CN109565040A - Lead storage battery - Google Patents

Lead storage battery Download PDF

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Publication number
CN109565040A
CN109565040A CN201780047806.8A CN201780047806A CN109565040A CN 109565040 A CN109565040 A CN 109565040A CN 201780047806 A CN201780047806 A CN 201780047806A CN 109565040 A CN109565040 A CN 109565040A
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storage battery
electrode material
lead storage
graphite
negative electrode
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CN201780047806.8A
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CN109565040B (en
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稻垣贤
京真观
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GS Yuasa International Ltd
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GS Yuasa International Ltd
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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
    • 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
    • H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
    • 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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  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Electrochemistry (AREA)
  • General Chemical & Material Sciences (AREA)
  • Battery Electrode And Active Subsutance (AREA)
  • Secondary Cells (AREA)

Abstract

The present invention provides a kind of lead storage battery, it is characterized in that, has positive plate, negative plate and electrolyte, the negative electrode material of above-mentioned negative plate is contained graphite or carbon fiber and is calculated as the barium element of 1.1mass% or more with barium sulfate conversion, and the positive electrode material of above-mentioned positive plate contains tin element.

Description

Lead storage battery
Technical field
The present invention relates to lead storage batteries.
Background technique
By lead storage battery with incomplete charged state (PSOC (part charged state, Partial state of Charge the purposes)) used becomes more.For example, proposing a kind of idling start and stop (Idling- to improve the fuel consumption of automobile Stop, omitted below is IS) vehicle, lead storage battery is used in IS vehicle with the state of undercharge.Other than the automobile-used way IS, also The electric power for charging to lead storage battery, and taking out from lead storage battery is avoided to increase because energy efficiency is improved, therefore lead stores Battery is placed mostly with the state of undercharge.
In lead storage battery, when electric discharge, water is generated in anode while two-plate consumes sulfuric acid.In addition, charging when from Two-plate releases sulfuric acid.The specific gravity of sulfuric acid is greater than water, therefore is easy savings in the lower part of lead storage battery, and the sulphur of electrolyte occurs Acid concentration generates phenomenon poor up and down (at stratification).When charge volume abundance, using latter stage of charging by gas that pole plate generates come Electrolyte is stirred, stratification is thus eliminated into.
But in the lead storage battery used with PSOC, since the gas generated by overcharge is few, therefore, it is difficult to eliminate Electrolyte at stratification.In the pole plate lower part that sulfuric acid concentration is got higher, charge acceptance is lower, and carries out sulfate in negative plate lower part Change (savings of lead sulfate).In addition, promote the deterioration on positive plate top since discharge and recharge reaction concentrates on pole plate top, Life performance reduces.
It is known in order to improve with the charge acceptance of the PSOC lead storage battery used and improve life performance and in negative electricity Graphite is added in the material of pole.
Following invention is described in patent document 1: a kind of " lead storage battery, which is characterized in that former with lead powder using making The battery paste of material is held in paste-type negative plate made of the collector of metal, in the negative active material with carbonaceous Material contains (a) bis-phenol sulfonic acid polymer and (b) sodium lignin sulfonate together, and the use level of (a) and (b) is as follows.It will be joined together (a) and (b) total when being set as 100 mass parts, make 50~80 mass parts of mixing ratio of (a), and relative to above-mentioned negative The quality of the raw material lead powder of pole active material makes (a) and (b) total 0.05 mass of mass %~0.3 % of fit quality." ([claim 1]), " lead storage battery described in any one of claim 1 to 3, which is characterized in that living in above-mentioned cathode Property substance in, containing average primary particle diameter is 10 μm or more of flaky graphite as carbonaceous material." ([claim 4]), " lead storage battery according to claim 4, which is characterized in that the content of above-mentioned flaky graphite is relative to fully charged state Under negative electrode active material quality be 0.5 mass of mass %~2.5 %." ([claim 5]), " according to claim 5 institute The lead storage battery stated, which is characterized in that other than above-mentioned flaky graphite, also contain carbon black." ([claim 6]).
Following invention is described in patent document 2: a kind of " battery paste use of the accumulator plate of lead storage battery Anti-piping compound, include barium sulfate, the carbon of high concentration and/or graphite and organic substance." (claim 1), " wanted according to right Anti-piping compound described in asking 1, wherein the carbon and/or graphite of high concentration make the sulphur on the negative electrode active material surface in lead storage battery The savings of lead plumbate reduces." (claim 10).
In patent document 3 for a kind of " swelling agent of battery paste, which is characterized in that containing barium sulfate, carbon and have Machine material, organic material are resistance to pyrolytic." (claim 1) invention, describe that " carbon indicates carbon black, activated carbon or stone Ink and their any one of mixture." " (paragraph [0029]).
Additionally, it is known that adding tin, spy in positive electrode material to improve with the performance of the PSOC lead storage battery used Determine the density of positive electrode material.
A kind of a kind of " flooded lead-acid battery, which is characterized in that be that idling start and stop are automobile-used is described in patent document 4 Flooded lead-acid battery has the positive plate being made of positive active material and positive screen, by negative electrode active material and negative electrode grid Negative plate that plate is constituted, the separator that positive plate and negative plate are separated and dipping positive plate and negative plate and separator and Liquid electrolyte with mobility, positive active material is in the state of being melted into completion, density 4.4g/cm3~4.8g/ cm3, and Sn is converted into metal Sn and contains 0.05mass%~1.0mass%." (claim 1) invention.
Existing technical literature
Patent document
Patent document 1: Japanese table WO2012/017702 public again
Patent document 2: Japanese Unexamined Patent Application Publication 2012-501519 bulletin
Patent document 3: Japanese Unexamined Patent Application Publication 2010-529619 bulletin
Patent document 4: Japanese Unexamined Patent Publication 2013-140677 bulletin
Summary of the invention
In lead storage battery, if containing conductive higher and partial size is larger compared with carbon black etc. in negative electrode material Graphite or carbon fiber (hereinafter, sometimes referred to as " graphite etc. "), then be able to extend the lead storage battery under the conditions of PSOC service life (with It is known as " PSOC service life " down).On the other hand, the inventors of the present invention have found to exist in negative electrode material for the first time containing graphite etc. The project of short circuit penetration is easy to happen in lead storage battery.The reason is not yet clear for it, but is presumed as follows.Speculate due to graphite etc. and charcoal It is black equal larger compared to partial size, therefore a portion is easy to be exposed to cathode plate surface.Graphite etc. since electric conductivity is higher, so When graphite etc. is exposed to cathode plate surface, it can be concentrated on its exposed division and Pb occurs2+Charging reaction.As a result, part is larger Lead tree to puncture separator direction grow, by charging current be easy concentrate pole plate top centered on occur infiltration it is short Road.
The present invention improves its purpose is to provide a kind of PSOC life performance in view of the above subject and inhibits short circuit penetration The lead storage battery of generation.
The lead storage battery of one embodiment of the present invention is characterized in that having positive plate, negative plate and electrolyte, above-mentioned negative The negative electrode material of pole plate is contained graphite or carbon fiber and is calculated as the barium element of 1.1mass% or more with barium sulfate conversion, on The positive electrode material for stating positive plate contains tin element.
According to one method of the present invention, it is capable of providing the generation that a kind of PSOC life performance improves and inhibits short circuit penetration Lead storage battery.
Detailed description of the invention
Fig. 1 is the main portion sectional view of the lead storage battery of one embodiment of the present invention.
Fig. 2 is performance plot (the barium content 1.0mass% of barium sulfate conversion, the positive-active for the influence for indicating content of graphite Material density 4.8g/cm3, Theil indices 0mass%).
Fig. 3 is the performance plot (content of graphite 1.0mass%, Theil indices 0mass%) for the influence for indicating barium content.
Fig. 4 is performance plot (content of graphite 1.0mass%, the positive active material for the influence for indicating barium content and Theil indices Density 4.2g/cm3)。
Fig. 5 is performance plot (content of graphite 1.0mass%, the positive active material for the influence for indicating barium content and Theil indices Density 4.2g/cm3)。
Fig. 6 is performance plot (content of graphite 1.0mass%, the barium sulfate conversion for the influence for indicating positive active material density Barium content 1.2mass%).
Fig. 7 is performance plot (content of graphite 1.0mass%, the barium sulfate conversion for the influence for indicating positive active material density Barium content 1.0mass%).
Fig. 8 is the performance plot (content of graphite 1.0mass%, Theil indices 0.01mass%) for the influence for indicating barium content.
Fig. 9 is performance plot (content of graphite 3.0mass%, the positive active material density for the influence for indicating content of carbon black 4.8g/cm3)。
Figure 10 be indicate graphite the influence of average grain diameter performance plot (content of graphite 3.0mass%, barium sulfate conversion Barium content 1.2mass%, positive active material density 4.8g/cm3, Theil indices 0.01mass%).
Specific embodiment
The lead storage battery of one embodiment of the present invention is characterized in that: have positive plate, negative plate and electrolyte, it is above-mentioned negative The negative electrode material of pole plate is contained graphite or carbon fiber and is calculated as the barium element of 1.1mass% or more with barium sulfate conversion, on The positive electrode material for stating positive plate contains tin element.It is described in detail below.
Negative plate is made of negative electrode collector and negative electrode material, and positive plate is by positive electrode collector and positive electrode material It constitutes, the solid component other than collector belongs to electrode material.Hereinafter, the content of graphite, the content of carbon fiber, barium element contain Amount, the content of carbon black are the content (mass%) after being melted into relative to the negative electrode material of fully charged state.In addition, tin element Content be chemical conversion after relative to fully charged state positive electrode material content (mass%).It should be noted that barium element Content is the content in terms of barium sulfate conversion, and the content of tin element is the content in terms of metallic tin conversion.
In order to make lead storage battery fully charged state, when being liquid formula battery, in 25 DEG C of sink, with 5 hour rate currents Constant current charging is carried out after reaching 2.5V/Cell, further carries out 2 hours constant current chargings with 5 hour rate currents. In addition, carrying out Constant Current Constant with 5 hour rate currents in 25 DEG C of air drain when to control valve type battery with 2.23V/Cell Voltage charging, the current value in constant voltage charging terminate to charge at the time of being 1mCA or less.5 hour rates in the specification Electric current is the current value that the nominal capacity of lead storage battery was discharged with 5 hours, for example, being 30Ah's if it is nominal capacity Battery, then 5 hour rate currents are 6A, 1mCA 30mA.
<electrode material>
As previously mentioned, the PSOC life performance for having the lead storage battery of the negative electrode material containing graphite etc. improves.
If the content of the graphite in negative electrode material etc. is 0.5mass% or more, the raising of PSOC life performance Effect is big, therefore the content of graphite in negative electrode material etc. is preferably 0.5mass% or more.If in negative electrode material The content of graphite etc. be 1.0mass% or more, then the improvement effect of PSOC life performance is bigger, therefore in negative electrode material The content of graphite etc. be more preferably 1.0mass% or more.
If the content of graphite in negative electrode material etc. be 2.5mass% hereinafter, if be easy negative electrode material Paste is filled in negative electrode collector, therefore the content of graphite in negative electrode material etc. is preferably 2.5mass% hereinafter, more preferably For 2.0mass% or less.
As graphite, for example, can enumerate flaky graphite, flaky graphite, amorphous graphite, expanded graphite, expansion graphite, Artificial graphite etc..Expansion graphite refers to the graphite that expansion finishes.Further, it is possible to use carbon fiber replaces graphite.Think graphite Higher in electric conductivity with carbon fiber and be greater than common in terms ofs carbon black etc., the effect in negative electrode material is also identical.For For carbon fiber, such as length is preferably 5 μm~500 μm, and length is more preferably 10 μm~300 μm.Graphite etc. is preferably scale Shape graphite or expansion graphite, more preferably flaky graphite.
If 300 μm of average grain diameter for making graphite hereinafter, if be not susceptible to short circuit penetration, therefore the average grain diameter of graphite Preferably 300 μm or less.In addition, PSOC life performance improves, therefore if making 100 μm of average grain diameter of graphite or more The average grain diameter of graphite is preferably 100 μm or more.It should be noted that the average grain diameter of graphite indicates to utilize laser diffraction formula granularity point The value for the partial size (D50) that the cumulative volume in size distribution when cloth measurement device is analyzed is 50%.
By adding graphite etc. in negative electrode material, so that PSOC life performance be made to improve, on the other hand, it is easy hair Raw short circuit penetration.It is not aware that ands adding graphite etc. in the negative electrode material in lead storage battery and is easy to happen so far Short circuit penetration.The inventors of the present invention's discovery can by negative electrode material with graphite etc. together containing in terms of barium sulfate conversion For 1.1mass% or more barium element and inhibit the generation of short circuit penetration.
1.1mass% or more can be calculated as with barium sulfate conversion by adding together in negative electrode material with graphite etc. Barium element and to inhibit the effect of short circuit penetration be that can not be expected according to common technical knowledge so far.Reason is: arriving Do not recognize the project that short circuit penetration is easy to produce because making negative electrode material contain graphite etc. so far, so far for It is only also not aware that and is calculated as 1.1mass% or more with barium sulfate conversion by being selected as the additive amount of barium element and can inhibit to permeate The effect that short circuit occurs.
The mechanism of action that adding barium element into negative electrode material can inhibit short circuit penetration to occur is still not clear, but speculates It is as follows.Think the barium element in negative electrode material being almost evenly scattered in negative electrode material in the form of barium sulfate Inside, functioned in electric discharge as the nucleation material of lead sulfate, to also generate sulfuric acid inside negative electrode material Lead.When also generating lead sulfate inside negative electrode material, the generation quantitative change of lead sulfate can be inhibited more on the surface of negative plate. A part dissolution of lead sulfate and generate lead ion, but if the lead sulfate amount on the surface of negative plate is reduced, then the table of negative plate The concentration of lead ion near face is also reduced, and lead ion is difficult in the electrolyte being diffused between positive/negative plate.As a result, exposing In graphite of polar board surface etc., when charging, is difficult to happen the reduction reaction of lead ion, is able to suppress from being exposed to polar board surface Lead tree from graphite etc. to positive plate direction growth.
When the content of the barium element in negative electrode material being made to be calculated as 1.2mass% or more with barium sulfate conversion, Neng Gou great The big generation for inhibiting short circuit penetration.Therefore, make the content of the barium element in negative electrode material by barium sulfate conversion in terms of preferably 1.2mass% or more.
When the content of the barium element in negative electrode material being made to be calculated as 3.0mass% or less with barium sulfate conversion, the PSOC longevity Performance is ordered to improve, thus make the content of barium element in negative electrode material preferably 3.0mass% in terms of barium sulfate conversion with Under.When the content of the barium element in negative electrode material being made to be calculated as 2.5mass% or less with barium sulfate conversion, PSOC life performance Greatly improve, thus make the content of barium element in negative electrode material more preferably 2.5mass% in terms of barium sulfate conversion with Under.
In order to make negative electrode material contain barium element, the barium or sulfuric acid of simple substance can be added in negative electrode material The barium compounds such as barium, barium carbonate.Even if thinking the barium of the simple substance other than barium sulfate, barium compound making an addition to negative electrode Material also becomes barium sulfate after addition.
For example preferably averagely aggregate particle size is 1~10 μm to barium sulfate in negative electrode material.In addition, negative electrode material In for example preferred average primary particle diameter of barium sulfate be 0.3~2.0 μm.
So that the content of the barium element in negative electrode material is calculated as 1.1mass% or more with barium sulfate conversion, further makes When positive electrode material contains tin element, short circuit penetration can be further suppressed.On the other hand, the barium member in negative electrode material When the content of element is calculated as 1.0mass% or less with barium sulfate conversion, even if positive electrode material is made to contain tin element, also it can't see Because of the short circuit penetration inhibitory effect caused by tin element.Up to the present the tin element in positive electrode material and infiltration are had no knowledge about Short circuit is related.Therefore, it is impossible to expect negative electrode material contain graphite etc. and by barium sulfate conversion in terms of containing 1.1mass% with On barium element when, by making positive electrode material contain tin element, be able to suppress short circuit penetration.In addition, in negative electrode material When the content of the barium element in terms of barium sulfate conversion in material is 1.1mass% or more and when being 1.0mass% or less, because of tin member Short circuit penetration inhibitory effect caused by element clearly changes, it can be said that making the content of the barium element in negative electrode material with sulphur Sour barium conversion is calculated as 1.1mass% or more with critical meaning.
Because when making the content 0.01mass% or more of the tin element in positive electrode material, can obviously inhibit to permeate Short circuit, so the content of the tin element in positive electrode material is made to be preferably 0.01mass% or more.It should be noted that as anode The existing forms of tin element in electrode material, it is believed that have metal, oxide, sulfate etc..
The mechanism of action for inhibiting short circuit penetration to occur because adding tin element into positive electrode material is still not clear, but pushes away It surveys as follows.Speculate because tin element has the effect of improving electric conductivity, when adding tin element in positive electrode material, meeting Make discharge and recharge reaction more uniformization of the up and down direction of positive plate, charging current is mitigated to the concentration on pole plate top.It fills When electric current is mitigated to the concentration on pole plate top, the growth of the lead tree on pole plate top is inhibited, and because of negative electrode material Short circuit penetration inhibitory effect caused by the barium sulfate of 1.1mass% or more in material plays synergistic effect, hence it is evident that inhibits infiltration short The generation on road.
The case where negative electrode material contains graphite etc. and is calculated as the barium element of 1.1mass% or more with barium sulfate conversion Under, when making to be free of tin element with positive electrode material when the content 0.15mass% or less of the tin element in positive electrode material It compares, PSOC life performance improves.Therefore, the content for making the tin element in positive electrode material be preferably 0.15mass% with Under.On the other hand, the content of the barium element in negative electrode material is calculated as the situation of 1.0mass% or less with barium sulfate conversion Under, even if making the content 0.15mass% of the tin element in positive electrode material hereinafter, with the not stanniferous member of positive electrode material It is compared when plain, PSOC life performance does not also improve.Whens having no knowledge about negative electrode material so far and containing graphite etc., by making The content of tin element in the content and positive electrode material of barium element in negative electrode material can make in specific range PSCO life performance improves.
The case where negative electrode material contains graphite etc. and is calculated as the barium element of 1.1mass% or more with barium sulfate conversion Under, when making to be free of tin element with positive electrode material when the content 0.10mass% or less of the tin element in positive electrode material It compares, PSOC life performance greatly improves.Therefore, it is more preferably the content of the tin element in positive electrode material 0.10mass% or less.Negative electrode material is contained graphite etc. and is calculated as the barium element of 1.1mass% or more with barium sulfate conversion In the case where, when making the content 0.08mass% or less of the tin element in positive electrode material, PSOC life performance is further It greatly improves, thus further preferably.Negative electrode material contains graphite etc. and is calculated as 1.1mass% or more with barium sulfate conversion Barium element in the case where, when making the content 0.06mass% or less of the tin element in positive electrode material, PSOC service life property It can especially greatly improve, thus particularly preferably.
The case where negative electrode material contains graphite etc. and is calculated as the barium element of 1.1mass% or more with barium sulfate conversion Under, when making to be free of tin element with positive electrode material when the content 0.03mass% or more of the tin element in positive electrode material It compares, PSOC life performance greatly improves.Therefore, the content for making the tin element in positive electrode material is preferably 0.03mass% More than.
Contain graphite etc. by negative electrode material and is calculated as the barium element and just of 1.1mass% or more with barium sulfate conversion Pole electrode material contains the improvement effect of PSOC life performance obtained from 0.15mass% tin element below in anode electrode The density of material is 3.6g/cm3Become larger when above.Therefore, the density for making positive electrode material is preferably 3.6g/cm3More than.Separately On the one hand, when the content of the barium element in negative electrode material is calculated as 1.0mass% or less with barium sulfate conversion, even if making anode The density of electrode material is 3.6g/cm3More than, compared with when positive electrode material is free of tin element, PSOC life performance is not yet It improves.
Contain graphite etc. by negative electrode material and is calculated as the barium element and just of 1.1mass% or more with barium sulfate conversion Pole electrode material contains the improvement effect of PSOC life performance obtained from 0.15mass% tin element below in anode electrode The density of material is 4.2g/cm3It is further enlarged when above.Therefore, the density of positive electrode material is made to be more preferably 4.2g/cm3 More than.The improvement effect of the PSOC life performance is 4.4g/cm due to the density in positive electrode material3Obviously become when above Greatly, therefore the density of positive electrode material is made to be particularly preferably 4.4g/cm3More than.
Because making the density 5.0g/cm of positive electrode material3When following, the initial capacity of lead storage battery is improved, so The density of positive electrode material is preferably 5.0g/cm3Below.
The lead storage battery of one embodiment of the present invention can further contain carbon black in negative electrode material.In negative electricity Pole material contain graphite etc. and with barium sulfate conversion be calculated as 1.1mass% or more barium element and positive electrode material contain tin member In the case where element, when further containing carbon black in negative electrode material, short circuit penetration can be further suppressed.On the other hand, The content of barium element in negative electrode material is converted when being calculated as 1.0mass% or less with barium sulfate or positive electrode material When without tin element, even if making to contain carbon black in negative electrode material, also it cannot inhibit to imitate because of the short circuit penetration caused by carbon black Fruit.
Inhibit short circuit penetration significantly when the content of the carbon black in negative electrode material being enable to be 0.1mass% or more, because And it is preferred that.Make to be easy to paste negative electrode material when the content 1.0mass% or less of the carbon black in negative electrode material to fill In negative electrode collector.Therefore, the content of the carbon black in negative electrode material is preferably 1.0mass% or less.
Hereinafter, the lead storage battery and its manufacturing method to an embodiment of the invention are successively described in detail.
<negative plate>
The negative plate not being melted into can make as follows.Firstly, addition water and sulfuric acid are gelatinized and are born in lead powder Pole electrode material paste.Can make negative electrode material paste further containing graphite, carbon fiber, barium sulfate, carbon black, as anti-piping compound Reinforcing materials such as lignin, synthetic resin fiber etc..Also the barium compounds such as barium, the barium carbonate of simple substance can be used instead of sulfuric acid Barium.
The content of lignin is arbitrary, and the synthesis anti-piping compound such as condensation product of sulfonated bisphenols can be used and replace wood Quality.The content of reinforcing material and the type of synthetic resin fiber are arbitrary.In addition, the type and manufacturing condition of lead powder are to appoint Meaning.Negative electrode material paste can also be made containing other additives, water-soluble synthesis polyelectrolyte etc..
After negative electrode material paste is filled in negative electrode collector, implement curing and dry, the negative plate that production is not melted into. Grid plate, casting screen, punching press screen etc. can be used for example in negative electrode collector.
<positive plate>
The positive plate not being melted into can make as follows.Firstly, addition water and sulfuric acid are gelatinized and are obtained just in lead powder Pole electrode material paste.Positive electrode material paste can be made containing reinforcing materials such as STANNOUS SULPHATE CRYSTALLINE, synthetic resin fiber etc..By the anode After electrode material paste is filled in positive electrode collector, implement curing and dry, the positive plate that production is not melted into.The type and system of lead powder The condition of making is arbitrary.Metallic tin etc. can be used instead of STANNOUS SULPHATE CRYSTALLINE, thus it is speculated that tin is in positive electrode material with metal, oxidation The form of object, sulphate etc. exists.The density of positive electrode material after chemical conversion is by changing in production anode electrode material Expect the additive amount of water when paste and is adjusted.It should be noted that positive electrode collector can be used for example grid plate, casting screen, Punching press screen etc..
<lead storage battery>
Lead storage battery can be made as follows.The negative plate not being melted into and the positive plate not being melted into are handed over across separator For stacking, the positive plate that the negative plate not being melted into is not melted into each other, is connected with strap separately from each other and electrode is made Plate group.Electrode plate group is contained in the battery chamber of battery case with the state being connected in series, sulfuric acid is added and is melted into, lead is made Battery.It can assemble electrode plate group after being melted into the negative plate not being melted into and the positive plate not being melted into and make lead Battery.Separator is, for example, synthetic resin system, preferably polyolefin system, further preferably polyethylene system.In addition, separator It is preferred that having from matrix rib outstanding.Matrix thickness, aggregate thickness of separator etc. are arbitrary, the matrix of separator Thickness is preferably 0.15mm~0.25mm.Positive plate and negative plate are preferably spaced 0.5mm~1.0mm.It can be by separator It is made and bag-shaped encases positive plate or negative plate.
It is negative plate Fig. 1 shows the major part of the electrode plate group 1 of the lead storage battery of one embodiment of the present invention, 2,3 are Positive plate, 4 be separator.Negative plate 2 is made of negative electrode collector 21 and negative electrode material 22, and positive plate 3 is by positive pole current collections Body 31 and positive electrode material 32 are constituted.Separator 4 is born with the bag-shaped storage in the inside of bag for having matrix 41 and rib 42 Pole plate 2, rib 42 is towards 3 side of positive plate.But it is also possible to which positive plate 3 is accommodated in by rib 42 towards positive plate 3 Separator 4, separator 4 can also not have rib 42.If in addition, separator is isolated by positive plate with negative plate, nothing It need to be bag-shaped, such as the glass isolator of small laminated, fixed pad also can be used etc..
The content of the barium element contained in negative electrode material after chemical conversion is quantified as follows.By the lead of fully charged state Battery disintegrates, and is washed and is dried to negative plate and removes sulfuric acid components, and negative electrode material is extracted.By negative electrode material Feed powder is broken, and the hydrogenperoxide steam generator 20mL of 300g/L is added relative to negative electrode material 100g, and being further added will Nitric acid obtained from the ion exchange water dilution of its 3 times of volumes of the concentrated nitric acid of 60mass% stirs lower heating 5 hours, makes lead Dissolution becomes plumbi nitras.Further dissolve barium sulfate, by the barium concentration in obtained aqueous solution by atom absorptiometry into Row is quantitative.The barium content of the barium sulfate conversion contained in negative electrode material is calculated using the barium concentration.
The content of the graphite and carbon black that contain in negative electrode material after chemical conversion is quantified as follows.By fully charged state Lead storage battery disintegrate, negative plate is washed and is dried and removes sulfuric acid components, extract negative electrode material.By negative electricity Pole material disintegrating, the hydrogenperoxide steam generator 20mL of 300g/L is added relative to negative electrode material 100g, and being further added will Nitric acid obtained from the ion exchange water dilution of its 3 times of volumes of the concentrated nitric acid of 60mass% stirs lower heating 5 hours, makes lead Dissolution becomes plumbi nitras.Further dissolve barium sulfate.Separated and being filtered to obtained aqueous solution graphite, carbon black, The solid components such as reinforcing material.
Next, being dispersed in water the solid component as obtained from filtering.Using reinforcing material can not by sieve Dispersion liquid is sieved 2 times by son, removes the reinforcing material washed, thus separating off carbon black and graphite.
Carbon black and graphite are added in negative electrode material paste together with organic anti-piping compound such as lignin, even if being melted into In negative electrode material afterwards, also due to the surface-active effect of organic anti-piping compound, carbon black and graphite are defeated and dispersed with its condensation product State exists.Because organic anti-piping compound dissolves out Yu Shuizhong and loses, so making to separate in above-mentioned a series of lock out operation After carbon black and graphite out is dispersed in water again, by the VANILLEX N for belonging to lignosulfonates as organic anti-piping compound (Jujo Paper Co., Ltd's system) is added 15g relative to water 100mL and is stirred, by the condensation product of carbon black and graphite with again Defeated and dispersed state carries out lock out operation below.
After aforesaid operations, the suspension containing carbon black and graphite is passed through into the substantial sieve for not passing through carbon black by graphite Son separates the two.In the operation, graphite remains on sieve, contains carbon black by the liquid of sieve.It will connect by above-mentioned one After the operation of string and isolated graphite and carbon black are washed and dried respectively, respective weight is weighed.Carbon fiber also with graphite It similarly separates, weighs weight.
The measuring method of the average grain diameter of graphite described below.Measurement device uses the laser diffraction formula of Shimadzu Seisakusho Ltd. Particle size distribution device SALD2200.Firstly, making graphite dispersion in the dispersion liquid for mixing water and surfactant and making In, 5 minutes ultrasonic waves are irradiated to the dispersion liquid for being dispersed with graphite using supersonic wave cleaning machine.Next, graphite will be dispersed with Dispersion liquid is directed into batch-type measuring cell (returning fraction セ Le), stirs 1 minute.Then, laser is irradiated, the granularity point of graphite is obtained Cloth.In the size distribution, in the range that minimum is set as 0.1 μm, maximum is set as 1000 μm, it is by cumulative volume The partial size of 50% (D50) is as average grain diameter.
The content of the tin element in positive electrode material after chemical conversion is quantified as follows.By the lead electric power storage of fully charged state Pond is disintegrated, and is washed and is dried to positive plate and removes sulfuric acid components, and positive electrode material is extracted.By positive electrode material powder It is broken, the hydrogenperoxide steam generator 20mL of 300g/L is added relative to positive electrode material 100g, is further added 60mass%'s Nitric acid obtained from the ion exchange water dilution of its 3 times of volumes of concentrated nitric acid stirs lower heating 5 hours, dissolves lead and tin.Benefit It is quantified, is calculated in positive electrode material with concentration of the ICP ICP Atomic Emission Spectrophotometer method to the tin element in obtained aqueous solution Tin element content.
The density of positive electrode material refers to the value of the bulk density of the positive electrode material of the fully charged state after chemical conversion, It is measured in the following manner.Disintegrate after battery full charge after making chemical conversion, to obtained positive plate implement washing with It is dry, thus remove the electrolyte in positive plate.Then, positive electrode material is separated from positive plate, the survey not crushed Determine sample.Sample is put into measurement container, after being vacuum-evacuated, mercury is full of with the pressure of 0.5~0.55psia, measurement is just Thus the stacking volume of pole electrode material finds out the accumulation of positive electrode material by the quality for measuring sample divided by stacking volume Density.It should be noted that volume obtained by the volume for measuring container is subtracted the injection volume of mercury is as stacking volume.
The PSOC life performance of the lead storage battery of present embodiment is excellent, even and if being used also not with part charged state Short circuit penetration, therefore the lead storage battery for being suitable for using under the parts charged states such as the automobile-used lead storage battery of idling start and stop easily occurs. In addition, the lead storage battery of present embodiment other than automobile-used lead storage battery of idling start and stop etc., applies also for fork lifter use Deng the lead storage battery of circulation purposes.Below in an example, lead storage battery is liquid formula, but may be control valve type.This reality The lead storage battery for applying mode is preferably the lead storage battery of liquid formula.
<other embodiment>
The present invention is not limited to above embodiment, in addition to those mentioned earlier, can also be to implement various changes, change Good mode is implemented.For example, the present invention can be implemented in such a way.
(1) a kind of lead storage battery, which is characterized in that have positive plate, negative plate and electrolyte, the cathode of above-mentioned negative plate Electrode material is contained graphite or carbon fiber and is calculated as the barium element of 1.1mass% or more with barium sulfate conversion, above-mentioned positive plate Positive electrode material contains tin element.
(2) according to the lead storage battery of (1), which is characterized in that it is below that above-mentioned positive electrode material contains 0.15mass% Tin element.
(3) according to the lead storage battery of (1) or (2), which is characterized in that the density of above-mentioned positive electrode material is 3.6g/cm3 More than.
(4) according to the lead storage battery of any one of (1)~(3), which is characterized in that above-mentioned negative electrode material contains charcoal It is black.
(5) according to the lead storage battery of any one of (1)~(4), which is characterized in that above-mentioned negative electrode material contains The graphite or carbon fiber of 0.5mass% or more.
(6) according to the lead storage battery of any one of (1)~(5), which is characterized in that above-mentioned negative electrode material contains 2.5mass% graphite below or carbon fiber.
(7) according to the lead storage battery of any one of (1)~(6), which is characterized in that above-mentioned graphite or carbon fiber are average grains Diameter is 300 μm of graphite below.
(8) according to the lead storage battery of any one of (1)~(7), which is characterized in that above-mentioned graphite or carbon fiber are average grains The graphite that diameter is 100 μm or more.
(9) according to the lead storage battery of any one of (1)~(8), which is characterized in that above-mentioned negative electrode material is with barium sulfate Conversion meter contains 3.0mass% barium element below.
(10) according to the lead storage battery of any one of (1)~(9), which is characterized in that above-mentioned positive electrode material contains The tin element of 0.01mass% or more.
(11) according to the lead storage battery of any one of (1)~(10), which is characterized in that the density of above-mentioned positive electrode material For 4.2g/cm3More than.
(12) according to the lead storage battery of any one of (1)~(11), which is characterized in that the density of above-mentioned positive electrode material For 5.0g/cm3Below.
(13) according to the lead storage battery of any one of (1)~(12), which is characterized in that above-mentioned negative electrode material contains The graphite or carbon fiber of 1.0mass% or more.
(14) according to the lead storage battery of any one of (1)~(13), which is characterized in that above-mentioned negative electrode material contains 2.0mass% graphite below or carbon fiber.
(15) according to the lead storage battery of any one of (1)~(14), which is characterized in that above-mentioned negative electrode material is with sulfuric acid Barium element of the barium conversion meter containing 1.2mass% or more.
(16) according to the lead storage battery of any one of (1)~(15), which is characterized in that above-mentioned negative electrode material is with sulfuric acid Barium conversion meter contains 2.5mass% barium element below.
(17) according to the lead storage battery of any one of (1)~(16), which is characterized in that by above-mentioned barium element with barium sulfate Form contains.
(18) according to the lead storage battery of any one of (1)~(17), which is characterized in that above-mentioned positive electrode material contains 0.10mass% tin element below.
(19) according to the lead storage battery of any one of (1)~(18), which is characterized in that above-mentioned positive electrode material contains 0.08mass% tin element below.
(20) according to the lead storage battery of any one of (1)~(19), which is characterized in that above-mentioned positive electrode material contains 0.06mass% tin element below.
(21) according to the lead storage battery of any one of (1)~(20), which is characterized in that above-mentioned positive electrode material contains The tin element of 0.03mass% or more.
(22) according to the lead storage battery of any one of (1)~(21), which is characterized in that the density of above-mentioned positive electrode material For 4.4g/cm3More than.
(23) according to the lead storage battery of any one of (1)~(22), which is characterized in that above-mentioned negative electrode material contains The carbon black of 0.1mass% or more.
(24) according to the lead storage battery of any one of (1)~(23), which is characterized in that above-mentioned negative electrode material contains 1.0mass% carbon black below.
(25) a kind of lead storage battery, which is characterized in that have positive plate, negative plate and electrolyte, above-mentioned negative plate is born Pole electrode material contain graphite or carbon fiber and by barium sulfate conversion in terms of about 1.1mass% or more barium element, above-mentioned anode The positive electrode material of plate contains tin element.
(26) according to the lead storage battery of (25), which is characterized in that above-mentioned positive electrode material contain about 0.15mass% with Under tin element.
(27) according to the lead storage battery of (25) or (26), which is characterized in that the density of above-mentioned positive electrode material is about 3.6g/cm3More than.
(28) according to the lead storage battery of any one of (25)~(27), which is characterized in that above-mentioned negative electrode material contains The graphite or carbon fiber of about 0.5mass% or more.
(29) according to the lead storage battery of any one of (1)~(28), which is characterized in that above-mentioned graphite or carbon fiber are scale Shape graphite or expansion graphite.
(30) according to the lead storage battery of any one of (1)~(29), which is characterized in that above-mentioned graphite or carbon fiber are scale Shape graphite.
(31) according to the lead storage battery of any one of (1)~(30), which is characterized in that above-mentioned lead storage battery is partially to fill The lead storage battery that electricity condition uses.
(32) according to the lead storage battery of any one of (1)~(31), which is characterized in that above-mentioned lead storage battery is liquid formula lead storage Battery.
(33) according to the lead storage battery of any one of (1)~(31), which is characterized in that above-mentioned lead storage battery is control valve type Lead storage battery.
(34) according to the lead storage battery of any one of (1)~(33), which is characterized in that above-mentioned lead storage battery is idling start and stop Automobile-used lead storage battery.
(35) a kind of vehicle is equipped with the lead storage battery of any one of (1)~(34).
Embodiment
Embodiment described below.It, can be according to the common sense of those skilled in the art and the disclosure of the prior art when implementing And change appropriate is carried out to embodiment.It should be noted that in embodiment, negative electrode material is known as negative electrode active material sometimes Positive electrode material is known as positive active material by matter.
(average grain diameter (D50) is 10~500 μ to the flaky graphite of mixing specified amount in the lead powder manufactured by ball-milling method M), the carbon black, shrinkproof of the barium sulfate (average primary particle diameter is 0.79 μm, and average aggregate particle size is 2.5 μm) of specified amount, specified amount The lignin (content 0.2mass%) of agent and synthetic resin fiber (content 0.1mass%) as reinforcing material, using water and Sulfuric acid is gelatinized, production negative electrode active material paste.Range of the content of flaky graphite in 0mass%~3.0mass% becomes Change.Range of the content of barium sulfate in 1.0mass%~4.0mass%.The content of carbon black 0mass%~ The range of 0.5mass%.
Made negative electrode active material paste is filled in the negative of the net type being made of Pb-Ca-Sn system alloy without antimony Pole screen (height 110mm × width 100mm × thickness 1.0mm) implements curing and dry, the negative plate that production is not melted into.
The reinforcing material of the STANNOUS SULPHATE CRYSTALLINE and 0.1mass% of mixing specified amount synthesizes tree in the lead powder manufactured by ball-milling method Rouge fiber (content 0.1mass%), is gelatinized using water and sulfuric acid, production positive active material paste.The content of STANNOUS SULPHATE CRYSTALLINE with Range of the metallic tin conversion meter in 0~0.3mass%.By made positive active material paste be filled in without antimony by The positive screen (height 110mm × width 100mm × thickness 1.2mm) for the net type that Pb-Ca-Sn system alloy is constituted implements curing And drying, make the positive plate not being melted into.It should be noted that after changing the amount of the water added in gelatinization and being adjusted to chemical conversion just The density of pole active material is 3.4g/cm3~5.0g/cm3。
The cathode not being melted into is encased with the polyethylene separator (0.1 μm of average pore diameter) for protruding rib from matrix Plate keeps the negative plate not being melted into 7 and the positive plate not being melted into 6 alternately laminated, by negative plate each other, positive plate separately from each other It is connected with strap and electrode plate group is made.In embodiment, using the separator with a thickness of 0.25mm of matrix, anode 0.7mm is divided between plate and negative plate.6 electrode plate groups are contained in the battery chamber of battery case with the state being connected in series, The sulfuric acid of specific gravity 1.285 is added at 20 DEG C, is melted into battery case, 5 hour rate capacity is made as 30Ah's with B20 size Flooded lead-acid battery.
Content, the content of graphite, the average grain diameter of graphite, the content of carbon black of the barium element contained in negative electrode active material Measurement carry out as follows.It the use of diameter is 1.4mm in the separating of carbon black and graphite in the negative active material and reinforcing material Sieve.Make the carbon black isolated and graphite dispersion in water after, addition as organic anti-piping compound belongs to lignosulfonates VANILLEX N (Jujo Paper Co., Ltd's system), the use of diameter is that 20 μm of sieve comes separating off carbon black and graphite.It should say It is bright, for having the lead storage battery for forming identical negative plate, select one in these lead storage batteries to be measured, measurement knot All lead storage batteries that fruit is suitable for having the negative plate of same composition.In addition, the tin element contained in positive active material The measurement of content, positive active material density carries out as previously mentioned.For having the lead storage battery for forming identical positive plate, One in these lead storage batteries is selected to be measured, all lead that measurement result is suitable for having the positive plate of same composition store Battery.
PSOC life test is carried out to the lead storage battery of fully charged state and short circuit penetration promotes test.The PSOC service life is tried The content tested is shown in table 1.1CA is 30A in the case where the battery that nominal capacity is 30Ah." 40 DEG C of gas " indicates the gas at 40 DEG C It is tested in slot.The content of PSOC life test is as follows.Firstly, (process 1) is discharged with the constant current of 1CA progress 59 seconds, And (process 2) is discharged with the constant current of 300A progress 1 second.Next, with the voltage of 2.4V, (charging current is most to each unit Greatly 50A) 10 seconds constant voltage chargings (process 3) are carried out, and (process 4) is discharged with the constant current of 1CA progress 5 seconds.It will Process 3 and process 4, which add up to, is repeated 5 times (process 5), further by 1~process of process 5,50 times (process 6) of total repetition.Process 6 After, to each unit with the constant voltage charging (process of voltage (charging current is up to 50A) progress 900 seconds of 2.4V 7).1~process of process 7,72 times (process 8) of total repetition is returned into 1 (process of process by 15 hours rest (processes 9) 10).1~process of process 10 is repeated until terminal voltage reaches 1.2V/Cell, terminal voltage is reached 1.2V/Cell's The cycle-index at moment is as PSOC service life number.It should be noted that being 1 circulation with 1~process of process 5.For example, by process 1 When~process 10 carries out 1 time, cycle-index is 3600 circulations.
The content of test is promoted to be shown in table 2 short circuit penetration.The test is under conditions of promoting the generation of short circuit penetration The test of progress, compared under the use condition of actual lead storage battery, the incidence of short circuit penetration is obviously got higher.Short circuit penetration Promote the content of test as follows.Firstly, carrying out constant current electric discharge until the voltage of each unit is 1.0V (process with 0.05CA 1).Next, connecting the resistance of 10 Ω between the positive terminal and negative terminal of lead storage battery, placed 23 hours under the state 50 minutes (process 2).Then, 10 minutes constant voltage charging (charging current maximums are carried out with the voltage of 2.4V to each unit For 50A) (process 3).Process 2 and process 3 are added up to (process 4) after being repeated 5 times lead storage battery disintegrates, short circuit occurs for research The ratio of lead storage battery.It should be noted that " 25 DEG C of water " expression is tested in 25 DEG C of sink.In Tables 1 and 2, CC is put The electric discharge of electrical representation constant current, CV charging indicate constant voltage charging, and CC charging indicates constant current charging.
[table 1 "
[table 2]
The result of test is promoted to be shown in 3~table of table 10 PSOC life test and short circuit penetration.In 3~table of table 10, PSOC service life number indicate each battery when the PSOC service life number of the battery A1 of table 3 is set as 100 PSOC service life number it Than.The PSOC service life is than indicating the PSOC service life number of each battery and the ratio between the PSOC service life number of battery of front end of each table.
[table 3]
[table 4]
[table 5]
[table 6]
According to table 5 and Fig. 2, it is known that in the lead storage battery that negative electrode active material contains graphite, and in addition to content of graphite It is compared for the lead storage battery of the same terms, PSOC life performance improves.The stone for making negative electrode active material contain 0.5mass% or more PSOC life performance greatly improves when black, PSOC life performance when the graphite for making negative electrode active material contain 1.0mass% or more Further greatly improve.
On the other hand, according to 3~table of table 6 and Fig. 2, it is known that in the lead storage battery that negative electrode active material contains graphite, with It is that the lead storage battery of the same terms is compared in addition to content of graphite, is easy to happen short circuit penetration.Up to the present it is not aware that this Short circuit penetration is easy to happen when sample makes negative electrode active material contain graphite.
According to 3~table of table 6 and Fig. 3, it is known that contain negative electrode active material and be calculated as 1.1mass% or more with barium sulfate conversion Barium element when be able to suppress short circuit penetration.Negative electrode active material contains the barium that 1.2mass% or more is calculated as with barium sulfate conversion It can inhibit short circuit penetration when element significantly.
According to 3~table of table 6 and Fig. 4, it is known that the content of the barium element in negative electrode active material is calculated as with barium sulfate conversion When 1.1mass% or more, short circuit penetration can be inhibited significantly and making positive active material contain tin element.Make positive-active The content of tin element in substance can obviously inhibit short circuit penetration when being 0.01mass% or more.On the other hand, negative electrode active When the content of barium element in substance is calculated as 1.0mass% or less with barium sulfate conversion, even if positive active material is made to contain tin Element, also cannot be because of the short circuit penetration inhibitory effect caused by tin element.
Up to the present the barium element being not aware that in negative electrode active material and tin element and infiltration in positive active material Short circuit is related thoroughly.Therefore, it is impossible to expect that the content of barium element in the negative active material is calculated as with barium sulfate conversion When 1.1mass% or more, it can obviously inhibit short circuit penetration and making positive active material contain tin element.In addition, negative The content of barium element in the electrode material of pole is converted with barium sulfate when being calculated as 1.1mass% or more and when 1.0mass% or less, because Short circuit penetration inhibitory effect caused by tin element clearly changes, it can be said that making the content of the barium element in negative electrode material 1.1mass% or more is calculated as with critical meaning with barium sulfate conversion.
According to 3~table of table 6 and Fig. 5, it is known that the content of barium element in the negative active material is calculated as with barium sulfate conversion In the case where 1.1mass% or more, compared with when positive active material is free of tin element, by making the tin in positive active material The content of element improves PSOC life performance for 0.15mass% or less.Make the content of the tin element in positive active material When for 0.10mass% or less, PSOC life performance is greatly improved, and makes the content of the tin element in positive active material When 0.08mass% or less, PSOC life performance is further greatly improved, and makes the content of the tin element in positive active material When 0.06mass% or less, PSOC life performance is especially greatly improved.On the other hand, barium element in the negative active material Content is calculated as in 1.0mass% situation below with barium sulfate conversion, compared with when positive active material is free of tin element, even if Make the content 0.15mass% of the tin element in positive active material hereinafter, PSOC life performance does not also improve.
Up to the present it is not aware that when negative electrode material contains graphite etc., by making the barium in negative electrode material The content of tin element in the content and positive electrode material of element can be such that PSOC life performance improves in specific range, this is Result outside expectation.
According to 3~table of table 6 and Fig. 6, it is known that contain graphite by negative electrode active material and be calculated as with barium sulfate conversion The barium element and positive active material of 1.1mass% or more contains the PSOC service life obtained from 0.15mass% tin element below The improvement effect of performance is 3.6g/cm in the density of positive active material3Become larger when above.The density of positive active material is 4.2g/cm3The improvement effect of PSOC life performance is further enlarged when above, and the density of positive active material is 4.4g/cm3With The improvement effect of PSOC life performance obviously becomes larger when upper.On the other hand, the content of the barium element in negative electrode active material is with sulphur When sour barium conversion is calculated as 1.0mass% or less, even if making the density 3.6g/cm of positive active material3More than, PSOC service life property Also it can not improve (Fig. 7).
According to 3~table of table 6 and Fig. 8, it is known that the content of the barium element in negative electrode active material is calculated as with barium sulfate conversion When 3.0mass% or less, PSOC life performance is improved.
[table 7]
Table 7 and Fig. 9 indicate result when negative electrode active material being made to contain carbon black.According to table 7 and Fig. 9, it is known that living in cathode Property substance contain graphite and barium element, the positive active material of 1.1mass% or more be calculated as with barium sulfate conversion and contain tin element In the case where, short circuit penetration is further suppressed when negative electrode active material being enable to contain carbon black.Make the charcoal in negative electrode active material Black content can inhibit short circuit penetration when being 0.1mass% or more significantly.On the other hand, barium element in negative electrode active material It, cannot be because of carbon black when content is calculated as 1.0mass% or less with barium sulfate conversion or when positive active material is free of tin element Caused short circuit penetration inhibitory effect.
[table 8]
Table 8 and Figure 10 indicate result when changing the average grain diameter of the graphite in negative electrode active material.According to table 8 and figure 10, it is known that make to be able to suppress short circuit penetration at 300 μm of average grain diameter of the graphite in negative electrode active material or less.In addition, can Know that PSOC life performance improves when making 100 μm of average grain diameter of the graphite in negative electrode active material or more.
[table 9]
[table 10]
Table 9 and table 10 indicate result when replacing flaky graphite containing expansion graphite in the negative active material.Root According to table 9 and table 10, it is known that replace flaky graphite also to obtain same result using expansion graphite.
Obtained the lead storage battery of the few liquid formula of short circuit penetration in embodiment, but separator glass isolator can also be made etc. and The lead storage battery of production control valve type.
Industrial availability
In accordance with the invention it is possible to a kind of lead storage battery that PSOC life performance improves and short circuit penetration is inhibited to occur is provided, Therefore useful in IS vehicular applications usually placed with the state of undercharge etc..
Symbol description
The electrode plate group of 1 lead storage battery
2 negative plates
3 positive plates
4 separators
21 negative electrode collectors
22 negative electrode materials
31 positive electrode collectors
32 positive electrode materials
41 matrixes
42 ribs

Claims (15)

1. a kind of lead storage battery, which is characterized in that have positive plate, negative plate and electrolyte,
The negative electrode material of the negative plate contains graphite or carbon fiber and is calculated as 1.1 mass % or more with barium sulfate conversion Barium element,
The positive electrode material of the positive plate contains tin element.
2. lead storage battery according to claim 1, which is characterized in that the positive electrode material contain 0.15 mass % with Under tin element.
3. lead storage battery according to claim 1 or 2, which is characterized in that the density of the positive electrode material is 3.6g/ cm3More than.
4. lead storage battery described in any one of claim 1 to 3, which is characterized in that the negative electrode material contains Carbon black.
5. lead storage battery according to any one of claims 1 to 4, which is characterized in that the negative electrode material contains The graphite or carbon fiber of 0.5 mass % or more.
6. lead storage battery according to any one of claims 1 to 5, which is characterized in that the negative electrode material contains 2.5 mass % graphite below or carbon fiber.
7. lead storage battery described according to claim 1~any one of 6, which is characterized in that the graphite or carbon fiber are flat Equal partial size is 300 μm of graphite below.
8. lead storage battery according to any one of claims 1 to 7, which is characterized in that the graphite or carbon fiber are flat The graphite that equal partial size is 100 μm or more.
9. lead storage battery described according to claim 1~any one of 8, which is characterized in that the negative electrode material is with sulphur Sour barium conversion meter contains 3.0 mass % barium element below.
10. lead storage battery described according to claim 1~any one of 9, which is characterized in that the positive electrode material contains The tin element of 0.01 mass % or more.
11. lead storage battery described according to claim 1~any one of 10, which is characterized in that the positive electrode material Density is 4.2g/cm3More than.
12. lead storage battery described according to claim 1~any one of 11, which is characterized in that the positive electrode material Density is 5.0g/cm3Below.
13. lead storage battery described according to claim 1~any one of 12, which is characterized in that the lead storage battery is with portion The lead storage battery that point charged state uses.
14. lead storage battery described according to claim 1~any one of 13, which is characterized in that the lead storage battery is liquid formula Lead storage battery.
15. a kind of vehicle, equipped with lead storage battery described in any one of claim 1~14.
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JP2013140677A (en) * 2011-12-28 2013-07-18 Gs Yuasa Corp Liquid lead-acid battery and battery system using the same
CN103066295A (en) * 2012-12-18 2013-04-24 超威电源有限公司 Internally formed lead plaster of storage battery suitable for high temperature area
CN103035923A (en) * 2012-12-18 2013-04-10 超威电源有限公司 Low-temperature-resistant storage battery internally formed lead plaster
JP2015005528A (en) * 2014-09-05 2015-01-08 株式会社Ｇｓユアサ Lead storage battery
CN105720240A (en) * 2014-12-18 2016-06-29 株式会社杰士汤浅国际 Lead-acid battery
CN105742555A (en) * 2014-12-24 2016-07-06 株式会社杰士汤浅国际 Valve-regulated lead storage battery

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