CN110462899A

CN110462899A - Lead storage battery

Info

Publication number: CN110462899A
Application number: CN201880022389.6A
Authority: CN
Inventors: 小山洁
Original assignee: Jishi Corp
Current assignee: Jishi Corp
Priority date: 2017-04-28
Filing date: 2018-04-26
Publication date: 2019-11-15
Anticipated expiration: 2038-04-26
Also published as: WO2018199242A1; JPWO2018199242A1; JP7180591B2; CN110462899B

Abstract

Lead storage battery has negative plate and positive plate.Above-mentioned negative plate contains negative electrode material, and above-mentioned negative electrode material contains carbon material and barium sulfate.Above-mentioned carbon material contains the 1st carbon material of the partial size with 32 μm or more and with the 2nd carbon material of the partial size less than 32 μm, the powder resistance R2 of above-mentioned 2nd carbon material the ratio between the powder resistance R1 relative to above-mentioned 1st carbon material, i.e. R2/R1 are more than 15 and less than 230.The content of barium sulfate in above-mentioned negative electrode material is 0.2 mass of mass %~0.7 %.The density of above-mentioned negative electrode material is 3.8g/cm³More than.

Description

Lead storage battery

Technical field

The present invention relates to a kind of lead storage batteries.

Background technique

Lead storage battery also can be used other than vehicle-mounted purposes, industrial applications in various uses.Lead storage battery contains cathode Plate, positive plate and electrolyte.Negative plate contains collector and negative electrode material.Negative electrode material contains carbon material, sulfuric acid Barium etc..A kind of negative electrode material is proposed in patent document 1, is containing graphite or carbon fiber, carbon black, barium sulfate, density 3.6~4.0g/cm³.A kind of negative electrode material is proposed in patent document 2, contains the barium sulfate less than 0.6mass%, Density is higher than 3.6g/cm³.The carbon content that negative electrode material is described in patent document 2 is 0.2mass% hereinafter, and making For the acetylene black of carbon.

Existing technical literature

Patent document

Patent document 1: Japanese Unexamined Patent Publication 2016-152131 bulletin

Patent document 2: Japanese Unexamined Patent Publication 2016-189260 bulletin

Summary of the invention

If usually improving the density of negative electrode material, cycle life is improved.But forming negative electrode material Density high negative plate when, if carbon black is added to negative electrode material, the coating of collector is reduced.Separately Outside, it because of the composition of negative electrode material, becomes difficult to charge after carrying out deep discharge sometimes, cycle life reduces.

Problem of the present invention is that make being easy to make for negative plate, while improving following for lead storage battery when carrying out deep discharge Ring life performance.

One aspect of the present invention is related to a kind of lead storage battery,

Above-mentioned lead storage battery has negative plate and positive plate,

Above-mentioned negative plate contains negative electrode material, and above-mentioned negative electrode material contains carbon material and barium sulfate,

Above-mentioned carbon material contain the 1st carbon material of the partial size with 32 μm or more and with the partial size less than 32 μm the 2nd Carbon material,

The powder resistance R2 of above-mentioned 2nd carbon material the ratio between the powder resistance R1 relative to above-mentioned 1st carbon material, i.e. R2/R1 More than 15 and less than 230,

The content of barium sulfate in above-mentioned negative electrode material is the 0.2 mass % of mass %~0.7,

The density of above-mentioned negative electrode material is 3.8g/cm³More than.

Above-mentioned aspect according to the present invention can easily make negative plate, while can also obtain when carrying out deep discharge To the high circulation life performance of lead storage battery.

Detailed description of the invention

Fig. 1 is the perspective view for schematically showing the state for removing the lid of the lead storage battery of one aspect of the present invention.

Fig. 2A is the main view of the lead storage battery of Fig. 1.

Fig. 2 B is that the arrow observed from the arrow direction of the IIB-IIB line of the lead storage battery of Fig. 2A shows sectional view.

Fig. 3 is cycle life performance and negative electricity obtained from indicating to evaluate lead storage battery A1~A8 and B1~B8 The chart of the relationship of the density of pole material.

Fig. 4 is cycle life obtained from indicating to evaluate lead storage battery A3, A11~A16, B3 and B11~B16 It can be with the chart of the relationship of the content of the barium sulfate in negative electrode material.

Specific embodiment

The lead storage battery that one aspect of the present invention is related to has negative plate and positive plate.Negative plate contains negative electrode material Material, above-mentioned negative electrode material contain carbon material and barium sulfate.Carbon material contains the 1st carbon materials of the partial size with 32 μm or more Material and the 2nd carbon material with the partial size less than 32 μm.Powder of the powder resistance R2 of 2nd carbon material relative to the 1st carbon material The ratio between resistance R1, i.e. R2/R1 are more than 15 and less than 230.The content of barium sulfate in negative electrode material be 0.2 mass %~ 0.7 mass %, the density of negative electrode material are 3.8g/cm³More than.

It is known usually in the negative plate of lead storage battery if improve negative electrode material density, negative electrode material Electric conductivity improve, furthermore distance between the negative electrode active material contained by negative electrode material becomes close, thus Pb²⁺The expansion of ion Scattered speed becomes larger, and charging reaction speed improves.Thus, it is believed that the sulfuric acid when density of negative electrode material is high, in negative plate The savings of lead is inhibited, and cycle life performance improves.

On the other hand, in the past, from the viewpoint of improving electric conductivity, carbon black is added in negative electrode material.Negative plate The thickener containing negative electrode material can be used to make, but the solvent contained by the thickener is largely adsorbed in charcoal clandestine meeting.Therefore, In In previous thickener containing carbon black, the mobility and scalability of thickener are greatly reduced, and thickener becomes the coating of collector It obtains extremely low.In addition, can be used usually from the viewpoint of negative electrode material is equably coated on collector using coating paste The coating of the machines such as the purposes special filling machine (paster) of material.But in the case where improving the density of negative electrode material, The solid component of thickener becomes more, therefore the coating of especially thickener reduces.For example, if carbon black is individually added to negative electricity So that the content of the carbon black in negative electrode material is 0.6 mass % in the material of pole, then the coating based on machine is able to carry out The density of the upper limit substantially 3.6g/cm³.Therefore, when carbon black is used alone, more than 3.6g/cm³And negative electrode material In the case that density is high, machinery coating is more difficult than previous.It is difficult in the case where being difficult to carry out the coating based on machine of thickener Industrially to manufacture negative plate.

The present inventors have noted that the density in negative electrode material is 3.6g/cm³In situation below, either individually make With the 1st carbon material or the 2nd carbon material, or and with both carbon materials, cycle life performance is all almost unchanged.Usual negative electricity The density of pole material is higher, and cycle life performance and charge acceptance can be higher, in the charge and discharge cycles comprising deep discharge It can inhibit the reduction of capacity.But it is found in the result of study of the present inventor: in the case where the 1st carbon material is used alone, Even if improving the density of negative electrode material, it is also hardly visible the additional improvement effect of cycle life.

It should be noted that commonly known carbon material has various powder resistances.The powder resistance of known dusty material is because of particle Shape, the crystallinity of partial size, the internal structure of particle and/or particle etc. and change.According to previous common technical knowledge, carbon material Powder resistance and the resistance of negative plate of lead storage battery be not directly dependent upon, be not considered as that shadow can be caused to cycle life performance It rings.

In addition, for the purpose for inhibiting short circuit penetration or savings being inhibited to assemble in the lead sulfate of negative plate, it is previous to study Into the negative electrode material of lead storage battery add barium sulfate.But since barium sulfate is non-conductor, according to negative electricity The composition of pole material, even if improving the density of negative electrode material sometimes, also when carrying out the charge and discharge cycles comprising deep discharge It cannot charge.In this case, cycle life performance also reduces.

Above-mentioned aspect according to the present invention is up to 3.8g/cm in the density of negative electrode material³It, will in the case where above Partial size is different, and powder resistance ratio R2/R1 is more than 15 and the 1st carbon material less than 230 and the 2nd carbon material combine.As a result, containing negative The scalability of the thickener (hereinafter also referred to as cathode thickener) of pole electrode material increases, and coating improves, therefore although negative electricity The density of pole material is high, but can also carry out mechanical coating, cathode easy to manufacture to cathode thickener when preparing cathode thickener Plate.In this way, above-mentioned aspect according to the present invention, even if the density of negative electrode material is high, but also can easily make negative Pole plate.It is believed that the coating raising of powder resistance ratio R2/R1 cathode thickener in above range is because of powder resistance ratio R2/ In the case where above-mentioned range, the surface state of each carbon material is optimized R1, can suitably inhibit the absorption of solvent.

It should be noted that the excellent coating of cathode thickener is to refer to using machine (specifically in this specification Paster cathode thickener) is coated on negative electrode collector.

In addition, above-mentioned aspect according to the present invention can be by the 1st carbon by combining the 1st carbon material and the 2nd carbon material Material and the 2nd carbon material are more uniformly filled into the layer of highdensity negative electrode material.Therefore, it is easy in negative electrode material Many conductive networks are formed in material.The density for improving negative electrode material will form the fine and close conductive mesh containing metal lead particles Network and charging reaction field, and charging reaction speed becomes larger in negative electrode material, cycle life performance improves.

In addition, the 0.2 mass % of mass %~0.7 of content by making the barium sulfate in negative electrode material, thus It carries out that charge and discharge can also be repeated when the charge and discharge cycles along with deep discharge.Therefore, even if in the feelings with deep discharge Under condition, it is also able to suppress the reduction of the cycle life performance of lead storage battery.It is imitated from the raising for further increasing cycle life performance From the perspective of fruit, the content of the barium sulfate in negative electrode material is preferably 0.2 mass of mass %~0.6 %.

The density of negative electrode material is preferably 4.1g/cm³More than.Even if the density of such negative electrode material is high In the case of, also due to the coating of negative plate is high, therefore the layer of uniform negative electrode material easy to form.In addition, due to shape At many conductive networks, therefore cycle life performance can be further increased.

Usually in the case where getting higher the density of negative electrode material, carried out as follows to maintain the coating of thickener Operation, that is, reduce the amount of the dilute sulfuric acid used when preparing thickener and/or reduce the sulfuric acid concentration in dilute sulfuric acid.As a result, meeting Reduce the sulphate amount in negative electrode material.If sulphate amount is reduced, the scalability enhancing of usual thickener, another party The amount in face, the lead sulfate in obtained negative plate in negative electrode material is reduced.If known (do not change such negative plate Learn the negative plate of conversion) when saving in an atmosphere, then the content that can lead to the problem of the ceruse in negative electrode material increases. Ceruse known to if in negative electrode material it is more containing quantitative change, falling off and/or bearing for negative electrode material occurs sometimes The reduction of the initial capacity of pole plate.For example, if to the ceruse for containing substantially 20 quality % or more in negative electrode material The negative plate of non-chemical conversion carries out chemical conversion, then occur sometimes negative electrode material fall off and/or the initial stage of negative plate The reduction of capacity.That is, can make the retention of the negative plate of non-chemical conversion reduces.From the negative plate for inhibiting non-chemical conversion From the perspective of the reduction of retention, the method used in the past includes connecing the negative plate after coating thickener with dilute sulfuric acid The method touched and sulfate radical is made to penetrate into cathode plate surface.But even with such method, also can not supply sufficiently Maintain the sulfate radical of retention.

In aforementioned aspect of the present invention, if the density of negative electrode material is excessively high, it is difficult to obtain sometimes higher Retention.Therefore, from the viewpoint of the high retention for the negative plate for ensuring non-chemical conversion, preferably make negative electrode material The density of material is less than 4.7g/cm³。

When preparing cathode thickener, in order not to reduce sulphate amount, preferably add not make cathode thickener scalability and The carbon material that retention reduces.As such carbon material, it is preferable to use the specific surface area S2 of the 2nd carbon material is relative to the 1st The ratio between specific surface area S1 of carbon material, i.e. S2/S1 are 350 the 1st carbon materials and the 2nd carbon material below.Show such S2/S1 1st carbon material of ratio and the effect of the 2nd carbon material are especially less than 4.7g/cm in the density of negative electrode material³In the case where show Work shows.In addition, specific surface area ratio S2/S1 is in 350 situations below, the coating of cathode thickener is improved.

Hereinafter, the lead storage battery that embodiments of the present invention are related to is illustrated for each main composition important document, but this Invention is not limited to the following embodiments and the accompanying drawings.

(negative plate)

The negative plate of lead storage battery contains negative electrode material.Negative plate usually can be by negative electrode collector (cathode grid etc.) It is constituted with negative electrode material.It should be noted that negative electrode material is to remove negative electrode collector from negative plate and obtain.

It should be noted that gasket is pasted on negative plate sometimes, applies the components such as paperboard.Contain such component in negative plate In the case where (affixed component), negative electrode material is to remove negative electrode collector and affixed component and obtain.But electrode plate With a thickness of the thickness including gasket.In the case where being pasted with gasket on separator, the thickness of gasket is also contained in separator Thickness.

Negative electrode material contains the negative electrode active material (lead or lead sulfate) for showing capacity by redox reaction. The negative electrode active material of charged state is spongiform metallic lead, but usually lead powder can be used to make for the negative plate of non-chemical conversion Make.In addition, negative electrode material contains carbon material and barium sulfate.Negative electrode material can further contain organic anti-piping compound Deng also can according to need containing other additives.

(carbon material)

Carbon material contains the 1st carbon material of the partial size with 32 μm or more and with the 2nd carbon materials of the partial size less than 32 μm Material.1st carbon material and the 2nd carbon material carry out separation using subsequent steps and are distinguished.

As each carbon material, such as carbon black, graphite, hard carbon, soft carbon can be enumerated etc..As carbon black, acetylene black, furnace can be illustrated Method carbon black, lampblack etc..As graphite, as long as the carbon material containing graphite type crystal structure, can be artificial graphite, day Any one of right graphite.

It should be noted that by the 1300cm of Raman spectrum in the 1st carbon material^-1~1350cm^-1Range occur peak (D band) With 1550cm^-1~1600cm^-1Range occur peak (G band) intensity ratio I_D/I_GIt is known as graphite for 0~0.9 carbon material.

1st carbon material and the 2nd carbon material can choose or adjust the kind for being used to prepare the carbon material of negative electrode material Class, specific surface area and/or aspect ratio etc. so that the 2nd carbon material powder resistance R1 of the powder resistance R2 relative to the 1st carbon material The ratio between, i.e. R2/R1 is more than 15 and less than 230.In addition, used carbon material may further be adjusted in addition to these elements Partial size.By selecting or adjusting these elements, the powder resistance of each carbon material of adjustable 1st carbon material and the 2nd carbon material, As a result, it is possible to adjust powder resistance ratio R2/R1.

At least one of as the 1st carbon material, such as be preferably selected from graphite, hard carbon and soft carbon.In particular, the 1st carbon materials Material preferably at least contains graphite.2nd carbon material preferably at least contains carbon black.When using these carbon materials, it is easy to adjust powder electricity R2/R1 is compared in resistance.

The ratio between powder resistance R1 of the powder resistance R2 of 2nd carbon material relative to the 1st carbon material (powder resistance ratio R2/R1) As long as more than 15 and less than 230.By making powder resistance ratio in such range, applied so that the high of negative electrode paste material can be obtained Cloth, and can be improved cycle life performance.From the viewpoint of obtaining more high circulation life performance, powder resistance ratio R2/ R1 is preferably 80 or more.In addition, powder resistance ratio R2/R1 is preferably 220 or less from the viewpoint of identical.From ensuring not change From the perspective of the high retention for learning the negative plate of conversion, powder resistance ratio R2/R1 is preferably smaller than 160, further preferably 150 or less.These lower limit values and upper limit value can be in any combination.Powder resistance ratio R2/R1 more than 15 and is for example 220 or less (alternatively, less than 160 or be 150 or less), 80 are more than and less than 230 (alternatively, 220 hereinafter, less than 160 or 150 or less).

The specific surface area S2 of 2nd carbon material the ratio between the specific surface area S1 relative to the 1st carbon material, i.e. S2/S1 are preferably 350 Below.Specific surface area ratio S2/S1 is in the case where such range, even if the density for increasing negative electrode material the case where Under, it can also further increase the coating of cathode thickener.In addition, using S2/S1 ratio be 350 the 1st carbon materials below and In the case where 2nd carbon material, it can be ensured that the high retention of the negative plate of non-chemical conversion.Based on such S2/S1 ratio The effect of retention is especially less than 4.7g/cm in the density of negative electrode material³(preferably 4.6g/cm³Hereinafter, further preferably 4.5g/cm³Show in the case where below).

The average aspect ratio of 1st carbon material for example can be 1~200,1.5~100 or 1.5~35.

The total of the content of the 1st carbon material and the 2nd carbon material in negative electrode material is, for example, 0.1 mass % or more, Preferably 0.2 mass % or more, from the viewpoint of the improvement effect for further increasing cycle life performance, preferably 0.3 matter Measure % or more.Total upper limit of the content of 1st carbon material and the 2nd carbon material also depends on the density, each of negative electrode material The type etc. of carbon material, such as can be 1.5 mass % or less.

In above-mentioned carbon material, the content of the 1st carbon material in negative electrode material is, for example, 0.05 mass % or more, from From the perspective of the coating of cathode thickener is high, cycle life improvement effect is high, preferably 0.1 mass % or more or 0.2 matter Measure % or more.The upper limit of the content of the 1st carbon material in negative electrode material also depends on the density of negative electrode material, carbon materials The type etc. of material, if for example, 1.5 mass % hereinafter, the content of the 1st carbon material and the 2nd carbon material it is total be adjusted to it is above-mentioned Range.

The content of the 2nd carbon material in negative electrode material is, for example, 0.03 mass % or more, from being easy in negative electrode It is formed from the perspective of conductive network in material, preferably 0.1 mass % or more, or 0.2 mass % or more.Negative electrode The upper limit of the content of the 2nd carbon material in material also depends on the density of negative electrode material, type of carbon material etc., for example, 1 mass % hereinafter, preferably 0.6 mass % hereinafter, further preferably 0.4 mass % or less.As long as the content of the 2nd carbon material Be adjusted to the content of the 1st carbon material and the 2nd carbon material is aggregated in above range.The content of 2nd carbon material for example can be with For 0.03 mass of mass %~1 % (alternatively, 0.6 mass % or less or 0.4 mass % or less), 0.1 mass of mass %~1 % (alternatively, 0.6 mass % or less or 0.4 mass % or less) or 0.2 mass of mass %~1 % (alternatively, 0.6 mass % or less or 0.4 mass % or less).

The determination method or analysis method of the physical property of carbon material are illustrated below.

(A) analysis of carbon material

(A-1) separation of carbon material

The lead storage battery of the fully charged state of chemical conversion is decomposed, negative plate is taken out, desulfuration is removed by washing Acid, is dried in vacuo and (is dried under subatmospheric pressure).Next, being taken from the negative plate after drying negative Pole electrode material, is crushed.The aqueous solution of nitric acid 30mL that 60 mass % concentration are added in sample is crushed to 5g, is carried out at 70 DEG C Heating.The ammonium hydroxide 30mL and water of disodium ethylene diamine tetraacetate 10g, 28 mass % concentration are further added in the mixture 100mL continues to heat, dissolves soluble ingredient.It is recycled to pretreated sample is thus carried out by filtering.Make to recycle Sample afterwards passes through 500 μm of mesh of sieve, removes the big ingredient of reinforcement material equidimension, will pass through the ingredient after sieving as carbon materials Material recycling.

Then, it when carrying out wet screening to the carbon material being recovered to using 32 μm of mesh of sieve, will be unable to through sieve pore Remain in the material on sieve as the 1st carbon material, using the material by sieve pore as the 2nd carbon material.That is, the partial size of each carbon material It is on the basis of the mesh size of sieve.Wet screening is referred to JIS Z8815:1994.Specifically, carbon material is placed on net On the sieve of 32 μm of eye, jog will be sieved 5 minutes while spilling ion exchange water and is sieved.Remain in the 1st carbon materials on sieve Material is recycled from sieve by rinsing ion exchange water, is separated by filtering from ion exchange water.Passed through by the 2nd carbon material of sieve It is recycled using membrane filter (0.1 μm of the mesh) filtering of nitrocellulose.The 1st carbon material and the 2nd carbon material of recycling Temperature respectively at 110 DEG C is 2 hours dry.As 32 μm of sieve of mesh, provided using having in JIS Z 8801-1:2006 , the sieve of the sieve that nominal (nominal) mesh is 32 μm.

It should be noted that the content of each carbon material in negative electrode material is found out in the following manner, that is, to according to upper The quality for stating each carbon material that step is separated to measures, and calculates the quality and crushes ratio (matter shared in sample in 5g Measure %).

In this specification, for liquid formula battery, the fully charged state of lead storage battery refers to the sink at 25 DEG C In constant current charging carried out after reaching 2.5V/ battery unit with the electric current of 0.2CA, further with 0.2CA progress 2 hours The state of constant current charging.In addition, for valve-regulated battery, fully charged state refer in 25 DEG C of air drain with 0.2CA carries out the constant-current constant-voltage charging of 2.23V/ battery unit, the charging current in constant voltage charging is Terminate the state of charging at the time of 1mCA or less.

It should be noted that 1CA refers to the current value (A) of the identical numerical value with the nominal capacity of battery (Ah) in this specification. For example, as long as nominal capacity is the battery of 30Ah, 1CA 30A, 1mCA 30mA.

(A-2) powder resistance of carbon material

The powder resistance R1 of the 1st carbon material and powder resistance R2 of the 2nd carbon material is the value measured in the following manner, That is, 0.5g sample is put into respectively for the 1st carbon material and the 2nd carbon material that will be isolated according to the step of above-mentioned (A-1) Powder resistance measures in system ((strain) Mitsubishi Chemical Analytech system, MCP-PD51 type), in pressure Under 3.18MPa, low resistance resistrivity meter ((strain) the Mitsubishi Chemical according to JIS K 7194:1994 is used Analytech system, Loresta-GX MCP-T700), the value measured by four probe method.

(A-3) specific surface area of carbon material

The specific surface area S1 of the 1st carbon material and specific surface area S2 of the 2nd carbon material is that the 1st carbon material and the 2nd carbon material are each From BET specific surface area.BET specific surface area is by using the 1st carbon material and the 2nd separated according to the step of above-mentioned (A-1) Carbon material is found out by gas adsorption method using BET formula respectively.Each carbon material is added by the temperature in nitrogen stream at 150 DEG C Heat 1 hour and pre-processed.Using pretreated carbon material, using following apparatus, each carbon materials are found out by following conditions The BET specific surface area of material.

Measurement device: Micromeritics society TriStar3000

Adsorbed gas: the nitrogen of 99.99% or more purity

Adsorption temp: liquid nitrogen boiling temperature (77K)

The calculation method of BET specific surface area: 7.2 according to JIS Z 8830:2013

(A-4) average aspect ratio of the 1st carbon material

The 1st carbon material separated according to the step of above-mentioned (A-1) is seen using optical microscopy or electron microscope It examines, selects 10 or more Arbitrary Particles, its enlarged photograph is shot.Next, the photo to each particle carries out image Processing, finds out the maximum gauge d2 in the maximum gauge d1 and the direction orthogonal with maximum gauge d1 of particle, by by d1 The aspect ratio of each particle is found out divided by d2.Obtained aspect ratio is averagely calculated into average aspect ratio.

(barium sulfate)

As long as the content of the barium sulfate contained in negative electrode material is 0.2 mass of mass %~0.7 %.Barium sulfate Content in the case where such range, due to not interfering the electronic conductivity between metal lead particles, so even carrying out deep Electric discharge is also easy reduction lead sulfate in charging.As a result, when along with the charge and discharge cycles of deep discharge, charging is difficult to carry out It is inhibited.Therefore, even if charge and discharge, cycle life can also be repeated in the charge and discharge cycles along with deep discharge The reduction of energy is inhibited.From the viewpoint of further increasing the improvement effect of cycle life performance, preferably 0.2 mass % ~0.6 mass %.

Being illustrated containing method for determination of amount to the barium sulfate contained in negative electrode material below.

(B) analysis of barium sulfate

(B-1) it is taken out from lead storage battery in the same manner as above-mentioned (A-1) and crushes sample, be taken out the sample of about 5g, it is quasi- Really weigh quality m1 (g).Weighed sample is put into the aqueous solution of nitric acid 30cm of 10 mass % concentration³In, heat molten Solution.After the cooling of obtained mixture, deionized water is added until volume becomes 100cm³, 30 minutes are stood, supernatant is adopted It gets in another beaker.Ammonium acetate 20g and water 30cm is added in remaining sediment³, dissolved by heating.It is molten by what is obtained Liquid is put into above-mentioned supernatant, makes its boiling, is heated after five minutes, is placed 1 hour in this state.The mixture that will be obtained The filtering of the membrane filter known to quality, recycles filtrate.The ingredient remained on membrane filter is sufficiently cleaned with water.It will be made Membrane filter is 2 hours dry at 110 DEG C, the quality after measurement is dry.The initial stage matter of membrane filter is subtracted from measured value Amount is so as to find out insoluble residue quality m2.Membrane filter after drying is put into porcelain crucible known to quality, is carried out Calcination ashing.Then, crucible is cooled to room temperature and quality measurement in drier, the initial stage matter of crucible is subtracted from the quality Amount, thus finds out the quality m3 of residue on ignition.

(B-2) filtrate recycled in above-mentioned (B-1) is taken into volumetric flask, deionized water is added until volume is 250cm³.Air-C is used using atom light absorption method₂H₂Flame selects the spectral line of 553.6nm to the atom absorbance of obtained solution It is measured.It should be noted that atom absorbance uses atomic absorption spectrophotometer ((strain) Shimadzu Seisakusho Ltd. system, AA7000F) It is measured.Based on the in addition manufactured calibration curve using the Ba salting liquid of normal concentration, found out by above-mentioned atom absorbance The concentration of barium element in solution finds out the quality m4 (mg) of the barium element contained in filtrate.Then, it is found out by following formula negative The content c1 (quality %) of the soluble barium sulfate contained in the electrode material of pole.

C1=100 × (M1/M2) × (m4/m1)

Here, M1 is barium sulfate (BaSO₄) molecular weight, M2 be barium (Ba) atomic weight.Use M1/M2=1.699's Value.

(B-3) it is calculated in negative electrode material according to the quality m3 of the residue on ignition of above-mentioned (B-1) by following formula The insoluble barium sulfate content c2 (quality %) contained.

C2=100 × m3/m1

Then, contain in the negative electrode material for finding out chemical conversion and fully charged state and adding up to c1 and c2 Some barium sulfate contents (quality %).

(organic anti-piping compound)

As organic anti-piping compound that negative electrode material contains, for the organic polymer containing element sulphur, usually in molecule Inside contain 1 or more, preferably multiple aromatic rings, while containing element sulphur in the form of sulfur-containing group.In sulfur-containing group, preferably Belong to the sulfonic group or sulfonyl of stable form.Sulfonic group can exist with acid type, can also exist as Na salt with salt form.

As organic anti-piping compound, lignin can be used for example, the organic anti-piping compound of synthesis also can be used.As synthesis The condensation product of aromatic compound and formaldehyde with sulfur-containing group can be used in organic anti-piping compound.As lignin, can lift Lignin derivatives such as lignin, lignin sulfonic acid or its salt (alkali metal salts such as sodium salt etc.) etc. out.Organic anti-piping compound can be single Solely using a kind of, can also combine two kinds it is used above.For example, it is also possible to and with lignin and with the fragrance of sulfur-containing group The condensation product of compounds of group and formaldehyde.As aromatic compound, it is preferable to use bisphenols, biphenyl class, naphthalenes etc..

The content of the organic anti-piping compound contained in negative electrode material is, for example, the 0.01 mass % of mass %~1.0, preferably For 0.02 mass of mass %~0.8 % or less.

Hereinafter, describing the quantitative approach of the organic anti-piping compound contained in negative electrode material.It, will before quantitative analysis Fully charged rear disintegrate of lead storage battery and negative plate of the acquisition as analysis object after chemical conversion.Obtained negative plate is implemented It washes and dries and remove the electrolyte in negative plate.Next, separating negative electrode material from negative plate and not crushed Initial stage sample.

[organic anti-piping compound]

The initial stage sample not crushed is crushed, so that smashed initial stage sample is impregnated in the NaOH aqueous solution of 1mol/L, mentions Take organic anti-piping compound.Insoluble component is filtered to remove from the NaOH aqueous solution containing the organic anti-piping compound extracted.If will obtain Filtrate (hereinafter also referred to as analysis object filtrate.) be concentrated after desalination, dried, then the powder of organic anti-piping compound can be obtained (hereinafter also referred to as analysis object powder).Desalination can and filtrate is incorporated in dialysis tubing and is impregnated in distilled water into Row.

Solution obtained from distilled water etc. is dissolved in as the infrared spectroscopy spectrum of analysis object powder, by analysis object powder Ultraviolet-visible absorption spectroscopy, object powder will be analyzed be dissolved in the NMR spectra, available of solution obtained from heavy water equal solvent Thermal cracking GC-MS of information of each compound of substance etc. is constituted to obtain information, thereby determines that organic anti-piping compound.

Measure the ultraviolet-visible absorption spectroscopy of above-mentioned analysis object filtrate.It is bent using spectral intensity and ready-made correction Line quantifies the content of organic anti-piping compound in negative electrode material.It cannot strictly determine the organic anti-of analysis object The structural formula of contracting agent and in the case where not being available the calibration curve of identical organic anti-piping compound, use display with as analysis object Similar ultraviolet-visible absorption spectroscopy, infrared spectroscopy spectrum, the NMR spectra of organic anti-piping compound etc. obtainable organic anti-piping compound And calibration curve is made.

(density of negative electrode material)

As long as the density of negative electrode material is 3.8g/cm³It is above, preferably 4.1g/cm³More than.Even if in density In the case where big in this way, high coating and excellent cycle life performance can be also obtained in the present invention.In addition it is possible to obtain The high retention of the negative plate of non-chemical conversion.The density of negative electrode material is, for example, 4.7g/cm³Below.It is true from being easy It protects from the perspective of the high retention of the negative plate of non-chemical conversion, preferably smaller than 4.7g/cm³, further preferably 4.6g/ cm³Below or 4.5g/cm³Below.These lower limit values and upper limit value can be in any combination.The density of negative electrode material is, for example, 3.8g/cm³~4.7g/cm³(or it is less than 4.7g/cm³、4.6g/cm³Below or 4.5g/cm³Below), 4.1g/cm³~4.7g/ cm³(or it is less than 4.7g/cm³、4.6g/cm³Below or 4.5g/cm³Below).

The density of negative electrode material refers to the bulk density of the negative electrode material of the fully charged state after chemical conversion Value, be measured in the following way.By the fully charged rear disintegration of the battery after chemical conversion, water is implemented to obtained negative plate It washes and dries, thus remove the electrolyte in negative plate.Then, negative electrode material is separated by negative plate, what acquisition did not crushed Measure sample.To measurement container in put into sample, after vacuumizing, with 0.5psia~0.55psia (≈ 3.45kPa~ Pressure 3.79kPa) fills mercury, measures the stacking volume of negative electrode material, will measure the quality of sample divided by stacking volume, Thus the bulk density of negative electrode material is found out.It should be noted that the injection volume that mercury will be subtracted from the volume of measurement container Obtained from volume as stacking volume.The density of negative electrode material by using Shimadzu Seisakusho Ltd.'s (strain) make from dynamic pressure mercury Instrument (AutoPore IV9505) and be measured.

(other)

Negative electrode collector can be formed by the casting of lead (Pb) or metal, lead or metal piece can also be processed and It is formed.As processing method, such as expansion processing (Expand processing), punching (Punching) processing can be enumerated.

The metal used in negative electrode collector can close for Pb-Sb system alloy, Pb-Ca system alloy, Pb-Ca-Sn system Any one of gold.These metals can be further containing at least one kind of work in Ba, Ag, Al, Bi, As, Se, Cu etc. For addition element.Wherein, preferably Pb-Sb system alloy, the alloy can further contain in Ag, Al, As, Se etc. at least 1 kind is used as addition element.

Negative plate can be cured and be dried and made not chemistry and turn by the way that cathode thickener is filled in negative electrode collector Then the negative plate of change makes the negative plate of non-chemical conversion carry out chemical conversion and be formed.Cathode thickener passes through in lead powder, carbon Water is added in material and organic anti-piping compound as needed and/or various additives and dilute sulfuric acid is kneaded to make.It is ripe When change, preferably cure under temperature above room temperature and high humility the negative plate of non-chemical conversion.

The chemical conversion of negative plate can be by making the polar plate group of the negative plate containing non-chemical conversion be impregnated in lead storage In the state of in the electrolyte containing sulfuric acid in the electric slot of battery, is charged and carried out to polar plate group.In addition, chemical conversion It can also be carried out before the assembling of lead storage battery or polar plate group.Spongiform metallic lead is generated by chemical conversion.

(positive plate)

The positive plate of lead storage battery has thickener formula and covering (cladding) formula.

Thickener formula positive plate has positive electrode collector and positive electrode material.Positive electrode material is held in positive pole current collections Body.As long as positive electrode collector is carried out similarly with negative electrode collector, formation, can by by the casting of lead or metal, The processing for the sheet material that lead or metal blank are rolled into is formed.

Clad type positive plate has the current collection of multiple porous pipes, the arbor being inserted into each pipe (core gold), connection arbor The seated that portion, the positive electrode material being filled in the pipe inserted with arbor are connected with by multiple pipes.By arbor and connection arbor Curren-collecting part be collectively referred to as positive electrode collector.

As the metal used in positive electrode collector, Pb-Ca system alloy, Pb-Sb system alloy, Pb-Ca-Sn can be enumerated It is alloy etc..Wherein, it is preferable to use Pb-Sb system alloy.

Positive electrode material contains positive active material (brown lead oxide or the sulphur by redox reaction phenomenon capacity Lead plumbate).Positive electrode material can according to need containing other additives.

The thickener formula positive plate of non-chemical conversion according to the case where negative plate by filling positive thickener to positive electrode collector, It cured, dried and obtained.Positive thickener is prepared and being kneaded lead powder, additive, water, sulfuric acid.

Clad type positive plate is by filling the lead powder of lead powder or pulpous state into the pipe inserted with arbor, with seated by multiple pipes It connects and is formed.

The positive plate further progress chemical conversion of the non-chemical conversion formed.Titanium dioxide is generated by chemical conversion Lead.The chemical conversion of positive plate can be carried out before the assembling of lead storage battery or polar plate group.

(separator)

The usual configuration isolation part between negative plate and positive plate.Non-woven fabrics, microporous membrane etc. can be used in separator.Between As long as the thickness of the separator between negative plate and positive plate, number are selected according to interpolar distance.

Non-woven fabrics is not textile fabric, gasket made of it is complexed, based on fiber.For example, 60 matter of separator Amount % or more is formed by fiber.As fiber, can be used glass fibre, polymer fiber (polyolefine fiber, acrylic fiber, Polyester fibers such as pet fiber etc.), paper pulp fiber etc..Wherein, preferred glass fibre.Non-woven fabrics can also To contain the ingredient in addition to fiber, such as acid proof inorganic particle can be contained, as polymer of binder etc..

On the other hand, microporous membrane is the porous sheet material based on the ingredient other than fibre composition, for example, passing through It is removing pore creating material formation pore after sheet by the constituent extrusion molding containing pore creating material (polymer powder and/or oil etc.) And it obtains.Microporous membrane with acid proof material preferably by constituting, preferably based on component of polymer.As polymer at Divide, preferably the polyolefin such as polyethylene, polypropylene.

Separator for example can be only made of non-woven fabrics, can also be only made of microporous membrane.In addition, separator is according to need Want object made of being the sandwich of non-woven fabrics and microporous membrane, being bonded variety classes or material of the same race or not With making object obtained by concave-convex clutch etc. in type or material of the same race.

(electrolyte)

Electrolyte is the aqueous solution containing sulfuric acid, the electrolyte after chemical conversion in the lead storage battery of fully charged state 20 DEG C of specific gravity is, for example, 1.10g/cm³~1.35g/cm³, preferably 1.10g/cm³~1.30g/cm³Or 1.20g/cm³~ 1.30g/cm³。

Fig. 1 is show schematically an example that the lid by the lead storage battery that embodiments of the present invention are related to is removed vertical Body figure.Fig. 2A is the main view of the lead storage battery of Fig. 1, and Fig. 2 B is that the arrow of the IIB-IIB line based on Fig. 2A shows sectional view.

Lead storage battery 1 has the electric slot 10 of storage polar plate group 11 and electrolyte 12.Polar plate group 11 is by respectively bearing multiple Pole plate 2 and positive plate 3 are laminated via separator 4 and are constituted.Here, negative plate 2 indicates the shape coated with bag-shaped separator 4 State, but the form of separator is not particularly limited.

The respective top of multiple negative plates 2 be provided with upwards current collection outstanding with ear (not shown).It is multiple just The respective top of pole plate 3 be also equipped with upwards current collection outstanding with ear (not shown).Moreover, the ear of negative plate 2 is each other Link integration by cathode busbar connector 5a.Equally, the ear of positive plate 3 each other also by anode with busbar connector 5b company Knot integration.Cathode is fixed with the lower end of negative terminal 6a with the top of busbar connector 5a, and anode is fixed with the top of busbar connector 5b There is the lower end of positive terminal 6b.

The lead storage battery that one aspect of the present invention is related to is recorded hereinafter, summarizing.

(1) one aspect of the present invention is a kind of lead storage battery,

Above-mentioned lead storage battery has negative plate and positive plate,

(2) in above-mentioned (1), preferably above-mentioned ratio, R2/R1 is 80 more than and less than 230.

(3) in above-mentioned (1) or (2), preferably above-mentioned ratio, i.e. R2/R1 is 80~220.

(4) in any one of above-mentioned (1)~(3), the density of preferably above-mentioned negative electrode material is 4.1g/cm³More than.

(5) in any one of above-mentioned (1)~(4), the density of preferably above-mentioned negative electrode material is less than 4.7g/cm³。

(6) in above-mentioned (5), specific surface of the specific surface area S2 of preferably above-mentioned 2nd carbon material relative to above-mentioned 1st carbon material The ratio between product S1, i.e. S2/S1 are 350 or less.

(7) in any one of above-mentioned (1)~(6), the content of the barium sulfate in preferably above-mentioned negative electrode material is 0.2 matter Measure the mass of %~0.6 %.

(8) in any one of above-mentioned (1)~(7), preferably above-mentioned ratio, i.e. R2/R1 is 80 more than and less than 160.

(9) in any one of above-mentioned (1)~(8), preferably above-mentioned ratio, i.e. R2/R1 is 80~150.

(10) in above-mentioned (6), the density of preferably above-mentioned negative electrode material is 4.6g/cm³Below or 4.5g/cm³Below.

(11) in any one of above-mentioned (1)~(10), above-mentioned 1st carbon material in preferably above-mentioned negative electrode material contains Amount is 0.05 mass % or more.

(12) in any one of above-mentioned (1)~(11), the content example of above-mentioned 1st carbon material in above-mentioned negative electrode material For example 1.5 mass % or less.

(13) in any one of above-mentioned (1)~(12), above-mentioned 2nd carbon material in preferably above-mentioned negative electrode material contains Amount is 0.1 mass % or more.

(14) in any one of above-mentioned (1)~(13), above-mentioned 2nd carbon material in preferably above-mentioned negative electrode material contains Amount is 0.6 mass % or less.

(15) in any one of above-mentioned (1)~(14), preferably above-mentioned 1st carbon material at least contains graphite, above-mentioned 2nd carbon materials Material at least contains carbon black.

[embodiment]

Hereinafter, the present invention is specifically described based on embodiment and comparative example, but the present invention is not limited to realities below Apply example.

" lead storage battery A1 "

According to the following steps, prepare positive plate and have that clad type pole plate 3 is opened, negative plate has the mark that thickener formula pole plate 4 is opened Claim fork truck (forklift) the lead storage battery A1 of capacity 200Ah.

(1) production of negative plate

Negative plate is by being painted into plate and grid-like negative electrode collector (long side length 271mm, short side for cathode thickener Length 142mm, thickness 2.8mm~3.7mm) and make.At this point, with the quality of the negative electrode material after chemical conversion for every 1 465 ± 6g of negative plate is opened, while the density of negative electrode material is the mode of the design value of table 1 to negative electrode collector and thickener painting The thickness of layer of cloth is adjusted.Being painted into for cathode thickener is carried out by using Paster (Winkel system) to become the lattice of collector The state that gate hole does not fall off.But in the case where being painted into of cathode thickener can not be carried out with Paster, using trowel with people Power is coated.

It should be noted that cathode thickener by using mixer (DALTON corporation) to lead powder, water, dilute sulfuric acid, barium sulfate, Carbon material, organic anti-piping compound are mixed to prepare.

As carbon material, carbon black (Ketjen black (registered trademark)) and graphite (flaky graphite, average grain diameter D are used₅₀: 110 μm).Become as organic anti-piping compound using sodium lignin sulfonate with the content contained by 100 mass % of negative electrode material The mode of 0.1 mass % adjusts additive amount and is matched with cathode thickener.Barium sulfate contained by 100 mass % of negative electrode material Content (design value) be 0.6 mass %.When preparing cathode thickener, the amount of the water and dilute sulfuric acid that are added in cathode thickener is adjusted So that the density of the negative electrode material after chemical conversion and full charge becomes design value shown in table 1.It should be noted that pressing According to the step of having been described, the battery of chemical conversion and fully charged state is disintegrated, is found out by the measurement sample being recovered to Negative electrode material density (measured value) and design value almost without difference.

(2) production of positive plate

As positive plate, covering pole plate obtained from the pipe filling positive electrode material to 14 outer diameter 10mm is used.Just The coating weight of pole electrode material is in such a way that the quality of the positive electrode material after chemical conversion is every 1 792 ± 8g of positive plate It is adjusted.

(3) assembling of lead storage battery

Obtained negative plate and positive plate are impregnated in the dilute sulfuric acid of 7 mass % of concentration, implement slot type in this state Chemical conversion (chemical conversion of タ Application Network).By after chemical conversion negative plate and positive plate be laminated via separator, thus make pole Board group.Obtained polar plate group is put into electric slot, 2000cm is injected³20 DEG C when specific gravity be 1.28 dilute sulfuric acid, thus make Make lead storage battery A1.The same total 4 lead storage battery A1 of production.

In this lead storage battery, the content of the 1st carbon material contained in negative electrode material is 0.4 mass %, the 2nd carbon material Content be 0.2 mass %.In addition, powder resistance ratio R2/R1 is 100.The specific surface area S2 of 2nd carbon material is relative to the 1st carbon The ratio between specific surface area S1 of material (=S2/S1) is 350.But these values are to take the negative plate of made lead storage battery Out, when the carbon material contained in negative electrode material being separated into the 1st carbon material and 2 carbon material according to above-mentioned steps, as The content of each carbon material contained in negative electrode material (100 mass %) and the value found out.The powder resistance R1 of each carbon material It is also asked according to above-mentioned steps by the lead storage battery after making with R2, powder resistance ratio R2/R1 and specific surface area ratio S2/S1 Out.

" lead storage battery A2~A8 "

It adjusts and adds in such a way that the design value of the density of the negative electrode material of chemical conversion is as value shown in table 1 Enter the amount of the water and dilute sulfuric acid to cathode thickener.In addition to this, it is carried out similarly with the case where lead storage battery A1, makes cathode Plate in addition to this, is carried out similarly using obtained negative plate with lead storage battery A1, assembles lead storage battery A2~A8.

" lead storage battery B1~B8 "

As carbon material, it is used only carbon black (Ketjen black (registered trademark)).In the lead storage battery, the content of the 2nd carbon material For 0.6 mass %.In addition to this, it is carried out similarly with lead storage battery A1, forms negative plate.Using obtained negative plate, this is removed In addition, it is carried out similarly with lead storage battery A1, assembles lead storage battery B1.

It adjusts and adds in such a way that the design value of the density of the negative electrode material of chemical conversion is as value shown in table 1 Enter the amount of the water and dilute sulfuric acid to cathode thickener.In addition to this, it is carried out similarly with the case where lead storage battery B1, makes cathode Plate in addition to this, is carried out similarly using obtained negative plate with lead storage battery B1, assembles lead storage battery B2~B8.

" lead storage battery D1 and D2 "

Carbon material is not used in the production of negative plate, on this basis with the negative electrode material of chemical conversion The mode that the design value of density becomes value shown in table 1 adjusts the amount of the water and dilute sulfuric acid that are added to cathode thickener.In addition to this, It is carried out similarly with lead storage battery A1, forms negative plate.It is in addition to this, same as lead storage battery A1 using obtained negative plate Ground carries out, and assembles lead storage battery D1 and D2 respectively.

" lead storage battery E1 and E2 "

As carbon material, it is used only carbon black (Ketjen black (registered trademark)).In the lead storage battery, the content of the 2nd carbon material For 0.2 mass %.In addition to this, it is carried out similarly with lead storage battery D1, forms negative plate.Using obtained negative plate, this is removed In addition, it is carried out similarly with lead storage battery A1, assembles lead storage battery E1.

It is carried out similarly the 0.4 mass % of content of the 2nd carbon material with lead storage battery E1 in addition to this, forms cathode Plate.It using obtained negative plate, in addition to this, is carried out similarly with lead storage battery A1, assembles lead storage battery E2.

" lead storage battery E3 "

As carbon material, it is used only carbon black (Ketjen black (registered trademark)).In the lead storage battery, the content of the 2nd carbon material For 0.4 mass %.In addition to this, it is carried out similarly with lead storage battery D2, forms negative plate.Using obtained negative plate, this is removed In addition, it is carried out similarly with lead storage battery A1, assembles lead storage battery E3.

[evaluation 1: coating]

Using the constituent of mixer (DALTON corporation) mixing negative electrode material, cathode thickener is thus prepared. Then, cathode thickener is coated on collector using Paster (Winkel system).According to following benchmark to coating when situation into Row evaluation.

A: the shape not fallen off from the grate opening of collector with thickener is obtained with 15 per minute or more speeds of production State is coated with collector made of cathode thickener.

B: it can not obtain not falling off from the grate opening of collector with thickener with 15 per minute or more speeds of production State coating cathode thickener made of collector.

[evaluation 2: the retention of the negative plate of non-chemical conversion]

The ceruse contained in negative electrode material when finding out the negative plate for saving non-chemical conversion as steps described below Content.

Firstly, the negative plate of non-chemical conversion is cured 2 days under conditions of 35 DEG C of temperature and relative humidity 90%, 60 DEG C after dry 6 hours, save 3 weeks in an atmosphere.The negative electrode material that about 5g is taken from the negative plate after preservation, measures it After quality W, crushed.The perchloric acid that smashed sample is put into 20 mass % concentration of room temperature (25 DEG C) immediately is water-soluble In liquid 50mL, place 10 minutes.It measures total quality m5 of the sample and high chloro acid solution that will put into and places 10 minutes Total quality m6 of sample and high chloro acid solution afterwards.The reduction amount Δ W=m6-m5 for finding out quality at this time, by following Formula and the content c3 (quality %) for calculating the ceruse in negative electrode material.

C3=Δ W × ((M3/M4)/W) × 100

Here, M3 is ceruse (PbCO₃) molecular weight, M4 be carbon dioxide (CO₂) molecular weight.Use M3/M4= 6.07 value.

Then, the value of the content c3 based on carbonate, according to following benchmark to the keeping quality of the negative plate of non-chemical conversion It can be carried out evaluation.It should be noted that the content M of carbonate indicates that retention is excellent less.

A: the content c3 of carbonate is less than 20 mass %.

B: the content c3 of carbonate is 20 mass % or more.

[evaluation 3: cycle life performance]

To 3 progress cycling life tests in 4 lead storage batteries made.Sink of the cycling life test at 35 DEG C In the circulation of following electric discharge and charging is repeated.At this point, every 100 times circulate in 30 DEG C of current discharges with 40A to termination Voltage 1.70V finds out discharge capacity at this time.

Electric discharge: with electric current 50A electric discharge 3 hours.

Charging: with electric current 37.5A charging 5 hours.

Average discharge capacity is found out by the discharge capacity of 3 lead storage batteries of every 100 times circulation measurements.By average at this The cycle-index T that t is found out in the following way at the time of discharge capacity is lower than 75% (i.e. the 150Ah) of nominal capacity 200Ah comes Evaluate cycle life performance.It is judged as the cycle-index T situation for being 1450 times or more to obtain high circulation life performance.

The averaged discharge of t at the time of cycle-index T is lower than 150Ah by above-mentioned average discharge capacity by following formula for the first time Capacity Q1 and its 100 times circulation before discharge test when average discharge capacity Q2 find out.

T=t- (150-Q1)/(Q2-Q1) × 100

The result of lead storage battery A1~A8, B1~B8, D1~D2 and E1~E3 is shown in table 1.Table 1 is shown in FIG. 3 The result of cycle life performance in the result of A1~A8 and B1~B8.

[table 1]

As shown in table 1 and Fig. 3, the density of negative electrode material is less than 3.8g/cm³When, the 2nd carbon material is being used alone Situation and and with powder resistance than in the case where two kinds of carbon materials of particular range, cycle life almost without significantling change, Respectively less than 1450 times circulations, and insufficient (A1, A7, A8, B1, B7, B8).In contrast, the density of negative electrode material is 3.8g/cm³When above, in combination powder resistance ratio in the case where the 1st carbon material of particular range and 2 carbon material, although The content of 2nd carbon material is few, but available situation (B2~B6) comparable cycle life performance with the 2nd carbon material of exclusive use (A2~A6).It is believed that this is because being easy to be formed in negative electrode material by the 1st carbon material of combination and the 2nd carbon material Many conductive networks.

In addition, as shown in table 1, in the case where 2 carbon material is used alone, if the density of negative electrode material is got higher (specifically, being 3.7g/cm³Above, 3.8g/cm³Above situation), then can not be coated with using machine cathode thickener (B1~ B6).In addition, the retention of the negative plate of non-chemical conversion is low in battery B1~B6.In contrast, by and use powder Resistance ratio is in the 1st carbon material of particular range and the 2nd carbon material, even if the density in negative electrode material is 3.7g/cm³With Upper, 3.8g/cm³In the case where above, also (A1~A6) can be coated using machine.It is thought that due to battery A1~ Optimize the surface state of each carbon material and meeting specific powder resistance ratio R2/R1 in A5, the appropriate suction for inhibiting solvent It is attached.It should be noted that the retention of the negative plate of non-chemical conversion reduces in battery A6.It is reduced from inhibition retention Viewpoint is set out, and the density of negative electrode material is preferably smaller than 4.7g/cm³。

" lead storage battery A11~A16 "

In such a way that the content of the barium sulfate in the negative electrode material of chemical conversion is as design value shown in table 2 Adjust the additive amount of barium sulfate.In addition to this, it is carried out similarly with for the case where lead storage battery A3, makes negative plate, use The negative plate arrived is carried out similarly with lead storage battery A1 in addition to this, assembles lead storage battery A11~A16.It should be noted that these The design value of the density of lead storage battery and the negative electrode material in lead storage battery A3 is 4.1g/cm³。

" lead storage battery B11~B16 "

In such a way that the content of the barium sulfate in the negative electrode material of chemical conversion is as design value shown in table 2 Adjust the additive amount of barium sulfate.In addition to this, and to be carried out similarly when lead storage battery B3, negative plate is made, uses what is obtained Negative plate is carried out similarly with lead storage battery A1 in addition to this, assembles lead storage battery B11~B16.It should be noted that these lead The design value of the density of battery and the negative electrode material in lead storage battery B3 is 4.1g/cm³。

For lead storage battery A11~A16 and B11~B16, evaluation is carried out similarly with lead storage battery A1.In addition, according to upper State the content of the barium sulfate in step measurement negative electrode material.By these evaluation result is shown in table 2.Also show together in table 2 The result of lead storage battery A3 and B3 out.The result of the cycle life performance of table 2 is shown in Fig. 4.

[table 2]

As shown in table 2 and Fig. 4, the content of the barium sulfate in negative electrode material be 0.2 mass of mass %~0.7 % and Combination powder resistance ratio is in the case where the 1st carbon material of particular range and 2 carbon material, although the content of the 2nd carbon material is few, But the available high circulation life performance with (B12~B15, B3) when 2 carbon material is used alone quite and more than 1450 circulations (A12~A15, A3).Think to be the reason of high circulation life performance can be obtained in these batteries: by combining the 1st carbon material With the 2nd carbon material, and make the barium sulfate content proper range of negative electrode material, to not interfere the metal lead button of negative plate Electronic conductivity between son, even if carrying out deep discharge, also in charging, lead sulfate is also easy to be reduced, and does not interfere to charge.From To from the perspective of more high circulation life performance, the content of barium sulfate is preferably 0.2~0.6 mass %.

In addition, coating is evaluated as B in lead storage battery B11~B16 and B3, the composition of negative electrode material is mixed When ingredient, it can not be coated using machine.Compared with these batteries, coating is especially in lead storage battery A11~A16 and A3 It improves.

" lead storage battery A21~A34 "

Amount, specific surface area and/or the average aspect ratio of each carbon material used are adjusted, and is further adjusted as needed The average grain diameter D of each carbon material₅₀.Ketjen black is replaced using acetylene black in lead storage battery A27, in lead storage battery A33 and A34 Use active carbon.It so carries out, powder resistance ratio R2/R1 is changed as table 3.In addition to this, in the same manner as lead storage battery A3 It carries out, makes negative plate.It using obtained negative plate, in addition to this, is carried out similarly with lead storage battery A1, assembles lead storage battery A21~A34.It should be noted that the design value of the density of the negative electrode material in these lead storage battery and lead storage battery A3 are same Sample is 4.1g/cm³。

" lead storage battery A41~A43 "

Amount, specific surface area and/or the average aspect ratio of each carbon material used are adjusted, and is further adjusted as needed The average grain diameter D of each carbon material₅₀.In lead storage battery A43, Ketjen black is replaced using acetylene black.So carry out, as table 3 that Sample changes powder resistance ratio R2/R1.In addition to this, it is carried out similarly with lead storage battery A1, makes negative plate, it is negative using what is obtained Pole plate is carried out similarly with lead storage battery A1 in addition to this, assembles lead storage battery A41~A43.But these lead storage battery In negative electrode material density design value and lead storage battery A6 be similarly 4.7g/cm³。

For lead storage battery A21~A34 and A41~A43, evaluation 1 and evaluation 2 are commented in the same manner as lead storage battery A1 Valence.It should be evaluation result is shown in table 3.The result of lead storage battery A3 and A6 is shown together in table 3.

[table 3]

As shown in table 3, it is more than 15 and in the case where less than 230 in powder resistance ratio R2/R1, high circulation service life property can be obtained Energy.In addition, the coating of cathode thickener is high less than 230.Think that powder resistance ratio is available in such range The reason of high circulation life performance, is: more conductive networks is formed in negative electrode material.Additionally, it is believed that the painting of cathode thickener The reason of cloth improves is: in the case where above range, the surface state of each carbon material optimizes powder resistance ratio R2/R1, The absorption of solvent can suitably be inhibited.From the viewpoint of obtaining more high circulation life performance, R2/R1 is than preferably 80 or more and small In 230 or 80~220.From the viewpoint of improving the retention of negative plate of non-chemical conversion, negative electrode material it is close Degree is preferably smaller than 4.7g/cm³, in addition, specific surface area ratio S2/S1 is preferably 350 or less.Its reason is: in specific surface area ratio In the case that S2/S1 is more than 350, because of the surface state for the carbon material being mixed in thickener, by the molten of the adsorption of carbon material Dosage becomes more, in order to ensure coating, it is necessary to reduce sulphate amount.

Industrial availability

The lead storage battery that one aspect of the present invention is related to can be used in valve-regulated and liquid formula lead storage battery, can be fine The industries electric power storages such as starting power supply, the storage of natural energy resources, electric vehicle (fork truck etc.) of the ground as automobile or motorcycle etc. The power supplys such as device.

Symbol description

1: lead storage battery

2: negative plate

3: positive plate

4: separator

5a: cathode busbar connector

5b: anode busbar connector

6a: negative terminal

6b: positive terminal

10: electric slot

11: polar plate group

12: electrolyte

Claims

1. a kind of lead storage battery, has negative plate and positive plate,

The negative plate contains negative electrode material, and the negative electrode material contains carbon material and barium sulfate,

The carbon material contains the 1st carbon material of the partial size with 32 μm or more and with the 2nd carbon materials of the partial size less than 32 μm Material,

The powder resistance R2 of 2nd carbon material the ratio between the powder resistance R1 relative to the 1st carbon material, i.e. R2/R1 are more than 15 and less than 230,

The content of barium sulfate in the negative electrode material is the 0.2 mass % of mass %~0.7,

The density of the negative electrode material is 3.8g/cm³More than.

2. lead storage battery according to claim 1, wherein the ratio, i.e. R2/R1 are 80 more than and less than 230.

3. lead storage battery according to claim 1 or 2, wherein the ratio, i.e. R2/R1 are 80~220.

4. lead storage battery described in any one of claim 1 to 3, wherein the density of the negative electrode material is 4.1g/cm³More than.

5. lead storage battery according to any one of claims 1 to 4, wherein the density of the negative electrode material is less than 4.7g/cm³。

6. lead storage battery according to claim 5, wherein the specific surface area S2 of the 2nd carbon material and the 1st carbon materials The ratio between specific surface area S1 of material, i.e. S2/S1 are 350 or less.

7. lead storage battery described according to claim 1~any one of 6, wherein the barium sulfate in the negative electrode material Content be 0.2 mass of mass %~0.6 %.

8. lead storage battery according to any one of claims 1 to 7, wherein the in the negative electrode material the described 1st The content of carbon material is 0.05 mass % or more.

9. lead storage battery described according to claim 1~any one of 8, wherein the in the negative electrode material the described 1st The content of carbon material is 1.5 mass % or less.

10. lead storage battery described according to claim 1~any one of 9, wherein described in the negative electrode material The content of 2 carbon materials is 0.1 mass % or more.

11. lead storage battery described according to claim 1~any one of 10, wherein described in the negative electrode material The content of 2nd carbon material is 0.6 mass % or less.

12. lead storage battery described according to claim 1~any one of 11, wherein the 1st carbon material at least contains stone Ink, the 2nd carbon material at least contain carbon black.