CN102903910B - High-temperature-resistant lead-acid battery cathode active substance and preparation method thereof - Google Patents
High-temperature-resistant lead-acid battery cathode active substance and preparation method thereof Download PDFInfo
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- CN102903910B CN102903910B CN201210395826.3A CN201210395826A CN102903910B CN 102903910 B CN102903910 B CN 102903910B CN 201210395826 A CN201210395826 A CN 201210395826A CN 102903910 B CN102903910 B CN 102903910B
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Abstract
The invention relates to a high-temperature-resistant lead-acid battery cathode active substance and a preparation method thereof. The active substance consists of lead powder, an adhesive, sulfuric acid, de-ionized water, barium sulfate, lignin and an high-temperature additive, wherein the high-temperature additive consists of aero oil, rosindone, anisaldehyde, KS15 graphite powder and humic acid; and the components are scientifically and reasonably proportioned, and the preparation process is complete and standard. The water loss and corrosion of a battery assembled by pole plates manufactured from the active substance provided by the invention are greatly reduced, the battery can be applicable to a high-temperature environment of 45-75 DEG C, and the cycle life of the battery is doubled in comparison with that of an existing battery.
Description
Technical field
The present invention relates to a kind of high temperature resistant lead-acid battery negative pole active substance and preparation method, belong to lead acid accumulator and make field.
Background technology
Along with communication, energy storage field development, valve-control sealed lead acid battery is more and more applied in hot environment, such as areas such as the base station of city roof, the telecommunications repeater, rural area of south China, outdoor wind and solar energy stored energy application and Africa, the Middle East.The valve-control sealed lead acid battery that prior art is produced is applied in above-mentioned hot environment, cycle life can reduce more than 50%, can be over 2 years, reason is mainly that existing lead-acid battery negative pole active substance can only adapt under normal temperature environment and uses, in hot environment, use to exist and accelerate dehydration and corrosion phenomenon, cause battery rapid failure, therefore develop the key that a kind of negative electrode active material that is adapted at using in hot environment just becomes the high temperature resistant lead acid accumulator of exploitation.
Summary of the invention
The object of the invention is to overcome the poor defect of existing lead acid accumulator high-temperature behavior, a kind of lead-acid battery negative pole active substance that is adapted to use under hot environment and preparation method are provided.
Technical scheme of the present invention is: a kind of high temperature resistant lead-acid battery negative pole active substance, comprise lead powder, binding agent, sulfuric acid, deionized water, barium sulfate, lignin, its improvements are to contain high temperature additive in this negative electrode active material, the component of described high temperature additive and mass percentage content are: aero oil 13%～16%, indulin 19%～22%, anisaldehyde 16%～19%, graphite powder 26%～29%, humic acid 18%～22%, in described negative electrode active material, the mass percentage content of each component is: lead powder 78%～80%, binding agent 0.1%～0.2%, density is the sulfuric acid 8%～9% of 1.3～1.4g/ml, deionized water 10%～11%, barium sulfate 0.6%～0.7%, lignin 0.1%～0.2%, high temperature additive 1.0%～1.5%.
In described high temperature additive, the mass percentage content of each component is preferably: aero oil 14%～15%, indulin 20%～21%, anisaldehyde 17%～18%, graphite powder 27%～28%, humic acid 19%～21%.
The preparation method of above-mentioned high temperature resistant lead-acid battery negative pole active substance is that operation is as follows:
(1) aero oil, indulin, anisaldehyde, graphite powder and humic acid is mixed in proportion, after fully stirring, make high temperature resistant additive;
(2) in proportion, lead powder, binding agent, barium sulfate, lignin and high temperature additive are mixed, under dry state, fully stir 10～15 minutes, in 6～8 minutes, at the uniform velocity add subsequently deionized water, stir while adding, after water injection, continue to stir 8～10 minutes, then to add density be the sulfuric acid of 1.3～1.4g/ml, the acid adding time is 19～20 minutes, after acid adding, continue to stir 10～12 minutes, make lead plaster; Be 65～75 ℃ with controlling temperature in cream process, while going out cream, temperature is 55～60 ℃.
The present invention is owing to adding specific high temperature additive, and to comprising that each component of high temperature additive has strict restriction, proportioning is scientific and reasonable, perfect technology standard, the negative electrode active material of making like this makes battery dehydration and corrosion be reduced to 1/2 of existing battery, under 45-75 ℃ of hot environment, use, the battery life that cycle life is produced than prior art doubles left and right.
Embodiment
Below by embodiment and Experimental Comparison, further illustrate the present invention.
One, embodiment
In embodiment 1,2, negative electrode active material of the present invention and mass percentage content are in Table 1, and wherein the component of high temperature additive and mass percentage content are in Table 2.
Table 1
Table 2
The preparation method of embodiment 1,2 is: (1) is mixed in table 2 ratio by aero oil, indulin, anisaldehyde, KS15 graphite powder and humic acid, after fully stirring, makes high temperature resistant additive; (2) in table 1 ratio, lead powder, binding agent, barium sulfate, lignin and high temperature additive are mixed, under dry state, stir 12 minutes (example 1), 13 minutes (example 2), subsequently in 6 minutes (example 1), in 8 minutes (example 2) at the uniform velocity add deionized water, stir while adding, after water injection after, continue to stir 8 minutes (example 1), 10 minutes (examples 2), adding density is the sulfuric acid of 1.3～1.4g/ml again, and the acid adding time is 19 minutes (example 1), 11 minutes (example 2), makes lead plaster; Be 70 ℃ with controlling temperature in cream process, while going out cream, temperature is 58 ℃.
Two, Experimental Comparison
1, battery preparation
The negative electrode active material providing according to the embodiment of the present invention, makes pole plate assembling making GFMJ-500 valve-control sealed lead acid battery with common process.Example one is made each 24, sample battery with example two, and with 10hr calculation of capacity, prepared battery positive electrode active material dry weight is 15.5g/Ah, and negative electrode active material dry weight is 10.8g/Ah.Be ± the 8g of Weight control tolerance of the active material of preparation, design capacity tolerance is 40min.Injection density 1.240g/ml(25 ℃) sulfuric acid, employing is internalized into four and fills three and put standard, change into after end, standing 48 hours, in 48 batteries making from example 1 and example 2, randomly draw each 6 and carry out respectively cycling life test under hot environment, the valve-control sealed lead acid battery of simultaneously inspecting original technology production by random samples contrasts detection, the 12V100A storage battery circulating inspector that checkout equipment adopts Zhangjiagang Jin Fan Electrosource, Inc. to produce.
2, cycling life test under hot environment
Cycle life method of testing: in 75 ℃ of environment, with constant voltage 14.1V, current limliting 75A charging 16h, then take constant current 50A and be discharged to final voltage 11.0V as a circulation, when the discharge capacity of whole Battery pack lower than rated capacity 80% time, end-of-life.
(1) capacity attenuation speed
The battery pack that example one is produced circulates first 20 times, discharge capacity is steady, the 20th discharge capacity is initial capacity 100.3%, while being circulated to the 200th time, discharge capacity is 99.7% of initial capacity, the battery pack that example two is produced circulates first 20 times, discharge capacity rises gradually, the 20th discharge capacity is initial capacity 103.5%, while being circulated to the 200th time, discharge capacity is 100.3% of initial capacity, and discharge capacity is initial capacity during the circulating battery to that original technology is produced 200 times 93.5%, the battery that the cell decay speed that this patent is produced is obviously produced than original technology is little.
(2) capacity circulating number of times
When two groups of sample battery cycle lifes stop, the circulating battery number of times that example 1 is made is 1007 times, and the circulating battery number of times that example 2 is made is 1091 times, and the battery cycle life that original technology is produced only has left and right 500 times, and the life-span improves greatly.
From above-mentioned result of the test, can illustrate, adopt negative electrode active material provided by the invention, can improve cycle life performance under battery high-temperature environment.
Claims (3)
1. a high temperature resistant lead-acid battery negative pole active substance, comprise lead powder, binding agent, sulfuric acid, deionized water, barium sulfate, lignin, it is characterized in that containing high temperature additive in this negative electrode active material, the component of described high temperature additive and mass percentage content are: aero oil 13%～16%, indulin 19%～22%, anisaldehyde 16%～19%, graphite powder 26%～29%, humic acid 18%～22%, in described negative electrode active material, the mass percentage content of each component is: lead powder 78%～80%, binding agent 0.1%～0.2%, density is the sulfuric acid 8%～9% of 1.3～1.4g/ml, deionized water 10%～11%, barium sulfate 0.6%～0.7%, lignin 0.1%～0.2%, high temperature additive 1.0%～1.5%.
2. high temperature resistant lead-acid battery negative pole active substance according to claim 1, is characterized in that, in described high temperature additive, the mass percentage content of each component is: aero oil 14%～15%, indulin 20%～21%, anisaldehyde 17%～18%, graphite powder 27%～28%, humic acid 19%～21%.
3. a preparation method for high temperature resistant lead-acid battery negative pole active substance as claimed in claim 1, is characterized in that operation is as follows:
(1) aero oil, indulin, anisaldehyde, graphite powder and humic acid is mixed in proportion, after fully stirring, make high temperature additive;
(2) in proportion, lead powder, binding agent, barium sulfate, lignin and high temperature additive are mixed, under dry state, fully stir 10～15 minutes, in 6～8 minutes, at the uniform velocity add subsequently deionized water, stir while adding, after water injection, continue to stir 8～10 minutes, then to add density be the sulfuric acid of 1.3～1.4g/ml, the acid adding time is 19～20 minutes, after acid adding, continue to stir 10～12 minutes, make lead plaster; Be 65～75 ℃ with controlling temperature in cream process, while going out cream, temperature is 55～60 ℃.
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN103337667A (en) * | 2013-06-26 | 2013-10-02 | 双登集团股份有限公司 | Negative pole active material, positive pole active material and electrolyte solution of valve-regulated lead acid battery |
| CN103594738B (en) * | 2013-12-12 | 2015-12-02 | 湖南丰日电源电气股份有限公司 | A kind of high temperature valve controlled sealed lead-acid accumulator |
| CN103618082A (en) * | 2013-12-12 | 2014-03-05 | 湖南丰日电源电气股份有限公司 | Negative active substance for valve regulated sealed lead-acid battery used at high temperature |
| WO2018199125A1 (en) * | 2017-04-28 | 2018-11-01 | 株式会社Ｇｓユアサ | Lead acid battery |
| CN109546097A (en) * | 2018-09-29 | 2019-03-29 | 骆驼集团蓄电池研究院有限公司 | A kind of high rate lead-acid accumulator negative pole lead paste, cell negative plate and the height of recharging recharges rate lead-acid accumulator |
| CN110233245A (en) * | 2019-04-23 | 2019-09-13 | 旭派电源有限公司 | A kind of lead carbon battery cathode assists the preparation method of agent prescription and cathode |
| CN112086646B (en) * | 2020-10-12 | 2022-01-07 | 天能集团（河南）能源科技有限公司 | High-temperature-resistant lead-acid storage battery and preparation method thereof |
| CN113437255A (en) * | 2021-05-26 | 2021-09-24 | 浙江南都电源动力股份有限公司 | Low-temperature negative pole piece and preparation method thereof |
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| JP2004281197A (en) * | 2003-03-14 | 2004-10-07 | Matsushita Electric Ind Co Ltd | Lead acid storage battery |
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