CN107026271A - Lead accumulator positive plate, lead accumulator, the manufacture method of lead accumulator positive plate - Google Patents
Lead accumulator positive plate, lead accumulator, the manufacture method of lead accumulator positive plate Download PDFInfo
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- CN107026271A CN107026271A CN201710061705.8A CN201710061705A CN107026271A CN 107026271 A CN107026271 A CN 107026271A CN 201710061705 A CN201710061705 A CN 201710061705A CN 107026271 A CN107026271 A CN 107026271A
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- grid
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/14—Electrodes for lead-acid accumulators
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/14—Electrodes for lead-acid accumulators
- H01M4/16—Processes of manufacture
- H01M4/20—Processes of manufacture of pasted electrodes
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/06—Lead-acid accumulators
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/06—Lead-acid accumulators
- H01M10/12—Construction or manufacture
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/14—Electrodes for lead-acid accumulators
- H01M4/16—Processes of manufacture
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
- H01M4/56—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of lead
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/64—Carriers or collectors
- H01M4/66—Selection of materials
- H01M4/661—Metal or alloys, e.g. alloy coatings
- H01M4/662—Alloys
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/64—Carriers or collectors
- H01M4/66—Selection of materials
- H01M4/68—Selection of materials for use in lead-acid accumulators
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/64—Carriers or collectors
- H01M4/70—Carriers or collectors characterised by shape or form
- H01M4/72—Grids
- H01M4/73—Grids for lead-acid accumulators, e.g. frame plates
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/64—Carriers or collectors
- H01M4/70—Carriers or collectors characterised by shape or form
- H01M4/80—Porous plates, e.g. sintered carriers
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/64—Carriers or collectors
- H01M4/82—Multi-step processes for manufacturing carriers for lead-acid accumulators
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M2004/026—Electrodes composed of, or comprising, active material characterised by the polarity
- H01M2004/028—Positive electrodes
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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
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P70/00—Climate change mitigation technologies in the production process for final industrial or consumer products
- Y02P70/50—Manufacturing or production processes characterised by the final manufactured product
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Abstract
The present invention provides a kind of lead accumulator positive plate, can improve the life performance and initial capacity of lead accumulator.Positive plate used in a kind of lead accumulator, including punching grid (10) and positive electrode material (20) with grid framework, there is deformation in the corner (15C) in the section vertical with bearing of trend of the above-mentioned grid framework of above-mentioned punching grid (10), and density when being melted into of above-mentioned positive electrode material (20) is 4.1 [g/cm3] more than.
Description
Technical field
The present invention relates to lead accumulator positive plate, lead accumulator, lead accumulator positive plate manufacture method.
Background technology
In the past, as the collector used in lead accumulator, the metal piece for having the slit by alternating expression is formd is drawn
That stretches draws in the net Ge Shan.Draw in the net Ge Shan its manufacture method in nature, in the design of the configuration of grid framework (lattice Zhan)
There is very big limitation.Therefore, the configuration of grid framework is optimized and makes the Potential distribution in pole plate entirety be evenly difficult
's.For drawing in the net for Ge Shan (expanded grid), due to the overall Potential distribution of pole plate it is unbalanced it is easy become big, because
And occur local corrosion, the problem of there is the lifetime of pole plate in its result.In addition, being used as the current collection used in lead accumulator
Body, there is casting grid.Casting grid is manufactured by pouring into a mould in the mould of grid and being compacted by the lead of melting.Cast grid
With drawing in the net compared with lattice coral, the design freedom of the configuration of grid framework is high.However, for casting grid for, if attempt by
The thickness of grid is thinning, then the lead dissolved when the lead of melting to be poured into the mould of grid is difficult to good flowing, therefore deposits
The problem of being difficult to that the thickness of grid is thinning.
As the collector of these problems can be eliminated, there is punching grid (with reference to following patent documents 1).Being punched grid is
The grid that is carried out by punch press process and is manufactured for the rolling piece being made up of metal.With draw in the net Ge Shan, casting grid compared with, be punched lattice
Grid can be designed more freely in grid.In addition, compared with casting grid, punching grid can be thinning by the thickness of grid.
The manufacture method of negative pole grid (grid) has been recorded in following patent documents 2.Describe " it should be appreciated that in order to right
Negative pole grid assigns the improvement paste adhesion properties more excellent than the quadrangular section manufactured by blank operation, can select any
The grid wire shaped of the amendment of quantity.According to various embodiments illustrated, the grid lines of amendment substantially has diamond, water chestnut
Shape, hexagon, octagon or ellipse ".Also, describe by by negative side punching grid grid framework (grid lines)
Grid section be formed as quadrangle to hexagon, octagon, so as to improve paste (negative electrode active material) and punching grid
Cementability.
Patent document 3 (Japanese Unexamined Patent Publication 2013-140677 publications) is disclosed " in the automobile-used flooded lead-acid battery of idling flameout
In, positive active material is in the state that chemical conversion is finished, and density is 4.4g/cm3~4.8g/cm3, and be converted into metal Sn and contain
There is the mass % of 0.05 mass %~1.0 Sn ".Also, describe " by the way that the density for being melted into the positive active material finished is set
For 4.4g/cm3~4.8g/cm3, so as to improve the durability when being used in the state of undercharge.Due to being accompanied by this liquid
The capacity of formula lead accumulator can be reduced, so containing 0.05 mass % by the way that Sn is converted into metal Sn in positive active material
~1.0 mass %, so as to suppress the reduction of capacity ".
As disclosed in patent document 3, not exclusively filled in lead accumulator as the automobile-used lead accumulator of idling flameout
In use, being carried by improving the density of positive electrode material under electricity condition (PSOC (Partial state of charge))
High life performance.On the other hand, initial capacity can be reduced if the density for improving positive electrode material.
Prior art literature
Patent document
Patent document 1：Japanese Unexamined Patent Publication 2014-235844 publications
Patent document 2：Japanese Unexamined Patent Application Publication 2010-520607 publications
Patent document 3：Japanese Unexamined Patent Publication 2013-140677 publications
The content of the invention
In order to improve the life performance of the lead accumulator used in PSOC, it is considered as desirable by the inventor to using than drawing in the net the lattice coral life-span
Longer punching grid further improves the density of positive electrode material as positive electrode collector.If however, improving positive pole electricity
The utilization rate reduction of the density of pole material then positive electrode material, therefore initial capacity can reduce.As described in patent document 3
Like that, by adding Sn in positive electrode material, so that initial capacity can be improved, but if Sn is added in positive electrode material
Can easily it be reduced with the use electrolyte of lead accumulator.The present inventor is in order to avoid electrolyte is with the use of lead accumulator
Reduce, to being studied using the method added in positive electrode material beyond Sn to improve initial capacity.
It is an object of the invention to provide the lead accumulator that the height of the life performance under PSOC, initial capacity are improved.
Possess punching grid and anode electrode with grid framework by the lead accumulator positive plate of this disclosure
Material, also, there are deformation, above-mentioned positive electrode material in the corner in the section vertical with bearing of trend of above-mentioned grid framework
Density when being melted into be 4.1g/cm3More than.
According to the positive plate by this disclosure, it is possible to increase the life performance and initial capacity of lead accumulator.
Brief description of the drawings
Fig. 1 is the top view of the positive electrode collector of an embodiment
Fig. 2 is the sectional view of positive plate (section is quadrangle)
Fig. 3 is the sectional view of positive plate (section is octagon)
Fig. 4 is the sectional view of positive plate (section is the non-polygon with fillet part)
Fig. 5 is the figure (about octagon) for the cross sectional shape for representing grid framework
Symbol description
10... positive electrode collector (punching grid)
12... frame bone
15... grid framework
15C... corners
20... positive electrode material (positive active material)
20A... pastes are full of layer
Embodiment
(summary of present embodiment)
Embodiments of the present invention described below.When implementing the present invention, according to the general knowledge of those skilled in the art and now
There is the disclosure of technology, can suitably change embodiment.It should illustrate, below, positive electrode material is referred to as positive-active
Material, negative electrode material is referred to as negative electrode active material.Positive plate is by positive electrode collector and positive active material (anode electrode material
Material) constitute, negative plate is made up of negative electrode collector and negative electrode active material, and the solid constituent beyond collector belongs to active material
(electrode material).In addition, grid is a kind of form of collector.
The lead accumulator of the present invention possesses electrode assembly, and the electrode assembly is for example by the negative pole using lead as active material principal component
Plate, using brown lead oxide as the positive plate of active material principal component and the porous distance piece structure being held between these pole plates
Into the electrode assembly is incorporated in electric groove, and is impregnated in the flowable electrolyte by principal component of dilute sulfuric acid.
The positive plate of the present invention is in the collection being made up of Pb-Sb systems alloy, Pb-Ca systems alloy, Pb-Ca-Sn systems alloy etc.
Formed by the active material that pasty state is filled in the grid portion of electric body.These each component parts can be according to purpose purposes from suitable
Select to use in local known part.
Positive electrode collector 10 is made up of the metal with lath-like microstructure.Metal with lath-like microstructure is, for example,
Rolling is carried out to metal.If being rolled to make its thinning to metal, contain in original metal
Lead button for constituting metal structure is grinded up, and lath-like microstructure occurs in the travel direction of rolling.Current collection is manufactured using casting
During body, the metal for constituting collector does not have lath-like microstructure.Metal with lath-like microstructure has high excellent of intensity
Point.
The corner 15C in the section vertical with its bearing of trend of the grid framework 15 of positive electrode collector 10 occurs by deforming.
" the corner 15C in section has deformation " refers to, the right angle shown in the corner 15C in the section of grid framework 15 shape from Fig. 2
Turn into the shape beyond the rectangular shapeds such as circular shape shown in oblique line shape, Fig. 4 shown in shape distortion into Fig. 3.It is especially excellent
Choosing is deformed into the shape softer than right angle.In Fig. 3, Fig. 4, all deformed examples of 4 corner 15C are shown, but also may be used
In the way of being only part corner 15C deformations.It should illustrate, the sectional view of the positive plate shown in Fig. 2~Fig. 4 is along in Fig. 1
Line A-A sectional view, and be that the 1st sub- bone 16 of grid framework 15 (is being upper and lower in Fig. 1 relative to its bearing of trend
To) vertical plane cutting section.Hereinafter, unless otherwise specified, the vertical with bearing of trend of grid framework 15 is cut
Face is abbreviated as in " section of grid framework ".
In addition, more than the polygon being shaped as more than pentagon in the section of grid framework 15, pentagon substantially polygon
Shape and non-polygon." polygon " refers to, it is all while be made up of straight line and with while number summit shape
Shape.In addition, " generally polygonal " refers to, even if its side is not straight line, it may have real with the summit of the number on side etc.
Polygonal shape can be considered as in matter.Fig. 5 is to represent, a part of side L1~L4 by the curve of outside lateral bend constitute it is big
Cause octagon.In addition, more than the polygon that the shape in the section of grid framework 15 is set to more than pentagon, pentagon substantially
During polygon, whole interior angles is preferably set to more than 90 °.
In addition, " non-polygon " refers to 2 kinds of following shapes.
(1) shape being only made up of curve
(2) shape of combination straight line and curve (wherein, not including generally polygonal)
(1) in such as comprising circular, ellipse.In addition, (2) are for example including 4 all songs of corner 15C shown in Fig. 4
Part corner 15C in the shape of line, 4 corner 15C is the shape of curve.In addition, in addition, also comprising elliptical shape
Deng.
As shown in figure 1, positive electrode collector 10 possesses ear 13, the grid framework 15 being connected with ear 13.Ear 13 can be with
It is directly connected to, can also be connected via frame bone 12 with grid framework 15 with grid framework 15.The configuration of grid framework 15 is any
, but grid framework 15 is preferably substantially linear.As long as because such constituted, it can further shorten to ear
13 current path, can reduce resistance.
Ear 13 is protruding outside to positive electrode collector 10.Ear 13 is in order to via tape (not shown) link positive plate
Set each other.Positive electrode collector 10 can have a frame bone 12 in the first edge 12A, and positive electrode collector 10 can also be with
The second opposed one edge 12A edge 12B has frame bone 12.In addition, positive electrode collector 10 can link the first edge 12A's
The 3rd edge 12C and the 4th edge 12D at end and the second edge 12B end have frame bone 12.Positive electrode collector 10 is preferably
One edge 12A, the second edge 12B, the 3rd edge 12C, the 4th edge 12D have frame bone 12.As long as being then for such composition
Repeated charge is set also to suppress positive plate extension.
Positive electrode collector 10 by from the rolling piece being made up of the metal with lath-like microstructure to not include ear
13 and the part of frame bone 12 and grid framework 15 cutting processing (1 time processing) is carried out to remove to be manufactured.So manufacture
Collector there is through hole 18.1 the processing for example, punch process such as punch press process, water-jet processing, Laser Processing etc..
Then inexpensively can largely it be processed if punch process such as punch press process, therefore, 1 processing preferably passes through punch press process etc.
Punch process is carried out.
However, in positive electrode collector 10 after being processed at 1 time, the section of grid framework 15 is rectangle, corner 15C shape
Shape is the rectangular shaped shown in Fig. 2.Therefore, enter to exercise grid framework 15 section corner 15C deformation processing (2 times plus
Work), manufacture positive electrode collector 10.Specifically, using 2 processing, the corner 15C in the section of grid framework 15 is made to be deformed into figure
Shape beyond the rectangular shapeds such as oblique line shape shown in 3, rounded shape shown in Fig. 4.2 processing can be to including corner
15C section is integrally carried out, and passes through such processing, additionally it is possible to which it is circular or ellipse to make the section deformation of grid framework 15.
In addition, 2 processing can be carried out only to partial grid framework, whole grid frameworks can also be carried out, but the whole lattice of preferred pair
Grid framework is carried out.When positive electrode collector 10 has frame bone 12, the section for processing after-frame bone 12 at 1 time is also rectangle, therefore can
To carry out 2 processing to frame bone 12.2 processing for example, punch process, machining, attrition process etc..If punching press plus
Work then inexpensively can be processed largely, so 2 processing is preferably carried out by punch process.Should illustrate, 1 time processing and 2 times
Processing can be carried out respectively, can also be carried out simultaneously.
Negative plate is the lattice in the collector being made up of Pb-Sb systems alloy, Pb-Ca systems alloy, Pb-Ca-Sn systems alloy etc.
Formed by the active material that pasty state is filled in grid portion.These each component parts can be according to purpose purposes known in appropriate
Part in select to use.Negative electrode collector is casting grid, draw in the net any of Ge Shan, punching grid etc..
Production process, filling work procedure, maturation process, back tender that positive plate and negative plate can be pasted by active material
Sequence, formation process are manufactured.
In the production process that active material is pasted, dilute sulfuric acid and additive are added with defined proportioning into lead powder, to it
Kneaded, thus make each active material paste of positive pole, negative pole.It should illustrate, can contain in positive active material paste
Sn。
In filling work procedure, the processing of each active material paste is filled respectively to positive electrode collector, negative electrode collector.By
This, obtains undried positive plate and negative plate.
Maturation process is the process for making undried positive plate and negative plate maturation.By undried pole plate in the wet of appropriateness
Maturation is carried out in the atmosphere of degree and temperature.Thereafter, by the way that processing is dried, the positive plate and negative pole that can be melted into
Plate.
Drying process is to the positive plate not being melted into after maturation and the withering process of negative plate.
In formation process, the positive plate and negative plate after drying process are placed in dilute sulfuric acid electrolyte and are passed through direct current
Stream carries out redox.Thus, the positive plate and negative plate being melted into.
Density when being melted into of positive electrode material is set to 4.1g/cm in the present invention3More than.When making positive plate,
By adjusting the amount of moisture that contains in positive active material paste, positive electrode material when being melted into so as to adjust it is close
Degree.Specifically, the production process pasted using active material, by adjusting the amount of moisture contained in positive active material paste, from
And the density of positive electrode material when being melted into can be adjusted.
The density of positive electrode material is determined as follows.By being melted into and the electrode full of electricity condition is disassembled and taken out, carry out
Wash and dry.Electrode material is utilized into mercury penetration method with the state do not crushed, determines complete per 1g apparent volumes v and per 1g
Portion pore volume u.It should illustrate, apparent volume v is the volume sum in the solid volume of electrode material and hole of holding one's breath.By electrode material
Material is filled in container known to volume V1, is determined using mercury penetration method equivalent to the volume V2 that fine pore is more than 100 μm.
Continue to be pressed into mercury, determine whole pore volume u, (V1-V2)-u is set to apparent volume v, utilized d=1/ (v+u)=1/
(V1-V2) density d of positive electrode material is tried to achieve.In the measure using mercury penetration method, maximum pressure is forced into
4.45psia (30.7Kpa), is set to 130 °, the surface tension of mercury is set to 484dynes/cm and is measured by contact angle.Should
Illustrate, refer to that the terminal voltage in the charging determined for continuous 3 times every 15 minutes shows that certain value (± 0.01V) is full of electricity condition
Only, the state charged with 5 hour rate currents.
Mono- embodiment ＞ of ＜
Hereinafter, one embodiment of the present invention is illustrated.
(positive plate)
Positive plate is so-called the paste-type, (punching of positive electrode collector 10 of the metal manufactured using punch press process
Grid) and positive active material 20.
Positive electrode collector 10 passes through the rolling piece to being made up of the Pb-Ca-Sn systems alloy without antimony with lath-like microstructure
Carry out punch press process (1 processing) and obtain.
Positive electrode collector 10 shown in Fig. 1 has frame bone 12 (12A~12D common name).Frame bone 12 have the first edge 12A,
Second edge 12B, the 3rd edge 12C and the 4th edge 12D.The the first edge 12A and the second edge 12B of frame bone 12 are along right and left
It is opposed in above-below direction to extension.3rd edge 12C of frame bone 12 and the 4th edge 12D are vertically extending, link respectively
First edge 12A and the second edge 12B left part and right part.In addition, setting ear 13 in the first edge 12A.
Grid framework 15 includes the 1st sub- bone 17 of sub- bone 16 and the 2nd.With straight between the first edge 12A and the second edge 12B
The mode of wire extension sets multiple 1 sub- bones 16.Multiple 2 sub- bones 17 are set in the way of intersecting with the 1st sub- bone 16.
2nd sub- bone 17 tilts the oblique of predetermined angular including the positive sacrococcygeal joint orthogonal with the 1st sub- bone 16 and relative to the 1st sub- bone 16
Bone.
In the positive electrode collector 10 obtained using punch press process, as long as not entering to exercise adding for the section deformation of grid framework 15
Work, then the section of grid framework 15 is just rectangle shown in Fig. 2.Punch process is implemented to positive electrode collector 10, grill frame is obtained
The shape distortion in the section of frame 15 is the octagonal positive electrode collector shown in Fig. 3.It should illustrate, in the following description, will
The positive electrode collector that the shape in the section of grid framework 15 does not deform is set to " 10A ", the shape in the section of grid framework 15
Shape is deformed into octagonal positive electrode collector and is set to " 10B ".
Prepared just by mixing lead oxides, the synthetic resin fiber of armature, water and sulfuric acid using ball-milling method
Pole active material paste.Positive active material paste is filled in positive electrode collector 10A and positive electrode collector 10B, implementation maturation,
Dry, be melted into, make width 100mm, height 110mm, thickness 1.4mm positive plate.As shown in Figure 2 and Figure 3, positive electrode active material
Matter 20 in the way of the grid framework 15 for covering positive electrode collector 10A, 10B to fill (paste is full of (over paste)).Positive pole is lived
Property material 20 thickness t2 phases as an example be " 1.4mm ", in contrast, positive electrode collector 10A, 10B thickness t1 make
It is " 1.0mm " for an example, thickness t3 of the paste full of layer 20A one side is 0.2mm.Contain in adjustment positive active material paste
Amount of moisture, the density for making positive active material when being melted into is 3.5g/cm3、4.2g/cm3、4.4g/cm3、4.7g/cm3
Positive plate.It should illustrate, positive active material can not carry out paste to positive electrode collector 10 and be full of.
(negative plate)
By mixing the lead oxides based on ball-milling method, barium sulfate, wooden, carbon black, the synthetic resin fiber of armature, water
Negative electrode paste is prepared with sulfuric acid.The paste is filled in the negative pole for drawing in the net lattice coral type being made up of the Pb-Ca-Sn systems alloy without antimony
Collector, implement maturation, drying, chemical conversion and make negative plate.
(battery composition)
6 pieces of positive plates and 7 pieces of negative plates for being accommodated in bag-shaped distance piece are alternately laminated.Distance piece can be used as liquid
The usually used distance piece of the distance piece of formula lead accumulator.It is, for example, possible to use using the polyolefin with micropore as principal component
Piece, using resin, glass fiber as principal component matt distance piece.By the mutual ear of the positive plate of stacking and negative plate each other
Ear electrode assembly is made with positive pole tape, the connection of negative pole tape by busbar cast welding (cast-on-strap) mode respectively.
6 electrode assemblies are connected in series and are accommodated in the electric groove of polypropylene, sulfuric acid is added and makes the liquid that electrolyte density is 1.285
Formula lead accumulator.
(measure of initial capacity)
Prepare to use positive electrode collector using positive electrode collector 10A lead accumulator in positive plate and in positive plate
10B lead accumulator, determines 5 hour rate capacity and is used as initial capacity.The measure of 5 hour rate capacity was with JIS D5301 (2006
Version) it is foundation to carry out." X1 " will be set to using 5 hour rate capacity of positive electrode collector 10B lead accumulator, uses positive pole collection
5 hour rate capacity of electric body 10A lead accumulator are set to " X2 ", and (1) calculates the rate of change Z of 5 hour rate capacity as the following formula.5 is small
When rate capacity rate of change Z represent grid framework 15 section shape from quadrangle be changed to octagon when 5 hour rates hold
The rate of change of amount, value is bigger, represents the raising effect of the 5 hour rate capacity as caused by the change of the shape in the section of grid framework 15
Fruit is bigger.Show the result in table 1.
Z=(X1-X2)/X2 × 100 (1)
[table 1]
| Density (the g/cm of positive active material3) | The rate of change Z (%) of 5 hour rate capacity |
| 3.5 | 3 |
| 4.2 | 11 |
| 4.4 | 12 |
| 4.7 | 12 |
The density of positive active material is 3.5g/cm3When, the rate of change Z of 5 hour rate capacity is 3%.On the other hand, just
The density of pole active material is 4.1g/cm3During the above, especially for 4.2g/cm3During the above, the rate of change Z of 5 hour rate capacity is
11~12%, and for 3.5g/cm3When compare, the density of positive active material is greatly improved.Thus, in positive active material
Density is 3.5g/cm3When, positive active material density be 4.1g/cm3During the above, in particular 4.2g/cm3During the above, it is based on
Make grid framework 15 section shape distortion caused by the rates of change of 5 hour rate capacity have very big difference.It should illustrate, will
The section of grid framework 15 be shaped so as to hexagon or be formed as shown in Fig. 4 make corner 15C for round-shaped grade it is non-
In the case of polygonal, identical result is also obtained.The model in specific positive active material density is not known so far
The raising effect of 5 hour rate capacity is set to become big by the shape distortion in the section for making grid framework 15 in enclosing, this is according to existing
What some common technical knowledges can not be expected.In addition, the factor of the initial capacity of influence lead accumulator is a lot, therefore for by positive pole
The density of active material is 4.1g/cm3More than, in particular 4.2g/cm3Above with the shape distortion in the section that makes grid framework 15
With reference to those skilled in the art need a considerable amount of trial and error to obtain, and are not what is be readily apparent that.During by by being melted into
Density be 4.1g/cm3More than, preferably 4.2g/cm3The shape in section of the positive active material above with making grid framework 15
The positive plate being bonded of the punching grid of shape deformation is used for lead accumulator, excellent so as to form the life performance under PSOC
Different and initial capacity also excellent lead accumulator.
If positive active material density is set into 4.3g/cm3More than, then the raising effect of 5 hour rate capacity more shows
Write, therefore more preferably.If positive active material density is set into 4.4g/cm3More than, then the raising effect of 5 hour rate capacity
It is particularly significant, therefore particularly preferably.
If positive active material density is more than 5.0g/cm3, then the influence change of initial capacity reduction is big, therefore preferably just
Pole active material density is 5.0g/cm3Hereinafter, in order that the reduction of initial capacity is in practical scope and more preferably positive-active
Material density is 4.8g/cm3Below.
The positive plate of present embodiment be perfectly suitable in order to improve the life performance under PSOC and positive electrode active material
Matter is highdensity idling flameout lead accumulator.
The present invention can be implemented in the following manner.
(1) a kind of positive plate, for lead accumulator, above-mentioned positive plate possesses punching grid and positive pole with grid framework
There are deformation, above-mentioned positive electrode material in electrode material, the corner in the section vertical with bearing of trend of above-mentioned grid framework
Density when being melted into be 4.1 [g/cm3] more than.
(2) a kind of positive plate, for lead accumulator, above-mentioned positive plate possesses punching grid and positive pole with grid framework
Electrode material, the cross sectional shape vertical with bearing of trend of above-mentioned grid framework for polygon more than pentagon, pentagon with
On generally polygonal, non-polygon in any one, density when being melted into of above-mentioned positive electrode material is 4.1 [g/
cm3] more than.
(3) a kind of positive plate, for lead accumulator, above-mentioned positive plate possesses to be made up of the metal with lath-like microstructure
Grid and positive electrode material, above-mentioned grid has grid framework, the section vertical with bearing of trend of above-mentioned grid framework
Corner have a deformation, density when being melted into of above-mentioned positive electrode material is 4.1 [g/cm3] more than.
(4) a kind of positive plate, for lead accumulator, above-mentioned positive plate possesses to be made up of the metal with lath-like microstructure
Grid and positive electrode material, above-mentioned grid has grid framework, the section vertical with bearing of trend of above-mentioned grid framework
Shape is any of more than pentagon polygon, more than pentagon generally polygonal, non-polygon, above-mentioned anode electrode
Density when being melted into of material is 4.1 [g/cm3] more than.
(5) positive plate recorded according to any one of (1)~(4), wherein, when being melted into of above-mentioned positive electrode material
Density is 4.2 [g/cm3] more than.
(6) positive plate recorded according to any one of (1)~(4), wherein, when being melted into of above-mentioned positive electrode material
Density is 4.3 [g/cm3] more than.
(7) positive plate recorded according to any one of (1)~(4), wherein, when being melted into of above-mentioned positive electrode material
Density is 4.4 [g/cm3] more than.
(8) positive plate recorded according to any one of (1)~(7), wherein, when being melted into of above-mentioned positive electrode material
Density is 5.0 [g/cm3] below.
(9) positive plate recorded according to any one of (1)~(7), wherein, when being melted into of above-mentioned positive electrode material
Density is 4.8 [g/cm3] below.
(10) a kind of lead accumulator, including the positive plate that any one of (1)~(9) are recorded.
(11) a kind of manufacture method of lead accumulator positive plate, is the lead electric power storage being made up of grid and positive electrode material
The manufacture method of pond positive plate, above-mentioned grid is formed by using cutting processing formation grid framework from metal piece, will
The corner in the section vertical with bearing of trend of above-mentioned grid framework is deformed, and by above-mentioned anode electrode material when being melted into
The density of material is set to 4.1 [g/cm3] more than.
(12) according to the manufacture method of the lead accumulator positive plate described in (11), wherein, above-mentioned grid be by with
The grid that the metal of lath-like microstructure is constituted.
(13) manufacture method of the lead accumulator positive plate according to described in (11) or (12), wherein, above-mentioned cutting adds
Work is punch process.
(14) manufacture method of the lead accumulator positive plate according to described in (11) or (12), wherein, above-mentioned cutting adds
Work is punch press process.
(15) manufacture method for the lead accumulator positive plate recorded according to any one of (11)~(14), wherein, will be upper
The corner for stating the section vertical with bearing of trend of grid framework is deformed using punch process.
Claims (15)
1. a kind of positive plate, for lead accumulator, the positive plate possesses：
Punching grid with grid framework and
Positive electrode material,
There is deformation in the corner in the section vertical with bearing of trend of the grid framework,
Density when being melted into of the positive electrode material is 4.1 [g/cm3] more than.
2. a kind of positive plate, for lead accumulator, the positive plate possesses：
Punching grid with grid framework and
Positive electrode material,
The cross sectional shape vertical with bearing of trend of the grid framework is more than polygon more than pentagon, pentagon big
Any one in polygon, non-polygon is caused,
Density when being melted into of the positive electrode material is 4.1 [g/cm3] more than.
3. a kind of positive plate, for lead accumulator, the positive plate possesses：
The grid that is made up of the metal with lath-like microstructure and
Positive electrode material,
The grid has grid framework,
There is deformation in the corner in the section vertical with bearing of trend of the grid framework,
Density when being melted into of the positive electrode material is 4.1 [g/cm3] more than.
4. a kind of positive plate, for lead accumulator, the positive plate possesses：
The grid that is made up of the metal with lath-like microstructure and
Positive electrode material,
The grid has grid framework,
The cross sectional shape vertical with bearing of trend of the grid framework is more than polygon more than pentagon, pentagon big
Any one in polygon, non-polygon is caused,
Density when being melted into of the positive electrode material is 4.1 [g/cm3] more than.
5. according to positive plate according to any one of claims 1 to 4, wherein, when being melted into of the positive electrode material
Density is 4.2 [g/cm3] more than.
6. according to positive plate according to any one of claims 1 to 4, wherein, when being melted into of the positive electrode material
Density is 4.3 [g/cm3] more than.
7. according to positive plate according to any one of claims 1 to 4, wherein, when being melted into of the positive electrode material
Density is 4.4 [g/cm3] more than.
8. according to positive plate according to any one of claims 1 to 7, wherein, when being melted into of the positive electrode material
Density is 5.0 [g/cm3] below.
9. according to positive plate according to any one of claims 1 to 7, wherein, when being melted into of the positive electrode material
Density is 4.8 [g/cm3] below.
10. a kind of lead accumulator, including positive plate according to any one of claims 1 to 9.
11. a kind of manufacture method of lead accumulator positive plate, is that the lead accumulator being made up of grid and positive electrode material is used
The manufacture method of positive plate,
The grid is formed from metal piece by using cutting processing formation grid framework,
The corner in the section vertical with bearing of trend of the grid framework is deformed,
The density of positive electrode material when being melted into is set to 4.1 [g/cm3] more than.
12. the manufacture method of lead accumulator positive plate according to claim 11, wherein, the grid is by with plate
What the metal of streaky structure was constituted.
13. the manufacture method of the lead accumulator positive plate according to claim 11 or 12, wherein, the cutting processing is
Punch process.
14. the manufacture method of the lead accumulator positive plate according to claim 11 or 12, wherein, the cutting processing is
Punch press process.
15. the manufacture method of the lead accumulator positive plate according to any one of claim 11~14, wherein, will be described
The corner in the section vertical with bearing of trend of grid framework is deformed by punch process.
Applications Claiming Priority (4)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2016018090 | 2016-02-02 | ||
| JP2016-018090 | 2016-02-02 | ||
| JP2016250841A JP7098874B2 (en) | 2016-02-02 | 2016-12-26 | Manufacturing method of lead-acid battery and positive electrode plate for lead-acid battery |
| JP2016-250841 | 2016-12-26 |
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| Publication Number | Publication Date |
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| CN107026271A true CN107026271A (en) | 2017-08-08 |
| CN107026271B CN107026271B (en) | 2022-03-01 |
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| Application Number | Title | Priority Date | Filing Date |
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| CN201710061705.8A Active CN107026271B (en) | 2016-02-02 | 2017-01-26 | Positive electrode plate for lead storage battery, and method for manufacturing positive electrode plate for lead storage battery |
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| JP (1) | JP7098874B2 (en) |
| KR (1) | KR20170092111A (en) |
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| CN112913058A (en) * | 2018-10-16 | 2021-06-04 | 株式会社杰士汤浅国际 | Current collector for lead-acid battery and method for producing same |
| EP3855536A4 (en) * | 2018-10-16 | 2022-08-03 | GS Yuasa International Ltd. | Lead storage battery and method for producing same |
| CN112913066A (en) * | 2018-10-16 | 2021-06-04 | 株式会社杰士汤浅国际 | Lead-acid battery |
| WO2020080419A1 (en) * | 2018-10-16 | 2020-04-23 | 株式会社Ｇｓユアサ | Lead storage battery |
| JP7248033B2 (en) * | 2018-10-16 | 2023-03-29 | 株式会社Ｇｓユアサ | Lead-acid battery and manufacturing method thereof |
| KR102138270B1 (en) | 2018-11-13 | 2020-07-27 | 충북대학교 산학협력단 | Manufacturing method of negative electrode coated with activated carbon as active materials for ultra battery and ultra battery comprising negative electrode for ultra battery manufactured the same |
| KR102133885B1 (en) * | 2018-11-19 | 2020-07-14 | (주)코멕스카본 | Porous carbon crucible using spherical phenolic resin and its manufacturing method |
| JP6677436B1 (en) * | 2019-09-26 | 2020-04-08 | 古河電池株式会社 | Lead storage battery |
| JP7463719B2 (en) * | 2019-12-25 | 2024-04-09 | 株式会社Ｇｓユアサ | Battery collectors and electrode plates |
| WO2021210244A1 (en) * | 2020-04-14 | 2021-10-21 | 株式会社Ｇｓユアサ | Current collector for lead storage battery, positive electrode plate for lead storage battery, and lead storage battery |
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| Publication number | Publication date |
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| KR20170092111A (en) | 2017-08-10 |
| JP7098874B2 (en) | 2022-07-12 |
| JP2017139215A (en) | 2017-08-10 |
| CN107026271B (en) | 2022-03-01 |
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