CN103296275A - Carbon-material-coated lead powder composite material and application thereof - Google Patents
Carbon-material-coated lead powder composite material and application thereof Download PDFInfo
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- CN103296275A CN103296275A CN2013102053314A CN201310205331A CN103296275A CN 103296275 A CN103296275 A CN 103296275A CN 2013102053314 A CN2013102053314 A CN 2013102053314A CN 201310205331 A CN201310205331 A CN 201310205331A CN 103296275 A CN103296275 A CN 103296275A
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Abstract
The invention discloses a carbon-material-coated lead powder composite material and an application thereof. The carbon-material-coated lead powder composite material is prepared by the following method: adding a carbon material, a thickening agent, a hydrogen evolution inhibiting agent, alcohol and de-ionized water into a reaction container; mixing uniformly and adding lead powder; carrying out ultrasonic dispersion and heating to remove water and alcohol so that the lead powder uniformly coats the carbon material; then utilizing a pipe type furnace to carry out sintering and carbonization under the protection of inert protection gas; and grinding and sieving to obtain the carbon-material-coated lead powder composite material. The composite material disclosed by the invention can be used as a cathode material of a lead-carbon super battery; a polar plate made of the carbon-material- coated lead powder composite material is good in mechanical strength; and meanwhile, the uniformity of the mixture of the carbon material and the lead powder can be effectively guaranteed; and the charging/discharging performance, the power density, the specific capacity and the cycle life of the battery which takes the composite material as the cathode material are improved to some extent.
Description
Technical field
The present invention relates to that a kind of material with carbon element coats the lead powder composite material and as the application of the negative material of plumbous carbon superbattery.
Background technology
Lead acid accumulator is in the historical development course in more than 100 years; all made great contribution in many application facet; especially in recent years environmental pollution and energy crisis propose new requirement to traditional energy; lead-acid battery is because relative cleaning, low in the pollution of the environment has obtained very big application in all fields.But its power density is not high, the drawbacks limit that cycle life is long its development.Particularly since battery under the part state-of-charge during high-multiplying power discharge, lead sulfate on negative pole constantly accumulation cause the negative pole sulfation, thereby cause lead acid accumulator cycle life far below its potential life-span.So will carry out modification to lead-acid battery, improve its power density, charge-discharge performance and cycle performance.
Ultracapacitor is a kind of novel energy storage device, characteristics such as have high power density, fast charging and discharging, have extended cycle life, but the relative battery of its energy density is lower, so with the use that is together in parallel of lead-acid battery and ultracapacitor, both learn from other's strong points to offset one's weaknesses, remedy shortcoming separately, performance advantage each other.
Superbattery is a kind of novel battery that ultracapacitor is combined with lead-acid battery, and it is that the pole plate of ultracapacitor and lead-acid battery is directly in parallel, the advantage of the capacitor of electric double layer can be fused in the lead-acid battery like this.Patent CN 101123139A discloses a kind of preparation method of superbattery, when changing into gluey nano-sized carbon electric osmose to the pole plate surface, form the structure of carbon lead-sheathing, but this may influence the effect that changes into, and polar board surface is when charging, can cause a large amount of liberations of hydrogen, make carbon be difficult to be combined closely with lead.Disclose in pole plate among the patent CN 102324524A, the carbon that will have capacitive property replaces negative plate bottom lead plaster, make a pole plate be divided into two parts up and down, what top was coated with is lead plaster, and the lower part then is carbon paste, though carbon can divide the electric current of a part, but carbon only and the combination of grid are not as combination plumbous and grid, when large current charge, carbon surface can cause a large amount of liberations of hydrogen, causes coming off of carbon.
Plumbous carbon battery is that material with carbon element is joined in the lead powder, make its even mixing by churned mechanically method, can improve the dispersiveness of lead powder on the one hand, while material with carbon element in charging and discharging process has played a kind of effect of buffer current to pole plate, in recycling, can play the effect that suppresses sulfation in addition.Patent CN 101969149A discloses some material with carbon elements has been joined the method for mixing in the lead powder, and liberation of hydrogen inhibitor such as some indium oxides have been added, played the effect that suppresses liberation of hydrogen, but because the density of material with carbon element and lead differs greatly, cause that both adhesions are bad, and the adding of material with carbon element can not guarantee to be mixed in the lead powder equably.Patent CN 102074744A discloses in material with carbon element a certain amount of lead in the first electro-deposition, prepare a kind of plumbous carbon composite, again composite material is joined the method for mixing in the lead powder, though can improve the adhesion of material with carbon element and lead powder like this, but the mechanical strength of pole plate still is nowhere near, and the uniformity that both mix is not good enough yet.
This shows, mainly contain two kinds of thinkings at improving one's methods of lead-acid battery electrode, a kind of is the surface that material with carbon element is coated in negative pole, form interior superbattery also, another kind is that material with carbon element is joined in the lead powder, make plumbous carbon electrode, at both shortcoming and advantages, the present invention adopts material with carbon element to coat the method for lead powder, has both made material with carbon element be coated on polar board surface equably and disperses wherein equably, has also stoped the accumulation of bulky grain lead sulfate, formed " two property " negative pole, not only improve the dispersiveness of lead powder, improved utilance, also improved the adhesion of lead powder and material with carbon element and the mechanical strength of pole plate.Add the liberation of hydrogen inhibitor when adopting material with carbon element to coat simultaneously, suppressed the liberation of hydrogen of material with carbon element.The plumbous carbon superbattery of making not only has the high power performance of material with carbon element, and the characteristic of lead powder high power capacity is also arranged, and has prolonged charge and discharge circulation life.
Summary of the invention
The objective of the invention is to overcome the deficiencies in the prior art, provide a kind of material with carbon element to coat the lead powder composite material and as the application of the negative material of plumbous carbon superbattery, the pole plate mechanical strength that adopts described material with carbon element coating lead powder composite material to make is good, simultaneously can effectively guarantee the uniformity that material with carbon element mixes with lead powder, the battery of making as negative material with this composite material all improves on charge-discharge performance, power density, specific capacity and cycle life.
For achieving the above object, the present invention adopts following technical scheme:
A kind of material with carbon element coats the lead powder composite material, it prepares by the following method: add material with carbon element, thickener, liberation of hydrogen inhibitor, alcohol and deionized water in reaction vessel, mix the back and add lead powder, remove moisture and alcohol through ultrasonic dispersion back heating, make lead powder coat material with carbon element equably, adopt tube furnace to carry out the sintering carbonization then under the protection of inert protective gas, grinding is sieved, and obtains the composite material that material with carbon element coats lead powder; The mass ratio that feeds intake of described material with carbon element, thickener, liberation of hydrogen inhibitor, alcohol, deionized water and lead powder is 0.5～10:0.1～5:0.01～1:20～100:20～100:20～100.
Further, described material with carbon element is one or several the combination in graphite, active carbon, carbohydrate, acetylene black, mesoporous carbon, Graphene and the carbon nano-tube.
Further, described thickener is one or several the combination in carbohydrate, cellulose family, polyacrylate, gelatin and the polyvinyl alcohol.
Further, described liberation of hydrogen inhibitor is one or several in indium oxide, bismuth oxide, zinc oxide, calcium oxide, gallium oxide, the lead oxide.
Further, described lead powder is conventional technical grade product, and particle diameter is at 0.5～20 μ m, degree of oxidation of lead powder: 70～80%.
Further, the mass ratio that feeds intake of described material with carbon element, thickener, liberation of hydrogen inhibitor, alcohol, deionized water and lead powder is preferably 1～5:0.5～2:0.01～0.05:50～80:20～50:30～60.
Further, described inert protective gas is preferably nitrogen or inert gas, the preferred argon gas of described inert gas or helium.
Further, ultrasonic jitter time is 0.5～6h.
Further, carburizing temperature is 200～600 ℃, and carbonization time is 0.5～10h.
Material with carbon element of the present invention coats the negative material application that the lead powder composite material can be used as plumbous carbon superbattery, and conventional method is adopted in the preparation of plumbous carbon superbattery, specifically comprises the steps:
(1) preparation of plumbous carbon superbattery cathode lead plaster:
1. raw material and weight portion proportioning thereof are as follows:
Material with carbon element coats lead powder composite material 90～100, barium sulfate 0.05～2, and density is the sulfuric acid 5～20 of 1.15g/ml, short fiber 0.01～0.5, conductive agent 0.1～5, deionized water 10～20; Wherein said conductive agent is a kind of in electrically conductive graphite, acetylene black, the carbon black;
2. get raw material according to said ratio, earlier material with carbon element is coated the lead powder composite material, barium sulfate, short fiber, conductive electrode is poured in the container, stir 5～10min, each component is fully mixed, add deionized water in the container fast then, the time that general control adds water is 1～2min, add the back and continue to stir 5～10min, slowly drip density again and be the sulfuric acid of 1.15g/ml to container, the time that general control adds sulfuric acid is 5～15min, adds the back and continues to stir 5～10min, and control lead plaster apparent density is at 3.8～4.5g/ml, in this process, will fully stir, and the control temperature is at 45～55 ℃;
(2) the plumbous carbon superbattery cathode lead plaster that step (1) is obtained is coated on the grid equably, and in being the sulfuric acid of 1.15g/ml, density floods 5～10s, then pole plate is placed in temperature and is 45～55 ℃, relative humidity and be under 90～100% the condition and solidified 24 hours, pole plate is put into 65 ℃ again, dry 24 hours, obtain green plate;
(3) change into outside the green plate that is cured is carried out in the sulfuric acid of 1.05g/ml, after the drying, obtain ripe pole plate, and dress up battery with the modal sets of " two positive is negative ".
The present invention can adopt following method to carry out the test of initial capacity after pole plate is dressed up battery with the modal sets of " two positive is negative ": after battery is full of electricity, with the electric current of 750mA it is discharged, cut-ff voltage is 1.75V; Adopt following method to carry out the test of charge-discharge performance: respectively with 500,700, the 750mA current charges is to voltage 2.42V, constant voltage 2.42V, time 2h, leave standstill 5min after, respectively with 500,700, the 750mA current discharge, cut-ff voltage 1.75V; Adopt following method to carry out the test of charge-discharge performance: with the 500mA current charges to voltage 2.42V, constant voltage 2.42V, time 2h, after leaving standstill 5min, with the 500mA current discharge, cut-ff voltage 1.75V, be a circulation, carry out 50 loop tests relatively.
Compared with prior art, beneficial effect of the present invention is:
A) lead powder of the present invention's employing coats through material with carbon element and handles, by in material with carbon element, adding thickener, carry out high temperature cabonization, make material with carbon element be coated on equably that the lead powder surface preparation forms, improve dispersiveness and the utilance of lead powder, the material with carbon element that is coated on the lead powder has the effect of buffer current, the coating of material with carbon element simultaneously to pole plate, can improve lead sulfate and plumbous transformation efficiency, suppress oarse-grained lead sulfate well and occur.Battery with the present invention's assembling is coated on plumbous surface with material with carbon element, makes carbon negative pole and plumbous negative pole have been carried out " also interior ", brings into play capacitive character and battery better, forms two property negative poles, and the characteristics of superbattery are arranged.In addition, because the adding of material with carbon element can reduce big electric current to the damage of pole plate, the effect of a kind of " shunting " is arranged, battery is had cushioning effect, but in charging process, can make battery shift to an earlier date liberation of hydrogen, and the liberation of hydrogen inhibitor that adds mainly is to reduce the liberation of hydrogen of battery in charging process, so just the performance that can guarantee carbon is brought into play, suppress the dry of electrolyte, extend the life of a cell, so the liberation of hydrogen inhibitor is the key factor of plumbous carbon superbattery.
B) composite material of material with carbon element coating lead powder of the present invention is directly compared with the material that the lead powder mixing forms with carbon, has stronger adhesion, so the pole plate that the composite material that adopts material with carbon element of the present invention to coat lead powder is made has good mechanical intensity.
C) specific discharge capacity, quality that adopts the plumbous carbon superbattery that the inventive method makes all is significantly improved than the utilance of power, lead powder and charge-discharge performance and cycle performance.
Description of drawings
Fig. 1 is the battery initial capacity figure of embodiment 1, embodiment 2 and comparative example 1;
Fig. 2 is that the battery 750mA of embodiment 1, embodiment 2 and comparative example 1 charges and discharge electrograph;
Fig. 3 is 50 cycle performance figure of battery of embodiment 1, embodiment 2 and comparative example 1;
Fig. 4 is that the battery of embodiment 1, embodiment 2 and comparative example 1 is recycled to the 50th time the electrograph that charges and discharge;
Fig. 5 is the CV curve chart that the electrode of embodiment 1, embodiment 2 and comparative example 1 changes into the back active material;
Fig. 6-1 and Fig. 6-2 is respectively SEM figure and the EDS figure of the battery circulation back positive and negative pole active matter of comparative example 1;
Fig. 7 is the SEM figure of the battery circulation back positive and negative pole active matter of embodiment 1;
Two figure are respectively the negative plate figure after embodiment 1 and comparative example 2 change into about among Fig. 8.
Embodiment
With specific embodiment technical scheme of the present invention is described further below, but protection scope of the present invention is not limited thereto:
Comparative example 1
(the rich metal material Co., Ltd of day roc in the Tianjin) directly mixed with other raw materials with commercial lead powder, it is not carried out the processing that carbon coats, weight proportion by following material is made lead-acid battery: lead powder 98, short fiber 0.2, barium sulfate 0.3, electrically conductive graphite 1.5, after mixing, add above-mentioned raw materials gross mass 18%, 1.15g/ml sulfuric acid and the deionized water of above-mentioned raw materials gross mass 12%, under 50 ℃, carry out and cream, after having applied pole plate, at 50 ℃, solidified 24 hours under the condition of relative humidity 90～98%, descended dry 24 hours at 65 ℃ then, obtain giving birth to negative plate, obtain ripe negative plate by the method that changes into outward.Adopt this negative plate and PbO
2The base positive plate, electrolyte adopts the sulfuric acid of 1.28g/ml, and dresses up plumbous carbon superbattery with the modal sets of " two positive is negative ".After tested, the chemical property of battery is shown in curve B lank among Fig. 1,2,3,4, wherein Fig. 1 is battery initial capacity figure, Fig. 2 charges and discharge electrograph for battery 750mA, Fig. 3 is 50 cycle performance figure of battery, Fig. 4 is recycled to the 50th time the electrograph that charges and discharge for battery, and Fig. 5 changes into the CV curve chart of back active material for electrode, and SEM figure and EDS that Fig. 6-1 and Fig. 6-2 is respectively battery circulation back positive and negative pole active matter scheme.
Comparative example 2
Commercial lead powder is directly mixed with other raw materials, it is not carried out the processing that carbon coats, weight proportion by following material is made lead-acid battery: lead powder 96, material with carbon element 3, short fiber 0.2, barium sulfate 0.3, electrically conductive graphite 0.5, after mixing, add above-mentioned raw materials gross mass 18%, 1.15g/ml sulfuric acid and the deionized water of above-mentioned raw materials gross mass 12%, under 50 ℃, carry out and cream, after having applied pole plate, at 50 ℃, solidified 24 hours under the condition of relative humidity 90～98%, descended dry 24 hours at 65 ℃ then, obtain giving birth to negative plate, obtain ripe negative plate by the method that changes into outward.
Embodiment 1
Get 2g graphite, 1.5g glucose and 0.01g indium oxide, add the deionized water of 30ml and the alcohol of 40ml, after stirring, add the 40g lead powder again, behind the ultrasonic dispersion 30min, move in 80 ℃ the water-bath, add thermal agitation, moisture in evaporate to dryness solution and alcohol take out the lead powder that graphite and glucose coat, and grind, put into tube furnace, under nitrogen atmosphere, carry out 200 ℃ of carbonization 2h, obtain the lead powder composite material that graphite coats.
Make plumbous carbon superbattery by the weight proportion of following material: graphite coats lead powder composite material 99, short fiber 0.2, barium sulfate 0.3, electrically conductive graphite 0.5, after mixing, add above-mentioned raw materials gross mass 18%, the sulfuric acid of 1.15g/ml and the deionized water of above-mentioned raw materials gross mass 12%, under 50 ℃, carry out and cream, after having applied pole plate, at 50 ℃, solidified 24 hours under the condition of relative humidity 90～98%, following dry 24 hours at 65 ℃ then, obtain giving birth to negative plate, obtain ripe negative plate by the method that changes into outward.Adopt this negative plate and PbO
2The base positive plate, electrolyte adopts the sulfuric acid of 1.28g/ml, and dresses up plumbous carbon superbattery with the modal sets of " two positive is negative ".After tested, chemical property is shown in curve G/IN among Fig. 1,2,3,4,5, and the SEM figure of battery circulation back positive and negative pole active matter as shown in Figure 7.The result shows that the initial capacity of battery is compared the common lead-acid battery of comparative example 1() promoted 36.7%; Carry out 750mA electric current charge-discharge test equally, the discharge capacity of battery also has 33.3% lifting; Aspect the cycle charge discharge electrical testing, the cycle performance of battery has also promoted 1.83 times; Pole plate after the circulation does not have obvious oarse-grained lead sulfate to occur; Negative electrode active material after changing into is carried out the test analysis of CV curve, redox peak current has obvious change big, and capacity also has lifting, the lead powder of the material with carbon element coating of the present invention's preparation is described, in battery charge and discharge process, material with carbon element and lead powder have synergy, have realized capacitive character and the battery of " two property " negative pole.
Embodiment 2
Get 4g glucose and 0.01g indium oxide, add the deionized water of 30ml and the alcohol of 40ml, after stirring, add the 40g lead powder again, behind the ultrasonic dispersion 30min, move in 80 ℃ the water-bath, add thermal agitation, moisture in evaporate to dryness solution and alcohol take out the lead powder that glucose coats, and grind, put into tube furnace, under nitrogen atmosphere, carry out 200 ℃ of carbonization 2h, obtain the lead powder composite material that carbon coats.
Make plumbous carbon superbattery by the weight proportion of following material: carbon coats lead powder composite material 99, short fiber 0.2, barium sulfate 0.3, electrically conductive graphite 0.5, after mixing, add above-mentioned raw materials gross mass 18%, the sulfuric acid of 1.15g/ml and the deionized water of above-mentioned raw materials gross mass 12%, under 50 ℃, carry out and cream, after having applied pole plate, at 50 ℃, solidified 24 hours under the condition of relative humidity 90～98%, following dry 24 hours at 65 ℃ then, obtain giving birth to negative plate, obtain ripe negative plate by the method that changes into outward.Adopt this negative plate and PbO
2The base positive plate, electrolyte adopts the sulfuric acid of 1.28g/ml, and dresses up plumbous carbon superbattery with the modal sets of " two positive is negative ".After tested, chemical property is shown in curve C/IN among Fig. 1,2,3,4,5, and the SEM figure of battery circulation back positive and negative pole active matter as shown in Figure 7.The result shows that the initial capacity of battery has promoted 29.5%; Carry out 750mA electric current charge-discharge test, the discharge capacity of battery also has 23.9% lifting; Aspect the cycle charge discharge electrical testing, the cycle performance of battery has also promoted 1.42 times; Pole plate after the circulation does not have obvious oarse-grained lead sulfate to occur; Negative electrode active material after changing into is carried out the test analysis of CV curve, redox peak current has obvious change big, and capacity also has lifting, the lead powder of the material with carbon element coating of the present invention's preparation is described, how in the battery charge and discharge process, material with carbon element and lead powder have synergy, have realized capacitive character and the battery of " two property " negative pole.
Embodiment 3
Get 2g graphite, 1.5g glucose and 0.02g indium oxide, add the deionized water of 40ml and the alcohol of 60ml, after stirring, add the 50g lead powder again, behind the ultrasonic dispersion 30min, move in 80 ℃ the water-bath, add thermal agitation, moisture in evaporate to dryness solution and alcohol take out the lead powder that graphite and glucose coat, and grind, put into tube furnace, under nitrogen atmosphere, carry out 200 ℃ of carbonization 5h, obtain the lead powder composite material that graphite coats.
Make plumbous carbon superbattery by the weight proportion of following material: graphite coats lead powder composite material 99, short fiber 0.2, barium sulfate 0.3, electrically conductive graphite 0.5, after mixing, add above-mentioned raw materials gross mass 18%, the sulfuric acid of 1.15g/ml and the deionized water of above-mentioned raw materials gross mass 12%, under 50 ℃, carry out and cream, after having applied pole plate, at 50 ℃, solidified 24 hours under the condition of relative humidity 90～98%, following dry 24 hours at 65 ℃ then, obtain giving birth to negative plate, obtain ripe negative plate by the method that changes into outward.Adopt this negative plate and PbO
2The base positive plate, electrolyte adopts the sulfuric acid of 1.28g/ml, and dresses up plumbous carbon superbattery with the modal sets of " two positive is negative ".After tested, the initial capacity of battery is compared the common lead-acid battery of comparative example 1() promoted 34.7%; Carry out 750mA electric current charge-discharge test equally, the discharge capacity of battery also has 32.3% lifting; Aspect the cycle charge discharge electrical testing, the cycle performance of battery has also promoted 1.76 times; Pole plate after the circulation does not have obvious oarse-grained lead sulfate to occur; Negative electrode active material after changing into is carried out the test analysis of CV curve, redox peak current has obvious change big, and capacity also has lifting, the lead powder of the material with carbon element coating of the present invention's preparation is described, in battery charge and discharge process, material with carbon element and lead powder have synergy, have realized capacitive character and the battery of " two property " negative pole.
Embodiment 4
Get 4g graphite, 1.5g sucrose and 0.03g bismuth oxide, add the deionized water of 40ml and the alcohol of 70ml, after stirring, add the 60g lead powder again, behind the ultrasonic dispersion 30min, move in 80 ℃ the water-bath, add thermal agitation, moisture in evaporate to dryness solution and alcohol take out the lead powder that graphite and glucose coat, and grind, put into tube furnace, under nitrogen atmosphere, carry out 200 ℃ of carbonization 2h, obtain the lead powder composite material that graphite coats.
Make plumbous carbon superbattery by the weight proportion of following material: graphite coats lead powder composite material 99, short fiber 0.2, barium sulfate 0.3, electrically conductive graphite 0.5, after mixing, add above-mentioned raw materials gross mass 18%, the sulfuric acid of 1.15g/ml and the deionized water of above-mentioned raw materials gross mass 12%, under 50 ℃, carry out and cream, after having applied pole plate, at 50 ℃, solidified 24 hours under the condition of relative humidity 90～98%, following dry 24 hours at 65 ℃ then, obtain giving birth to negative plate, obtain ripe negative plate by the method that changes into outward.Adopt this negative plate and PbO
2The base positive plate, electrolyte adopts the sulfuric acid of 1.28g/ml, and dresses up plumbous carbon superbattery with the modal sets of " two positive is negative ".After tested, the initial capacity of battery is compared the common lead-acid battery of comparative example 1() promoted 31.9%; Carry out 750mA electric current charge-discharge test equally, the discharge capacity of battery also has 25.1 lifting; Aspect the cycle charge discharge electrical testing, the cycle performance of battery has also promoted 1.77 times; Pole plate after the circulation does not have obvious oarse-grained lead sulfate to occur; Negative electrode active material after changing into is carried out the test analysis of CV curve, redox peak current has obvious change big, and capacity also has lifting, the lead powder of the material with carbon element coating of the present invention's preparation is described, in battery charge and discharge process, material with carbon element and lead powder have synergy, have realized capacitive character and the battery of " two property " negative pole.
Embodiment 5
Get 2g graphite, 0.8g sucrose and 0.05g bismuth oxide, add the deionized water of 30ml and the alcohol of 70ml, after stirring, add the 50g lead powder again, behind the ultrasonic dispersion 30min, move in 80 ℃ the water-bath, add thermal agitation, moisture in evaporate to dryness solution and alcohol take out the lead powder that graphite and glucose coat, and grind, put into tube furnace, under nitrogen atmosphere, carry out 200 ℃ of carbonization 5h, obtain the lead powder composite material that graphite coats.
Make plumbous carbon superbattery by the weight proportion of following material: graphite coats lead powder composite material 99, short fiber 0.2, barium sulfate 0.3, electrically conductive graphite 0.5, after mixing, add above-mentioned raw materials gross mass 18%, the sulfuric acid of 1.15g/ml and the deionized water of above-mentioned raw materials gross mass 12%, under 50 ℃, carry out and cream, after having applied pole plate, at 50 ℃, solidified 24 hours under the condition of relative humidity 90～98%, following dry 24 hours at 65 ℃ then, obtain giving birth to negative plate, obtain ripe negative plate by the method that changes into outward.Adopt this negative plate and PbO
2The base positive plate, electrolyte adopts the sulfuric acid of 1.28g/ml, and dresses up plumbous carbon superbattery with the modal sets of " two positive is negative ".After tested, the initial capacity of battery is compared the common lead-acid battery of comparative example 1() promoted 32.9%; Carry out 750mA electric current charge-discharge test equally, the discharge capacity of battery also has 25.3% lifting; Aspect the cycle charge discharge electrical testing, the cycle performance of battery has also promoted 1.68 times; Pole plate after the circulation does not have obvious oarse-grained lead sulfate to occur; Negative electrode active material after changing into is carried out the test analysis of CV curve, redox peak current has obvious change big, and capacity also has lifting, the lead powder of the material with carbon element coating of the present invention's preparation is described, how in the battery charge and discharge process, material with carbon element and lead powder have synergy, have realized capacitive character and the battery of " two property " negative pole.
Embodiment 6
Get 4g glucose and 0.02g bismuth oxide, add the deionized water of 20ml and the alcohol of 80ml, after stirring, add the 60g lead powder again, behind the ultrasonic dispersion 30min, move in 80 ℃ the water-bath, add thermal agitation, moisture in evaporate to dryness solution and alcohol take out the lead powder that glucose coats, and grind, put into tube furnace, under nitrogen atmosphere, carry out 200 ℃ of carbonization 2h, obtain the lead powder composite material that carbon coats.
Make plumbous carbon superbattery by the weight proportion of following material: carbon coats lead powder composite material 98, short fiber 0.2, barium sulfate 0.3, electrically conductive graphite 1.5, after mixing, add above-mentioned raw materials gross mass 18%, the sulfuric acid of 1.15g/ml and the deionized water of above-mentioned raw materials gross mass 12%, under 50 ℃, carry out and cream, after having applied pole plate, at 50 ℃, solidified 24 hours under the condition of relative humidity 90～98%, following dry 24 hours at 65 ℃ then, obtain giving birth to negative plate, obtain ripe negative plate by the method that changes into outward.Adopt this negative plate and PbO
2The base positive plate, electrolyte adopts the sulfuric acid of 1.28g/ml, and dresses up plumbous carbon superbattery with the modal sets of " two positive is negative ".After tested, the initial capacity of battery has promoted 28.5%; Carry out 750mA electric current charge-discharge test, the discharge capacity of battery also has 24.1% lifting; Aspect the cycle charge discharge electrical testing, the cycle performance of battery has also promoted 1.35 times; Pole plate after the circulation does not have obvious oarse-grained lead sulfate to occur; Negative electrode active material after changing into is carried out the test analysis of CV curve, redox peak current has obvious change big, and capacity also has lifting, the lead powder of the material with carbon element coating of the present invention's preparation is described, how in the battery charge and discharge process, material with carbon element and lead powder have synergy, have realized capacitive character and the battery of " two property " negative pole.
Embodiment 7
Get 4g glucose and 0.05g bismuth oxide, add the deionized water of 40ml and the alcohol of 80ml, after stirring, add the 60g lead powder again, behind the ultrasonic dispersion 30min, move in 80 ℃ the water-bath, add thermal agitation, moisture in evaporate to dryness solution and alcohol take out the lead powder that glucose coats, and grind, put into tube furnace, under nitrogen atmosphere, carry out 400 ℃ of carbonization 2h, obtain the lead powder composite material that carbon coats.
Make plumbous carbon superbattery by the weight proportion of following material: carbon coats lead powder composite material 98, short fiber 0.2, barium sulfate 0.3, electrically conductive graphite 1.5, after mixing, add above-mentioned raw materials gross mass 18%, the sulfuric acid of 1.15g/ml and the deionized water of above-mentioned raw materials gross mass 12%, under 50 ℃, carry out and cream, after having applied pole plate, at 50 ℃, solidified 24 hours under the condition of relative humidity 90～98%, following dry 24 hours at 65 ℃ then, obtain giving birth to negative plate, obtain ripe negative plate by the method that changes into outward.Adopt this negative plate and PbO
2The base positive plate, electrolyte adopts the sulfuric acid of 1.28g/ml, and dresses up plumbous carbon superbattery with the modal sets of " two positive is negative ".After tested, the initial capacity of battery has promoted 26.5%; Carry out 750mA electric current charge-discharge test, the discharge capacity of battery also has 23.1% lifting; Aspect the cycle charge discharge electrical testing, the cycle performance of battery has also promoted 1.25 times; Pole plate after the circulation does not have obvious oarse-grained lead sulfate to occur; Negative electrode active material after changing into is carried out the test analysis of CV curve, redox peak current has obvious change big, and capacity also has lifting, the lead powder of the material with carbon element coating of the present invention's preparation is described, how in the battery charge and discharge process, material with carbon element and lead powder have synergy, have realized capacitive character and the battery of " two property " negative pole.
Embodiment 8
Get 2g graphite, 0.8g glucose and 0.05g zinc oxide, add the deionized water of 30ml and the alcohol of 70ml, after stirring, add the 50g lead powder again, behind the ultrasonic dispersion 30min, move in 80 ℃ the water-bath, add thermal agitation, moisture in evaporate to dryness solution and alcohol take out the lead powder that graphite and glucose coat, and grind, put into tube furnace, under nitrogen atmosphere, carry out 200 ℃ of carbonization 2h, obtain the lead powder composite material that graphite coats.
Make plumbous carbon superbattery by the weight proportion of following material: graphite coats lead powder composite material 99, short fiber 0.2, barium sulfate 0.3, electrically conductive graphite 0.5, after mixing, add above-mentioned raw materials gross mass 18%, the sulfuric acid of 1.15g/ml and the deionized water of above-mentioned raw materials gross mass 12%, under 50 ℃, carry out and cream, after having applied pole plate, at 50 ℃, solidified 24 hours under the condition of relative humidity 90～98%, following dry 24 hours at 65 ℃ then, obtain giving birth to negative plate, obtain ripe negative plate by the method that changes into outward.Adopt this negative plate and PbO
2The base positive plate, electrolyte adopts the sulfuric acid of 1.28g/ml, and dresses up plumbous carbon superbattery with the modal sets of " two positive is negative ".After tested, the initial capacity of battery is compared the common lead-acid battery of comparative example 1() promoted 32.1%; Carry out 750mA electric current charge-discharge test equally, the discharge capacity of battery also has 24.8% lifting; Aspect the cycle charge discharge electrical testing, the cycle performance of battery has also promoted 1.75 times; Pole plate after the circulation does not have obvious oarse-grained lead sulfate to occur; Negative electrode active material after changing into is carried out the test analysis of CV curve, redox peak current has obvious change big, and capacity also has lifting, the lead powder of the material with carbon element coating of the present invention's preparation is described, in battery charge and discharge process, material with carbon element and lead powder have synergy, have realized capacitive character and the battery of " two property " negative pole.
Embodiment 9
Get 2g graphite, 1.5g glucose, add the deionized water of 30ml and the alcohol of 40ml, after stirring, add the 40g lead powder again, behind the ultrasonic dispersion 30min, move in 80 ℃ the water-bath, add thermal agitation, moisture in evaporate to dryness solution and alcohol take out the lead powder that graphite and glucose coat, and grind, put into tube furnace, under nitrogen atmosphere, carry out 200 ℃ of carbonization 2h, obtain the lead powder composite material that graphite coats.
Make plumbous carbon superbattery by the weight proportion of following material: graphite coats lead powder composite material 99, short fiber 0.2, barium sulfate 0.3, electrically conductive graphite 0.5, after mixing, add above-mentioned raw materials gross mass 18%, the sulfuric acid of 1.15g/ml and the deionized water of above-mentioned raw materials gross mass 12%, under 50 ℃, carry out and cream, after having applied pole plate, at 50 ℃, solidified 24 hours under the condition of relative humidity 90～98%, following dry 24 hours at 65 ℃ then, obtain giving birth to negative plate, obtain ripe negative plate by the method that changes into outward.Adopt this negative plate and PbO
2The base positive plate, electrolyte adopts the sulfuric acid of 1.28g/ml, and dresses up plumbous carbon superbattery with the modal sets of " two positive is negative ".After tested, the initial capacity of battery is compared the common lead-acid battery of comparative example 1() promoted 30.9%; Carry out 750mA electric current charge-discharge test equally, the discharge capacity of battery also has 24.7% lifting; Aspect the cycle charge discharge electrical testing, the cycle performance of battery has also promoted 1.71 times; Pole plate after the circulation does not have obvious oarse-grained lead sulfate to occur; Negative electrode active material after changing into is carried out the test analysis of CV curve, redox peak current has obvious change big, and capacity also has lifting, the lead powder of the material with carbon element coating of the present invention's preparation is described, in battery charge and discharge process, material with carbon element and lead powder have synergy, have realized capacitive character and the battery of " two property " negative pole.
Get 4g glucose, add the deionized water of 30ml and the alcohol of 40ml, after stirring, add the 40g lead powder again, behind the ultrasonic dispersion 30min, move in 80 ℃ the water-bath, add thermal agitation, moisture in evaporate to dryness solution and alcohol take out the lead powder that glucose coats, and grind, put into tube furnace, under nitrogen atmosphere, carry out 200 ℃ of carbonization 5h, obtain the lead powder composite material that carbon coats.
Make plumbous carbon superbattery by the weight proportion of following material: carbon coats lead powder composite material 98, short fiber 0.2, barium sulfate 0.3, electrically conductive graphite 1.5, after mixing, add above-mentioned raw materials gross mass 18%, the sulfuric acid of 1.15g/ml and the deionized water of above-mentioned raw materials gross mass 12%, under 50 ℃, carry out and cream, after having applied pole plate, at 50 ℃, solidified 24 hours under the condition of relative humidity 90～98%, following dry 24 hours at 65 ℃ then, obtain giving birth to negative plate, obtain ripe negative plate by the method that changes into outward.Adopt this negative plate and PbO
2The base positive plate, electrolyte adopts the sulfuric acid of 1.28g/ml, and dresses up plumbous carbon superbattery with the modal sets of " two positive is negative ".After tested, the initial capacity of battery has promoted 28.1%; Carry out 750mA electric current charge-discharge test, the discharge capacity of battery also has 20.0% lifting; Aspect the cycle charge discharge electrical testing, the cycle performance of battery has also promoted 1.22 times; Pole plate after the circulation does not have obvious oarse-grained lead sulfate to occur; Negative electrode active material after changing into is carried out the test analysis of CV curve, redox peak current has obvious change big, and capacity also has lifting, the lead powder of the material with carbon element coating of the present invention's preparation is described, in battery charge and discharge process, material with carbon element and lead powder have synergy, have realized capacitive character and the battery of " two property " negative pole.
Claims (6)
1. a material with carbon element coats the lead powder composite material, it prepares by the following method: add material with carbon element, thickener, liberation of hydrogen inhibitor, alcohol and deionized water in reaction vessel, mix the back and add lead powder, remove moisture and alcohol through ultrasonic dispersion back heating, make lead powder coat material with carbon element equably, adopt tube furnace to carry out the sintering carbonization then under the protection of inert protective gas, grinding is sieved, and obtains the composite material that material with carbon element coats lead powder; The mass ratio that feeds intake of described material with carbon element, thickener, liberation of hydrogen inhibitor, alcohol, deionized water and lead powder is 0.5～10:0.1～5:0.01～1:20～100:20～100:20～100.
2. material with carbon element as claimed in claim 1 coats the lead powder composite material, it is characterized in that: described material with carbon element is one or several the combination in graphite, active carbon, carbohydrate, acetylene black, mesoporous carbon, Graphene and the carbon nano-tube; Described thickener is one or several the combination in carbohydrate, cellulose family, polyacrylate, gelatin and the polyvinyl alcohol; Described liberation of hydrogen inhibitor is one or several in indium oxide, bismuth oxide, zinc oxide, calcium oxide, gallium oxide, the lead oxide.
3. material with carbon element as claimed in claim 2 coats the lead powder composite material, and it is characterized in that: the mass ratio that feeds intake of described material with carbon element, thickener, liberation of hydrogen inhibitor, alcohol, deionized water and lead powder is preferably 1～5:0.5～2:0.01～0.05:50～80:20～50:30～60.
4. coat the lead powder composite material as the described material with carbon element of one of claim 1～3, it is characterized in that: carburizing temperature is 200～600 ℃, and carbonization time is 0.5～10h.
5. material with carbon element as claimed in claim 4 coats the lead powder composite material, and it is characterized in that: ultrasonic jitter time is 0.5～6h.
6. material with carbon element as claimed in claim 1 coats the lead powder composite material as the application of the negative material of plumbous carbon superbattery.
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