CN103296275B - Carbon-material-coatlead lead powder composite material and application thereof - Google Patents
Carbon-material-coatlead lead powder composite material and application thereof Download PDFInfo
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- CN103296275B CN103296275B CN201310205331.4A CN201310205331A CN103296275B CN 103296275 B CN103296275 B CN 103296275B CN 201310205331 A CN201310205331 A CN 201310205331A CN 103296275 B CN103296275 B CN 103296275B
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- WABPQHHGFIMREM-UHFFFAOYSA-N lead(0) Chemical compound [Pb] WABPQHHGFIMREM-UHFFFAOYSA-N 0.000 title claims abstract description 97
- 239000002131 composite material Substances 0.000 title claims abstract description 47
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 167
- 229910052799 carbon Inorganic materials 0.000 claims abstract description 121
- 239000000463 material Substances 0.000 claims abstract description 82
- 238000000034 method Methods 0.000 claims abstract description 41
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 32
- 239000008367 deionised water Substances 0.000 claims abstract description 31
- 229910021641 deionized water Inorganic materials 0.000 claims abstract description 31
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 30
- 239000001257 hydrogen Substances 0.000 claims abstract description 19
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 19
- 238000002156 mixing Methods 0.000 claims abstract description 17
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims abstract description 16
- 238000003763 carbonization Methods 0.000 claims abstract description 15
- 239000003112 inhibitor Substances 0.000 claims abstract description 13
- 239000002562 thickening agent Substances 0.000 claims abstract description 10
- 239000007789 gas Substances 0.000 claims abstract description 5
- 230000001681 protective effect Effects 0.000 claims abstract description 4
- 238000006243 chemical reaction Methods 0.000 claims abstract description 3
- 238000000227 grinding Methods 0.000 claims abstract description 3
- 238000010438 heat treatment Methods 0.000 claims abstract description 3
- 238000005245 sintering Methods 0.000 claims abstract description 3
- 239000010439 graphite Substances 0.000 claims description 39
- 229910002804 graphite Inorganic materials 0.000 claims description 39
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 claims description 6
- 229910000416 bismuth oxide Inorganic materials 0.000 claims description 6
- TYIXMATWDRGMPF-UHFFFAOYSA-N dibismuth;oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[Bi+3].[Bi+3] TYIXMATWDRGMPF-UHFFFAOYSA-N 0.000 claims description 6
- 229910003437 indium oxide Inorganic materials 0.000 claims description 6
- PJXISJQVUVHSOJ-UHFFFAOYSA-N indium(iii) oxide Chemical compound [O-2].[O-2].[O-2].[In+3].[In+3] PJXISJQVUVHSOJ-UHFFFAOYSA-N 0.000 claims description 6
- 239000006230 acetylene black Substances 0.000 claims description 3
- 150000001720 carbohydrates Chemical class 0.000 claims description 3
- 239000011787 zinc oxide Substances 0.000 claims description 3
- 108010010803 Gelatin Proteins 0.000 claims description 2
- 239000004372 Polyvinyl alcohol Substances 0.000 claims description 2
- BRPQOXSCLDDYGP-UHFFFAOYSA-N calcium oxide Chemical compound [O-2].[Ca+2] BRPQOXSCLDDYGP-UHFFFAOYSA-N 0.000 claims description 2
- ODINCKMPIJJUCX-UHFFFAOYSA-N calcium oxide Inorganic materials [Ca]=O ODINCKMPIJJUCX-UHFFFAOYSA-N 0.000 claims description 2
- 239000000292 calcium oxide Substances 0.000 claims description 2
- 229910021393 carbon nanotube Inorganic materials 0.000 claims description 2
- 239000002041 carbon nanotube Substances 0.000 claims description 2
- 238000005255 carburizing Methods 0.000 claims description 2
- 239000001913 cellulose Substances 0.000 claims description 2
- 229920002678 cellulose Polymers 0.000 claims description 2
- AJNVQOSZGJRYEI-UHFFFAOYSA-N digallium;oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[Ga+3].[Ga+3] AJNVQOSZGJRYEI-UHFFFAOYSA-N 0.000 claims description 2
- 229910001195 gallium oxide Inorganic materials 0.000 claims description 2
- 229920000159 gelatin Polymers 0.000 claims description 2
- 239000008273 gelatin Substances 0.000 claims description 2
- 235000019322 gelatine Nutrition 0.000 claims description 2
- 235000011852 gelatine desserts Nutrition 0.000 claims description 2
- 229910021389 graphene Inorganic materials 0.000 claims description 2
- 229910000464 lead oxide Inorganic materials 0.000 claims description 2
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 claims description 2
- 229920000058 polyacrylate Polymers 0.000 claims description 2
- 229920002451 polyvinyl alcohol Polymers 0.000 claims description 2
- YEXPOXQUZXUXJW-UHFFFAOYSA-N oxolead Chemical compound [Pb]=O YEXPOXQUZXUXJW-UHFFFAOYSA-N 0.000 claims 1
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 56
- 238000012360 testing method Methods 0.000 description 34
- TZCXTZWJZNENPQ-UHFFFAOYSA-L barium sulfate Chemical compound [Ba+2].[O-]S([O-])(=O)=O TZCXTZWJZNENPQ-UHFFFAOYSA-L 0.000 description 28
- 239000002994 raw material Substances 0.000 description 28
- 239000000843 powder Substances 0.000 description 20
- WQZGKKKJIJFFOK-GASJEMHNSA-N Glucose Natural products OC[C@H]1OC(O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-GASJEMHNSA-N 0.000 description 18
- 239000008103 glucose Substances 0.000 description 18
- 239000002253 acid Substances 0.000 description 17
- 230000008569 process Effects 0.000 description 17
- 230000000052 comparative effect Effects 0.000 description 15
- 239000000835 fiber Substances 0.000 description 14
- PIJPYDMVFNTHIP-UHFFFAOYSA-L lead sulfate Chemical compound [PbH4+2].[O-]S([O-])(=O)=O PIJPYDMVFNTHIP-UHFFFAOYSA-L 0.000 description 14
- 238000003756 stirring Methods 0.000 description 14
- 230000015572 biosynthetic process Effects 0.000 description 13
- 239000006071 cream Substances 0.000 description 12
- 239000003792 electrolyte Substances 0.000 description 12
- HTUMBQDCCIXGCV-UHFFFAOYSA-N lead oxide Chemical compound [O-2].[Pb+2] HTUMBQDCCIXGCV-UHFFFAOYSA-N 0.000 description 12
- 230000008859 change Effects 0.000 description 11
- 238000013019 agitation Methods 0.000 description 10
- 239000007773 negative electrode material Substances 0.000 description 10
- 239000012299 nitrogen atmosphere Substances 0.000 description 10
- 230000000694 effects Effects 0.000 description 7
- 239000011505 plaster Substances 0.000 description 4
- 230000008901 benefit Effects 0.000 description 3
- 150000002431 hydrogen Chemical class 0.000 description 3
- 238000002360 preparation method Methods 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- 229930006000 Sucrose Natural products 0.000 description 2
- CZMRCDWAGMRECN-UGDNZRGBSA-N Sucrose Chemical compound O[C@H]1[C@H](O)[C@@H](CO)O[C@@]1(CO)O[C@@H]1[C@H](O)[C@@H](O)[C@H](O)[C@@H](CO)O1 CZMRCDWAGMRECN-UGDNZRGBSA-N 0.000 description 2
- 238000009825 accumulation Methods 0.000 description 2
- 239000011149 active material Substances 0.000 description 2
- 239000006258 conductive agent Substances 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 239000011261 inert gas Substances 0.000 description 2
- 239000005720 sucrose Substances 0.000 description 2
- 230000019635 sulfation Effects 0.000 description 2
- 238000005670 sulfation reaction Methods 0.000 description 2
- 229910052786 argon Inorganic materials 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000003990 capacitor Substances 0.000 description 1
- 239000006229 carbon black Substances 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 238000007598 dipping method Methods 0.000 description 1
- 238000007599 discharging Methods 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- 238000004070 electrodeposition Methods 0.000 description 1
- 238000004146 energy storage Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 239000001307 helium Substances 0.000 description 1
- 229910052734 helium Inorganic materials 0.000 description 1
- SWQJXJOGLNCZEY-UHFFFAOYSA-N helium atom Chemical compound [He] SWQJXJOGLNCZEY-UHFFFAOYSA-N 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 239000002105 nanoparticle Substances 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 238000004064 recycling Methods 0.000 description 1
- 230000009466 transformation Effects 0.000 description 1
Classifications
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
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- Battery Electrode And Active Subsutance (AREA)
Abstract
The invention discloses a kind of Carbon-material-coatlead lead powder composite material and application thereof; described Carbon-material-coatlead lead powder composite material is prepared by the following method: in reaction vessel, add material with carbon element, thickener, liberation of hydrogen inhibitor, alcohol and deionized water; lead powder is added after mixing; heating removing moisture and alcohol after ultrasonic disperse; make lead powder coated upper material with carbon element equably; then tube furnace is adopted to carry out sintering carbonization under the protection of inert protective gas; grinding is sieved, and obtains the composite material of the coated lead powder of material with carbon element.Composite material of the present invention can be used as the negative material application of plumbous carbon superbattery, the pole plate mechanical strength that Carbon-material-coatlead lead powder composite material described in employing is made is good, effectively can ensure the uniformity that material with carbon element mixes with lead powder, the battery made using this composite material as negative material all improves in charge-discharge performance, power density, specific capacity and cycle life simultaneously.
Description
Technical field
The present invention relates to the application of a kind of Carbon-material-coatlead lead powder composite material and the negative material as plumbous carbon superbattery thereof.
Background technology
Lead acid accumulator is in the historical development course of more than 100 years; great contribution has all been made in many application aspect; especially environmental pollution in recent years and energy crisis propose new requirement to traditional energy; lead-acid battery, due to relative clean, low in the pollution of the environment, obtains very large application in all fields.But its power density is not high, the shortcoming that cycle life is not grown limits its development.Particularly because battery is under partial state of charge during high-multiplying power discharge, lead sulfate on negative pole constantly accumulation cause negative pole sulfation, thus life-span causing cycle life of lead-acid accumulator potential far below it.So modification will be carried out to lead-acid battery, improve its power density, charge-discharge performance and cycle performance.
Ultracapacitor is a kind of novel energy storage device, the feature such as there is high power density, fast charging and discharging, have extended cycle life, but its energy density is relative to lower battery, use so lead-acid battery and ultracapacitor are together in parallel, both learn from other's strong points to offset one's weaknesses, make up respective shortcoming, play advantage each other.
Superbattery is a kind of novel battery be combined with lead-acid battery by ultracapacitor, and it is by directly in parallel for the pole plate of ultracapacitor and lead-acid battery, the advantage of the capacitor of electric double layer can be fused in lead-acid battery like this.Patent CN101123139A discloses a kind of preparation method of superbattery, when changing into by gluey nano-sized carbon electric osmose to polar board surface, form the structure of carbon lead-sheathing, but this may affect the effect changed into, and polar board surface is when charging, a large amount of liberations of hydrogen can be caused, make carbon be difficult to be combined closely with lead.Disclose in patent CN 102324524A in pole plate, the carbon with capacitive property is replaced negative plate bottom lead plaster, one piece of pole plate is made to be divided into upper and lower two parts, what upper part was coated with is lead plaster, and lower part is then carbon paste, although carbon can divide the electric current of a part, but carbon only and the combination of grid are the combinations not as plumbous and grid, when large current charge, carbon surface can cause a large amount of liberation of hydrogen, causes coming off of carbon.
Plumbous carbon battery joins in lead powder by material with carbon element, its Homogeneous phase mixing is made by churned mechanically method, the dispersiveness of lead powder can be improved on the one hand, in the process of discharge and recharge, material with carbon element serves a kind of effect of buffer current to pole plate simultaneously, in addition in recycling, the effect suppressing sulfation can be played.Patent CN 101969149A discloses the method being joined by some material with carbon elements and mix in lead powder, and add the liberation of hydrogen inhibitor such as some indium oxides, serve the effect suppressing liberation of hydrogen, but because material with carbon element is very large with plumbous density difference, cause both adhesions bad, and can not ensure to be mixed in equably in lead powder adding of material with carbon element.Patent CN 102074744A to disclose in material with carbon element a certain amount of lead in first electro-deposition, prepare a kind of plumbous carbon composite, again composite material is joined the method mixed in lead powder, although the adhesion of material with carbon element and lead powder can be improved like this, but the mechanical strength of pole plate is still nowhere near, both uniformities of mixing are not good enough yet.
As can be seen here, two kinds of thinkings are mainly contained for improving one's methods of lead-acid battery electrode, a kind of is surface material with carbon element being coated in negative pole, form interior superbattery also, another kind joins in lead powder by material with carbon element, make plumbous carbon electrode, for both shortcoming and advantage, the present invention adopts the method for the coated lead powder of material with carbon element, both made material with carbon element be coated on polar board surface equably and disperseed wherein equably, also the accumulation of bulky grain lead sulfate is prevented, define " two property " negative pole, not only improve the dispersiveness of lead powder, improve utilance, also improve the adhesion of lead powder and material with carbon element and the mechanical strength of pole plate.Simultaneously adopt material with carbon element carry out coated while add liberation of hydrogen inhibitor, inhibit the liberation of hydrogen of material with carbon element.The plumbous carbon superbattery made, not only has the high power performance of material with carbon element, also has the characteristic of lead powder high power capacity, extend charge and discharge circulation life.
Summary of the invention
The object of the invention is to overcome the deficiencies in the prior art, the application of a kind of Carbon-material-coatlead lead powder composite material and the negative material as plumbous carbon superbattery thereof is provided, the pole plate mechanical strength that Carbon-material-coatlead lead powder composite material described in employing is made is good, effectively can ensure the uniformity that material with carbon element mixes with lead powder, the battery made using this composite material as negative material all improves in charge-discharge performance, power density, specific capacity and cycle life simultaneously.
For achieving the above object, the present invention adopts following technical scheme:
A kind of Carbon-material-coatlead lead powder composite material, it is prepared by the following method: in reaction vessel, add material with carbon element, thickener, liberation of hydrogen inhibitor, alcohol and deionized water, lead powder is added after mixing, heating removing moisture and alcohol after ultrasonic disperse, make lead powder coated upper material with carbon element equably, then adopt tube furnace to carry out sintering carbonization under the protection of inert protective gas, grinding is sieved, and obtains the composite material of the coated lead powder of material with carbon element; 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 carbon nano-tube.
Further, described thickener is one or several the combination in carbohydrate, cellulose family, polyacrylate, gelatin and polyvinyl alcohol.
Further, described liberation of hydrogen inhibitor is one or several in indium oxide, bismuth oxide, zinc oxide, calcium oxide, gallium oxide, lead oxide.
Further, described lead powder is conventional technical grade product, particle diameter at 0.5 ~ 20 μm, 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, the ultrasonic disperse time is 0.5 ~ 6h.
Further, carburizing temperature is 200 ~ 600 DEG C, and carbonization time is 0.5 ~ 10h.
Carbon-material-coatlead lead powder composite material of the present invention can be used as the negative material application of plumbous carbon superbattery, and the preparation of plumbous carbon superbattery adopts conventional method, specifically comprises the steps:
(1) preparation of plumbous carbon superbattery cathode lead plaster:
1. raw material and weight as follows:
Carbon-material-coatlead lead powder composite material 90 ~ 100, barium sulfate 0.05 ~ 2, 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 the one in electrically conductive graphite, acetylene black, carbon black;
2. raw material is got according to said ratio, first by Carbon-material-coatlead lead powder composite material, barium sulfate, short fiber, conductive electrode is poured in container, stir 5 ~ 10min, each component is fully mixed, then deionized water is added in container fast, the time that general control adds water is 1 ~ 2min, add rear continuation stirring 5 ~ 10min, slowly dripping density is again that the sulfuric acid of 1.15g/ml is in container, the time that general control adds sulfuric acid is 5 ~ 15min, add rear continuation stirring 5 ~ 10min, control apparent density of lead paste at 3.8 ~ 4.5g/ml, to fully stir in the process, and control temperature is at 45 ~ 55 DEG C,
(2) plumbous carbon superbattery cathode lead plaster step (1) obtained is coated on grid equably, and be dipping 5 ~ 10s in the sulfuric acid of 1.15g/ml in density, then pole plate is placed in that temperature is 45 ~ 55 DEG C, relative humidity is solidify 24 hours under the condition of 90 ~ 100%, again pole plate is put into 65 DEG C, dry 24 hours, obtain green plate;
(3) green plate be cured is carried out tank formation in the sulfuric acid of 1.05g/ml, after drying, obtain ripe pole plate, and dress up battery with the modal sets of " two positive negative ".
After pole plate is dressed up battery with the modal sets of " two positive negative " by the present invention, following method can be adopted to carry out the test of initial capacity: after battery is full of electricity, discharge with the electric current of 750mA to it, cut-ff voltage is 1.75V; Adopt following method to carry out the test of charge-discharge performance: respectively with 500,700,750mA current charges to voltage 2.42V, constant voltage 2.42V, time 2h, after leaving standstill 5min, respectively with 500,700,750mA current discharge, cut-ff voltage 1.75V; Following method is adopted to carry out the test of charge-discharge performance: with 500mA current charges to voltage 2.42V, constant voltage 2.42V, time 2h, after leaving standstill 5min, with 500mA current discharge, cut-ff voltage 1.75V, be a circulation, carry out 50 loop tests and compare.
Compared with prior art, beneficial effect of the present invention is:
A) lead powder that the present invention adopts is through the coated process of material with carbon element, by adding thickener in material with carbon element, carry out high temperature cabonization, make material with carbon element be coated on lead powder surface to be equably prepared from, improve dispersiveness and the utilance of lead powder, the material with carbon element be coated on lead powder has the effect of buffer current to pole plate, and material with carbon element is coated simultaneously, lead sulfate and plumbous transformation efficiency can be improved, suppress oarse-grained lead sulfate to occur well.Material with carbon element is coated on plumbous surface with the battery of the present invention's assembling, makes Carbon anode and plumbous negative pole carry out " inside also ", play capacitive character and cell performance better, form two property negative pole, have the feature of superbattery.In addition, because adding of material with carbon element can reduce the damage of big current to pole plate, there is the effect of one " shunting ", have cushioning effect to battery, but battery can be made in charging process to shift to an earlier date liberation of hydrogen, and the liberation of hydrogen inhibitor added mainly reduces the liberation of hydrogen of battery in charging process, so just can ensure that the performance of carbon is played, suppress the dry of electrolyte, extend the life of a cell, so liberation of hydrogen inhibitor is the key factor of plumbous carbon superbattery.
B), compared with the material that composite material and the carbon of the coated lead powder of material with carbon element of the present invention are directly mixed to form with lead powder, there is stronger adhesion, therefore the pole plate adopting the composite material of the coated lead powder of material with carbon element of the present invention to make, there is extraordinary mechanical strength.
C) specific discharge capacity of the plumbous carbon superbattery that obtains of the inventive method, quality is adopted all to be significantly improved than the utilance of power, lead powder and charge-discharge performance and cycle performance.
Accompanying drawing explanation
Fig. 1 is the battery initial capacity figure of embodiment 1, embodiment 2 and comparative example 1;
Fig. 2 is the battery 750mA charge and discharge electrograph of embodiment 1, embodiment 2 and comparative example 1;
Fig. 3 is battery 50 cycle performance figure of embodiment 1, embodiment 2 and comparative example 1;
Fig. 4 is that the circulating battery of embodiment 1, embodiment 2 and comparative example 1 is to the charge and discharge electrograph of the 50th time;
Fig. 5 is embodiment 1, the electrode of embodiment 2 and comparative example 1 changes into the CV curve chart of rear active material;
After Fig. 6-1 and Fig. 6-2 is respectively the circulating battery of comparative example 1, the SEM figure and EDS of positive and negative pole active matter schemes;
Fig. 7 is the SEM figure of positive and negative pole active matter after the circulating battery of embodiment 1;
In Fig. 8 left and right two figure be respectively embodiment 1 and comparative example 2 change into after negative plate figure.
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
Business lead powder (Tianjin Zhong Tianpengbo metal material Co., Ltd) is directly mixed with other raw materials, the coated process of carbon is not carried out to it, lead-acid battery is made: lead powder 98 by the weight proportion of following material, 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%, carry out and cream at 50 DEG C, after having applied pole plate, at 50 DEG C, solidify 24 hours under the condition of relative humidity 90 ~ 98%, then at 65 DEG C dry 24 hours, obtain raw negative plate, ripe negative plate is obtained by the method for tank formation.Adopt this negative plate and PbO
2base positive plate, electrolyte adopts the sulfuric acid of 1.28g/ml, and dresses up plumbous carbon superbattery with the modal sets of " two positive negative ".After tested, the chemical property of battery is as shown in curve B lank in Fig. 1,2,3,4, wherein Fig. 1 is battery initial capacity figure, Fig. 2 is battery 750mA charge and discharge electrograph, Fig. 3 is battery 50 cycle performance figure, Fig. 4 is circulating battery to the charge and discharge electrograph of the 50th time, and Fig. 5 is the CV curve chart that electrode changes into rear active material, and after Fig. 6-1 and Fig. 6-2 is respectively circulating battery, the SEM figure and EDS of positive and negative pole active matter schemes.
Comparative example 2
Business lead powder is directly mixed with other raw materials, the coated process of carbon is not carried out to it, lead-acid battery is made: lead powder 96 by the weight proportion of following material, 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%, the sulfuric acid of 1.15g/ml and the deionized water of above-mentioned raw materials gross mass 12%, carry out and cream at 50 DEG C, after having applied pole plate, at 50 DEG C, solidify 24 hours under the condition of relative humidity 90 ~ 98%, then at 65 DEG C dry 24 hours, obtain raw negative plate, ripe negative plate is obtained by the method for tank formation.
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 40g lead powder again, after ultrasonic disperse 30min, move in the water-bath of 80 DEG C, carry out adding thermal agitation, until moisture in evaporate to dryness solution and alcohol, take out graphite and the coated lead powder of glucose, grind, put into tube furnace, in a nitrogen atmosphere, carry out 200 DEG C of carbonization 2h, obtain the powder composite of graphite coat.
Plumbous carbon superbattery is made: graphite coat powder composite 99, short fiber 0.2, barium sulfate 0.3, electrically conductive graphite 0.5 by the weight proportion of following material, 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%, carry out and cream at 50 DEG C, after having applied pole plate, at 50 DEG C, solidify 24 hours under the condition of relative humidity 90 ~ 98%, then at 65 DEG C dry 24 hours, obtain raw negative plate, obtain ripe negative plate by the method for tank formation.Adopt this negative plate and PbO
2base positive plate, electrolyte adopts the sulfuric acid of 1.28g/ml, and dresses up plumbous carbon superbattery with the modal sets of " two positive negative ".After tested, chemical property is as shown in curve G/IN in Fig. 1,2,3,4,5, and after circulating battery, the SEM figure of positive and negative pole active matter as shown in Figure 7.Result shows, the initial capacity of battery compares comparative example 1(conventional lead acid battery) improve 36.7%; Carry out 750mA current charge-discharge electrical testing equally, the discharge capacity of battery also has the lifting of 33.3%; In cycle charge discharge electrical testing, the cycle performance of battery also improves 1.83 times; Pole plate after circulation does not have obvious oarse-grained lead sulfate to occur; Negative electrode active material after changing into is carried out to the test analysis of CV curve, redox peak current has obviously change large, and capacity also has lifting, the lead powder that material with carbon element prepared by the present invention is coated is described, in battery charge and discharge process, material with carbon element and lead powder have synergy, achieve the capacitive character of " two property " negative pole and cell performance.
Embodiment 2
Get 4g glucose and 0.01g indium oxide, add the deionized water of 30ml and the alcohol of 40ml, after stirring, add 40g lead powder again, after ultrasonic disperse 30min, move in the water-bath of 80 DEG C, carry out adding thermal agitation, until moisture in evaporate to dryness solution and alcohol, take out the lead powder that glucose is coated, grind, put into tube furnace, in a nitrogen atmosphere, carry out 200 DEG C of carbonization 2h, obtain the powder composite that carbon is coated.
Plumbous carbon superbattery is made: the coated powder composite 99 of carbon, short fiber 0.2, barium sulfate 0.3, electrically conductive graphite 0.5 by the weight proportion of following material, 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%, carry out and cream at 50 DEG C, after having applied pole plate, at 50 DEG C, solidify 24 hours under the condition of relative humidity 90 ~ 98%, then at 65 DEG C dry 24 hours, obtain raw negative plate, obtain ripe negative plate by the method for tank formation.Adopt this negative plate and PbO
2base positive plate, electrolyte adopts the sulfuric acid of 1.28g/ml, and dresses up plumbous carbon superbattery with the modal sets of " two positive negative ".After tested, chemical property is as shown in curve C/IN in Fig. 1,2,3,4,5, and after circulating battery, the SEM figure of positive and negative pole active matter as shown in Figure 7.Result shows, the initial capacity of battery improves 29.5%; Carry out 750mA current charge-discharge electrical testing, the discharge capacity of battery also has the lifting of 23.9%; In cycle charge discharge electrical testing, the cycle performance of battery also improves 1.42 times; Pole plate after circulation does not have obvious oarse-grained lead sulfate to occur; Negative electrode active material after changing into is carried out to the test analysis of CV curve, redox peak current has obviously change large, and capacity also has lifting, the lead powder that material with carbon element prepared by the present invention is coated is described, how in battery charge and discharge process, material with carbon element and lead powder have synergy, achieve the capacitive character of " two property " negative pole and cell performance.
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 50g lead powder again, after ultrasonic disperse 30min, move in the water-bath of 80 DEG C, carry out adding thermal agitation, until moisture in evaporate to dryness solution and alcohol, take out graphite and the coated lead powder of glucose, grind, put into tube furnace, in a nitrogen atmosphere, carry out 200 DEG C of carbonization 5h, obtain the powder composite of graphite coat.
Plumbous carbon superbattery is made: graphite coat powder composite 99, short fiber 0.2, barium sulfate 0.3, electrically conductive graphite 0.5 by the weight proportion of following material, 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%, carry out and cream at 50 DEG C, after having applied pole plate, at 50 DEG C, solidify 24 hours under the condition of relative humidity 90 ~ 98%, then at 65 DEG C dry 24 hours, obtain raw negative plate, obtain ripe negative plate by the method for tank formation.Adopt this negative plate and PbO
2base positive plate, electrolyte adopts the sulfuric acid of 1.28g/ml, and dresses up plumbous carbon superbattery with the modal sets of " two positive negative ".After tested, the initial capacity of battery compares comparative example 1(conventional lead acid battery) improve 34.7%; Carry out 750mA current charge-discharge electrical testing equally, the discharge capacity of battery also has the lifting of 32.3%; In cycle charge discharge electrical testing, the cycle performance of battery also improves 1.76 times; Pole plate after circulation does not have obvious oarse-grained lead sulfate to occur; Negative electrode active material after changing into is carried out to the test analysis of CV curve, redox peak current has obviously change large, and capacity also has lifting, the lead powder that material with carbon element prepared by the present invention is coated is described, in battery charge and discharge process, material with carbon element and lead powder have synergy, achieve the capacitive character of " two property " negative pole and cell performance.
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 60g lead powder again, after ultrasonic disperse 30min, move in the water-bath of 80 DEG C, carry out adding thermal agitation, until moisture in evaporate to dryness solution and alcohol, take out graphite and the coated lead powder of glucose, grind, put into tube furnace, in a nitrogen atmosphere, carry out 200 DEG C of carbonization 2h, obtain the powder composite of graphite coat.
Plumbous carbon superbattery is made: graphite coat powder composite 99, short fiber 0.2, barium sulfate 0.3, electrically conductive graphite 0.5 by the weight proportion of following material, 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%, carry out and cream at 50 DEG C, after having applied pole plate, at 50 DEG C, solidify 24 hours under the condition of relative humidity 90 ~ 98%, then at 65 DEG C dry 24 hours, obtain raw negative plate, obtain ripe negative plate by the method for tank formation.Adopt this negative plate and PbO
2base positive plate, electrolyte adopts the sulfuric acid of 1.28g/ml, and dresses up plumbous carbon superbattery with the modal sets of " two positive negative ".After tested, the initial capacity of battery compares comparative example 1(conventional lead acid battery) improve 31.9%; Carry out 750mA current charge-discharge electrical testing equally, the discharge capacity of battery also has the lifting of 25.1; In cycle charge discharge electrical testing, the cycle performance of battery also improves 1.77 times; Pole plate after circulation does not have obvious oarse-grained lead sulfate to occur; Negative electrode active material after changing into is carried out to the test analysis of CV curve, redox peak current has obviously change large, and capacity also has lifting, the lead powder that material with carbon element prepared by the present invention is coated is described, in battery charge and discharge process, material with carbon element and lead powder have synergy, achieve the capacitive character of " two property " negative pole and cell performance.
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 50g lead powder again, after ultrasonic disperse 30min, move in the water-bath of 80 DEG C, carry out adding thermal agitation, until moisture in evaporate to dryness solution and alcohol, take out graphite and the coated lead powder of glucose, grind, put into tube furnace, in a nitrogen atmosphere, carry out 200 DEG C of carbonization 5h, obtain the powder composite of graphite coat.
Plumbous carbon superbattery is made: graphite coat powder composite 99, short fiber 0.2, barium sulfate 0.3, electrically conductive graphite 0.5 by the weight proportion of following material, 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%, carry out and cream at 50 DEG C, after having applied pole plate, at 50 DEG C, solidify 24 hours under the condition of relative humidity 90 ~ 98%, then at 65 DEG C dry 24 hours, obtain raw negative plate, obtain ripe negative plate by the method for tank formation.Adopt this negative plate and PbO
2base positive plate, electrolyte adopts the sulfuric acid of 1.28g/ml, and dresses up plumbous carbon superbattery with the modal sets of " two positive negative ".After tested, the initial capacity of battery compares comparative example 1(conventional lead acid battery) improve 32.9%; Carry out 750mA current charge-discharge electrical testing equally, the discharge capacity of battery also has the lifting of 25.3%; In cycle charge discharge electrical testing, the cycle performance of battery also improves 1.68 times; Pole plate after circulation does not have obvious oarse-grained lead sulfate to occur; Negative electrode active material after changing into is carried out to the test analysis of CV curve, redox peak current has obviously change large, and capacity also has lifting, the lead powder that material with carbon element prepared by the present invention is coated is described, how in battery charge and discharge process, material with carbon element and lead powder have synergy, achieve the capacitive character of " two property " negative pole and cell performance.
Embodiment 6
Get 4g glucose and 0.02g bismuth oxide, add the deionized water of 20ml and the alcohol of 80ml, after stirring, add 60g lead powder again, after ultrasonic disperse 30min, move in the water-bath of 80 DEG C, carry out adding thermal agitation, until moisture in evaporate to dryness solution and alcohol, take out the lead powder that glucose is coated, grind, put into tube furnace, in a nitrogen atmosphere, carry out 200 DEG C of carbonization 2h, obtain the powder composite that carbon is coated.
Plumbous carbon superbattery is made: the coated powder composite 98 of carbon, short fiber 0.2, barium sulfate 0.3, electrically conductive graphite 1.5 by the weight proportion of following material, 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%, carry out and cream at 50 DEG C, after having applied pole plate, at 50 DEG C, solidify 24 hours under the condition of relative humidity 90 ~ 98%, then at 65 DEG C dry 24 hours, obtain raw negative plate, obtain ripe negative plate by the method for tank formation.Adopt this negative plate and PbO
2base positive plate, electrolyte adopts the sulfuric acid of 1.28g/ml, and dresses up plumbous carbon superbattery with the modal sets of " two positive negative ".After tested, the initial capacity of battery improves 28.5%; Carry out 750mA current charge-discharge electrical testing, the discharge capacity of battery also has the lifting of 24.1%; In cycle charge discharge electrical testing, the cycle performance of battery also improves 1.35 times; Pole plate after circulation does not have obvious oarse-grained lead sulfate to occur; Negative electrode active material after changing into is carried out to the test analysis of CV curve, redox peak current has obviously change large, and capacity also has lifting, the lead powder that material with carbon element prepared by the present invention is coated is described, how in battery charge and discharge process, material with carbon element and lead powder have synergy, achieve the capacitive character of " two property " negative pole and cell performance.
Embodiment 7
Get 4g glucose and 0.05g bismuth oxide, add the deionized water of 40ml and the alcohol of 80ml, after stirring, add 60g lead powder again, after ultrasonic disperse 30min, move in the water-bath of 80 DEG C, carry out adding thermal agitation, until moisture in evaporate to dryness solution and alcohol, take out the lead powder that glucose is coated, grind, put into tube furnace, in a nitrogen atmosphere, carry out 400 DEG C of carbonization 2h, obtain the powder composite that carbon is coated.
Plumbous carbon superbattery is made: the coated powder composite 98 of carbon, short fiber 0.2, barium sulfate 0.3, electrically conductive graphite 1.5 by the weight proportion of following material, 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%, carry out and cream at 50 DEG C, after having applied pole plate, at 50 DEG C, solidify 24 hours under the condition of relative humidity 90 ~ 98%, then at 65 DEG C dry 24 hours, obtain raw negative plate, obtain ripe negative plate by the method for tank formation.Adopt this negative plate and PbO
2base positive plate, electrolyte adopts the sulfuric acid of 1.28g/ml, and dresses up plumbous carbon superbattery with the modal sets of " two positive negative ".After tested, the initial capacity of battery improves 26.5%; Carry out 750mA current charge-discharge electrical testing, the discharge capacity of battery also has the lifting of 23.1%; In cycle charge discharge electrical testing, the cycle performance of battery also improves 1.25 times; Pole plate after circulation does not have obvious oarse-grained lead sulfate to occur; Negative electrode active material after changing into is carried out to the test analysis of CV curve, redox peak current has obviously change large, and capacity also has lifting, the lead powder that material with carbon element prepared by the present invention is coated is described, how in battery charge and discharge process, material with carbon element and lead powder have synergy, achieve the capacitive character of " two property " negative pole and cell performance.
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 50g lead powder again, after ultrasonic disperse 30min, move in the water-bath of 80 DEG C, carry out adding thermal agitation, until moisture in evaporate to dryness solution and alcohol, take out graphite and the coated lead powder of glucose, grind, put into tube furnace, in a nitrogen atmosphere, carry out 200 DEG C of carbonization 2h, obtain the powder composite of graphite coat.
Plumbous carbon superbattery is made: graphite coat powder composite 99, short fiber 0.2, barium sulfate 0.3, electrically conductive graphite 0.5 by the weight proportion of following material, 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%, carry out and cream at 50 DEG C, after having applied pole plate, at 50 DEG C, solidify 24 hours under the condition of relative humidity 90 ~ 98%, then at 65 DEG C dry 24 hours, obtain raw negative plate, obtain ripe negative plate by the method for tank formation.Adopt this negative plate and PbO
2base positive plate, electrolyte adopts the sulfuric acid of 1.28g/ml, and dresses up plumbous carbon superbattery with the modal sets of " two positive negative ".After tested, the initial capacity of battery compares comparative example 1(conventional lead acid battery) improve 32.1%; Carry out 750mA current charge-discharge electrical testing equally, the discharge capacity of battery also has the lifting of 24.8%; In cycle charge discharge electrical testing, the cycle performance of battery also improves 1.75 times; Pole plate after circulation does not have obvious oarse-grained lead sulfate to occur; Negative electrode active material after changing into is carried out to the test analysis of CV curve, redox peak current has obviously change large, and capacity also has lifting, the lead powder that material with carbon element prepared by the present invention is coated is described, in battery charge and discharge process, material with carbon element and lead powder have synergy, achieve the capacitive character of " two property " negative pole and cell performance.
Embodiment 9
Get 2g graphite, 1.5g glucose, add the deionized water of 30ml and the alcohol of 40ml, after stirring, add 40g lead powder again, after ultrasonic disperse 30min, move in the water-bath of 80 DEG C, carry out adding thermal agitation, until moisture in evaporate to dryness solution and alcohol, take out graphite and the coated lead powder of glucose, grind, put into tube furnace, in a nitrogen atmosphere, carry out 200 DEG C of carbonization 2h, obtain the powder composite of graphite coat.
Plumbous carbon superbattery is made: graphite coat powder composite 99, short fiber 0.2, barium sulfate 0.3, electrically conductive graphite 0.5 by the weight proportion of following material, 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%, carry out and cream at 50 DEG C, after having applied pole plate, at 50 DEG C, solidify 24 hours under the condition of relative humidity 90 ~ 98%, then at 65 DEG C dry 24 hours, obtain raw negative plate, obtain ripe negative plate by the method for tank formation.Adopt this negative plate and PbO
2base positive plate, electrolyte adopts the sulfuric acid of 1.28g/ml, and dresses up plumbous carbon superbattery with the modal sets of " two positive negative ".After tested, the initial capacity of battery compares comparative example 1(conventional lead acid battery) improve 30.9%; Carry out 750mA current charge-discharge electrical testing equally, the discharge capacity of battery also has the lifting of 24.7%; In cycle charge discharge electrical testing, the cycle performance of battery also improves 1.71 times; Pole plate after circulation does not have obvious oarse-grained lead sulfate to occur; Negative electrode active material after changing into is carried out to the test analysis of CV curve, redox peak current has obviously change large, and capacity also has lifting, the lead powder that material with carbon element prepared by the present invention is coated is described, in battery charge and discharge process, material with carbon element and lead powder have synergy, achieve the capacitive character of " two property " negative pole and cell performance.
Embodiment 10
Get 4g glucose, add the deionized water of 30ml and the alcohol of 40ml, after stirring, add 40g lead powder again, after ultrasonic disperse 30min, move in the water-bath of 80 DEG C, carry out adding thermal agitation, until moisture in evaporate to dryness solution and alcohol, take out the lead powder that glucose is coated, grind, put into tube furnace, in a nitrogen atmosphere, carry out 200 DEG C of carbonization 5h, obtain the powder composite that carbon is coated.
Plumbous carbon superbattery is made: the coated powder composite 98 of carbon, short fiber 0.2, barium sulfate 0.3, electrically conductive graphite 1.5 by the weight proportion of following material, 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%, carry out and cream at 50 DEG C, after having applied pole plate, at 50 DEG C, solidify 24 hours under the condition of relative humidity 90 ~ 98%, then at 65 DEG C dry 24 hours, obtain raw negative plate, obtain ripe negative plate by the method for tank formation.Adopt this negative plate and PbO
2base positive plate, electrolyte adopts the sulfuric acid of 1.28g/ml, and dresses up plumbous carbon superbattery with the modal sets of " two positive negative ".After tested, the initial capacity of battery improves 28.1%; Carry out 750mA current charge-discharge electrical testing, the discharge capacity of battery also has the lifting of 20.0%; In cycle charge discharge electrical testing, the cycle performance of battery also improves 1.22 times; Pole plate after circulation does not have obvious oarse-grained lead sulfate to occur; Negative electrode active material after changing into is carried out to the test analysis of CV curve, redox peak current has obviously change large, and capacity also has lifting, the lead powder that material with carbon element prepared by the present invention is coated is described, in battery charge and discharge process, material with carbon element and lead powder have synergy, achieve the capacitive character of " two property " negative pole and cell performance.
Claims (5)
1. a Carbon-material-coatlead lead powder composite material, it is prepared by the following method: in reaction vessel, add material with carbon element, thickener, liberation of hydrogen inhibitor, alcohol and deionized water, lead powder is added after mixing, heating removing moisture and alcohol after ultrasonic disperse, make lead powder coated upper material with carbon element equably, then tube furnace is adopted to carry out sintering carbonization under the protection of inert protective gas, carburizing temperature is 200 ~ 600 DEG C, carbonization time is 0.5 ~ 10h, grinding is sieved, and obtains the composite material of the coated lead powder of material with carbon element; 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; Described material with carbon element is one or several the combination in graphite, active carbon, acetylene black, mesoporous carbon, Graphene and carbon nano-tube.
2. Carbon-material-coatlead lead powder composite material as claimed in claim 1, is characterized in that: described thickener is one or several the combination in carbohydrate, cellulose family, polyacrylate, gelatin and polyvinyl alcohol; Described liberation of hydrogen inhibitor is one or several in indium oxide, bismuth oxide, zinc oxide, calcium oxide, gallium oxide, lead oxide.
3. Carbon-material-coatlead lead powder composite material as claimed in claim 2, 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 1 ~ 5:0.5 ~ 2:0.01 ~ 0.05:50 ~ 80:20 ~ 50:30 ~ 60.
4. the Carbon-material-coatlead lead powder composite material as described in one of claims 1 to 3, is characterized in that: the ultrasonic disperse time is 0.5 ~ 6h.
5. Carbon-material-coatlead lead powder composite material as claimed in claim 1 is as the application of the negative material of plumbous carbon superbattery.
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| CN103956484B (en) * | 2014-04-17 | 2017-06-20 | 深圳市瑞达电源有限公司 | Graphene coated lead composite material and preparation method thereof, lead-acid battery |
| CN104600254B (en) * | 2014-12-10 | 2017-01-11 | 湖南安圣电池有限公司 | Lead carbon electrode and preparation method thereof |
| CN106876711B (en) * | 2015-12-13 | 2019-08-09 | 中国科学院大连化学物理研究所 | A kind of metallic element adulterates carbon-coated lead powder and its preparation and application |
| CN107230776B (en) * | 2016-03-23 | 2019-11-12 | 曾怡仁 | Production method, the structure of lead carbon electrode piece and the structure of lead carbon battery of lead carbon engagement |
| CN106129368B (en) * | 2016-08-23 | 2019-02-19 | 宁波中科孚奇能源科技有限公司 | Absorbent charcoal composite material, preparation method and the lead carbon battery using the absorbent charcoal composite material |
| CN106654217A (en) * | 2017-01-09 | 2017-05-10 | 江苏海宝电池科技有限公司 | Composite carbon negative-electrode active material for lead carbon power battery as well as preparation method and application of composite carbon negative-electrode active material |
| CN108318558B (en) * | 2018-01-12 | 2019-08-16 | 湖南大学 | Load the ordered mesopore carbon and its preparation method and application of hollow sphere bismuth oxide |
| CN108717969B (en) * | 2018-04-23 | 2021-01-26 | 超威电源集团有限公司 | Preparation method and application of graphene-coated lead-lead oxide composite material |
| CN111509197B (en) * | 2019-01-31 | 2021-11-19 | 山东欧铂新材料有限公司 | Modified activated carbon composite material for negative electrode of lead-carbon battery, preparation method of modified activated carbon composite material and lead-carbon battery |
| CN110286147B (en) * | 2019-06-26 | 2020-09-15 | 浙江大学 | Carbon-coated zinc oxide material for acetone gas sensing and preparation method thereof |
| CN112928261B (en) * | 2021-02-24 | 2022-08-05 | 超威电源集团有限公司 | Lead powder with lead oxide activated carbon graphene core-shell structure and preparation method thereof |
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