CN103296234B - Valve-regulated lead-acid battery - Google Patents
Valve-regulated lead-acid battery Download PDFInfo
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- CN103296234B CN103296234B CN201310050690.7A CN201310050690A CN103296234B CN 103296234 B CN103296234 B CN 103296234B CN 201310050690 A CN201310050690 A CN 201310050690A CN 103296234 B CN103296234 B CN 103296234B
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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
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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
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- Y02P70/00—Climate change mitigation technologies in the production process for final industrial or consumer products
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Abstract
A kind of valve-regulated lead-acid battery, its have resinous electricity groove and be accommodated in above-mentioned electricity groove by positive plate and negative plate across the opposed pole plate group of dividing plate and electrolyte, wherein, at least one place between aforementioned barriers and above-mentioned positive plate and between aforementioned barriers and above-mentioned negative plate is configured with the sulfate containing alkali metal or alkaline-earth metal.Or, aforementioned barriers includes the 1st dividing plate formed by glass fiber mat and the 2nd dividing plate formed by glass fiber mat or non-woven fabrics, above-mentioned 1st dividing plate neighboringly configures with above-mentioned positive plate, above-mentioned 2nd dividing plate neighboringly configures with above-mentioned negative plate, configures sulfate and be configured with the sulfate containing alkali metal or alkaline-earth metal between above-mentioned 1st dividing plate and above-mentioned positive plate, between above-mentioned 2nd dividing plate and above-mentioned negative plate or between above-mentioned 1st dividing plate and above-mentioned 2nd dividing plate.Above-mentioned lead accumulator can be greatly decreased after the operation injecting electrolyte the generation of dendrite short circuit when continuing charging, and reliability is high.
Description
Technical field
The present invention relates to the technology of dendrite short circuit fault when suppression produces valve-regulated lead-acid battery.
Background technology
In recent years, global warming is considered a problem, for being come by the internal combustion engine such as petrol engine, Diesel engine
The vehicle driven, it is desirable to cut down CO2Discharge capacity.Particularly, go-cart, fork truck etc. are driven in the airtight working spaces such as warehouse
Vehicle for, the degree of above-mentioned requirements is bigger.In response to these requirements, the most urgently carry out a part with internal combustion engine be
The vehicle of power is converted to the research of electric motor car.
As the main power source of the go-cart of motorized, fork truck etc., it is widely used than nickel-hydrogen accumulator, lithium secondary battery more just
Suitable and maneuverable lead accumulator.Lead accumulator is roughly divided into open and valve-regulated both, for such use, in the past
Have employed the open lead accumulator that can carry out the periodic maintenance such as fluid infusion operation.But, in recent years, in order to reduce due to operation
Deng and the manpower burden etc. that produces, be currently in use and need not the valve-regulated lead-acid battery of maintenance itself and (particularly add positive pole
Plate and the number of negative plate and type that two-forty charge-discharge characteristic is improved) as main power source.
Store for adding the valve-regulated lead of the number of positive plate and negative plate to improve two-forty charge-discharge characteristic
For battery, it is known that owing to correspondingly setting the least by pole plate distance each other, therefore injecting the sulphur as electrolyte
When continuing to be charged after the operation of acid, it is susceptible to the dendrite short circuit produced due to the dissolution of lead ion.
And, lead-acid accumulator is after fluid injection and when charging (being internalized into) starts, owing to sulfuric acid is from pole plate group four circumference pole
Plate group switching centre spreads, and along with chemical reaction, sulfuric acid is consumed, and causes the pH value at pole plate group switching centre relatively to raise, due to pH
The rising of value, the dissolution for lead ion provides favourable environment.When charging starts, lead ion is reduced to gold in dividing plate
Belonging to lead, this metallic lead likely runs through dividing plate makes positive plate/negative plate be connected and cause dendrite short circuit.
The method suppressed dendrite short circuit in the past is typically to add a certain amount of additive in the electrolytic solution, but this
Method can not fundamentally stop the generation of dendrite short circuit.
It addition, in order to dendrite short circuit is suppressed, also the dividing plate being arranged between pole plate has been carried out meticulous research.Its
In, it is believed that make inorganic compound solid as described in Japanese Unexamined Patent Publication 2001-283810 publication (hereinafter referred to as patent document 1)
It is scheduled in the internal voids of the dividing plate based on glass fibre, can prevent dendrite from growing up physically.
Patent Document 1 discloses a kind of closed lead accumulator dividing plate, it is being obtained by with the wet type method of manufacturing paper with pulp
Fine glass fibre be main body sheet material in disperse inorganic powder, this inorganic powder is solid by water-soluble inorganic salt
It is scheduled in the hole of above-mentioned sheet material.This water-soluble inorganic salt is mainly deposited sticking to the state on above-mentioned inorganic powder surface
?.The effect of above-mentioned inorganic powder is dispersed in the hole of dividing plate, is controlled the pore structure of dividing plate so that dividing plate
Pore structure become complicated and be similar to labyrinth such that it is able to prevent PbSO4The direct through diaphragm internal of crystal, it is possible to make branch
Brilliant through dividing plate and distance (i.e. time) required for being connected by two pole plates extends, it is possible to reduce the generation of dendrite short circuit
Rate.Above-mentioned inorganic powder mainly is fixed on glass fibre suppress it at dividing plate by the effect of above-mentioned water-soluble inorganic salt
Fall off during work.Aforementioned barriers is to have disperseed above-mentioned inorganic powder and above-mentioned nothing by being immersed in by fiberglass packing sheet material
The solution of machine water-soluble inorganic salt is made.Above-mentioned inorganic powder is silica, aluminum oxide or titanium dioxide.Above-mentioned
Inorganic water-soluble inorganic salts can be sulfate.
But, even if using such as the prior art as described in patent document 1(includes patent document 1) physically hinder branch
The method of brilliant growing path, can not be greatly decreased in above-mentioned operation produced rough sledding.For as patent document 1 that
Sample makes SiO2Be arranged in the inside of glass fiber mat dividing plate in inorganic compound, the method for physically dendrite inhibition short circuit is come
Say, in the case of the sulfuric acid concentration used when charging is low, in addition to the lead ion of dissolution sharply increases, inorganic compound
Configuration variance also makes a difference, therefore, it is difficult to dendrite inhibition is short-circuit.
Summary of the invention
It is an object of the invention to, it is provided that solve the valve-regulated lead-acid battery of the problems referred to above, it is greatly decreased and is injecting electricity
Continue dendrite short circuit when being charged after solving the operation of liquid, and productivity ratio and reliability are high.
In order to solve the problems referred to above, inventor is through conscientious research, found that permissible by position configuring
Becoming the sulfate of the source of supply of sulfate ion, lead ion is combined with the sulfate ion of this sulfate, forms lead sulfate during charging,
It is thus possible to the dendrite short circuit (precipitation of lead ion) that suppression is caused by the supply deficiency of sulfate ion.This effect i.e. can be passed through
In the position that lead ion dissolution is promoted, i.e. between dividing plate from pole plate (positive plate or negative plate) or different two every
Rather than configure sulfate in the inside of dividing plate (preferably on the surface of dividing plate) between plate to play.
The present invention relates to following content.
(1) a kind of valve-regulated lead-acid battery, its have resinous electricity groove and be accommodated in described electricity groove by positive pole
Plate and negative plate are across the opposed pole plate group of dividing plate and electrolyte, wherein,
At least one place configuration between described dividing plate and described positive plate and between described dividing plate and described negative plate
There is the sulfate containing alkali metal or alkaline-earth metal.
(2) valve-regulated lead-acid battery as described in above-mentioned (1), wherein, described sulfate is alkali metal sulfates or alkaline earth
Metal sulfate.
(3) valve-regulated lead-acid battery as described in above-mentioned (2), wherein, described sulfate is sodium sulphate.
(4) valve-regulated lead-acid battery as described in above-mentioned (1), wherein, between described positive plate and described negative plate away from
From for 0.4～1.0mm.
(5) valve-regulated lead-acid battery as described in above-mentioned (1), wherein, the configuration amount of described sulfate be 0.008～
0.3g/cm2。
(6) valve-regulated lead-acid battery as described in above-mentioned (1) or (3), wherein, the configuration amount of described sulfate is 0.010
～0.2g/cm2。
(7) valve-regulated lead-acid battery as described in above-mentioned (1), wherein, at least by described pole plate group in pad-face direction
Central portion up and down and time left and right carries out trisection respectively is configured with described sulfate.
(8) valve-regulated lead-acid battery as described in above-mentioned (1) or (7), wherein, on the surface of positive plate and negative plate or
Described sulfate it is configured with on the surface of dividing plate described in person.
(9) valve-regulated lead-acid battery as described in above-mentioned (1), wherein, every among described positive plate and described negative plate
The area of one is 135cm2～288cm2。
(10) valve-regulated lead-acid battery as described in above-mentioned (1), wherein, described electrolyte is the sulfuric acid comprising sulfuric acid and water
The aqueous solution.
(11) valve-regulated lead-acid battery as described in above-mentioned (1) or (10), wherein, the proportion of described electrolyte is 1.200
～1.310g/cm3。
(12) a kind of valve-regulated lead-acid battery, its have resinous electricity groove and be accommodated in described electricity groove by positive pole
Plate and negative plate are across the opposed pole plate group of dividing plate and electrolyte, wherein,
Described dividing plate includes the 1st dividing plate that formed by glass fiber mat and is formed by glass fiber mat or non-woven fabrics
2nd dividing plate,
Described 1st dividing plate neighboringly configures with described positive plate, and described 2nd dividing plate neighboringly configures with described negative plate,
Between described 1st dividing plate and described positive pole, between described 2nd dividing plate and described negative pole or described 1st dividing plate
And it is configured with the sulfate containing alkali metal or alkaline-earth metal between described 2nd dividing plate.
(13) valve-regulated lead-acid battery as described in above-mentioned (12), wherein, described sulfate is alkali metal sulfates or alkali
Earth metal sulfate.
(14) valve-regulated lead-acid battery as described in above-mentioned (13), wherein, described sulfate is sodium sulphate.
(15) valve-regulated lead-acid battery as described in above-mentioned (12), wherein, between described positive plate and described negative plate
Distance is 0.4～1.0mm.
(16) valve-regulated lead-acid battery as described in above-mentioned (12), wherein, the configuration amount of described sulfate be 0.008～
0.3g/cm2。
(17) valve-regulated lead-acid battery as described in above-mentioned (12) or (14), wherein, the configuration amount of described sulfate is
0.010～0.2g/cm2。
(18) valve-regulated lead-acid battery as described in above-mentioned (12), wherein, at least by described pole plate group in pad-face side
It is configured with described sulfate to the central portion up and down and time left and right carries out trisection respectively.
(19) valve-regulated lead-acid battery as described in above-mentioned (12) or (18), wherein, at described 1st dividing plate or the described 2nd
Described sulfate it is configured with on the surface of dividing plate.
(20) valve-regulated lead-acid battery as described in above-mentioned (12), wherein, among described positive plate and described negative plate
The area of each is 135cm2～288cm2。
(21) valve-regulated lead-acid battery as described in above-mentioned (12), wherein, described electrolyte is the sulphur comprising sulfuric acid and water
Aqueous acid.
(22) valve-regulated lead-acid battery as described in above-mentioned (12) or (21), wherein, the proportion of described electrolyte is 1.200
～1.310g/cm3。
Invention effect
By the present invention, suppressed the dissolution of lead ion by the sulfate configured, and then dendrite inhibition poor short circuit
Occurring, result can be greatly decreased dendrite short circuit in the case of not reducing battery behavior such that it is able to provides suitable as electricity
The valve-regulated lead-acid battery of the main power source of motor-car.
Accompanying drawing explanation
Fig. 1 is the schematic perspective view of an embodiment of the pole plate group of the valve-regulated lead-acid battery representing the present invention.
Fig. 2 is the schematic perspective view of another embodiment of the pole plate group of the valve-regulated lead-acid battery representing the present invention.
Fig. 3 is to represent the figure of the position of optimum configuration sulfate in the present invention.
Fig. 4 (a) is the figure of the effect of the valve-regulated lead-acid battery representing the present invention, and Fig. 4 (b) is also the valve representing the present invention
The figure of the effect of control formula lead accumulator.
Fig. 5 is the figure of the effect of the valve-regulated lead-acid battery representing the present invention.
Fig. 6 is the figure of the effect of the valve-regulated lead-acid battery representing the present invention.
Symbol description
1 positive plate
2 negative plates
3 the 1st dividing plates
4 the 2nd dividing plates
3a dividing plate
Detailed description of the invention
Hereinafter, use accompanying drawing that preferred embodiment of the present invention is illustrated.
The first aspect of the invention relates to a kind of valve-regulated lead-acid battery, and it has resinous electricity groove and is accommodated in
In above-mentioned electricity groove by positive plate and negative plate across the opposed pole plate group of dividing plate and electrolyte, wherein, in aforementioned barriers
And at least one place between above-mentioned positive plate and between aforementioned barriers and above-mentioned negative plate is configured with containing alkali metal or alkaline earth
The sulfate of metal.
In this first aspect, preferably configure on the surface of positive plate and negative plate or on the surface of aforementioned barriers
There is above-mentioned sulfate, be thus configured with between aforementioned barriers and above-mentioned positive plate and between aforementioned barriers and above-mentioned negative plate
State sulfate.
Aforementioned barriers can be the shape such as sheet, bag-shaped, U-shaped.In above-mentioned pole plate group, for example, it is possible to by positive plate U
Shape or bag-shaped dividing plate encase.
Fig. 1 shows the schematic perspective view of the pole plate group used in this first aspect.As shown in fig. 1, by positive pole
Plate 1 and negative plate 2 are alternately laminated across dividing plate 3a, and the lug of multiple positive plates 1 and the lug of multiple negative plate 2 are each divided
Han Jie not concentrate in together, thus constitute the pole plate group used in this first aspect.
The second aspect of the invention relates to a kind of valve-regulated lead-acid battery, and it has resinous electricity groove and is accommodated in
In above-mentioned electricity groove by positive plate and negative plate across the opposed pole plate group of dividing plate and electrolyte, wherein, aforementioned barriers bag
Include the 1st dividing plate formed by glass fiber mat and the 2nd dividing plate formed by glass fiber mat or non-woven fabrics, the above-mentioned 1st every
Plate neighboringly configures with above-mentioned positive plate, and above-mentioned 2nd dividing plate neighboringly configures with above-mentioned negative plate, above-mentioned 1st dividing plate with on
State between positive plate, between above-mentioned 2nd dividing plate and above-mentioned negative plate or configure between above-mentioned 1st dividing plate and above-mentioned 2nd dividing plate
There is the sulfate containing alkali metal or alkaline-earth metal.
In this second aspect, preferably on the surface of positive plate and negative plate or on the surface of the 1st dividing plate and/or
Configure sulfate on the surface of the 2nd dividing plate, thus between above-mentioned 1st dividing plate and above-mentioned positive plate, above-mentioned 2nd dividing plate is with above-mentioned
It is configured with the sulfuric acid containing alkali metal or alkaline-earth metal between negative plate or between above-mentioned 1st dividing plate and above-mentioned 2nd dividing plate
Salt.
Above-mentioned 1st dividing plate and the 2nd dividing plate can be the shapes such as sheet, bag-shaped, U-shaped.In above-mentioned pole plate group, such as, can
So that positive plate U-shaped or the 1st bag-shaped dividing plate are encased, negative plate U-shaped or the 2nd bag-shaped dividing plate are encased.
It addition, as the non-woven fabrics for the 2nd dividing plate, it is possible to use formed by synthetic fibers such as polypropylene and carried out each
Plant the non-woven fabrics of hydrophilicity-imparting treatment.
As a rule, glass fibre separator can inhale acid well, and non-woven fabrics dividing plate has good intensity thus can
To be effectively prevented short circuit.
Fig. 2 shows the schematic perspective view of the pole plate group used in this second aspect.As shown in Figure 2, will with by
The positive plate 1 that the 1st dividing plate 3 that glass fiber mat is formed encases with the 2nd formed by glass fiber mat or non-woven fabrics every
The negative plate 2 that plate 4 encases is alternately laminated, and the lug of multiple positive plates 1 and the lug of multiple negative plate 2 is each respectively welded
Concentrate in together, thus constitute the pole plate group used in this second aspect.
The above-mentioned sulfate used in the present invention is preferably alkali metal sulfates or alkali earth metal sulfate.Above-mentioned alkali gold
Genus can be the lithium (Li) of periodic table of elements group ia, sodium (Na), potassium (K), rubidium (Rb), caesium (Cs), francium (Fr).Above-mentioned alkaline earth gold
Genus can be the beryllium (Be) of periodic table of elements group iia, magnesium (Mg), calcium (Ca), strontium (Sr), barium (Ba), radium (Ra).Wherein, on
State sulfate and be more preferably sodium sulphate, this is because the sodium included in sodium sulphate is when battery over-discharge, it is possible to short to dendrite
Inhibitory action is played on road, and sodium sulphate is more economical compared with other material in price.
In the valve-regulated lead-acid battery of the present invention, the area of each among above-mentioned positive plate and above-mentioned negative plate is excellent
Elect 135cm as2～288cm2, this is because if polar plate area is less than 135cm2, then the diffusion velocity of sulfuric acid can quickly spread
The shortest to the time at pole plate center, therefore sulfuric acid does not causes beneficially lead ion dissolution due to the consumption in diffusion
Condition, result battery is inherently less likely to occur dendrite short circuit, accordingly even when be configured with sulfate also will not play dendrite inhibition
The effect of short circuit.And if polar plate area is higher than 288cm2, then big due to polar plate area, the speed of sulfuric acid diffusion can be very slow, makes
Becoming the consumption of sulfuric acid, thus cause the environment being prone to lead ion dissolution, dendrite short circuit is inevitable, and such sulfate rises equally
Effect less than the short circuit of fine dendrite inhibition.
In the present invention, electrolyte preferably comprises the aqueous sulfuric acid of sulfuric acid and water, and the proportion of this electrolyte is preferably
1.200～1.310g/cm3.A small amount of interpolation being dissolved completely in this electrolyte can be also comprised in above-mentioned electrolyte
Agent such as silica, sodium tetraborate, sodium sulphate etc..
As the active material cream of positive plate and negative plate, use following active material cream: to lead and lead oxides
Mixed powder interpolation has resistance to sulfuric acid synthetic resin fiber, various additive, carries out kneading with water and dilute sulfuric acid and forms.Its
In, for the purpose of the efficient activity, raising initial capacity characteristic of chemical conversion, can be to active material cream (the positive pole work for positive plate
Property material cream) add red lead.Can suppress negative it addition, add to the active material cream (negative electrode active material cream) for negative plate
The lignin compound of the Volume Changes (shrink, expand) of the active material of pole plate, there is formation exoelectrical reaction thing (lead sulfate)
Generate core and make the barium sulfate of the function that reaction homogenizes.Further, to by the metal containing substantially no antimony, (lead-calcium closes
Gold, Lead-tin alloy etc.) formed draw in the net grid (expanded lattice) fill respectively above-mentioned positive active material cream and
Negative electrode active material cream, it is also possible to the cream paper being used for preventing active material from coming off is added to polar board surface, thus makes positive pole
Plate and negative plate.
Distance between positive plate and negative plate is preferably 0.4～1.0mm.When this distance is less than 0.4mm, then spacing is not
Foot, is therefore easier to the short circuit occurring to produce due to positive plate 1 and contacting of negative plate 2.When above-mentioned distance is more than 1.0mm
Time, battery capacity can compare and significantly decreases.
The particle diameter of the sulfate used in the present invention is preferably below 500 μm, is smearing this is because particle diameter is excessive
During be difficult to attachment, and can extend injecting the dissolution time of sodium sulphate after electrolyte, thus sodium sulphate is smeared in impact
Effect.
In order to fully meet the effect of the present invention, the configuration amount of the per unit area of sulfate is preferably 0.008～0.3g/
cm2.Configuration amount at sulfate is less than 0.008g/cm2In the case of, dendrite short circuit can occur more significantly, corresponding to this,
Initial capacity and cycle life all can reduce.But, the configuration amount of sulfate is more than 0.3g/cm2Time, due to superfluous sulfate
Make sulfuric acid concentration raise (sulfate ion concentration also increases), superfluous can generate before charging and understand as the lead sulfate of discharging product
Cause sulfation, thus the capacity produced due to undercharge can be occurred significantly to reduce and observe the fall of cycle life
Low.
The configuration amount of the per unit area of above-mentioned sulfate is more preferably 0.010～0.2g/cm2, more preferably 0.1
～0.2g/cm2.Especially with sodium sulphate as all the more so during above-mentioned sulfate.
In the present invention, the mode that above-mentioned sulfate preferably carries out smearing in the form of a powder configures, because will
Sulfate dissolves the poor effect carrying out in the electrolytic solution configuring.
Fig. 3 is to represent the figure of the position of optimum configuration sulfate in the present invention.Inventor finds, by pole plate group at pole plate
Central portion (the 5th part) when direction, face upper and lower (Y-direction) and left and right (X-direction) carries out trisection (amounting to nine deciles) respectively is
The latest by the position of electrolyte permeability (supply sulfate ion) after injection electrolyte.That is, this position is easiest to become dendrite short circuit
Starting point.Therefore, as long as at least configuring sulfate at this central portion (the 5th part), even if not joining in whole pad-face direction
Put sulfate, also can obtain predetermined effect.
This pole plate group is received into have element cell resinous electricity groove in, then top configuration lid and make this lid with
Electricity groove is bonding, is consequently formed the semi-finished product not being melted into.Liquid injection port from the lid being arranged on these semi-finished product injects electrolyte, energising
Implement chemical conversion, in liquid injection port, then configure safety valve, thus make the valve-regulated lead-acid battery of the present invention.
Then, use embodiment, the effect of the valve-regulated lead-acid battery of the present invention is described in detail further.
(embodiment 1)
Embodiment 1 prepares a kind of valve-regulated lead-acid battery, and it has resinous electricity groove and is accommodated in above-mentioned electricity groove
In by positive plate and negative plate across the opposed pole plate group of dividing plate and electrolyte, wherein, aforementioned barriers includes by glass
The 1st dividing plate that fibrofelt pad is formed and the 2nd dividing plate that formed by glass fiber mat or non-woven fabrics, above-mentioned 1st dividing plate is with above-mentioned
Positive plate neighboringly configures, and above-mentioned 2nd dividing plate neighboringly configures with above-mentioned negative plate, at above-mentioned 1st dividing plate and above-mentioned positive plate
Between, be configured with alkali metal between above-mentioned 2nd dividing plate and above-mentioned negative plate or between above-mentioned 1st dividing plate and above-mentioned 2nd dividing plate
Or alkali earth metal sulfate.Concrete preparation method is as follows.
(1) manufacture of positive plate
With the weight ratio of about 100:15:10, raw material lead powder (lead and the mixture of lead oxide), water and dilute sulfuric acid are carried out
Mediate, thus obtain the anode diachylon as positive active material.
On the other hand, it is squeezed into comprising the Pb alloy containing about 0.07 mass %Ca and about 1.3 mass %Sn by casting
The. g., lead tape that 1.3mm is thick, uses reciprocating daraf(reciprocal of farad) of cutting to obtain drawing in the net grid.Then, above-mentioned positive pole is filled above-mentioned drawing in the net on grid
Lead plaster.Then, by cutting off, curing, it is dried and chemical conversion, it is possible to obtain positive plate.Above-mentioned chemical conversion can be assembled into pole plate
Carry out before group, it is also possible to carrying out later in being assembled into pole plate group and being assembled to the housing of lead accumulator.
(2) manufacture of negative plate
With about 100:5:10 weight ratio, raw material lead powder, water, dilute sulfuric acid are mediated, thus obtain as negative electrode active
The cathode lead plaster of material.
The Pb alloy raw material that will contain about 0.07 mass %Ca and about 0.25 mass %Sn is squeezed into predetermined thickness by casting
The. g., lead tape of such as 0.65mm, uses reciprocating daraf(reciprocal of farad) of cutting to obtain drawing in the net grid.Then, above-mentioned bearing is filled above-mentioned drawing in the net on grid
Pole lead plaster.Then, by cutting off, curing, it is dried and chemical conversion, it is possible to obtain negative plate.Above-mentioned chemical conversion can assemble poling
Carry out before plate group, it is also possible to carrying out later in being assembled into pole plate group and being assembled to the housing of lead accumulator.
(3) manufacture of lead accumulator
The area of each among above-mentioned positive plate and above-mentioned negative plate is 135cm2～288cm2, above-mentioned positive plate is used
U-shaped the 1st dividing plate formed by glass fiber mat encases, the above-mentioned negative plate bag formed by glass fiber mat or non-woven fabrics
Shape the 2nd dividing plate encases, by the most overlapping to 5 above-mentioned positive plates and 6 above-mentioned negative plates, and above-mentioned 1st dividing plate with on
State between positive plate, between above-mentioned 2nd dividing plate and above-mentioned negative plate or between above-mentioned 1st dividing plate and above-mentioned 2nd dividing plate with powder
The mode that the form at end carries out smearing configures alkali metal or alkali earth metal sulfate, thus obtains the pole plate group shown in Fig. 2.With
After, respectively each positive pole ear is welded to each negative lug together with, it is thus achieved that positive bus and negative bus-bar.
6 pole plate groups are accommodated in respectively in 6 element cells separated by spaced walls in resinous electricity groove.By inciting somebody to action
The negative bus-bar of one pole plate group is connected in series with the positive bus of adjacent pole plate group, the most successively by each pole plate group
It is connected in series, namely each cell is together in series.
Then, battery cover is installed on the opening of battery container.Subsequently, set from battery cover liquid inlet to
Pouring proportion in each cell into is 1.200～1.310g/cm3Sulfuric acid as electrolyte, and enter in the cell housing
Row chemical conversion.After chemical conversion, the valve with the gas for being produced by inside battery and pressure venting is fixed in liquid inlet,
Thus obtain lead accumulator.
Embodiment 1
Embodiment 1 is the embodiment of above-mentioned embodiment 1.Each among the most above-mentioned positive plate and above-mentioned negative plate
Area be 120cm2, employing proportion is 1.255g/cm3Sulfuric acid, and as shown in table 1, change sulfate has that it's too late plants
Class, pole plate group stacked direction on the allocation position of sulfate, in addition, other makes nominal the most according to the method described above
Voltage is the valve-regulated lead-acid battery (battery 1～61) of 12V.And, in these batteries, between positive plate 1 and negative plate 2
Distance is 0.7mm, and the configuration amount of the per unit area of sulfate is 0.1g/cm2, sulfate on the pad-face direction of pole plate group
Allocation position be only the 5th part (local configuration) of Fig. 3.Further, by charged electrical on the basis of the active matter quality of positive plate 1
Amount is set to 0.41Ah/g to implement primary charging.And, in order to make dendrite short circuit be susceptible to, by the injection rate of electrolyte by
The common 50ml/ second is reduced to the 15ml/ second, thus make battery.Appreciation condition and result are as follows.
Table 1
(dendrite short circuit test)
Under 25 DEG C of environment, carry out 2.45V constant voltage charging (maximum current is 24A) of 12 hours, then dismantle battery,
The number of the dendrite short circuit that range estimation produces between pole plate.As shown in table 1, in the battery 1 being configured without sulfate, create big
The dendrite short circuit of amount, but in other batteries being configured with sulfate, regardless of the kind of sulfate, dendrite short circuit is the most significantly
Reduce.It is believed that in the battery 1 being configured without sulfate, the lead ion produced between positive plate 1 and negative plate 2 is adjoint
Charging to be received electronics by negative plate 2 and separate out, thus produce dendrite short circuit.It follows that by as the present invention by sulphur
Hydrochlorate is properly configured between positive plate 1 and negative plate 2, and dendrite short circuit can be greatly decreased.This may be considered by the most former
Because of produced result: the lead ion produced between positive plate 1 and negative plate 2 dissolves with from the sulfate properly configured
Sulfate ion combine, thus charging time be formed as lead sulfate such that it is able to make the lead ion of the root as dendrite short circuit
It is greatly decreased.But, even if configure lead sulfate as described in Patent Document 1 in the inside of the 1st dividing plate 3, lead ion can not be with sulphur
Acid ion is effectively combined, thus the effect above disappears (battery 38～49).From this result, by will containing alkali metal or
The sulfate of alkaline-earth metal is arranged between dividing plate and positive plate 1, between dividing plate and negative plate 2 or the 1st dividing plate the 3 and the 2nd every
Between plate 4, the effect of the present invention can be obtained.Particularly, sulfate is arranged in the electricity between the 1st dividing plate the 3 and the 2nd dividing plate 4
The effect in pond 26～37 is big, and this is it is believed that be because, relative to the speed producing lead ion between positive plate 1 and negative plate 2
Degree, the speed that the sulfate ion from sulfate of the present invention is combined (the generation source cutting off dendrite) with above-mentioned lead ion is slower,
Therefore sulfate is arranged in as lead ion produce the positive plate 1 in source or negative plate 2 to a certain degree away from position
Can be more successfully to lead when being arranged in than by sulfate time (between the 1st dividing plate 3 and the 2nd dividing plate 4) around the generation source of lead ion
Ion supply sulfate ion.
Embodiment 2
The configuration amount of the per unit area of sulfate is studied.And, in addition to the configuration amount of sulfate, other
All constitute in the same manner as above-mentioned battery 27.Research contents and result are as follows.
(initial capacity validation test)
In the environment of 25 DEG C, carry out being discharged to depth of discharge for 80% with 3 times of time rates (1/3C), confirm initial capacity.
It is represented in Fig. 4 (a) and (b) in the lump with the number of produced dendrite short circuit when confirming initial capacity.By acquired results
Understanding, even if being configured with sulfate, the configuration amount at sulfate is less than 0.008g/cm2In the case of, also can send out more significantly
Raw dendrite short circuit, corresponding to this, initial capacity can reduce.Configuration amount at sulfate is 0.008～0.3g/cm2In the case of,
The number of the dendrite short circuit produced is 0, and initial capacity is good.But, the configuration amount of sulfate is more than 0.3g/cm2Time,
Owing to superfluous sulfate makes sulfuric acid concentration raise, before charging can superfluous generation as the lead sulfate of discharging product, thus meeting
The capacity produced due to undercharge is occurred to reduce significantly.
(cycling life test)
In the environment of 25 DEG C, will carry out being discharged to depth of discharge with 3 times of time rates (1/3C) to be 80%, carry out 12 hours
The discharge and recharge of 2.45V constant voltage charging (maximum current is 24A) carrys out implementation evaluation as 1 circulation.The results are shown in Fig. 5
In.And, using discharge capacity is initial capacity actual value less than 75% moment terminate as cycle life.
From acquired results, even if being configured with sulfate, the configuration amount at sulfate is less than 0.008g/cm2Situation
Under, dendrite short circuit can occur more significantly, corresponding to this, cycle life can reduce.Configuration amount at sulfate be 0.008～
0.3g/cm2In the case of, it is possible to obtain the characteristic that 1000 circulations are above.But, the configuration amount of sulfate is more than 0.3g/cm2Time,
Owing to superfluous sulfate makes sulfuric acid concentration raise, as discharging product lead sulfate before charging can superfluous generation and can cause
Sulfation, such that it is able to observe the reduction of cycle life.
As can be known from the above results, the suitable configuration amount of sulfate is 0.008～0.3g/cm2。
Embodiment 3
To polar plate spacing from studying.And, except polar plate spacing from addition to, other is in the same manner as above-mentioned battery 27
Constitute.Research contents is identical with the initial capacity validation test of embodiment 2 (including that dendrite short circuit is tested).The results are shown in figure
In 6.From acquired results, polar plate spacing from during less than 0.4mm, is then spaced deficiency, is therefore easier to occur due to positive plate 1
The short circuit produced with contacting of negative plate 2, and polar plate spacing is from during more than 1.0mm, battery capacity can compare and significantly decreases.
Thus result understands, and in the present invention, optimum polar plate spacing is from for 0.4～1.0mm.
(embodiment 2)
Embodiment 2 prepares a kind of valve-regulated lead-acid battery, and it has resinous electricity groove and is accommodated in above-mentioned electricity groove
In by positive plate and negative plate across the opposed pole plate group of dividing plate and electrolyte, wherein, above-mentioned positive plate with above-mentioned every
Plate encases, between aforementioned barriers and above-mentioned positive plate and between aforementioned barriers and above-mentioned negative plate at least one place be configured with
Alkali metal or alkali earth metal sulfate.
Lead accumulator prepared by embodiment 2 is except only employing a kind of dividing plate (not having the 2nd dividing plate) and thus making sulphur
Beyond the allocation position of hydrochlorate is slightly different, other condition is identical with embodiment 1 with key element.So eliminating it
It is described in detail.
Embodiment 4
Embodiment 4 is the embodiment of above-mentioned embodiment 2.Each among the most above-mentioned positive plate and above-mentioned negative plate
Area be 211cm2, employing proportion is 1.255g/cm3Sulfuric acid, and as shown in table 2, change sulfate has that it's too late plants
Class, pole plate group stacked direction on the allocation position of sulfate, and there is no the 2nd dividing plate, in addition, other is all according to upper
State the method described in embodiment 1, make valve-regulated lead-acid battery that nominal voltage is 12V (battery 1a～25a, 38a～
61a).And, in these batteries, the distance between positive plate 1 and negative plate 2 is 0.7mm, the per unit area of sulfate
Configuration amount is 0.1g/cm2, the allocation position of the sulfate on the pad-face direction of pole plate group is only the 5th part of Fig. 3 (locally
Configuration).Further, charge capacity is set to 0.41Ah/g to implement primary charging on the basis of the active matter quality of positive plate 1.And
And, in order to make dendrite short circuit be susceptible to, the injection rate of electrolyte is reduced to the 15ml/ second by the common 50ml/ second, thus
Make battery.Further, dendrite short circuit test and evaluation are carried out according to method same as in Example 1, result such as table 2 below institute
Show.
Table 2
Embodiment 5
The configuration amount of the per unit area of sulfate is studied.And, in addition to the configuration amount of sulfate, other
All constitute in the same manner as the battery 15a described in above-mentioned table 2.Initial capacity confirmation is carried out according to method same as in Example 2
Test and cycling life test, acquired results is as shown in Table 3 below.
Table 3
As can be known from the above results, the suitable configuration amount of sulfate is 0.008～0.3g/cm2。
Embodiment 6
To polar plate spacing from studying.And, except polar plate spacing from addition to, other with above-mentioned table 2 described in electricity
Pond 15a is similarly constituted.Research contents is identical with the initial capacity validation test of embodiment 2 (including that dendrite short circuit is tested), institute
Obtain result as shown in table 4 below.
Table 4
As can be known from the above results, polar plate spacing from during less than 0.4mm, is then spaced deficiency, be therefore easier to occur due to
The short circuit that positive plate 1 produces with contacting of negative plate 2, and polar plate spacing is from during more than 1.0mm, battery capacity can ratio more significant
Ground reduces.Thus result understands, and in the present invention, optimum polar plate spacing is from for 0.4～1.0mm, more preferably 0.5～
1.0mm。
Embodiment A-1～A-12, embodiment B and comparative example 1～8
By the size changing polar plate area, polar plate area is studied.And, in addition to polar plate area, also make
The sulfate i.e. configuration amount of sodium sulphate and the electrolyte i.e. proportion of sulfuric acid are changed, other all according to institute in embodiment 4
The condition that arranges identical for battery 15a stated is to prepare pole plate group and lead accumulator.Then at the beginning of the lead accumulator to above-mentioned gained
Phase capacity and cycle life are measured, and the concrete condition that arranges and the result of gained are shown in table 5 below.
Table 5
By embodiment A-1～the result of A-5 gained, in the valve-regulated lead-acid battery of the present invention, at electrolyte
Proportion and sulfate configuration amount keep constant in the case of, along with polar plate area is at 135cm2～288cm2In the range of by
Cumulative height, initial capacity can be gradually increased, and cycle life can be gradually lowered, but cycle life remains acceptable model
Enclose.But, as shown in the result of comparative example 7 gained, if polar plate area is too high, although then initial capacity is the highest, but follow
The ring life-span can be greatly lowered.On the other hand, as shown in the result of embodiment B gained, if polar plate area is the lowest, then
Although cycle life is the highest, but initial capacity can be the lowest.
It addition, by the result of embodiment B gained compared with the result of comparative example 1 gained and embodiment A-1～A-
The result of 5 gained understands respectively compared with the result of comparative example 2～6 gained, and proportion and polar plate area at electrolyte keep
In the case of constant, the configuration of sulfate can make cycle life significantly improve.
Furthermore, by embodiment A-6～the result of A-12 gained, in the valve-regulated lead-acid battery of the present invention,
The configuration amount of polar plate area and sulfate keep constant in the case of, along with the proportion of electrolyte changes, keeping the initial stage
When capacity is identical value, cycle life can substantially change, but when the proportion of electrolyte is 1.200～1.310g/cm3's
In the range of, cycle life is higher.
It addition, by the result of embodiment A-11 gained compared with the result of comparative example 8 gained, even if at pole plate
In the case of the proportion of area and electrolyte is preferred value, without configuration sulfate, cycle life also can significantly reduce.
Industrial applicibility
The present invention can suppress to produce dendrite short circuit fault during valve-regulated lead-acid battery, the most not only industrial applicibility
Height, and its serviceability is high.
Claims (17)
1. a valve-regulated lead-acid battery, its have resinous electricity groove and be accommodated in described electricity groove by positive plate with negative
Pole plate is across the opposed pole plate group of dividing plate and electrolyte, wherein,
Smear in the form of a powder on the surface of described positive plate and described negative plate or on the surface of described dividing plate
Mode be configured with the sulfate containing alkali metal or alkaline-earth metal, so that between described dividing plate and described positive plate and institute
At least one place in stating between dividing plate and described negative plate is configured with described sulfate,
The configuration amount of described sulfate is 0.008～0.3g/cm2,
The area of each among described positive plate and described negative plate is 135cm2～288cm2。
2. valve-regulated lead-acid battery as claimed in claim 1, wherein, described sulfate is alkali metal sulfates or alkaline-earth metal
Sulfate.
3. valve-regulated lead-acid battery as claimed in claim 2, wherein, described sulfate is sodium sulphate.
4. valve-regulated lead-acid battery as claimed in claim 1, wherein, the distance between described positive plate and described negative plate is
0.4～1.0mm.
5. the valve-regulated lead-acid battery as described in claim 1 or 3, wherein, the configuration amount of described sulfate be 0.010～
0.2g/cm2。
6. valve-regulated lead-acid battery as claimed in claim 1, wherein, at least described pole plate group is upper and lower in pad-face direction
Central portion when carrying out trisection respectively with left and right is configured with described sulfate.
7. valve-regulated lead-acid battery as claimed in claim 1, wherein, described electrolyte is that the sulfuric acid comprising sulfuric acid and water is water-soluble
Liquid.
8. the valve-regulated lead-acid battery as described in claim 1 or 7, wherein, the proportion of described electrolyte be 1.200～
1.310g/cm3。
9. a valve-regulated lead-acid battery, its have resinous electricity groove and be accommodated in described electricity groove by positive plate with negative
Pole plate is across the opposed pole plate group of dividing plate and electrolyte, wherein,
Described dividing plate includes the 1st dividing plate formed by glass fiber mat and the formed the 2nd by glass fiber mat or non-woven fabrics
Dividing plate,
Described 1st dividing plate neighboringly configures with described positive plate, and described 2nd dividing plate neighboringly configures with described negative plate,
On the surface of described positive plate and described negative plate or at the surface of described 1st dividing plate and/or described 2nd dividing plate
The mode carrying out in the form of a powder on surface smearing is configured with the sulfate containing alkali metal or alkaline-earth metal, so that
Between described 1st dividing plate and described positive pole, between described 2nd dividing plate and described negative pole or described 1st dividing plate and the described 2nd
Described sulfate it is configured with between dividing plate,
The configuration amount of described sulfate is 0.008～0.3g/cm2,
The area of each among described positive plate and described negative plate is 135cm2～288cm2。
10. valve-regulated lead-acid battery as claimed in claim 9, wherein, described sulfate is alkali metal sulfates or alkaline earth gold
Belong to sulfate.
11. valve-regulated lead-acid batteries as claimed in claim 10, wherein, described sulfate is sodium sulphate.
12. valve-regulated lead-acid batteries as claimed in claim 9, wherein, the distance between described positive plate and described negative plate
It is 0.4～1.0mm.
13. valve-regulated lead-acid batteries as described in claim 9 or 11, wherein, the configuration amount of described sulfate be 0.010～
0.2g/cm2。
14. valve-regulated lead-acid batteries as claimed in claim 9, wherein, at least by described pole plate group on pad-face direction
Lower and time left and right carries out trisection respectively central portion is configured with described sulfate.
15. valve-regulated lead-acid batteries as described in claim 9 or 14, wherein, at described 1st dividing plate or described 2nd dividing plate
Described sulfate it is configured with on surface.
16. valve-regulated lead-acid batteries as claimed in claim 9, wherein, described electrolyte is the sulfuric acid water comprising sulfuric acid and water
Solution.
17. valve-regulated lead-acid batteries as described in claim 9 or 16, wherein, the proportion of described electrolyte be 1.200～
1.310g/cm3。
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| JP2013519289A JP5325359B1 (en) | 2012-03-01 | 2013-03-01 | Control valve type lead acid battery |
| PCT/JP2013/001263 WO2013128941A1 (en) | 2012-03-01 | 2013-03-01 | Valve-regulated lead-acid battery |
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| WO2021226000A1 (en) * | 2020-05-04 | 2021-11-11 | Daramic, Llc | Metal sulfate systems for lead-acid batteries |
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| CN1967912A (en) * | 2005-11-18 | 2007-05-23 | 上海耀国能源科技有限公司 | Polar plate and electrolyte of lead storage battery applied for electromotion aid car |
| CN201845836U (en) * | 2010-07-16 | 2011-05-25 | 天能电池集团有限公司 | Lead-acid battery |
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| JPH06223867A (en) * | 1993-01-22 | 1994-08-12 | Japan Storage Battery Co Ltd | Lead-acid battery |
| JPH08264202A (en) * | 1995-03-24 | 1996-10-11 | Japan Storage Battery Co Ltd | Lead-acid battery |
| JP2002110220A (en) * | 2000-09-29 | 2002-04-12 | Furukawa Battery Co Ltd:The | Lead-acid battery |
| JP4737815B2 (en) * | 2000-11-13 | 2011-08-03 | 日本板硝子株式会社 | Sealed lead acid battery |
| JP4737816B2 (en) * | 2000-11-13 | 2011-08-03 | 日本板硝子株式会社 | Sealed separator for sealed lead-acid battery |
| JP4956858B2 (en) * | 2001-03-01 | 2012-06-20 | パナソニック株式会社 | Control valve type lead acid battery |
| JP4287622B2 (en) * | 2002-06-28 | 2009-07-01 | デュポン帝人アドバンスドペーパー株式会社 | COATING SEPARATOR, MANUFACTURING METHOD THEREOF, AND ELECTRIC AND ELECTRONIC COMPONENT USING THE SAME |
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| CN1967912A (en) * | 2005-11-18 | 2007-05-23 | 上海耀国能源科技有限公司 | Polar plate and electrolyte of lead storage battery applied for electromotion aid car |
| CN201845836U (en) * | 2010-07-16 | 2011-05-25 | 天能电池集团有限公司 | Lead-acid battery |
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| CN103296234A (en) | 2013-09-11 |
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Effective date of registration: 20170907 Address after: Liaoning, Shenyang economic and Technological Development Zone, Kunming Lake Street, No. 51 Co-patentee after: GS Yuasa International Corporation Patentee after: Panasonic Storage Battery (Shenyang) Co., Ltd. Address before: 110141 Shenyang economic and Technological Development Zone, Kunming, Lake Street, No. 51, No. Co-patentee before: Matsushita Electric Industrial Co., Ltd. Patentee before: Panasonic Storage Battery (Shenyang) Co., Ltd. |