CN105161770A - Lead plaster additive for lead-acid storage battery, and preparation method and application therefor - Google Patents
Lead plaster additive for lead-acid storage battery, and preparation method and application therefor Download PDFInfo
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- CN105161770A CN105161770A CN201510506822.1A CN201510506822A CN105161770A CN 105161770 A CN105161770 A CN 105161770A CN 201510506822 A CN201510506822 A CN 201510506822A CN 105161770 A CN105161770 A CN 105161770A
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
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Abstract
The invention discloses a lead plaster additive for a lead-acid storage battery. The lead plaster additive for the lead-acid storage battery comprises the following components in percentage by mass: 0.5-5% of preprocessed one-dimensional carbon nanomaterial, 0.5-6% of dispersing agent and the balance of deionized water. The lead plaster additive for the lead-acid storage battery can effectively restrain the phenomena of sulfation and hydrogen evolution simultaneously, as well as can improve the charge-discharge speed and the service life of the battery. The invention also discloses a preparation method for the lead plaster additive for the lead-acid storage battery, comprising the steps specifically: (1) preparing a pre-processed carbon nano tube; and (2) mixing. The preparation method for the lead plaster additive for the lead-acid storage battery is simple in processing steps, high in operability and suitable for industrial large-scale production.
Description
Technical field
The present invention relates to Lead-acid Battery Technology field, especially relate to a kind of Lead-acid Storage Battery paste additive and preparation method thereof, application.
Background technology
Because energy crisis and problem of environmental pollution become increasingly conspicuous, the focus of global concern concentrates on sustainable, reproducible power resource and energy-storage system more and more.Lead acid accumulator has technical maturity, security performance is good, cost is low, stable performance and resource rate of recovery advantages of higher again, still has very large occupation rate of market so far.But at present lead-acid battery is in use for some time, and charge acceptance can poor, the actual capacity that is filled with and store and seldom, have a strong impact on battery service condition in practice.Negative terminal surface sulfation is serious in addition, and oarse-grained vitriol can cause pole plate mechanical deformation and expansion, causes cell performance loss; Can not effectively carry out converting back spongy lead, make battery cycle life limited.Therefore, how slowing down the trend of battery sulfation, improving the useful life of battery and reduce the internal resistance of cell is the problem needing solution at present badly.
Application publication number: CN102709567A, the Chinese patent of Shen Qing Publication day: 2012.10.03 discloses a kind of lead-acid battery, belongs to lead-acid battery field, and it can solve the problem that existing lead-acid battery high-rate performance is poor and cycle life is short.The present invention adds conductive agent and Carbon Materials by the negative pole to lead-acid battery, the problem such as solve existing lead-acid battery high-rate performance difference and cycle life is short.Its weak point is: with the addition of Carbon Materials in the battery, Carbon Materials is one or more in active carbon, expanded graphite, spherical graphite, natural flake graphite, the interpolation of these Carbon Materials makes the liberation of hydrogen of battery cathode comparatively serious, therefore in this invention by adding liberation of hydrogen inhibitor (in zinc sulfate, zinc oxide, bismuth oxide one or more) to suppress the liberation of hydrogen of negative pole, but liberation of hydrogen inhibitor can cause self discharge to battery, reduce battery.
Summary of the invention
The present invention is the above-mentioned technical problem existing for the Lead-acid Storage Battery paste additive in order to solve prior art, provide one effectively can suppress sulfation and hydrogen evolution phenomenon simultaneously, improve battery charge acceptance and the Lead-acid Storage Battery paste additive in useful life.
Present invention also offers a kind of preparation method of Lead-acid Storage Battery paste additive, processing step is simple, workable, is applicable to industrialization large-scale production.
To achieve these goals, the present invention is by the following technical solutions:
A kind of Lead-acid Storage Battery paste additive, described Lead-acid Storage Battery paste additive is made up of the component of following mass percentage: 0.5 ~ 5% pretreated One-dimensional nanoreticular carbon materials, 0.5 ~ 6% dispersant, and surplus is deionized water.Lead-acid Storage Battery paste additive of the present invention efficiently solves One-dimensional nanoreticular carbon materials and easily to reunite the problem of not easily disperseing, and find in actual applications, One-dimensional nanoreticular carbon materials is compared to other active carbons, expanded graphite, spherical graphite, the Carbon Materials such as natural flake graphite can effectively suppress sulfation, and One-dimensional nanoreticular carbon materials has excellent high-ratio surface character, electron conduction and unique mechanical property, the microstructure of pole piece can be improved, increase specific area, for active material provides extra porousness, thus improve capacity and the cryogenic property of battery, in addition, One-dimensional nanoreticular carbon materials can form stable conductive mesh structure in lead plaster, thus greatly improve the charging rate of battery and put spot speed, the reaction rate difference reduced between discharge and recharge reduces, the charge acceptance of battery improves, stable conductive mesh structure can make the homogeneous current distribution by active material, the PbSO of larger particles can not be produced
4, thus suppress sulfation, dispersant to improve the dispersive property of One-dimensional nanoreticular carbon materials further, and on battery performance without impact.
As preferably, described One-dimensional nanoreticular carbon materials is the carbon nano-fiber that carbon nano-tube or fibre diameter are less than 100nm.
As preferably, described pretreated One-dimensional nanoreticular carbon materials obtains by the following method: be immersed in by One-dimensional nanoreticular carbon materials in 70% nitric acid and/or 95 ~ 98% sulfuric acid, ultrasonic process 1 ~ 72h under 20 ~ 90 DEG C of conditions, with in succession in neutral, obtaining pretreated One-dimensional nanoreticular carbon materials to pH with deionized water, NaOH or Ammonia, deionized water washing after filtering.One-dimensional nanoreticular carbon materials is carried out preliminary treatment, the dispersiveness of One-dimensional nanoreticular carbon materials in water can be improved, and the Lead-acid Storage Battery paste additive good stability obtained, thus solve the One-dimensional nanoreticular carbon materials problem that easy reunion not easily disperses in water.
As preferably, described One-dimensional nanoreticular carbon materials is the carbon nano-fiber that carbon nano-tube or fibre diameter are less than 100nm.
As preferably, described dispersant is lauryl sodium sulfate, neopelex, PVP or polyacrylic acid.Using lauryl sodium sulfate, neopelex, PVP or polyacrylic acid as dispersant in the present invention, except pretreated One-dimensional nanoreticular carbon materials can be made dispersed, the liberation of hydrogen overpotential for oxygen evolution of cell active materials can also be improved, and then suppress the loss of discharge and recharge moisture, reduce the battery failure caused because moisture dries up.
A preparation method for Lead-acid Storage Battery paste additive, the concrete steps of described preparation method are:
(1) pretreated One-dimensional nanoreticular carbon materials is prepared: be immersed in by One-dimensional nanoreticular carbon materials in 70% nitric acid or 95 ~ 98% sulfuric acid, ultrasonic process 1 ~ 72h under 20 ~ 90 DEG C of conditions, with in succession washing to pH in neutral with deionized water, NaOH or Ammonia, deionized water after filtering, obtain pretreated One-dimensional nanoreticular carbon materials, stand-by.
(2) mix: after taking each component by above-mentioned mass percentage proportioning, dispersant is added deionized water for stirring evenly after, add pretreated One-dimensional nanoreticular carbon materials, after ultrasonic disperse, namely obtain Lead-acid Storage Battery paste additive.
An application for Lead-acid Storage Battery paste additive as claimed in claim 1, embody rule method is: when preparing lead acid accumulator lead plaster, is incorporated as the Lead-acid Storage Battery paste additive of lead powder quality 5 ~ 20% in lead plaster.Lead plaster is cathode lead plaster or anode diachylon
Therefore, the present invention has following beneficial effect:
(1) Lead-acid Storage Battery paste additive of the present invention effectively can suppress sulfation and hydrogen evolution phenomenon simultaneously, improves battery charge acceptance and useful life;
(2) Lead-acid Storage Battery paste additive preparation method of the present invention, processing step is simple, workable, is applicable to industrialization large-scale production.
Embodiment
Below by embodiment, the present invention will be further described.
In the present invention, if not refer in particular to, all percentage is unit of weight, and all devices and raw material all can be buied from market or the industry is conventional, and the method in following embodiment, if no special instructions, is this area conventional method.
Embodiment 1
A kind of Lead-acid Storage Battery paste additive, it is made up of the component of following mass percentage: 2% pretreated Single Walled Carbon Nanotube, 1% dispersant, and surplus is deionized water, and dispersant is polyacrylic acid.
This Lead-acid Storage Battery paste additive obtains by the following method:
(1) pretreated Single Walled Carbon Nanotube is prepared: Single Walled Carbon Nanotube be immersed in 95% sulfuric acid, ultrasonic process 5h under 40 DEG C of conditions, with in succession in neutral, obtaining pretreated Single Walled Carbon Nanotube to pH with deionized water, Ammonia, deionized water washing after filtering, stand-by.
(2) mix: after taking each component by above-mentioned mass percentage proportioning, dispersant is added deionized water for stirring evenly after, add pretreated Single Walled Carbon Nanotube, after ultrasonic disperse, namely obtain Lead-acid Storage Battery paste additive.
Get A, B, C, D tetra-groups (often organizing four) specification respectively and be 6-DZM-12(48V-12Ah) and the identical test cell of manufacture craft, the lead plaster additive that the present embodiment is obtained is added with in the anode diachylon of wherein A Battery pack, the lead plaster additive that the present embodiment is obtained is added with in the cathode lead plaster of B Battery pack, the lead plaster additive that the present embodiment is obtained is all added with in the positive and negative electrode lead plaster of C battery, lead plaster additive of the present invention is not all added, as control cell in the positive and negative electrode lead plaster of D Battery pack.
According to national standard, four Battery packs are tested, test result shows, A, B, the capacity of C battery, low temperature capacity, charge acceptance is all better than control cell D, especially optimum with the combination property of C battery, compared to D Battery pack, C battery capacity improves more than 8%, low temperature capacity improves more than 11%, charge acceptance improves more than 45%, cycle life is 150 times time, C battery discharge capacity remains on 13.5Ah, and control cell discharge capacity is 12.2Ah, cycle life has greatly improved, and the battery of all interpolations lead plaster additive of the present invention, in cyclic process, dehydration situation is suitable with control cell, all there is not serious phenomenon of losing water.
From test result, Lead-acid Storage Battery paste additive of the present invention effectively can improve simultaneously effectively suppression sulfation and hydrogen evolution phenomenon, improves battery charging and discharging speed and useful life.
Embodiment 2
A kind of Lead-acid Storage Battery paste additive, it is made up of the component of following mass percentage: 0.5% pretreated multi-walled carbon nano-tubes, 0.5% dispersant, and surplus is deionized water, and dispersant is PVP.
This Lead-acid Storage Battery paste additive obtains by the following method:
(1) pretreated multi-walled carbon nano-tubes is prepared: be immersed in by multi-walled carbon nano-tubes in 95% sulfuric acid, ultrasonic process 1h under 90 DEG C of conditions, with in succession in neutral, obtaining pretreated multi-walled carbon nano-tubes to pH with deionized water, NaOH, deionized water washing after filtering, stand-by.
(2) mix: after taking each component by above-mentioned mass percentage proportioning, dispersant is added deionized water for stirring evenly after, add pretreated multi-walled carbon nano-tubes, after ultrasonic disperse, namely obtain Lead-acid Storage Battery paste additive.
Embodiment 3
A kind of Lead-acid Storage Battery paste additive, it is made up of the component of following mass percentage: 5% pretreated fibre diameter is less than the carbon nano-fiber of 100nm, 6% dispersant, and surplus is deionized water, and dispersant is lauryl sodium sulfate.
This Lead-acid Storage Battery paste additive obtains by the following method:
(1) carbon nano-fiber that pretreated fibre diameter is less than 100nm is prepared: carbon nano-fiber fibre diameter being less than 100nm is immersed in 70% nitric acid, ultrasonic process 72h under 20 DEG C of conditions, with in succession washing to pH in neutral with deionized water, sodium hydroxide solution, deionized water after filtering, obtain the carbon nano-fiber that pretreated fibre diameter is less than 100nm, stand-by.
(2) mix: after taking each component by above-mentioned mass percentage proportioning, dispersant is added deionized water for stirring evenly after, add the carbon nano-fiber that pretreated fibre diameter is less than 100nm, after ultrasonic disperse, namely obtain Lead-acid Storage Battery paste additive.
The application process of Lead-acid Storage Battery paste additive of the present invention is: with in cream process, be incorporated as the Lead-acid Storage Battery paste additive of the present invention of lead powder quality 5 ~ 20% in lead plaster.
Above-described embodiment is one of the present invention preferably scheme, not does any pro forma restriction to the present invention, also has other variant and remodeling under the prerequisite not exceeding the technical scheme described in claim.
Claims (7)
1. a Lead-acid Storage Battery paste additive, is characterized in that, described Lead-acid Storage Battery paste additive is made up of the component of following mass percentage: 0.5 ~ 5% pretreated One-dimensional nanoreticular carbon materials, 0.5 ~ 6% dispersant, and surplus is deionized water.
2. a kind of Lead-acid Storage Battery paste additive according to claim 1, it is characterized in that, described pretreated One-dimensional nanoreticular carbon materials obtains by the following method: be immersed in by One-dimensional nanoreticular carbon materials in 70% nitric acid and/or 95 ~ 98% sulfuric acid, ultrasonic process 1 ~ 72h under 20 ~ 90 DEG C of conditions, with in succession in neutral, obtaining pretreated One-dimensional nanoreticular carbon materials to pH with deionized water, NaOH or Ammonia, deionized water washing after filtering.
3. a kind of Lead-acid Storage Battery paste additive according to claim 1 and 2, is characterized in that, described One-dimensional nanoreticular carbon materials is the carbon nano-fiber that carbon nano-tube or fibre diameter are less than 100nm.
4. a kind of Lead-acid Storage Battery paste additive according to claim 1, is characterized in that, described dispersant is lauryl sodium sulfate, neopelex, PVP or polyacrylic acid.
5. a preparation method for Lead-acid Storage Battery paste additive as claimed in claim 1, is characterized in that, the concrete steps of described preparation method are:
(1) pretreated One-dimensional nanoreticular carbon materials is prepared: be immersed in by One-dimensional nanoreticular carbon materials in 70% nitric acid or 95 ~ 98% sulfuric acid, ultrasonic process 1 ~ 72h under 20 ~ 90 DEG C of conditions, with in succession washing to pH in neutral with deionized water, NaOH or Ammonia, deionized water after filtering, obtain pretreated One-dimensional nanoreticular carbon materials, stand-by;
(2) mix: after taking each component by above-mentioned mass percentage proportioning, dispersant is added deionized water for stirring evenly after, add pretreated One-dimensional nanoreticular carbon materials, after ultrasonic disperse, namely obtain Lead-acid Storage Battery paste additive.
6. preparation method according to claim 5, is characterized in that, described One-dimensional nanoreticular carbon materials is the carbon nano-fiber that carbon nano-tube or fibre diameter are less than 100nm.
7. an application for Lead-acid Storage Battery paste additive as claimed in claim 1, is characterized in that, embody rule method is: when preparing lead acid accumulator lead plaster, is incorporated as the Lead-acid Storage Battery paste additive of lead powder quality 5 ~ 20% in lead plaster.
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| CN201510506822.1A CN105161770A (en) | 2015-08-18 | 2015-08-18 | Lead plaster additive for lead-acid storage battery, and preparation method and application therefor |
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Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105845940A (en) * | 2016-04-22 | 2016-08-10 | 超威电源有限公司 | Aqueous carbon nanotube dispersion liquid used for lead-acid storage battery, and preparation method and application for aqueous carbon nanotube dispersion liquid |
| CN106353352A (en) * | 2016-10-11 | 2017-01-25 | 超威电源有限公司 | Detection method for dispersion effect of carbon material in lead-acid storage battery |
| CN106410190A (en) * | 2016-11-16 | 2017-02-15 | 双登集团股份有限公司 | Lead-acid storage battery positive lead paste preparation method |
| CN107634209A (en) * | 2017-09-22 | 2018-01-26 | 武汉亿维登科技发展有限公司 | A kind of positive electode of lead battery lead plaster |
| CN108493448A (en) * | 2018-05-18 | 2018-09-04 | 无锡德碳科技股份有限公司 | A kind of diachylon of negative electrode of lead carbon battery, preparation method, negative plate of lead-carbon battery and lead carbon battery |
| CN108736003A (en) * | 2018-05-31 | 2018-11-02 | 深圳市瑞达电源有限公司 | A kind of cathode pole cream for lead charcoal start and stop accumulator |
| CN109148846A (en) * | 2018-08-07 | 2019-01-04 | 超威电源有限公司 | A kind of tubular cells anode diachylon and preparation method thereof |
| CN112259709A (en) * | 2020-10-21 | 2021-01-22 | 骆驼集团(安徽)再生资源有限公司 | Production process of lead-acid storage battery pole plate |
| CN113161539A (en) * | 2021-02-05 | 2021-07-23 | 肇庆理士电源技术有限公司 | Trace acidized carbon nanotube negative plate and lead paste and preparation method thereof |
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Cited By (13)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105845940A (en) * | 2016-04-22 | 2016-08-10 | 超威电源有限公司 | Aqueous carbon nanotube dispersion liquid used for lead-acid storage battery, and preparation method and application for aqueous carbon nanotube dispersion liquid |
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| CN106353352B (en) * | 2016-10-11 | 2019-12-06 | 超威电源有限公司 | Method for detecting dispersion effect of carbon material in lead-acid storage battery |
| CN106353352A (en) * | 2016-10-11 | 2017-01-25 | 超威电源有限公司 | Detection method for dispersion effect of carbon material in lead-acid storage battery |
| CN106410190A (en) * | 2016-11-16 | 2017-02-15 | 双登集团股份有限公司 | Lead-acid storage battery positive lead paste preparation method |
| CN107634209A (en) * | 2017-09-22 | 2018-01-26 | 武汉亿维登科技发展有限公司 | A kind of positive electode of lead battery lead plaster |
| CN108493448A (en) * | 2018-05-18 | 2018-09-04 | 无锡德碳科技股份有限公司 | A kind of diachylon of negative electrode of lead carbon battery, preparation method, negative plate of lead-carbon battery and lead carbon battery |
| CN108736003A (en) * | 2018-05-31 | 2018-11-02 | 深圳市瑞达电源有限公司 | A kind of cathode pole cream for lead charcoal start and stop accumulator |
| CN109148846A (en) * | 2018-08-07 | 2019-01-04 | 超威电源有限公司 | A kind of tubular cells anode diachylon and preparation method thereof |
| CN109148846B (en) * | 2018-08-07 | 2021-08-17 | 超威电源集团有限公司 | Tubular battery anode lead paste and preparation method thereof |
| CN112259709A (en) * | 2020-10-21 | 2021-01-22 | 骆驼集团(安徽)再生资源有限公司 | Production process of lead-acid storage battery pole plate |
| CN112259709B (en) * | 2020-10-21 | 2021-07-27 | 骆驼集团(安徽)再生资源有限公司 | Production process of lead-acid storage battery pole plate |
| CN113161539A (en) * | 2021-02-05 | 2021-07-23 | 肇庆理士电源技术有限公司 | Trace acidized carbon nanotube negative plate and lead paste and preparation method thereof |
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Application publication date: 20151216 |