lead accumulator with its use when
Between extension, corrosion is produced because of the oxidation of positive electrode collector, thus cause the sectional area of positive electrode collector to reduce, whole positive pole
The electric conductivity of plate declines.The result is that voltage characteristic when battery carries out high rate discharging declines.The corruption of such positive electrode collector
When erosion further develops, final positive electrode collector is broken in itself.Thus battery capacity is caused to decline rapidly.
During lead accumulator use, when discharge and recharge is repeated, battery performance can be reduced gradually.When cell performance
When can reduce, inner pressure of battery rises sometimes, so as to apply larger pressure between positive plate and negative plate.At this moment, electrode
Group is susceptible to compress or deforms.That is, electrode group has the tendency of easily to be squeezed bad when inner pressure of battery rises.
On the other hand, as the miniaturization and lightweight of electronic equipment are developed rapidly, the lead electric power storage as power supply is also required that
Pond has less volume and charge/discharge capacity higher, and it is to keep capacity constant to reduce the spacing between battery plus-negative plate plate
In the case of reduce the effective way of volume, but positive/negative plate is by obtain the too near danger for just having internal short-circuit.In positive plate
Between negative plate, the dividing plate being made up of the porous material of insulating properties is accompanied, the effect of the dividing plate is exactly that can both make positive/negative plate
Close proximity to and them can be avoided to contact with each other short circuit.Good separator material needs to absorb (absorption) with good electrolyte
Performance and mechanical strength high.From from the viewpoint of the volume for reducing pole plate group, preferably dividing plate is more thinned.When positive plate with
When negative plate is short-circuited, internal temperature of battery can rise, and at this moment also require that pole plate group has the function of ensuring security.And,
From from the viewpoint of the power characteristic and charge/discharge capacity for maintaining battery, in addition it is also necessary to ensure ion permeability and the absorption of dividing plate
With the performance for keeping electrolyte.
In addition, lead accumulator is during use, when discharge and recharge is repeated, battery performance can be reduced gradually.When
During battery performance reduction, inner pressure of battery rises sometimes, so as to apply larger pressure between positive plate and negative plate.This
When, because dividing plate is Porous, compared with positive plate and negative plate, it is easier to compression occurs or deforms.That is, inner pressure of battery rises
When dividing plate have the tendency of easily to be squeezed it is bad.As dividing plate occurs compression or deforms, the porosity of dividing plate is reduced, as a result the hole of dividing plate
The amount of the electrolyte retained in gap is reduced, and can hinder the movement of ion, so as to being repeated with discharge and recharge, battery impedance
Gradually increase.
In view of the structure and performance of dividing plate largely effect on the volume of lead accumulator, power characteristic, charge/discharge capacity and
Cycle life, so proposing the various schemes being improved to the structure and performance of dividing plate in the prior art.
The flat 2011-238492 of Japanese Patent Application Laid-Open discloses a kind of hermetic type lead accumulator dividing plate, and it is one
Trilaminate structure obtained from one layer of fine fiber layer, above-mentioned fine fiber layer are covered each by two surfaces of layer layers
Be made up of the glass fibre that avarage fiber diameter is 0.4~1.0 μm and average pore size be less than 3.5 μm, above-mentioned layers by
Avarage fiber diameter is that 1.3~4.0 μm of glass fibre composition and average pore size are more than 4.0 μm and are above-mentioned fine fiber layer
More than 1.5 times of average pore size, wherein, in above-mentioned three-layer laminate, the avarage fiber diameter of above-mentioned glass fibre is 1.2
More than μm, the ratio between thickness of above-mentioned fine fiber layer and above-mentioned layers is 10/90~50/50.By using aforementioned barriers, can
Effectively to improve the oppressive force reducing effect and anti-electrolyte stratification effect that prevent pole plate group after electrolyte is impregnated with, so that
Improve the life-span of hermetic type lead accumulator；Also, by promoting the electrolyte mobility of the thickness direction of dividing plate, improve height
Electrolyte supply liquid when rate is discharged, so that the charge-discharge characteristic of closed lead accumulator is further improved.
Hermetic type lead accumulator involved by the embodiment of the flat 2011-238492 of Japanese Patent Application Laid-Open employs close
It is 1.30g/cm to spend3Sulfuric acid solution.
Chinese patent application CN1224535A discloses a kind of glass fibre separator for battery, and the dividing plate includes mutual
The cellulose fibril of the glass fibre aggregation of entanglement and 0.2~20 weight % being dispersed in glass fibre, it is essentially all
Glass fiber diameter no more than about 20 μm, at least the glass fiber diameter of 5 weight % be less than 1 μm, the cellulose fibril come
From the very low wood pulp of Canadian beating degree such as redwood slurry or China fir slurry, by the use of the plain fibrillation of fibre improve it is above-mentioned every
The tensile strength of plate.It is 1.286g/cm that density is used in the embodiment of Chinese patent application CN1224535A3Sulfuric acid come to upper
The performance for stating dividing plate is tested.
Chinese patent application CN1276920A discloses a kind of absorbing separator for by analysing valve control type lead-acid accumulator battery, its bag
Include ground floor, the second layer that glass fibre is constituted and the conjunction that is placed between the ground floor and the second layer being made up of glass fibre
Resin band.This dividing plate improves the mechanicalnesses such as tensile strength by being applied in combination for glass layer and synthetic resin band
Matter.
On the other hand, all the time, for lead accumulator with the aspects such as the composition and physical property of electrolyte also carry out it is various
Research.Well known in the art, the electrolyte generally used in lead accumulator is that density is 1.20~1.28g/cm3Left and right
Aqueous sulfuric acid, even if adding other additives in the aqueous sulfuric acid, the density of the electrolyte of gained is also in 1.32g/cm3
Below.
Chinese patent application CN1113352A discloses a kind of electrolyte for lead accumulator, and the electrolyte is by dilute sulphur
Acid, activated carbon, cadmium sulfate and cobaltous sulfate are constituted, and its each component percentage by weight is:Density is 1.28g/cm3Dilute sulfuric acid 98~
99.8%, activated carbon 0.05~0.8%, cadmium sulfate 0.03~1.0%, cobaltous sulfate 0.02~0.6%.Can by simple calculating
Know, the density of the electrolyte is less than 1.32g/cm3。
Chinese utility model patent application CN2076712U discloses a kind of lead accumulator, wherein the electrolyte for using is acid
Class thing, its density is 1.27~1.32g/cm3, the lead accumulator is characterised by using Pb-Ca-Al alloy electrode come instead of existing
The electrode made by antimonial lead or pure lead, to cause that in charge and discharge process gas leakage amount is few, electrolyte solution loss is small.
As described above, in the prior art, studying always by the composition to dividing plate the Nomenclature Composition and Structure of Complexes or electrolyte
With some performances that the aspect such as physical property could be adjusted to improve lead accumulator.But, in the prior art, there is not yet by same
When specific setting is carried out to composition and physical property of dividing plate the Nomenclature Composition and Structure of Complexes and electrolyte etc. to provide with good high rate
Flash-over characteristic and can effectively suppress short circuit generation lead accumulator.
Therefore, the present invention is precisely in order to obtaining such lead accumulator and completing.
The content of the invention
The technical problems to be solved by the invention
It is an object of the invention to provide can suppress with good high rate discharging characteristic and effectively the lead of short circuit generation
Battery.
Solve the means of the problem
The present invention passes through to use specific multilayer insulating panel and density in the electrolyte of particular range, so as to solve above-mentioned skill
Art problem.
That is, the present invention relates to following content.
(1) a kind of lead accumulator, it has multiple cells, the cell have pole plate group, electrolyte and
Cell room, the pole plate group is accommodated in the cell room with impregnated in the state of electrolyte, and the pole plate group is
It is alternately arranged across dividing plate by multi-disc positive plate and multi-disc negative plate and is formed, wherein, the dividing plate is by multiple glass layer structures
Into the spacing in the pole plate group between adjacent positive plate and negative plate is 0.8~1.2mm, and the electrolyte is with sulphur
Acid is for main component and density is 1.32~1.36g/cm3, wherein the multiple glass layer is by inner layer glass fibrage
Two surfaces on be laminated glass outer fibrage respectively and form, wherein the inner layer glass fibrage is by avarage fiber diameter
For 4.3~4.9 μm raw glass fibers constitute and average pore size be 11.0~14.0 μm, the glass outer fibrage be by
Avarage fiber diameter is that 3.6~4.2 μm of thin glass fiber composition and average pore size is 7.0~10.0 μm.
(2), the lead accumulator according to above-mentioned (1), wherein, the dividing plate when assembling forms battery with 0.33~
0.56 compression ratio is compressed.
(3), the lead accumulator according to above-mentioned (1) or (2), wherein, the multiple glass layer is three layers, its bag
Containing an inner layer glass fibrage and two glass outers being layered in respectively on two surfaces of the inner layer glass fibrage
Fibrage.
(4), the lead accumulator according to above-mentioned (1) or (2), wherein, the spacing is 0.9~1.1mm.
(5), the lead accumulator according to above-mentioned (1) or (2), wherein, the density of the electrolyte for 1.33~
1.35g/cm3。
(6), the lead accumulator according to above-mentioned (1), wherein, the electrolyte is that the sulfuric acid comprising sulfuric acid and water is water-soluble
Liquid.
(7), the lead accumulator according to above-mentioned (1) or (6), wherein, it is also complete comprising a small amount of energy in the electrolyte
Additive of the CL in the electrolyte.
(8), the lead accumulator according to above-mentioned (1) or (2), wherein, the inner layer glass fibrage it is described average
Fibre diameter is 4.5~4.8 μm.
(9), the lead accumulator according to above-mentioned (1) or (2), wherein, the glass outer fibrage it is described average
Fibre diameter is 3.8~4.0 μm.
(10), the lead accumulator according to above-mentioned (1) or (2), wherein, the inner layer glass fibrage it is described average
Aperture is 12.0~13.0 μm.
(11), the lead accumulator according to above-mentioned (1) or (2), wherein, the glass outer fibrage it is described average
Aperture is 8.0~9.0 μm.
Invention effect
According to the present invention, by using specific multilayer insulating panel and density in the electrolyte of particular range, thus, it is possible to provide
Can suppress with good high rate discharging characteristic and effectively the lead accumulator of short circuit generation.
Brief description of the drawings
Fig. 1 is the schematic diagram of the pole plate group with multilayer insulating panel in lead accumulator of the invention.
Fig. 2 is three layers of schematic diagram of the structure of dividing plate used in lead accumulator of the invention.
Fig. 3 is five layers of schematic diagram of the structure of dividing plate used in lead accumulator of the invention.
The schematic diagram of influences of the Fig. 4 for the dividing plate and density of electrolyte used in lead accumulator to high rate discharging capacity.
Fig. 5 is the schematic diagram of the configuration mode of three layers of dividing plate described in Fig. 2 in pole plate group.
Specific embodiment
Hereinafter, the present invention will be described referring to the drawings.In the accompanying drawings, for the purpose of simplifying the description, to substantially the same
The constitutive requirements of function represented with same reference symbol.In addition, the present invention is not limited to following implementation method.
The present invention relates to a kind of lead accumulator, it has multiple cells, and above-mentioned cell has pole plate group, electrolysis
Liquid and cell room, above-mentioned pole plate group are accommodated in above-mentioned cell room with impregnated in the state of electrolyte, above-mentioned pole
Plate group is formed across dividing plate is alternately laminated by multi-disc positive plate and multi-disc negative plate, wherein, aforementioned barriers are by multiple glass fibers
Dimension layer stackup is formed, and using the electrolyte of specific density scope.
Present invention discover that while improving in the density of the electrolyte of lead accumulator, to the composition and knot of multilayer insulating panel
Compressive state row regulation when structure and multilayer insulating panel configuration are between positive plate and negative plate, enables to lead accumulator
Short-circuit generation can be suppressed with good high rate discharging characteristic and effectively.
In lead accumulator, the electrolyte for generally using is that density is 1.20~1.28g/cm3The aqueous sulfuric acid of left and right,
Even if other additives are added and dissolved in the aqueous sulfuric acid, the density of the electrolyte of gained is also in 1.32g/cm3Below.
Generally, it is considered that when using being improved as the density of the aqueous sulfuric acid of electrolyte, sulfuric acid can be caused in lead accumulator field
Chemical reaction between lead is more active, so that lead is difficult to separate out, the capacity of battery is improved.But, on the other hand,
When using being improved as the density of the aqueous sulfuric acid of electrolyte, and the viscosity of sulfuric acid is excessive, have impact on electrolyte in dividing plate
In circulation, adsorb sulfuric acid in dividing plate and also easily flow downward or precipitate downwards, thus sulfuric acid is susceptible to layering, from
And influence the cycle life of battery.
In order to prevent being layered in the larger sulfuric acid of dividing plate Midst density, attempt adjusting the Nomenclature Composition and Structure of Complexes of dividing plate
Section, as a result finds, when dividing plate fibrage less using the aperture being made up of the less fine fibre of fibre diameter, can be preferable
Ground suppress sulfuric acid layering, but to a certain extent simultaneously will also result in sulfuric acid be difficult flowing, so as to influence the capacity of battery.In
It is, the less fibrage in aperture that will be made up of the less fine fibre of fibre diameter of trial and by the larger crude fibre of fibre diameter
The stepped construction that the larger fibrage in the aperture of composition is laminated is used as dividing plate, as a result finds, can be with such dividing plate
Take into account the capacity and cycle life of battery.
Lead accumulator is also required that with good high rate discharging characteristic, and this requires adjacent positive pole in above-mentioned pole plate group
Spacing between plate and negative plate is smaller, but if if too small, the precipitate such as dendrite is accessible to occur short circuit to electrode
Rough sledding, and can to configure the dividing plate between above-mentioned positive plate and negative plate produce compression, also can to electrolysis
Distribution of the liquid in dividing plate produces some to influence, specifically, when the spacing between above-mentioned positive plate and negative plate is too small, every
Flaggy can be overly compressed, and electrolyte can only keep small amount, so that the reduction of high rate discharging capacity.In above-mentioned positive plate and negative pole
When spacing between plate is larger, the dividing plate configured between above-mentioned positive plate and negative plate can be recessed so that haptoreaction
Area is reduced, the reduction of high rate discharging capacity.
In the present invention, the main component of electrolyte is sulfuric acid and density is 1.32~1.36g/cm3, the electrolyte is preferred
It is the aqueous sulfuric acid comprising sulfuric acid and water, also the electrolyte can be dissolved completely in comprising a small amount of in above-mentioned electrolyte
In additive such as silica, sodium tetraborate, sodium sulphate etc., the content of above-mentioned additive is, for example, in above-mentioned electrolyte
0.2~1.0 weight %.From from the aspect of the capacity for improving battery, the density of electrolyte is set as 1.32g/cm3More than.From
Prevent sulfuric acid from layering occurring and from the aspect of influenceing the cycle life of battery, the density of electrolyte is set as 1.36g/cm3With
Under.The density of above-mentioned electrolyte is preferably 1.33~1.35g/cm3。
In the present invention, aforementioned barriers are made up of multiple glass layers, wherein above-mentioned multiple glass layers are including
Glass outer fibrage is laminated respectively on two surfaces of layer glass layer to form, above-mentioned inner layer glass fibrage is by with flat
The equal larger raw glass fiber of fibre diameter be that main body is constituted and average pore size be it is larger, above-mentioned glass outer fibrage be by
With avarage fiber diameter be that less thin glass fiber is constituted as main body and average pore size is smaller.
Above-mentioned inner layer glass fibrage can be containing 70~100 weight % above-mentioned raw glass fiber and 0~30 weight %
The organic fiber with acid resistance and hot-melt-bondable.Above-mentioned glass outer fibrage can contain 70~100 weight %
Above-mentioned thin glass fiber and 0~30 weight % the organic fiber with acid resistance and hot-melt-bondable.As above-mentioned tool
There is the organic fiber of acid resistance and hot-melt-bondable, can include：Polyolefine fiber, polyester fiber, polyacrylonitrile fibre,
Polyaramide fibers etc..
Above-mentioned inner layer glass fibrage is preferably made up of above-mentioned raw glass fiber, i.e., above-mentioned raw glass fiber is in above-mentioned internal layer
Content in glass layer is 100 weight %.
Above-mentioned glass outer fibrage is preferably made up of above-mentioned thin glass fiber, i.e., above-mentioned thin glass fiber is in above-mentioned outer layer
Content in glass layer is 100 weight %.
Above-mentioned inner layer glass fibrage is preferably to be made up of the raw glass fiber that avarage fiber diameter is 4.3~4.9 μm
And average pore size is 11.0~14.0 μm.It is 3.6~4.2 μm that above-mentioned glass outer fibrage is preferably by avarage fiber diameter
Thin glass fiber into and average pore size be 7.2~10.0 μm.
From from the aspect of taking into account the capacity and cycle life of battery, the above-mentioned average fiber of above-mentioned inner layer glass fibrage
Diameter is preferably 4.5~4.8 μm, and the above-mentioned avarage fiber diameter of above-mentioned glass outer fibrage is preferably 3.8~4.0 μm.
From from the aspect of taking into account the capacity and cycle life of battery, the above-mentioned average pore size of above-mentioned inner layer glass fibrage
Preferably 12.0~13.0 μm, the above-mentioned average pore size of above-mentioned glass outer fibrage is preferably 8.0~9.0 μm.
The thickness of above-mentioned inner layer glass fibrage is preferably 0.9~1.4mm.
Above-mentioned glass outer fibrage can be one, or multiple.The thickness of each glass outer fibrage is excellent
Elect 0.2~0.45mm as.
Above-mentioned inner layer glass fibrage is formed preferably through wet type pulping method, and above-mentioned glass outer fibrage is preferred
Also formed again by wet type pulping method with above-mentioned inner layer glass fibrage.
Above-mentioned multiple glass layers for constituting aforementioned barriers are preferably three layers, and it includes an inner layer glass fiber
Layer and two glass outer fibrages being layered in respectively on two surfaces of above-mentioned inner layer glass fibrage.Fig. 2 is the present invention
Lead accumulator used in three layers of schematic diagram of the structure of dividing plate.As shown in Fig. 2 aforementioned barriers include an inner layer glass
Fibrage 5a and two glass outer fibrage 5b being layered in respectively on two surfaces of above-mentioned inner layer glass fibrage 5a.On
State inner layer glass fibrage to be formed by wet type pulping method, above-mentioned glass outer fibrage is also fine with above-mentioned inner layer glass
Dimension layer is formed again by wet type pulping method, using preceding that an above-mentioned inner layer glass fibrage and two is above-mentioned outer
Layer glass fibre layer stackup and form three layers of dividing plate, that is, on two surfaces of above-mentioned inner layer glass fibrage
It is laminated two above-mentioned glass outer fibrages and turns into three layers of dividing plate.
Above-mentioned multiple glass layers for constituting aforementioned barriers can also be five layers, and it includes an inner layer glass fibre
Dimension layer, two the first glass outer fibrages being layered in respectively on two surfaces of above-mentioned inner layer glass fibrage and difference
It is layered in two the second glass outer fibrages on two surfaces of above-mentioned first glass outer fibrage.At this moment, in above-mentioned
Layer glass layer is using the larger crude fibre of fibre diameter, and above-mentioned second glass outer fibrage is less using fibre diameter
Fine fibre, above-mentioned first glass outer fibrage uses fibre of the fibre diameter between above-mentioned crude fibre and above-mentioned fine fibre
Dimension.Fig. 3 is five layers of schematic diagram of the stepped construction of dividing plate used in lead accumulator of the invention.As shown in figure 3, it is above-mentioned every
Plate comprising inner layer glass fibrage 5a, be layered in respectively on two surfaces of above-mentioned inner layer glass fibrage 5a two the
One glass outer fibrage 5b and be layered in respectively on two surfaces of above-mentioned first glass outer fibrage 5b two second
Glass outer fibrage 5c.
In the present invention, the spacing between positive plate adjacent in the above-mentioned pole plate group and negative plate is 0.8~1.2mm,
From from the aspect of the high rate discharging characteristic of battery, above-mentioned spacing is preferably 0.9~1.1mm.
In the present invention, between aforementioned barriers are configured in adjacent positive plate and negative plate in the above-mentioned pole plate group, should
Dividing plate is compressed when assembling forms battery with 0.33~0.56 compression ratio.The compression ratio is by the gross thickness of aforementioned barriers
And the difference of the spacing between above-mentioned positive plate and negative plate is calculated divided by the gross thickness of aforementioned barriers.
Fig. 1 is the schematic diagram of the pole plate group with multilayer insulating panel in lead accumulator of the invention.Above-mentioned pole plate group be by
Multi-disc positive plate and multi-disc negative plate are alternately arranged across aforementioned barriers and form.
Fig. 5 is the schematic diagram of the configuration mode of three layers of dividing plate described in Fig. 2 in pole plate group.
The collector of above-mentioned positive plate is preferably to draw in the net grid (hereinafter sometimes referred to as exp), at this moment as the collection of positive plate
The grid that draws in the net of electric body does not have horizontal edge bone, and the electric conductivity of positive pole will not be made excessive, therefore the electrical collector of positive pole relatively declines, from
And when avoiding high rate discharging positive electrode active material overdischarge such that it is able to obtain the effect of battery long lifetime.Negative plate
Collector can be draw in the net grid or casting grid (hereinafter sometimes referred to as cast).
In lead accumulator, battery capacity is exactly the capacitance for criticizing pole, and the exoelectrical reaction of battery is across dividing plate phase
Towards positive pole and negative pole between carry out, it is therefore desirable that the two sides of positive pole is practised physiognomy with negative pole to therefore being filled from raising
From the viewpoint of discharging efficiency and cost control, the outermost of preferably above-mentioned pole plate group is negative plate, i.e. negative plate ratio
Positive plate is more 1.
Lead accumulator of the invention is preferably valve-regulated lead-acid battery.
Fig. 4 is compound glass fibrage dividing plate (multilayer insulating panel) used in lead accumulator of the invention and is electrolysed liquid-tight
Spend the schematic diagram of the influence to high rate discharging capacity.As shown in figure 4, by using above-mentioned compound glass fibrage dividing plate and 1.32
~1.36g/cm3Higher density scope electrolyte, can be than using existing single layer separator and same density range
Electrolyte realizes considerably higher high rate discharging capacity.In fig. 4, the curve representated by multilayer insulating panel is respectively by ratio described later
Drawn compared with the result obtained by example 1, embodiment 1~5 and comparative example 2 and formed, the curve representated by single layer separator is respectively by rear
Result obtained by the comparative example 7-13 for stating is drawn and is formed.
And, the content according to Fig. 4 also knows, when the density of electrolyte is less than 1.32g/cm3Or higher than 1.36g/
cm3In the case of, high rate discharging capacity can be reduced substantially.
Hereinafter, the present invention is specifically explained based on embodiment, but these embodiments are illustration of the invention, this
Invention is not limited to these embodiments.
(embodiment 1)
(1) making of pole plate group
Three layers of dividing plate being laminated using three fibrages being made up of 100 weight % glass fibres respectively, that is,
The three layers of dividing plate for being laminated two glass outer fibrages on the two of inner layer glass fibrage surfaces and being formed, wherein interior
The average fibre diameter of the glass fibre that layer glass layer is used is 4.6 μm, and the average pore size of inner layer glass fibrage is
12.6 μm, the average fibre diameter of the glass fibre that glass outer fibrage is used is 3.9 μm, glass outer fibrage it is flat
Equal aperture is 8.39 μm, wherein, the thickness of inner layer glass fibrage is 1.4mm, and the thickness in monolayer of glass outer fibrage is
0.4mm, the gross thickness of dividing plate is inner layer glass fibrage and two glass outer fibrage sums, is 1.8mm.
According to above-mentioned identical mode, multi-disc positive plate and multi-disc negative plate are alternately weighed across aforementioned barriers respectively
Folded, so as to obtain pole plate group, the piece number of above-mentioned multi-disc positive plate is 4~9, and the piece number of above-mentioned multi-disc negative plate is 5~10.
(2) manufacture of lead accumulator
The positive pole ear of same polarity in the single pole plate group of above-mentioned acquisition is connected to together respectively and obtains positive bus,
It is the negative lug of same polarity is welded together and obtain negative bus-bar.Each pole plate group is received in the cell housing respectively
The multiple cell rooms separated by spaced walls in.By by a negative bus-bar for pole plate group and adjacent pole plate group
Positive bus are welded, and so as to two adjacent pole plate groups be connected in series, have thus successively been connected in series each pole plate group
Come, that is, each cell is together in series.In above-mentioned pole plate group, the spacing between adjacent positive plate and negative plate
It is 1.0mm, the compression ratio of dividing plate is 0.44.
In the pole plate group that above-mentioned multiple is connected in series, a pole plate group in two pole plate groups at final two ends
Positive bus be connected with positive terminal, the negative bus-bar of another pole plate group is connected with negative terminal.Then, by battery
Lid is installed on the opening of battery container.Then, poured into each cell from liquid inlet set on battery cover
Concentration is 1.32g/cm3Aqueous sulfuric acid as electrolyte, and be melted into the cell housing.After chemical conversion, will have
There are gas and the valve of pressure venting for inside battery is produced to be fixed in liquid inlet, so as to obtain lead accumulator.
(3) performance to lead accumulator is evaluated
High rate discharging capacity and short-circuit incidence to the lead accumulator of above-mentioned gained are measured, and the result of gained is shown in
In table described later 1.
The assay method of discharge capacity is as follows：
Battery specifications：12V, 20Ah
Charge condition：Charged with the constant voltage of 14.7V, at most charged 12 hours
Discharging condition：With 60A (3C) constant current discharge, until voltage is down to 9.6V
Specifically, the new product battery manufactured within 30 days is carried out into voltage, after the measure of internal resistance and weight, in environment temperature
Spend under the conditions of 25 DEG C by with 60A (3C) constant current discharge, discharge into 9.6V terminate after, record discharge time (unit is hour,
It is abbreviated as h), thus calculating discharge capacity.
Short-circuit incidence assay method is as follows：
After assembling is made battery, charged after being melted into, then discharged 9 hours with 0.1C, by the voltage of at this moment gained
It is judged to there occurs short circuit in the battery of below 10.0V.There occurs short-circuit cell number institute in the battery sum for being produced
The percentage for accounting for is used as short-circuit incidence.That is, the battery of the cell number of short-circuit incidence (%)=there occurs short circuit/produced is total
Number.
(embodiment 2~5)
In embodiment 2~5, except the density for making electrolyte is respectively 1.33~1.36g/cm3Outside, other according to
Setting condition same as Example 1 is obtained pole plate group and lead accumulator.Then to the high rate of the lead accumulator of above-mentioned gained
Discharge capacity and short-circuit incidence are measured, and the result of specific setting condition and gained is shown in table described later 1.
(comparative example 1,2)
In comparative example 1,2, except the density for making electrolyte is respectively 1.30 and 1.38g/cm3Outside, other according to
Setting condition same as Example 1 is obtained pole plate group and lead accumulator.Then to the high rate of the lead accumulator of above-mentioned gained
Discharge capacity and short-circuit incidence are measured, and the result of specific setting condition and gained is shown in table described later 1.
Knowable to the result of the gained of embodiment 1~5, when the density of electrolyte is respectively 1.32~1.36g/cm3Scope
It is interior, it is possible to achieve good high rate discharging capacity and short-circuit incidence is low.
But, knowable to the result of the gained of comparative example 1 and 2, when the density of electrolyte is less than 1.32g/cm3Or exceed
1.36g/cm3When, high rate discharging capacity can decrease, or be susceptible to short circuit.It is believed that its reason is, in comparative example
It is less 1.30g/cm as the density of the aqueous sulfuric acid of electrolyte in 13So that the chemical reaction between sulfuric acid and lead
Less active, facial pallor is easily separated out, and causes to be susceptible to short circuit, and cause high rate discharging capacity relatively low.In comparative example 2, make
For the density of the aqueous sulfuric acid of electrolyte is larger 1.38g/cm3So that the viscosity of sulfuric acid is excessive, have impact on electrolyte and exists
Circulation in dividing plate, so as to cause high rate discharging capacity relatively low.
In sum, in the case of using identical multilayer insulating panel, the density of electrolyte is improved to a certain extent
When, can cause that the high rate discharging capacity of battery is improved, and short circuit is less likely to occur.But, when by the close of electrolyte
When degree is further improved, the high rate discharging capacity of battery can decrease on the contrary.Therefore, from the high rate discharging capacity for improving battery
From the aspect of occurring with suppression short circuit, the density of electrolyte is preferably set as 1.32~1.36g/cm3, more preferably 1.33~
1.35g/cm3。
(embodiment 6~9)
In embodiment 6~9 so that the spacing in the pole plate group between adjacent positive plate and negative plate is respectively 0.8
~1.2mm, the compression ratio of dividing plate are 0.56~0.33, using identical multilayer insulating panel, and keep the density of electrolyte to be
1.34g/cm3Constant, in addition, other are obtained pole plate group and lead electric power storage according to setting condition same as Example 3
Pond.Then the high rate discharging capacity to the lead accumulator of above-mentioned gained is measured with short-circuit incidence, specifically sets condition
It is shown in table described later 1 with the result of gained.
(comparative example 3,4)
In comparative example 3,4, except causing that the spacing between adjacent positive plate and negative plate in pole plate group is respectively
0.7mm, 1.3mm, the compression ratio of dividing plate are respectively outside 0.61 and 0.28, and other are according to setting bar same as Example 6
Part is obtained pole plate group and lead accumulator.Then the high rate discharging capacity to the lead accumulator of above-mentioned gained enters with short-circuit incidence
Row is determined, and the result of specific setting condition and gained is shown in table described later 1.
Knowable to the result of the gained of embodiment 6~9, in the case of using identical multilayer insulating panel and density of electrolyte,
When the spacing between positive plate and negative plate adjacent in pole plate group be respectively 0.8~1.2mm, dividing plate compression ratio be 0.56
In the range of~0.33, it is possible to achieve the good high rate discharging capacity and rate that is short-circuited is very low.
But, knowable to the result of the gained of comparative example 3 and 4, when between positive plate and negative plate adjacent in pole plate group
Spacing less than 0.8mm or more than 1.2mm, dividing plate compression ratio less than 0.33 or during more than 0.56, high rate discharging capacity meeting
Decrease, and be possible to be susceptible to short circuit.It is believed that its reason is, it is adjacent in pole plate group in comparative example 4
Spacing between positive plate and negative plate is larger 1.3mm, and the compression ratio of dividing plate is less 0.28 so that configuration is above-mentioned
Dividing plate between positive plate and negative plate can be recessed so that haptoreaction area is reduced, the reduction of high rate discharging capacity.Than
In compared with example 3, the less 0.7mm of spacing in the pole plate group between adjacent positive plate and negative plate, the compression ratio of dividing plate be compared with
Big 0.61 so that the precipitate such as dendrite is accessible to the rough sledding for occurring short circuit to electrode, and dividing plate internal layer glass
Glass fibrage can be overly compressed, and electrolyte can only keep small amount, so as to cause the reduction of high rate discharging capacity.
In sum, in the case of using identical multilayer insulating panel and density of electrolyte, put from the high rate for improving battery
Capacitance and it is less likely to occur from the aspect of short circuit, preferably by between positive plate and negative plate adjacent in the pole plate group
Away from being set as in the range of 0.8~1.2mm, the compression ratio of dividing plate be set as in the range of 0.56~0.33.
(embodiment 10~14)
In embodiment 10~14, become the inner layer glass fibrage in dividing plate and the thickness of glass outer fibrage
Change, other are obtained pole plate group and lead accumulator according to condition is set with the identical of embodiment 6~9.Then to above-mentioned gained
Lead accumulator high rate discharging capacity and short-circuit incidence be measured, after the result of specific setting condition and gained is shown in
In the table 1 stated.
(comparative example 5,6)
In comparative example 5,6, except causing that the spacing between adjacent positive plate and negative plate in pole plate group is respectively
0.7mm, 1.3mm, the compression ratio of dividing plate are respectively outside 0.61 and 0.28, and other are according to setting bar same as in Example 10
Part is obtained pole plate group and lead accumulator.Then the high rate discharging capacity to the lead accumulator of above-mentioned gained enters with short-circuit incidence
Row is determined, and the result of specific setting condition and gained is shown in table described later 1.
Knowable to the result of embodiment 10~14 and the gained of comparative example 5,6, even if the inner layer glass fibrage in dividing plate
In the case of being changed within the specific limits with the thickness of glass outer fibrage, when adjacent positive plate in pole plate group and
Spacing between negative plate is respectively the compression ratio of 0.8~1.2mm, dividing plate in the range of 0.56~0.33, still can be real
The now good high rate discharging capacity and rate that is short-circuited is very low.
(comparative example 7~13)
In comparative example 7~13, multilayer insulating panel is not used, but use the single layer separator being made up of glass fibre, the list
Layer dividing plate avarage fiber diameter and average pore size as shown in table 1, in addition, other respectively according to comparative example 1, implement
Example 1~5, the identical of comparative example 2 set condition pole plate group and lead accumulator is obtained.Then to the lead accumulator of above-mentioned gained
High rate discharging capacity and short-circuit incidence are measured, and the result of specific setting condition and gained is shown in table described later 1.
Result by comparative example 7~13 respectively with corresponding comparative example 1, embodiment 1~5, the gained of comparative example 2 is compared
Understand, high rate discharging capacity is substantially reduced.It is believed that its reason is, single layer separator compared with multilayer insulating panel, in single layer separator
The flowing of middle electrolyte, distribution and circulate it is bad, so causing the high rate discharging capacity substantially to reduce.
Industrial applicibility
The invention provides with low cost and function admirable lead accumulator, the battery can be applied to electric automobile, electricity
The electrical source of power of dynamic bicycle, battery-operated motor cycle, Segway Human Transporter, Moped Scooter etc..
Claims (11)
1. a kind of lead accumulator, it has multiple cells, and the cell has pole plate group, electrolyte and monomer electricity
Pond room, the pole plate group is accommodated in the cell room with impregnated in the state of electrolyte, and the pole plate group is by multi-disc
Positive plate and multi-disc negative plate are alternately arranged across dividing plate and form, wherein, the dividing plate is made up of multiple glass layers, in institute
It is 0.8~1.2mm to state the spacing between adjacent positive plate and negative plate in pole plate group, and it with sulfuric acid is main that the electrolyte is
Composition and density are 1.32~1.36g/cm3, wherein the multiple glass layer is by two tables in inner layer glass fibrage
Glass outer fibrage is laminated on face respectively to form, wherein the inner layer glass fibrage be by avarage fiber diameter be 4.3~
4.9 μm of raw glass fiber is constituted and average pore size is 11.0~14.0 μm, and the glass outer fibrage is by average fine
The thin glass fiber composition and average pore size for tieing up a diameter of 3.6~4.2 μm is 7.0~10.0 μm.
2. lead accumulator according to claim 1, wherein, the dividing plate is when assembling forms battery with 0.33~0.56
Compression ratio is compressed.
3. lead accumulator according to claim 1 and 2, wherein, the multiple glass layer is three layers, and it includes one
Inner layer glass fibrage and two glass outer fibrages being layered in respectively on two surfaces of the inner layer glass fibrage.
4. lead accumulator according to claim 1 and 2, wherein, the spacing is 0.9~1.1mm.
5. lead accumulator according to claim 1 and 2, wherein, the density of the electrolyte is 1.33~1.35g/cm3。
6. lead accumulator according to claim 1, wherein, the electrolyte is the aqueous sulfuric acid comprising sulfuric acid and water.
7. the lead accumulator according to claim 1 or 6, wherein, can be dissolved completely in comprising a small amount of in the electrolyte
Additive in the electrolyte.
8. lead accumulator according to claim 1 and 2, wherein, the average fiber of the inner layer glass fibrage is straight
Footpath is 4.5~4.8 μm.
9. lead accumulator according to claim 1 and 2, wherein, the average fiber of the glass outer fibrage is straight
Footpath is 3.8~4.0 μm.
10. lead accumulator according to claim 1 and 2, wherein, the average pore size of the inner layer glass fibrage is
12.0~13.0 μm.
11. lead accumulators according to claim 1 and 2, wherein, the average pore size of the glass outer fibrage is
8.0~9.0 μm.
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Families Citing this family (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20140272535A1 (en) * | 2013-03-15 | 2014-09-18 | Hollingsworth & Vose Company | Three-region battery separator |
| JP6846933B2 (en) * | 2014-05-05 | 2021-03-24 | ダラミック エルエルシー | Improved lead-acid battery separators, batteries and methods of manufacturing them |
| US9293748B1 (en) * | 2014-09-15 | 2016-03-22 | Hollingsworth & Vose Company | Multi-region battery separators |
| JP6699383B2 (en) * | 2016-06-15 | 2020-05-27 | 日立化成株式会社 | Lead acid battery |
| CN106848413B (en) * | 2017-01-20 | 2019-10-01 | 天能电池集团股份有限公司 | A kind of lead storage battery pole group |
| CN109841767A (en) * | 2017-11-27 | 2019-06-04 | 广西明福科技有限公司 | A kind of safety-type lead storage battery |
| JP6927325B2 (en) * | 2017-12-05 | 2021-08-25 | 昭和電工マテリアルズ株式会社 | Separator for lead-acid battery and lead-acid battery |
| CN113964449B (en) * | 2021-09-02 | 2024-04-19 | 浙江南都电源动力股份有限公司 | Glass fiber separator for improving power performance of lead-acid storage battery and forming method |
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| CN1571208A (en) * | 2004-05-08 | 2005-01-26 | 安阳成翔电器有限公司 | Valve controlled type fully-sealed colloidal electrolyte lead-acid accumulator |
| CN102265427A (en) * | 2008-11-11 | 2011-11-30 | 日本板硝子株式会社 | Separator for sealed lead acid battery and sealed lead acid battery |
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| JP5432813B2 (en) * | 2010-05-11 | 2014-03-05 | 日本板硝子株式会社 | Sealed lead-acid battery separator and sealed lead-acid battery |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN1571208A (en) * | 2004-05-08 | 2005-01-26 | 安阳成翔电器有限公司 | Valve controlled type fully-sealed colloidal electrolyte lead-acid accumulator |
| CN102265427A (en) * | 2008-11-11 | 2011-11-30 | 日本板硝子株式会社 | Separator for sealed lead acid battery and sealed lead acid battery |
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