CN101246961A - Anode material of lead-acid battery and its production method - Google Patents
Anode material of lead-acid battery and its production method Download PDFInfo
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- CN101246961A CN101246961A CNA2008100599370A CN200810059937A CN101246961A CN 101246961 A CN101246961 A CN 101246961A CN A2008100599370 A CNA2008100599370 A CN A2008100599370A CN 200810059937 A CN200810059937 A CN 200810059937A CN 101246961 A CN101246961 A CN 101246961A
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Abstract
The present invention discloses an anode material of lead-acid battery, the components and weight percentage content are: 0.2-2% of carbon nano-tube, 0.2-2% of polyacrylonitrile short fiber, 60-90% of PbO<SUB>2</SUB>, others is ceruse. Graphitized process carbon nano-tube as anode additive, not only resists rigor corruption of electrochemical circumstance in lead-acid battery, adds specific surface area of anode active material, enhance charge and discharge capability of electrode, improves circle capability, enhances formation efficiency, but also improve the utilization rate of active material and discharging capacity of lead-acid battery. In the conditions of 0.5c-10c current, the utilization rate of active material can be improved of 15-25%. The present invention has simple technique, low cost and is suitable for large-scare production and application.
Description
Technical field
The present invention relates to positive electrode of lead accumulator and preparation method thereof.
Background technology
At present both at home and abroad the consistent difficult problem of thinking that lead accumulator exists of lead accumulator academic research community mainly shows: active material utilization low (just very 30-35%, negative pole is 40-45%), battery specific energy low (generally at 30-35wh/kg).For reducing positive electrode resistance and improving positive electrode active material utilization, amorphous carbon occurred in recent years, graphite etc. are as additive.Though these interpolations have shown good performance at the battery circulation initial stage, because the inner harsh applied environment of lead accumulator has just lost effect along with the carrying out of circulating is very fast.A lot of to the anode additive research of lead accumulator at present: Baker has proposed his view (R.T.K.Baker to the interpolation mechanism of graphite, M.A.Barber, P.S.Barber, P.S.Harris, F.S.Feates, R.J.Waite.Nucleation and growth of carbon deposits from the nickel catalyzeddecomposition of acetylene.J.Catal., 1972,26:51), think that the interpolation of graphite causes osmotic pressure, the interpolation of graphite can improve the wetting characteristics of sulfuric acid to active material, has increased diffusion depth, thereby has improved the discharge performance of battery.Open heart Buddhist and think and add the big electric current output performance that " carbon sol " made under the certain process conditions of people can improve positive plate in right amount in the lead accumulator anode diachylon, help battery discharge.(open heart Buddhist, Wu Jishu, Zhong Dingshou, good fortune is established virtue, experiment of lead paste additive for lead-acid battery, battery industry, 2005,10 (2) 67-69)
New carbon such as CNT (carbon nano-tube), carbon nano-fiber has been the focus of international field of new research since being found always.In addition, carbon nano-tube is owing to its high strength, big specific surface and draw ratio and quantum scale effect, at superpower composite material, Electrophotosensitive and luminescent material, fields such as energy storage material have potential widely using value, have become one of research focus of current material science.
The good toughness of carbon nano-tube, Stability Analysis of Structures, having minimum yardstick and excellent mechanical property, is that desirable 1-dimention nano strengthens, toughening material.The directed electric conductivity excellence of carbon nano-tube can be served as good additive in electrochemical material.
The carbon nanotubes layer becomes clad structure, has excellent conducting performance and corrosion resistance.It will have very big meaning to the raising of the positive electrode utilance of lead accumulator as the anode additive material of lead accumulator.
Summary of the invention
The purpose of this invention is to provide a kind of anode material of lead-acid battery that is beneficial to raising lead-acid battery electrode utilance and preparation method thereof.
Anode material of lead-acid battery of the present invention, its component and weight percent content thereof are:
Carbon nano-tube 0.2-2%,
Orlon 0.2-2%,
PbO
260-90%, all the other are lead powder, and above-mentioned Orlon length is 5-15mm, and diameter is the 20-200 micron.
The preparation method of anode material of lead-acid battery may further comprise the steps:
1) concentrated sulfuric acid and red fuming nitric acid (RFNA) are pressed mass ratio mixed in 1: 1～10: 1, add dispersant and carbon nano-tube then and mix the ultrasonic 0.5～3h in back, add deionized water dilution suction filtration to neutral, 60～120 ℃ of baking 5～20h, obtain nitration mixture sonicated carbon nano-tube, to place quartz boat through the carbon nano-tube of nitration mixture sonicated again, under nitrogen atmosphere protection in 800～1200 ℃, insulation 8～12h, cool off with stove, obtain the graphitization processing carbon nano-tube, wherein dispersant is 0.1～1% of the concentrated sulfuric acid and a red fuming nitric acid (RFNA) gross mass, and CNT (carbon nano-tube) is 1～5% of the concentrated sulfuric acid and a red fuming nitric acid (RFNA) gross mass;
2) with Orlon and PbO
2Powder and lead powder mixed by mass ratio in 0.02: 5.98: 4～0.2: 9.3: 0.5;
3) with graphitization processing carbon nano-tube and step 2) mixture mix 1～5h by 0.2: 99.8～2: 98 ball millings of mass ratio, obtain anode material of lead-acid battery.
Above-mentioned dispersant can adopt neopelex, polyvinyl alcohol or sodium carboxymethyl.
More even for ball milling is mixed, can be in above-mentioned steps 3) when ball milling mixes, drip the 1-5ml absolute ethyl alcohol.
Advantage of the present invention is:
1) low temperature graphitization was handled carbon nano-tube not only can be resisted harsh electrochemical environment in the lead acid accumulator as additive corrosion during lead accumulator used, increase the specific area of positive active material, the charging and discharging capabilities of intensifier electrode, improve its cycle performance, improve formation efficiency, and can improve the discharge capacity of active material utilization and lead accumulator.Under the 0.5c-10c current conditions, the active material utilization in simulated battery can improve 15%-20%.
2) preparation technology is simple, and is with low cost, is suitable for large-scale production and application.
3) applied widely, the lead accumulator that can be used for various uses and model is in order to improve the utilance of electrode material.
4) low temperature graphitization is handled the more complete rule of its structure afterwards in the carbon nano-tube process, helps the carrying out of electrochemical reaction, improves active material utilization.
Description of drawings
Fig. 1 is the active material utilization curve of electrode.Wherein, curve 1 has added the graphitization processing carbon nano-tube, and curve 2 does not add carbon nano-tube.
Embodiment
Embodiment 1
1) the 50g concentrated sulfuric acid and 25g red fuming nitric acid (RFNA) are mixed, add 0.1g neopelex and 0.1g carbon nano-tube then and mix the ultrasonic 1h in back, add deionized water dilution suction filtration to neutral, 60 ℃ of baking 8h obtain nitration mixture sonicated carbon nano-tube; To place diameter through the carbon nano-tube of nitration mixture sonicated again is the 100mm quartz boat, and in 800 ℃, insulation 8h with the stove cooling, obtains middle low temperature graphitization and handles carbon nano-tube under nitrogen atmosphere protection.
2) with 0.1g short fiber and 35g PbO
2Powder and 14.9g lead powder mix.
3) middle low temperature graphitization is handled carbon nano-tube and step 2) mixture be 1: 99 agate jar of packing into by mass ratio, drip the 3ml absolute ethyl alcohol therein, rotating speed 200r/min ball milling mixing 2h, obtaining apparent density is 3.8g/cm
3Anode material of lead-acid battery.Carbon nanotubes 1% in this anode material of lead-acid battery, Orlon 0.2%, PbO
270%, all the other are lead powder.
The positive electrode that utilizes this example to make prepares test electrode and tests.At electric current is that active principle utilance under the 0.5c condition is seen 1 a of Fig. 1 curve, records this electrode than the electrode material utilization of not adding carbon nano-tube and improves 16.85%.
1) the 40g concentrated sulfuric acid and 10g red fuming nitric acid (RFNA) are mixed, add 0.12g polyvinyl alcohol and 0.1g carbon nano-tube then and mix the ultrasonic 0.5h in back, add deionized water dilution suction filtration to neutral, 80 ℃ of baking 10h obtain nitration mixture sonicated carbon nano-tube; To place diameter through the carbon nano-tube of nitration mixture sonicated again is the 100mm quartz boat, and in 900 ℃, insulation 10h with the stove cooling, obtains the graphitization processing carbon nano-tube under nitrogen atmosphere protection.
2) with 1g short fiber and 45g PbO
2Powder and 4g lead powder mix.
3) middle low temperature graphitization is handled carbon nano-tube and step 2) mixture be 0.2: 99.8 agate jar of packing into by mass ratio, Dropwise 5 ml absolute ethyl alcohol therein, rotating speed 200r/min ball milling mixing 3h, obtaining apparent density is 3.8g/cm
3Anode material of lead-acid battery.Carbon nanotubes 0.2% in this anode material of lead-acid battery, Orlon 2%, PbO
290%, all the other are lead powder.
The positive electrode that utilizes this example to make prepares test electrode and tests.At electric current is that active principle utilance under the 1.5c condition is seen 1 b of Fig. 1 curve, records this electrode than the electrode material utilization of not adding carbon nano-tube and improves 15.22%.
Embodiment 3
1) the 50g concentrated sulfuric acid and 50g red fuming nitric acid (RFNA) are mixed, add 0.2g neopelex and 0.4g carbon nano-tube then and mix the ultrasonic 2h in back, add deionized water dilution suction filtration to neutral, 100 ℃ of baking 12h obtain nitration mixture sonicated carbon nano-tube; To place diameter through the carbon nano-tube of nitration mixture sonicated again is the 100mm quartz boat, and in 1200 ℃, insulation 12h with the stove cooling, obtains the graphitization processing carbon nano-tube under nitrogen atmosphere protection.
2) with 0.5g short fiber and 30g PbO
2Powder and 19.5g lead powder mix.
3) middle low temperature graphitization is handled carbon nano-tube and step 2) mixture be 2: 98 agate jars of packing into by mass ratio, drip the 4ml absolute ethyl alcohol therein, rotating speed 400r/min ball milling mixing 1h, obtaining apparent density is 4.3g/cm
3Anode material of lead-acid battery.Carbon nanotubes 2% in this anode material of lead-acid battery, Orlon 1%, PbO
260%, all the other are lead powder.
The positive electrode that utilizes this example to make prepares test electrode and tests.At electric current is that active principle utilance under the 3.5c condition is seen 1 c of Fig. 1 curve, records this electrode than the electrode material utilization of not adding carbon nano-tube and improves 20.07%.
Embodiment 4
1) the 80g concentrated sulfuric acid and 10g red fuming nitric acid (RFNA) are mixed, add 0.18g sodium carboxymethyl and 0.18g carbon nano-tube then and mix the ultrasonic 1.5h in back, add deionized water dilution suction filtration to neutral, 120 ℃ of baking 8h obtain nitration mixture sonicated carbon nano-tube; To place diameter through the carbon nano-tube of nitration mixture sonicated again is the 100mm quartz boat, and in 1200 ℃, insulation 10h with the stove cooling, obtains the graphitization processing carbon nano-tube under nitrogen atmosphere protection.
2) with 0.5g short fiber and 35g PbO
2Powder and 14.5g lead powder mix.
3) middle low temperature graphitization is handled carbon nano-tube and step 2) mixture be 1.5: 98.5 agate jars of packing into by mass ratio, drip the 4ml absolute ethyl alcohol therein, rotating speed 350r/min ball milling mixing 1h, obtaining apparent density is 4.0g/cm
3Anode material of lead-acid battery.Carbon nanotubes 1.5% in this anode material of lead-acid battery, Orlon 1%, PbO
270%, all the other are lead powder.
The positive electrode that utilizes this example to make prepares test electrode and tests.At electric current is to record this electrode under the 10c condition to improve 17.37% than the electrode material utilization of not adding carbon nano-tube.
Claims (4)
1. anode material of lead-acid battery is characterized in that its component and weight percent content thereof are:
Carbon nano-tube 0.2-2%,
Orlon 0.2-2%,
PbO
260-90%, all the other are lead powder, and above-mentioned Orlon length is 5-15mm, and diameter is the 20-200 micron.
2. the preparation method of anode material of lead-acid battery according to claim 1 is characterized in that may further comprise the steps:
1) concentrated sulfuric acid and red fuming nitric acid (RFNA) are pressed mass ratio mixed in 1: 1～10: 1, add dispersant and carbon nano-tube then and mix the ultrasonic 0.5～3h in back, add deionized water dilution suction filtration to neutral, 60～120 ℃ of baking 5～20h, obtain nitration mixture sonicated carbon nano-tube, to place quartz boat through the carbon nano-tube of nitration mixture sonicated again, under nitrogen atmosphere protection in 800～1200 ℃, insulation 8～12h, cool off with stove, obtain the graphitization processing carbon nano-tube, wherein dispersant is 0.1～1% of the concentrated sulfuric acid and a red fuming nitric acid (RFNA) gross mass, and CNT (carbon nano-tube) is 1～5% of the concentrated sulfuric acid and a red fuming nitric acid (RFNA) gross mass;
2) with Orlon and PbO
2Powder and lead powder mixed by mass ratio in 0.02: 5.98: 4～0.2: 9.3: 0.5;
3) with graphitization processing carbon nano-tube and step 2) mixture mix 1～5h by 0.2: 99.8～2: 98 ball millings of mass ratio, obtain anode material of lead-acid battery.
3. the preparation method of anode material of lead-acid battery according to claim 2 is characterized in that said dispersant is neopelex, polyvinyl alcohol or sodium carboxymethyl.
4. the preparation method of anode material of lead-acid battery according to claim 2 when it is characterized in that the step 3) ball milling mixes, drips the 1-5ml absolute ethyl alcohol.
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| CNA2008100599370A CN101246961A (en) | 2008-03-04 | 2008-03-04 | Anode material of lead-acid battery and its production method |
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Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101771164A (en) * | 2010-03-05 | 2010-07-07 | 上海农新投资管理咨询有限公司 | Storage battery using carbon nano material to carry out fast charging and increase multiple electric capacity |
| CN101841029A (en) * | 2010-05-20 | 2010-09-22 | 江苏双登集团有限公司 | Cathode active material of lead-acid battery for UPS (Uninterruptible Power Supply) |
| WO2013011516A1 (en) * | 2011-07-20 | 2013-01-24 | Vulcan Automotive Industries Ltd | Funcionalized carbon nanotube composite for use in lead acid battery |
| CN103022427A (en) * | 2012-11-28 | 2013-04-03 | 上海锦众信息科技有限公司 | Method for preparing positive pole plate for 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 |
| CN109802099A (en) * | 2018-12-29 | 2019-05-24 | 河南中汇新材科技有限公司 | Merge the lead electrode production method and its lead-acid accumulator of silicon nitride |
| CN112635761A (en) * | 2019-09-24 | 2021-04-09 | 广隆光电科技股份有限公司 | Negative electrode lead paste composition of lead-acid battery, negative plate and lead-acid battery |
| CN114974923A (en) * | 2021-07-05 | 2022-08-30 | 上海派景新能源科技有限公司 | Electrode material for super capacitor and preparation method thereof |
-
2008
- 2008-03-04 CN CNA2008100599370A patent/CN101246961A/en active Pending
Cited By (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101771164A (en) * | 2010-03-05 | 2010-07-07 | 上海农新投资管理咨询有限公司 | Storage battery using carbon nano material to carry out fast charging and increase multiple electric capacity |
| CN101841029A (en) * | 2010-05-20 | 2010-09-22 | 江苏双登集团有限公司 | Cathode active material of lead-acid battery for UPS (Uninterruptible Power Supply) |
| WO2013011516A1 (en) * | 2011-07-20 | 2013-01-24 | Vulcan Automotive Industries Ltd | Funcionalized carbon nanotube composite for use in lead acid battery |
| US9413001B2 (en) | 2011-07-20 | 2016-08-09 | Bar Ilan University | Functionalized carbon nanotube composite |
| CN103022427A (en) * | 2012-11-28 | 2013-04-03 | 上海锦众信息科技有限公司 | Method for preparing positive pole plate for 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 |
| CN109802099A (en) * | 2018-12-29 | 2019-05-24 | 河南中汇新材科技有限公司 | Merge the lead electrode production method and its lead-acid accumulator of silicon nitride |
| CN109802099B (en) * | 2018-12-29 | 2022-11-29 | 河南诺兰特新材科技有限公司 | Method for manufacturing lead electrode fused with silicon nitride and lead-acid storage battery thereof |
| CN112635761A (en) * | 2019-09-24 | 2021-04-09 | 广隆光电科技股份有限公司 | Negative electrode lead paste composition of lead-acid battery, negative plate and lead-acid battery |
| CN114974923A (en) * | 2021-07-05 | 2022-08-30 | 上海派景新能源科技有限公司 | Electrode material for super capacitor and preparation method thereof |
| CN114974923B (en) * | 2021-07-05 | 2024-01-23 | 上海派景新能源科技有限公司 | Electrode material for super capacitor and preparation method thereof |
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Open date: 20080820 |