CN103008653B - Carbon coated lead composite material and preparation method thereof - Google Patents
Carbon coated lead composite material and preparation method thereof Download PDFInfo
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- CN103008653B CN103008653B CN201210588414.1A CN201210588414A CN103008653B CN 103008653 B CN103008653 B CN 103008653B CN 201210588414 A CN201210588414 A CN 201210588414A CN 103008653 B CN103008653 B CN 103008653B
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Abstract
The invention discloses a carbon coated lead composite material and a preparation method thereof. The carbon coated lead composite material is a spherical material with a shell and core structure; the outer shell of the spherical material is a carbon material and the inner core of the spherical material is a lead material; and by using simple raw materials, the carbon coated lead composite material is prepared according to a hydrothermal carbonization process. The dimension of the carbon coated lead composite material is 0.1-20 microns, and lead and carbon weight ratio of the carbon coated lead composite material is (20-80) : (80-20). The carbon coated lead composite material disclosed by the invention has the advantages as follows: the lead and the carbon are closely combined; when being used as a super battery active carbon additive, the carbon coated lead composite material can be more uniformly mixed together with the Pb powder; problems that active carbon materials are separated out, cathode active substances are peeled off and so on in the battery recycling process can be avoided; and through the close combination of the lead and the carbon, hydrogen evolution phenomenon of the carbon material can be also suppressed to a certain degree.
Description
Technical field
The invention belongs to active carbon hybrid material field, be specifically related to the preparation method of the coated lead composite material of a kind of charcoal.
Background technology
It is fast-developing that energy crisis and Environment Protection Policy are constantly promoting new energy technology.Ultracapacitor is also called electrochemical capacitor or double layer capacitor, is a kind of novel energy-storing device with more high power density and energy density.Ultracapacitor has that long service life, adaptive capacity to environment are strong, efficiency for charge-discharge advantages of higher.Have passed through the development of nearly 30 years, supercapacitor technologies makes great progress, and particularly constantly makes a breakthrough in high-specific surface area, large specific capacity active carbon.But because the cost of ultracapacitor is still very high, and energy density is always low than secondary cell, and needing the application of high-energy-density, superbattery only can play the part of miscellaneous function, plays cushioning effect, or plays the effect of supplementary peak point current.Battery and ultracapacitor cut both ways, and in order to integrate both advantages, i.e. " superbattery " researcher is attempting the mixture of both inventions.The main feature of superbattery is: cost is low, energy density is high, energy storage amount is large, service life cycle is long, adaptive capacity to environment is strong.Ultracapacitor is mixed with traditional lead acid batteries, the advantage of price and performance can better be embodied, thus in traditional application of lead-acid accumulator, and new electrokinetic cell application obtains better development space.
NPHaigh etc. are studied plumbous charcoal superbattery.So-called superbattery, the parallel connection outside of ultracapacitor and lead-acid battery is used evolve as " inside also ", by the high-specific-power of double layer capacitor, long-life blend of predominance in lead-acid battery, while maintenance " outward also " improves power, extending battery life advantage, circuit can be simplified again, improve specific energy, and reduce total cost.LTLam etc. are with PbO
2for the mixture of positive pole, Pb and active carbon (AC) is negative pole, devise a kind of current collection container and lead-acid battery in the plumbic acid capacitance device of one, power density is higher but with low cost.Although the research report both at home and abroad about superbattery all shows that superbattery is the very promising power supply new technology of one, the exploitation of superbattery still runs into very large challenge.Simply mixed as negative material with active carbon by Pb, although can embody some superbattery function in a short time, as large current density electrical characteristics, because active carbon after circulating for a long time is separated out, peeled off, cause negative pole efflorescence, cycle life is deteriorated.In addition, because the heavy dose of active carbon is added, cause negative pole liberation of hydrogen to aggravate, battery dehydration is serious.Therefore the complex technique of plumbous Carbon Materials is still the key of restriction superbattery technology.
Summary of the invention
The object of the invention is to overcome the performance deficiency that existing activated carbon for super capacitors is applied in superbattery, propose coated lead composite material of a kind of charcoal and preparation method thereof.This plumbous carbon composite is by hydro-thermal, charring process preparation, and method is simply convenient to mass production.This plumbous carbon composite has core-shell structure, and shell is active carbon, kernel is plumbous and lead oxide.The special plumbous charcoal combined state of the coated lead of this charcoal, makes Carbon Materials have more stable bonding state in circulating battery process, can not cause coming off of the precipitation of Carbon Materials and negative electrode active material.And the combination of plumbous charcoal can suppress the hydrogen evolution phenomenon that produces due to the introducing of Carbon Materials to a certain extent.This plumbous carbon composite can mix with cathode lead plaster as active material additive, adapts to the manufacturing process that lead-acid accumulator is traditional.
Object of the present invention can be reached by following measures:
The coated lead composite material of a kind of charcoal, it is characterized in that the coated lead composite material of this charcoal is ball-type core-shell structure, shell is charcoal, core is plumbous and lead oxide, by hydro-thermal, charring process preparation, particle diameter is 0.05 ~ 20 micron, and nucleocapsid weight ratio is (20 ~ 80): (80 ~ 20).
Further, nucleocapsid weight ratio is: (20 ~ 70): (80 ~ 30).
Further, the particle diameter of the coated lead composite material of described charcoal is 0.1 ~ 20 micron.
The preparation method of the coated lead composite material of above-mentioned charcoal, is characterized in that comprising the following steps:
(1) lead salt is dissolved in deionized water, is designated as solution A;
(2) alkali is dissolved in deionized water, is designated as solution B;
(3) be added drop-wise in solution A by solution B, stir 2 ~ 3h, then proceed to hydrothermal reaction kettle, at 160 ~ 200 DEG C of isothermal reaction 10 ~ 12h, removing supernatant liquor, obtains product C;
(4) organic carbon source is dissolved in deionized water, slowly add in reactor, stir 2 ~ 3h, then at 180 ~ 220 DEG C of reaction under high pressure 10 ~ 12h, product is filtered, filter residue deionized water and ethanol is washed respectively, 80 ~ 90 DEG C of vacuum drying 6 ~ 8h, obtain product D, the weight ratio of lead salt and organic carbon source is 1:(0.1 ~ 3);
(5) by product D at 400 ~ 600 DEG C, under an argon atmosphere constant temperature charing 3 ~ 8h, naturally cool after obtain the coated lead composite material of product charcoal.
Further, described lead salt is lead acetate, plumbi nitras or its mixture.
Further, described alkali is NaOH, potassium hydroxide or its mixture.
Further, the weight ratio of described lead salt consumption and alkali consumption is (5 ~ 20): (2 ~ 5).
Further, described organic carbon source is selected from glucose, sucrose, polysorbate60, polyvinylpyrrolidone or starch.
The present invention has prepared a kind of novel plumbous carbon composite by hydro-thermal, charring process, and this composite has core-shell structure, and the charcoal of shell and the lead of kernel and lead oxide have good bonding state and stability.Because this coated combination not give only Carbon Materials and the close density of Pb, Carbon Materials is obtained when mixing with Pb powder and better mixes dispersity, and can ensure that Carbon Materials is not separated out in circulating battery process, do not cause negative electrode active material to come off.The bonding state that plumbous charcoal is good also can be good at suppressing the hydrogen evolution phenomenon caused by Carbon Materials.The coated lead composite material of the charcoal that the present invention develops is particularly suitable for the Carbon Materials additive as superbattery.
Accompanying drawing explanation
The scanning electron micrographs of the plumbous carbon composite of Fig. 1 prepared by embodiment 1.
Scanning electron microscopy-power spectrum the picture of the plumbous carbon composite of Fig. 2 prepared by embodiment 1.
The thermogravimetric curve in air atmosphere of the plumbous carbon composite of Fig. 3 prepared by embodiment 1.
The scanning electron micrographs of the plumbous carbon composite of Fig. 4 prepared by embodiment 2.
Detailed description of the invention
Below by embodiment, illustrate outstanding feature of the present invention and obviously progress further, be only implementation content of the present invention is described and is not limited to the present invention.
Embodiment 1
(1) taking 5g lead acetate is dissolved in the deionized water of 30mL, is designated as solution A.
(2) taking 2gNaOH is dissolved in the deionized water of 50mL, is designated as solution B.
(3) per minute be added drop-wise in A by B with 20, magnetic agitation 2h, then proceeds to 100mL hydrothermal reaction kettle, and at 160 DEG C of isothermal reaction 12h, removing supernatant, obtains product C.
(4) taking 0.5g polyvinylpyrrolidone is dissolved in 70mL deionized water, slowly adds in reactor, magnetic agitation 2h, then at 180 DEG C of temperature reaction 12h, product is filtered, filter residue deionized water and ethanol are washed repeatedly respectively, 80 DEG C of vacuum drying 6h, obtain product D.
(5) by D, at 400 DEG C, under Ar gas atmosphere, constant temperature carbonizes 3h, naturally obtains the coated lead composite material of product charcoal after cooling.
As shown in Figure 1, 2, the particle size of the coated lead composite material of charcoal is about 5 microns to product microscopic appearance, is shown by the energy spectrum analysis of Fig. 2, and composite mainly contains lead, lead oxide and charcoal three kinds of components.As shown in Figure 3, the remaining rate of the weight at 800 DEG C is 69.8% to product thermal weight loss situation in air atmosphere, shows that this product nucleocapsid weight ratio is 30.2:69.8.
Embodiment 2
(1) taking 20g plumbi nitras is dissolved in the deionized water of 30mL, is designated as solution A.
(2) taking 5g KOH is dissolved in the deionized water of 50mL, is designated as solution B.
(3) per minute be added drop-wise in A by B with 20, magnetic agitation 3h, then proceeds to 100mL hydrothermal reaction kettle, and at 200 DEG C of isothermal reaction 10h, removing supernatant, obtains product C.
(4) taking 60g sucrose is dissolved in 70mL deionized water, slowly adds in reactor, magnetic agitation 3h, and then at 220 DEG C of temperature reaction 10h, filtered by product, wash respectively repeatedly filter residue deionized water and ethanol, 80 DEG C of vacuum drying 8h, obtain product D.
(5) by D, at 600 DEG C, under Ar gas atmosphere, constant temperature carbonizes 8h, naturally obtains the coated lead composite material of product charcoal after cooling.
As shown in Figure 4, the particle size of the coated lead composite material of charcoal is about 0.5 ~ 15 micron to product microscopic appearance, and thermogravimetric analysis shows shell nuclear weight than being 18.9:81.1.
Embodiment 3
(1) take 6g plumbi nitras, 8g lead acetate is dissolved in the deionized water of 30mL, be designated as solution A.
(2) take 3g KOH, 2g NaOH is dissolved in the deionized water of 50mL, be designated as solution B.
(3) per minute be added drop-wise in A by B with 20, magnetic agitation 2.5h, then proceeds to 100mL hydrothermal reaction kettle, and at 190 DEG C of isothermal reaction 11h, removing supernatant, obtains product C.
(4) taking 28g glucose is dissolved in 70mL deionized water, slowly adds in reactor, magnetic agitation 2.5h, then at 200 DEG C of temperature reaction 11h, product is filtered, filter residue deionized water and ethanol are washed repeatedly respectively, 90 DEG C of vacuum drying 7h, obtain product D.
(5) by D, at 500 DEG C, under Ar gas atmosphere, constant temperature carbonizes 6h, naturally obtains the coated lead composite material of product charcoal after cooling.
Product Morphology analysis shows, the particle size of the coated lead composite material of charcoal is about 0.2 ~ 15 micron, and thermogravimetric analysis shows its shell nuclear weight than being 39.1:60.9.
Embodiment 4
(1) take 10g plumbi nitras, 10g lead acetate is dissolved in the deionized water of 30mL, be designated as solution A.
(2) take 1g KOH, 1g NaOH is dissolved in the deionized water of 50mL, be designated as solution B.
(3) per minute be added drop-wise in A by B with 20, magnetic agitation 2h, then proceeds to 100mL hydrothermal reaction kettle, and at 170 DEG C of isothermal reaction 12h, removing supernatant, obtains product C.
(4) taking 12g polysorbate60 is dissolved in 70mL deionized water, slowly adds in reactor, magnetic agitation 2h, and then at 210 DEG C of temperature reaction 12h, filtered by product, wash respectively repeatedly filter residue deionized water and ethanol, 85 DEG C of vacuum drying 6h, obtain product D.
(5) by D, at 550 DEG C, under Ar gas atmosphere, constant temperature carbonizes 7h, naturally obtains the coated lead composite material of product charcoal after cooling.
Product Morphology analysis shows, the particle size of the coated lead composite material of charcoal is about 0.5 ~ 12 micron, and thermogravimetric analysis shows its shell nuclear weight than being 42.1:57.9.
Claims (5)
1. the preparation method of the coated lead composite material of charcoal, the coated lead composite material of this charcoal is ball-type core-shell structure, shell is charcoal, core is plumbous and lead oxide, by hydro-thermal, charring process preparation, particle diameter is 0.05 ~ 20 micron, and nucleocapsid weight ratio is (20 ~ 80): (80 ~ 20) is characterized in that comprising the following steps:
(1) lead salt is dissolved in deionized water, is designated as solution A;
(2) alkali is dissolved in deionized water, is designated as solution B;
(3) be added drop-wise in solution A by solution B, stir 2 ~ 3h, then proceed to hydrothermal reaction kettle, at 160 ~ 200 DEG C of isothermal reaction 10 ~ 12h, removing supernatant liquor, obtains product C;
(4) organic carbon source is dissolved in deionized water, slowly add in reactor, stir 2 ~ 3h, then at 180 ~ 220 DEG C of reaction under high pressure 10 ~ 12h, product is filtered, filter residue deionized water and ethanol is washed respectively, 80 ~ 90 DEG C of vacuum drying 6 ~ 8h, obtain product D, the weight ratio of lead salt and organic carbon source is 1:(0.1 ~ 3);
(5) by product D at 400 ~ 600 DEG C, under an argon atmosphere constant temperature charing 3 ~ 8h, naturally cool after obtain the coated lead composite material of product charcoal.
2. the preparation method of the coated lead composite material of charcoal according to claim 1, is characterized in that described lead salt is lead acetate, plumbi nitras or its mixture.
3. the preparation method of the coated lead composite material of charcoal according to claim 1, is characterized in that described alkali is NaOH, potassium hydroxide or its mixture.
4. the preparation method of the coated lead composite material of charcoal according to claim 1, is characterized in that the weight ratio of described lead salt consumption and alkali consumption is for (5 ~ 20): (2 ~ 5).
5. the preparation method of the coated lead composite material of charcoal according to claim 1, is characterized in that described organic carbon source is selected from glucose, sucrose, polysorbate60, polyvinylpyrrolidone or starch.
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| CN104393250B (en) * | 2014-10-22 | 2017-06-13 | 南京航空航天大学 | The lead-acid battery preparation method and composite negative plate of lead carbon composite |
| CN106684378B (en) * | 2016-12-20 | 2019-07-09 | 华南师范大学 | A kind of lead charcoal composite particles and preparation method thereof |
| CN110480004B (en) * | 2019-08-29 | 2021-11-09 | 南京理工大学 | Method for preparing carbon-coated nano aluminum powder by hydrothermal method |
| CN111370652B (en) * | 2020-02-26 | 2021-08-17 | 天能电池集团股份有限公司 | Lead storage battery negative plate for starting motorcycle and preparation method thereof |
| CN111515409B (en) * | 2020-04-08 | 2022-09-06 | 大连理工大学 | Preparation method of carbon-coated magnetic nickel-cobalt core-shell structure microspheres |
| CN112670505B (en) * | 2020-10-28 | 2022-03-29 | 浙江工业大学 | Preparation method and application method of lead-carbon battery negative electrode additive material |
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| CN1501530A (en) * | 2002-11-19 | 2004-06-02 | 比亚迪股份有限公司 | Lead dioxide coated carbon material, making method and zinc-nickel battery containing the same |
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| CN102050437A (en) * | 2009-10-29 | 2011-05-11 | 上海比亚迪有限公司 | Carbon composite material, and preparation method and application thereof |
| CN102148351A (en) * | 2010-02-06 | 2011-08-10 | 清华大学 | Preparation method for electrode material of lithium battery |
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| CN1501530A (en) * | 2002-11-19 | 2004-06-02 | 比亚迪股份有限公司 | Lead dioxide coated carbon material, making method and zinc-nickel battery containing the same |
| JP2007311180A (en) * | 2006-05-18 | 2007-11-29 | Teijin Ltd | Negative electrode for lithium secondary battery, and its manufacturing method |
| CN101494286A (en) * | 2007-12-04 | 2009-07-29 | 法拉赛斯能源公司 | Secondary battery material |
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