CN1677721A - Negative-pole active material for lead battery, negative pole and lead battery making method - Google Patents

Negative-pole active material for lead battery, negative pole and lead battery making method Download PDF

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Publication number
CN1677721A
CN1677721A CNA2004100319808A CN200410031980A CN1677721A CN 1677721 A CN1677721 A CN 1677721A CN A2004100319808 A CNA2004100319808 A CN A2004100319808A CN 200410031980 A CN200410031980 A CN 200410031980A CN 1677721 A CN1677721 A CN 1677721A
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China
Prior art keywords
lignin
carbon
lead
lead powder
battery
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CNA2004100319808A
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Chinese (zh)
Inventor
坪井裕一
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Yuasa Corp
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Japan Storage Battery Co Ltd
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Priority to CNA2004100319808A priority Critical patent/CN1677721A/en
Publication of CN1677721A publication Critical patent/CN1677721A/en
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    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/10—Energy storage using batteries
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P70/00—Climate change mitigation technologies in the production process for final industrial or consumer products
    • Y02P70/50—Manufacturing or production processes characterised by the final manufactured product

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  • Battery Electrode And Active Subsutance (AREA)

Abstract

In method for preparing active material of cathode in use for lead accumulator, 0.5 - 1.5%Wt lignin and 0.5 - 5.0%Wt carbon related to lead powder are added to lead powder. In method for preparing cathode in use for lead accumulator through coating lead powder on basal body, 0.5 - 1.5%Wt lignin and 0.5 - 5.0%Wt carbon related to lead powder are added to lead powder. The lead accumulator prepared according to the disclosed method possesses good performance of charging and discharging cycle lifetime in high temperature.

Description

Lead accumulator negative electrode active material, negative pole and lead accumulator autofrettage
Technical field
The invention relates to a kind of manufacturing lead accumulator negative electrode active material, negative pole and lead accumulator autofrettage.
Background technology
Be used for that the negative plate of lead accumulator normally makes by the following method.In the lead powder that contains 65～80% left and right sides lead monoxides, add the lignin of trace, barium sulfate, carbon etc., the uncommon sulfuric acid of adding mixes and makes pastel again.This pastel is filled in the collector body as matrix,, change into the process of (active material that lead powder is become be in charged state through energising) through overcuring (making the humidity and the temperature that keep suitable on every side) after, make lead powder become the powder of the Pb of active material.
Barium sulfate becomes the PbSO that generates in exoelectrical reaction 4The nucleus of crystallization.Therefore, by adding barium sulfate, improved the discharge performance of lead accumulator.
The purpose of carbon is the current efficiency that improves when changing into, and normally adds about 0.1～0.3% mass percent.
Lignin is the accessory substance in making pulping process, is that the propyl benzene that manufactures with the waste liquid that produces in the pulp production is the natural polymer organic compound of essential structure.According to the manufacture method of paper pulp, lignin can be divided into two big classes.Be referred to as ox-hide lignin (thiolignin) according to what soda process and sulfate process generated, be referred to as sulphite lignin (lignosulfonic acid) by what sulfurous method generated.Usually, with respect to lead powder, adding mass percent is about 0.1～0.3%.The lignin that adds in negative pole is adsorbed on the surface of negative electrode active material, plays the function of anti-piping compound.The crystallization of the lead sulfate that lignin generates in the time of can increasing negative discharge is considered to suppress the effect of negative pole specific area of its active material when charging.By these effects, can think that the high efficiency discharge performance and the life performance of battery is improved.
But, be adsorbed on the lignin on active material surface, can be from the negative plate in charging and discharging process being dissolved out gradually.The lignin that is dissolved out is oxidized into carbon dioxide and disappears on positive plate.Thereby particularly battery is used under hot environment, perhaps in the occasion of overcharging, has the problem that the effect of lignin can not continue for a long time.Also have, add the lignin of volume for its effect is prolonged, the charging of battery is subjected to electrical property lowly to cause undercharge.Therefore, have the problem of the lifetime of battery on the contrary.Add the lignin of volume, the charging of battery is subjected to the electrical property why can be low, does not also separate bright fully.But have because adsorbed the Pb of reactant 2+And hindered the explanation of charging reaction, or because being adsorbed on the surface of active material, lignin makes the low explanation of electric conductivity of active material.
Summary of the invention
Of the present invention one of them be, use in the manufacture method of negative electrode active material at lead accumulator, so that to have added mass percent with respect to above-mentioned lead powder in lead powder be 0.5～1.5% lignin and be that 0.5～5.0% carbon is feature with respect to the mass percent of above-mentioned lead powder.
Also have, of the present invention one of them be, the lead accumulator of coating lead powder is with in the negative pole autofrettage on matrix, with being 0.5～1.5% lignin with respect to the mass percent of above-mentioned lead powder and be that 0.5～5.0% carbon is added in the above-mentioned negative pole with respect to the mass percent of above-mentioned lead powder being feature.So-called here " add mass percent with respect to above-mentioned lead powder and be 0.5～1.5% lignin; and be that 0.5～5.0% carbon is in negative pole with respect to the mass percent of above-mentioned lead powder " be not limited on matrix, be coated with that lignin and carbon are added to situation in the negative pole behind the lead powder, also comprised by being coated with the lead powder that has added lignin and carbon in advance on matrix, making lignin and carbon be added to situation in the negative pole.
In addition, be meant the mixture of PbO and Pb at the lead powder described in this detailed book.But, during negative pole is made, except that PbO and Pb, added Pb again in use 3O 4Mixture the time, the lead powder described in this detailed book then is meant PbO and Pb and Pb 3O 4Mixture.
By above-mentioned the present invention, lignin is able to continue for a long time as the effect of anti-piping compound, and the good charging that can obtain lead accumulator is subjected to electrical property.That is to say, thereby the present invention improves the performance that charging is subjected to electricity by the carbon that adds volume in negative pole, the charging of negative pole is subjected to the reduction of electrical property when compensating the lignin that has been added volume in negative pole.This result makes when the charging that does not reduce negative pole is subjected to electrical property, and lignin is kept for a long time as the effect of anti-piping compound.Carbon then has the absorption lignin on the one hand makes it to maintain the interior effect of negative pole, forms the effect of conductive network on the other hand in addition.Also have, the average diameter that is added to the primary particle of the carbon in the negative pole wishes to be not more than 0.1 μ m.
Concrete execution mode
Followingly be described according to embodiments of the invention.
Embodiment 1
The inventor has made to contain and has added the various different lignin amounts and the negative plate of carbon amount for effect of the present invention is described.
Contain the lead powder 100kg that mass percent is about the Pb of 75% PbO and about 25% respectively, with proportion be about 20 liters of 1.15 uncommon sulfuric acid, stir the mixed starchiness thing made from mixing as the lignin of the barium sulfate 0.5 quality % of additive and ormal weight and carbon.After this starchiness thing being filled in the grid of matrix,, be made into the negative plate that contains different lignin and carbon amount through carrying out slaking and drying.Utilize these negative plates to be made into the enclosed-type battery of the baffle-type of 2V60Ah.Use these batteries, carrying out electric current in the time of 50 ℃ is the discharges in 15 minutes of 1CA, reaches the cyclic test repeatedly in 2.4V voltage (maximum current is 1CA) charging in 30 minutes.Carry out the discharge of 1CA after per 50 circulations, when discharge capacity is lower than 15Ah, be judged as the life-span of battery.Also has the magnificent Nicholas N board wooden sodium sulfonate that lignin in the present embodiment has been to use that Nippon Paper Chemicals Co., Ltd. produces.In addition, the electrification that used carbon has been to use Deuki Kagaku Kogyo Co., Ltd to produce is black, and it is the acetylene black of 0.50 μ m for the primary particle diameter.About positive plate, then all used identical positive plate.
Table 1 be listed be battery list of making and the period of representing its life-span.Here, the life-span period that shows in the table 1 is to be assumed to be 100 o'clock relative number with the life-span period of battery No.1.
Table 1
Battery No. Lignin addition (with respect to the quality % of lead powder) Carbon addition (with respect to the quality % of lead powder) The life-span period Appendix
????1 ????0.2 ????0.2 ????100 Existing battery
????2 ????0.5 ????110 Control cell
????3 ????2.0 ????120 Control cell
????4 ????5.0 ????95 Control cell
????5 ????7.0 ????90 Control cell
????6 ????0.5 ????0.2 ????95 Control cell
????7 ????0.5 ????205 Battery of the present invention
????8 ????2.0 ????235 Battery of the present invention
????9 ????5.0 ????220 Battery of the present invention
????10 ????7.0 ????125 Control cell
????11 ????1.0 ????0.2 ????90 Control cell
????12 ????0.5 ????250 Battery of the present invention
????13 ????2.0 ????280 Battery of the present invention
????14 ????5.0 ????240 Battery of the present invention
????15 ????7.0 ????110 Control cell
????16 ????1.5 ????0.2 ????80 Control cell
????17 ????0.5 ????240 Battery of the present invention
????18 ????2.0 ????250 Battery of the present invention
????19 ????5.0 ????215 Battery of the present invention
????20 ????7.0 ????90 Control cell
????21 ????2.0 ????0.2 ????60 Control cell
????22 ????0.5 ????100 Control cell
????23 ????2.0 ????120 Control cell
????24 ????5.0 ????95 Control cell
????25 ????7.0 ????70 Control cell
(battery No.1) compares with existing battery, and in the occasion of the battery (battery No.6,11,16,21) that has only the lignin amount to increase, the life performance of battery reduces.Can think that this is because the increase of lignin amount, the electrical property that is subjected to of charging reduces, and this result makes the undercharge of pole plate, and has caused the capacity of battery low.Also have,, when the carbon amount is added to 2.0%, can observe some improvement of the life performance of battery in the occasion of the battery (battery No.2,3,4,5) that has only the carbon amount to increase.But when increasing more carbon amount, the life performance of battery occurs low on the contrary.Can think, when the amount of having only carbon increases,, thereby make lignin reduce the effect of active material because carbon has adsorbed lignin.
In contrast to this, when lignin adds with 0.5～1.5% amount respectively, and the occasion of the battery of the present invention (battery No.7～9,12～14,17～19) that carbon also adds with 0.5～5.0% amount has obtained the life performance more than 2 times of existing battery No.1.Can think, this is that increase owing to the carbon amount has suppressed the charging that the increase when the lignin amount causes and is subjected to the low of electrical property, thereby and since carbon adsorbed lignin make it to maintain continue two that the high efficiency discharge performance that makes battery in the negative pole is able to over a long time former resulting.
Embodiment 2
Next be by the method identical, made the negative plate that adds carbon, made baffle-type enclosed-type battery similarly to Example 1, and carried out the test identical with embodiment 1 with different primary particle average diameters with embodiment 1.The average diameter of having used primary particle in the test is respectively 4 kinds of carbon of 0.5 μ m, 0.1 μ m, 0.05 μ m, 0.01 μ m.The addition of lignin is 0.5% (lower limit) and 1.5% (upper limit), and the addition of carbon is 0.5% (lower limit) and 5.0% (upper limit).
Table 2 be listed be battery list of making and the period of representing its life-span.Here, the life-span period that shows in the table 1 is identical with embodiment 1, is assumed to be with the life-span period of battery No.1 that 100 o'clock relative number represents.
Table 2
Battery No. Lignin addition (with respect to the quality % of lead powder) Carbon addition (with respect to the quality % of lead powder) The average diameter of the primary particle of carbon (μ m) The life-span period
????26 ????0.5 ????0.5 ????0.5 ????155
????27 ????0.1 ????200
????28 ????0.05 ????205
????29 ????0.02 ????220
????30 ????5.0 ????0.5 ????170
????31 ????0.1 ????210
????32 ????0.05 ????220
????33 ????0.02 ????230
????34 ????1.5 ????0.5 ????0.5 ????180
????35 ????0.1 ????240
????36 ????0.05 ????240
????37 ????0.02 ????250
????38 ????5.0 ????0.5 ????160
????39 ????0.1 ????210
????40 ????0.05 ????215
????41 ????0.02 ????230
When the amount of lignin 0.5～1.5%, and the amount of carbon is in 0.5～5.0% scope the time, no matter the average diameter size of the primary particle of the carbon that adds is compared with existing battery No.1, the cycle life performance of battery of the present invention improves.But, when the average diameter of primary particle when 0.1 μ m is following, cycle life performance has obtained significant raising.
In the present embodiment, used the magnificent Buddhist nun's lachs N as Nippon Paper Chemicals Co., Ltd.'s production of main component with wooden sodium sulfonate.In addition, using is magnificent Buddhist nun's lachs HW that Nippon Paper Chemicals Co., Ltd. produces equally, the KRAFTPLEX that Mead Westvaco company produces, KRAFTSPERSE DD-5, POLYFON F, REAX series, the VANISPERS A that Borregaard company produces, VANISPERSE HT-1 etc. are that the lignin of essential structure also can obtain same effect with the propyl benzene, and the present patent application person confirmed in other test.In the present invention, the lignin of use all produces effect no matter be ox-hide lignin (thiolignin) or sulphite lignin (lignosulfonic acid).
Also having, in the present embodiment as carbon, used acetylene black, is that the electrification that Deuki Kagaku Kogyo Co., Ltd produces is deceived.In addition, the present patent application person confirmed, used the NITERON series of new daily use chemicals carbon company, the SEAST series of East Sea carbon company, the situation of furnace blacks such as the KETJENBLACK EC of KETJENBLACK INTERNATIONAL company and EC600JD also can obtain same effect.That is to say that the carbon black beyond the acetylene black also can obtain same effect.
Also have, the addition of barium sulfate in the present embodiment is 0.5 quality %.But effect of the present invention is not subjected to it to add quantitative limitation, and the fact of the addition of interdependent barium sulfate was not confirmed by applicant of the present invention yet.
Also have, in the present embodiment,, used the mixture of the Pb of the PbO of about 75 quality % and about 25 quality % as lead powder.In addition, the mass ratio of the PbO in lead powder is 50～90% situation, also can obtain the application's effect.
Also have, in the present embodiment, lignin and carbon are added to latter made pastel in the lead powder, be filled in the grid of matrix after, carried out slaking and changed into.But the present invention is not limited to such occasion, after lead powder is coated onto on the matrix, makes negative pole, adds lignin to this negative pole again and also is fine.
In addition, the present invention is no matter be to mix back interpolation lignin and carbon at lead powder and uncommon sulfuric acid, or adding uncommon sulfuric acid again after lead powder and lignin and the carbon mixing all is fine.Any occasion no matter is so long as the mass ratio of lead powder and lignin and carbon in the scope of appointment, can both obtain same effect.
Present embodiment be record and narrate about the baffle-type enclosed-type battery, undoubtedly, even liquid-type battery or gel formula battery also can obtain same effect.
Also have, when measuring the mean particle diameter of carbon, used laser inflection formula particle size distribution device (the hole field makes made LA-920) specifically.
As mentioned above, lead accumulator negative electrode active material of the present invention, negative pole, or the autofrettage of lead accumulator, compare with existing autofrettage, can make to be manufactured on the lead accumulator that the cycle life performance of repeated charge is good under the hot conditions and to become possibility, the value of its industry is very large.

Claims (6)

  1. At lead accumulator with in the manufacture method of negative electrode active material, so that to have added mass percent with respect to above-mentioned lead powder in lead powder be 0.5～1.5% lignin and be that 0.5～5.0% carbon is feature with respect to the mass percent of above-mentioned lead powder.
  2. 2. in the autofrettage of active material according to claim 1, being not more than 0.1 μ m with the average diameter of the primary particle of above-mentioned carbon is feature.
  3. 3. the lead accumulator that is coated with lead powder on matrix is with in the negative pole autofrettage, with being 0.5～1.5% lignin with respect to the mass percent of above-mentioned lead powder and be that 0.5～5.0% carbon adds in the above-mentioned negative pole with respect to the mass percent of above-mentioned lead powder being feature.
  4. 4. lead accumulator according to claim 3 is with in the negative pole autofrettage, and being not more than 0.1 μ m with the average diameter of the primary particle of above-mentioned carbon is feature.
  5. 5. in the lead accumulator autofrettage, the active material of making to use autofrettage according to claim 1, the autofrettage perhaps according to claim 3 and negative pole made is a feature.
  6. 6. in the lead accumulator autofrettage according to claim 5, being not more than 0.1 μ m with the average diameter of the primary particle of above-mentioned carbon is feature.
CNA2004100319808A 2004-03-31 2004-03-31 Negative-pole active material for lead battery, negative pole and lead battery making method Pending CN1677721A (en)

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Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP2153481A1 (en) * 2007-06-06 2010-02-17 Hammond Group, Inc. Lead-acid battery expanders with improved life at high temperatures
EP2324524A1 (en) * 2008-09-02 2011-05-25 Hammond Group, Inc. Improved expanders for lead-acid batteries
CN105936981A (en) * 2016-04-14 2016-09-14 华北电力大学 Metal lead-toughened lead oxide ceramic and preparation method thereof
CN112242524A (en) * 2020-09-15 2021-01-19 骆驼集团蓄电池研究院有限公司 Formula and preparation method of negative lead plaster for improving high and low temperature performance of lead-acid storage battery

Cited By (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP2153481A1 (en) * 2007-06-06 2010-02-17 Hammond Group, Inc. Lead-acid battery expanders with improved life at high temperatures
EP2153481A4 (en) * 2007-06-06 2011-08-24 Hammond Group Inc Lead-acid battery expanders with improved life at high temperatures
EP2324524A1 (en) * 2008-09-02 2011-05-25 Hammond Group, Inc. Improved expanders for lead-acid batteries
EP2324524A4 (en) * 2008-09-02 2013-12-04 Hammond Group Inc Improved expanders for lead-acid batteries
CN105936981A (en) * 2016-04-14 2016-09-14 华北电力大学 Metal lead-toughened lead oxide ceramic and preparation method thereof
CN105936981B (en) * 2016-04-14 2018-04-10 华北电力大学 A kind of lead oxide ceramics of metallic lead toughness reinforcing and preparation method thereof
CN112242524A (en) * 2020-09-15 2021-01-19 骆驼集团蓄电池研究院有限公司 Formula and preparation method of negative lead plaster for improving high and low temperature performance of lead-acid storage battery
CN112242524B (en) * 2020-09-15 2022-07-15 骆驼集团蓄电池研究院有限公司 Formula and preparation method of negative lead plaster for improving high and low temperature performance of lead-acid storage battery

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