CN104393250A - Preparation method for lead-carbon composite material of lead acid battery and composite negative plate - Google Patents
Preparation method for lead-carbon composite material of lead acid battery and composite negative plate Download PDFInfo
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- CN104393250A CN104393250A CN201410564028.8A CN201410564028A CN104393250A CN 104393250 A CN104393250 A CN 104393250A CN 201410564028 A CN201410564028 A CN 201410564028A CN 104393250 A CN104393250 A CN 104393250A
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/362—Composites
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/14—Electrodes for lead-acid accumulators
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
- H01M4/56—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of lead
- H01M4/57—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of lead of "grey lead", i.e. powders containing lead and lead oxide
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/58—Selection of substances as active materials, active masses, active liquids of inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy; of polyanionic structures, e.g. phosphates, silicates or borates
- H01M4/583—Carbonaceous material, e.g. graphite-intercalation compounds or CFx
- H01M4/5835—Comprising fluorine or fluoride salts
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- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
Abstract
The invention provides a preparation method for a lead-carbon composite material of a lead acid battery and a composite negative plate. The lead-carbon composite material of the lead acid battery is prepared through chemical action between lead salt and a precursor. Since lead is a high-hydrogen-evolution overpotential metal, the hydrogen evolution overpotential of the carbon material obtained through preparation is improved obviously after the carbon material is modified through lead oxide, so as to achieve the purpose that the carbon material is matched with the lead cathode potential. More importantly, according to the preparation method, a carbon source and lead salt are combined firstly, and then lead oxide is loaded on the carbon material in an in-situ manner through calcination, so that the dimensions of lead oxide particles loaded on the prepared composite material are nanoscale, good dispersibility, no accumulation or agglomeration are achieved, a very good hydrogen suppression effect is achieved, and the affinity of the carbon material to active materials is improved. The lead/carbon composite negative plate prepared from the lead-carbon composite material can improve the cycling stability of the battery, and the cycle life of the battery is greatly prolonged under a high rate partial state of charge (HPRSoC).
Description
Technical field
The present invention relates to field of electrochemical power source, specifically a kind of lead-acid battery preparation method of plumbous carbon composite and composite negative plate.
Background technology
Along with the worsening shortages of traditional energy, new energy technology more and more obtains the attention of people, and therefore, a lot of country all starts to pay attention to the research to new forms of energy power vehicle.As the core of power vehicle, electrokinetic cell plays conclusive effect.On the current technology, the battery of alternative comparative maturity has lithium ion battery, Ni-MH battery and lead-acid battery, but by the consideration of some aspect such as fail safe and price factors, lithium ion battery and Ni-MH battery are difficult to be applied on a large scale at short notice.Relative to first two battery, traditional lead acid batteries is cheap, and fail safe is good, technology maturation, and also have other battery incomparable advantage--the old and useless battery rate of recovery is high, this makes the extensive use of lead-acid battery on new forms of energy power vehicle become possibility.But hybrid vehicle electrokinetic cell used require its can under high magnification partial state of charge fast charging and discharging, there is the ability of big current fast charging and discharging, and traditional lead acid batteries is when running in such a situa-tion, negative plate can build up a large amount of irreversible lead sulfate crystal, and form hard sulfuric acid lead layer on the surface of lead, the resistance of active material on electrode will be made like this to increase, inner active material can not get effective utilization, reduce the charge efficiency of battery, finally cause the inefficacy of battery.
For the problems referred to above, 2004, the Commonwealth Scientific and Industrial Research Organization (CSIR O) of Australia first proposed " superbattery " this concept, go so far as present plumbous carbon battery, both principles are the same in fact, all that material with carbon element is used lead-acid battery, by the hybrid accumulator that ultracapacitor and lead acid accumulator merge into a single whole, when battery runs under high magnification partial state of charge, electrode for capacitors (material with carbon element) can share plumbous cathodal current, play a buffer, the plumbous negative pole of available protecting, avoid the irreversible sulfation of negative pole, thus promote the cycle life of battery.This hybrid technology can be accelerated at automobile and export fast and input charge during braking, can improve the power nature of battery, extend battery cycle life of (HPRSoC) under high magnification partial state of charge.
But because the operating potential of material with carbon element and the operating potential of plumbous negative pole differ greatly, if both be compounded in an individual system, in discharge process, most of discharging current all comes from plumbous negative pole, and when charging, material with carbon element preferentially will charge than plumbous negative pole.More seriously, because the hydrogen-evolution overpotential of material with carbon element itself is lower, battery can there is very serious hydrogen evolution phenomenon in material with carbon element after arriving latter stage of charging, and makes battery dehydration serious, reduces the charge efficiency of battery, greatly affect the performance of battery.
Add the problem of rear generation for material with carbon element, researcher both domestic and external has also carried out a lot of research.Publication number is that the Chinese patent of 102024946A discloses a kind of super lead storage battery negative plate formula, adding on the basis of various carbon materials in lead plaster, reached the object pressing down hydrogen by the one or more combination of adding in tin oxide, bismuth oxide, cerium oxide.But this mechanical agitation is simply difficult to liberation of hydrogen inhibitor to mix with lead plaster, therefore liberation of hydrogen inhibitor is difficult to play its effect pressing down hydrogen.
Publication number is propose liberation of hydrogen inhibitor (In in the Chinese patent of 102306784A
2o
3, Bi
2o
3and Ga
2o
3one or more mixed compounds) be loaded on active carbon by ball-milling method or solvent precipitation, the active carbon overpotential of hydrogen evolution of modification is improved, thus significantly improves the cycle performance of battery.Publication number is that the Chinese patent of 102263250A utilizes simple infusion process by the surface of PbO load at active carbon, improves the cycle life of battery under high magnification partial state of charge.
Document (H. Q. Wang, J. G. Yu, Y. N. Zhao, et al. A facile route for PbO C nanocomposites:An electrode candidate for lead-acid batteries with enhanced capacitance [J]. Journal of Power Sources, 224 (2013): 125-131) a kind of method that lead/carbon composite electrode material (abbreviation PbO@C nano combination electrode material) prepared by starch of different proportion and plumbi nitras is proposed in, the electrode discharge capacity prepared with this combination electrode material is maximum can reach 205 mAh g
-1, and capacity still has 185 mAh g after circulation 100 is enclosed
-1.
Above-mentioned several patents are all utilize simple chemical deposition by the load of liberation of hydrogen inhibitor on the surface of material with carbon element, but the method like this only by simple dipping and precipitation cannot by uniform for liberation of hydrogen inhibitor load on the carbon material, and but this makes liberation of hydrogen inhibitor to play well hydrogen effect.And the loaded article particle size obtained by this method is excessive, and the reunion of heap sum very easily occurs, such additive can affect battery performance on the contrary, does not reach the object of expection.And although the people such as H.Q.Wang it is also proposed a kind of method preparing PbO@C nano combination electrode material in the literature, but what they mainly discussed is replace lead powder to use as the electrode raw material of lead-acid battery PbO@C nano combination electrode material, instead of as a kind of additive; And the PbO@C nano combination electrode material provided in document is just obtained by simple physical mixed and calcining, and the combination electrode material main body of preparation is lead oxide, and the effect of material with carbon element mainly prevents reunion and the volumetric expansion of lead oxide.
Summary of the invention
The present invention causes the problem of service life reduction to solve existing lead-acid battery due to hydrogen evolution phenomenon, provide preparation method and the composite negative plate of the plumbous carbon composite of a kind of lead-acid battery, can be good at the hydrogen evolution phenomenon improving plumbous carbon battery negative pole, increase substantially the cyclical stability of battery and the cycle life under high magnification partial state of charge.
The preparation method of plumbous carbon composite comprises the following steps lead-acid battery provided by the invention:
1) join in ethanol by organic carbon source, be heated to 70 ° of more than C, make it be dissolved in ethanol completely, the molar concentration of solution is 1 ~ 5mol/L;
2) join in above-mentioned solution by the solubility lead salt of 0.5 mol/L, the mol ratio of organic carbon source and solubility lead salt is 2 ~ 10:1, constantly stirs in a heated condition, until ethanol all evaporates, obtains white powder;
3) by above-mentioned white powder at N
2under atmosphere, with 1 ~ 5
othe heating rate of C/min, at temperature lower calcination 2 ~ 12 h of 550 ~ 600 ° of C, obtains plumbous carbon composite.
Organic carbon source described in step 1) is the organic substance containing benzoic acid group, can be benzoic acid or p-aminobenzoic acid.
Step 2) described in solubility lead salt be one in acetate, nitrate, hydrochloride and complex salt containing lead element.
Present invention also offers and a kind ofly comprise the composite negative plate of described lead-acid battery with plumbous carbon composite, comprise following component: lead powder, sulfuric acid solution, barium sulfate, lignin, humic acid, short fiber, distilled water, acetylene black, graphite, lead/carbon composite electrode material, wherein, sulfuric acid solution quality is 4% ~ 18% of lead powder quality; Barium sulfate quality is 0.1% ~ 3.0% of lead powder quality; Lignin quality is 0.1% ~ 2.0% of lead powder quality; Humic acid quality is 0.1% ~ 2.0% of lead powder quality; Short fiber quality is 0.01% ~ 0.2% of lead powder quality; Distilled water quality is 5% ~ 20% of lead powder quality; Acetylene black quality is 0.1% ~ 2.5% of lead powder quality; Graphite quality is 0.1% ~ 2.5% of lead powder quality; Plumbous carbon composite quality is 0.5% ~ 10% of lead powder quality.
Further restriction, described plumbous carbon composite quality is 1% ~ 6% of lead powder quality.
Further restriction, described plumbous carbon composite quality is 1% ~ 3% of lead powder quality.
Further restriction, described degree of oxidation of lead powder is 78%.
Further restriction, described sulfuric acid solution density is 1.4 g/mL.
All batchings carried out and cream according to general technique, apparent density of lead paste controls at 4.2 ~ 4.5 g/cm
3, can cathode lead plaster be obtained.Above-mentioned obtained cathode lead plaster is coated on negative electrode grid, and is conventionally cured and changes into, can composite negative plate be obtained.
Beneficial effect of the present invention is:
1, the plumbous carbon composite (hereinafter referred to as PbO@C composite) in the present invention is compared only by simply flooding the composite material obtained with intermediate processing with other, the PbO size of load is not only nanoscale, and can well-proportioned dispersion on the carbon material, thus better inhibitory action can be played to the liberation of hydrogen behavior of material with carbon element.Experimental result shows, relative to common commercial active carbon, the overpotential of hydrogen evolution of PbO@C composite improves 150 more than mV;
2, nano level PbO uniform load on the carbon material, effectively can not only suppress the liberation of hydrogen situation on material with carbon element, and can for discharge and recharge reaction provides multiple avtive spot in circulating battery process, along with the PbO be carried on material with carbon element electrochemical conversion to Pb in the use procedure of battery, Pb in itself and lead plaster can form a kind of cross-linked structure, thus material with carbon element is pinned at lead plaster inside, fundamentally solve the problem that in traditional handicraft, pole plate carbon is separated out, greatly improve the useful life of battery;
3, composite material of the present invention is the composite material of uniform load nanometer PbO on the carbon material, which increase the compatibility of material with carbon element anticathode active material, enable the two mixing fully with during cream, the problem of the mixing inequality brought due to the greatest differences of surface property between material with carbon element and lead powder when solving traditional handicraft and cream;
4, adopt the battery charging and discharging that lead of the present invention/carbon compound polar plate is assembled into functional, cycle life performance is superior, particularly under high magnification partial state of charge, the cycle-index of (HPRSoC) can reach 9375 times, relative to conventional lead acid battery, performance improves clearly, is applicable to being applied on hybrid-electric car.
Accompanying drawing explanation
Fig. 1: reaction principle figure of the present invention.
Fig. 2: the XRD phenogram of the PbO@C composite that embodiment 5 obtains;
Fig. 3: the SEM figure of the PbO@C composite that embodiment 5 obtains;
Fig. 4: the thermogravimetric curve of the PbO@C composite that embodiment 5 obtains;
Fig. 5: the PbO@C composite that embodiment 5 obtains and the linear scan curve comparison of active carbon;
Fig. 6: the PbO@C composite that embodiment 5 obtains and the current versus time curve of active carbon under the permanent electromotive force of-1.4 V contrast;
Fig. 7: the cyclical stability of battery under 0.5 C that the battery that embodiment 6 obtains obtains with comparative example 1 and comparative example 2 compares;
Fig. 8: battery cycle-index of (HPRSoC) under high magnification partial state of charge that the battery that embodiment 6 obtains obtains with comparative example 1 and comparative example 2 compares;
Fig. 9: the battery that the obtained battery of embodiment 6 and comparative example 1 obtain different partial circulating charging/discharging voltage curve comparisons of (HPRSoC) under high magnification partial state of charge;
Figure 10: after the circulating battery that the obtained battery of embodiment 6 and comparative example 1 obtain, the SEM of negative plate schemes to contrast.
Embodiment
The present invention is using this kind of organic substance containing benzoic acid group of benzoic acid (p-aminobenzoic acid etc.) as carbon source, and reason is, between their energy and metal ions, substitution reaction occurs, and is closely linked by chemical bond and metal ion.Conveniently explain reaction mechanism of the present invention, specifically set forth for benzoic acid and lead acetate below.As shown in Figure 1, when reacting as the benzoic acid of carbon source and lead acetate, the carboxyl hydrogen on benzoic acid will be replaced by lead ion, and a lead ion can replace two carboxyl hydrogen.In this way benzoic acid and lead ion are combined, then in the mode of calcining by the load of lead oxide original position on the carbon material.
The composite material of a kind of nano level lead oxide uniform load on material with carbon element can be obtained by above-mentioned mode, this composite material can be good at the hydrogen evolution phenomenon improving plumbous carbon battery negative pole, increases substantially the cyclical stability of battery and the cycle life under high magnification partial state of charge.
Below in conjunction with specific embodiment, the invention will be further described.
Below by way of specific embodiment, foregoing of the present invention is described in further detail.But this should be interpreted as content of the present invention is only limitted to following example.
Embodiment 1
The preparation method of the PbO@C composite of the present embodiment is: the benzoic acid of certain mass joins in ethanol by <1>, is heated to 70 ° of C, makes it be dissolved in ethanol completely, and solution concentration is 1 mol/L; The plumbi nitras of 0.5 mol/L joins in above-mentioned solution by <2>, constantly stirs in a heated condition, until ethanol all evaporates, obtains white powder; <3> by above-mentioned white powder at N
2under atmosphere, with 1
othe heating rate of C/min is 600
otemperature lower calcination 12 h of C, obtains the PbO@C composite of black.
Embodiment 2
The preparation method of the PbO@C composite of the present embodiment is: the benzoic acid of certain mass joins in ethanol by <1>, is heated to 70 ° of C, makes it be dissolved in ethanol completely, and solution concentration is 2 mol/L; The salt lead plumbate of 0.5 mol/L joins in above-mentioned solution by <2>, constantly stirs in a heated condition, until ethanol all evaporates, obtains white powder; <3> by above-mentioned white powder at N
2under atmosphere, with 5
othe heating rate of C/min is 500
otemperature lower calcination 7 h of C, obtains the PbO@C composite of black.
Embodiment 3
The preparation method of the PbO@C composite of the present embodiment is: the benzoic acid of certain mass joins in ethanol by <1>, is heated to 70 ° of C, makes it be dissolved in ethanol completely, and solution concentration is 3 mol/L; The lead acetate of 0.5 mol/L joins in above-mentioned solution by <2>, constantly stirs in a heated condition, until ethanol all evaporates, obtains white powder; <3> by above-mentioned white powder at N
2under atmosphere, with 3
othe heating rate of C/min is 550
otemperature lower calcination 2 h of C, obtains the PbO@C composite of black.
Embodiment 4
The present embodiment place different from embodiment 1 is that benzoic concentration becomes 5 mol/L, and all the other are identical with embodiment 1.
Embodiment 5
(1) preparation method and the ratio of PbO@C composite and the identical of embodiment 3 in the present embodiment.
(2) batching needed for cathode lead plaster carried out and proportioning according to certain formula, wherein required batching has: oxidizability is the lead powder of 78%; Density is the sulfuric acid solution of 1.4 g/mL; Barium sulfate; Lignin; Humic acid; Short fiber; Distilled water; Acetylene black; Graphite; PbO@C composite.Wherein, sulfuric acid solution quality is 10% of lead powder quality; Barium sulfate quality is 2% of lead powder quality; Lignin quality is 1% of lead powder quality; Humic acid quality is 1% of lead powder quality; Short fiber quality is 0.1% of lead powder quality; Distilled water quality is 10% of lead powder quality; Acetylene black quality is 1% of lead powder quality; Graphite quality is the adding proportion of 1%, PbO@C composite of lead powder quality is 1.0% of lead powder quality.
(3) all batchings carried out and cream according to general technique, apparent density of lead paste controls at 4.2 g/cm
3.
(4) above-mentioned obtained cathode lead plaster is coated on negative electrode grid, and is conventionally cured and changes into, obtained composite negative plate.
(5) performance test:
A, XRD characterize: Fig. 2 is the XRD diffraction pattern of this composite material, and by this diffracting spectrum and standard card contrast, the peak energy on gained peak and PbO standard card reaches one_to_one corresponding; Material with carbon element without obvious peak, illustrates that the carbon that we obtain is amorphous carbon in this diffracting spectrum.Can confirm that the material obtained by us is PbO@C composite from XRD diffraction pattern.
B, SEM characterize: Fig. 3 is the SEM photo of PbO@C composite, wherein the nanometer PbO for load of arrow mark.As seen from Figure 2, size is in the PbO uniform particles load of tens ran on porous carbon materials, and Granular composite is good, between do not pile sum and reunite.
C, thermogravimetric analysis: Fig. 4 is the thermogravimetric curve of PbO@C composite, and this curve is in air atmosphere with 10 by composite material
othe heating rate of C/min is from 30
oc is warmed up to 800
orecord under C.In temperature-rise period, the carbon in composite material can slowly be burnt, and the PbO of load is by stable existence, therefore can be obtained the concrete content of the nanometer PbO of material with carbon element and load in composite material by thermogravimetric curve.As can be seen from Figure 4, the carbon in composite material is 300
oc ~ 500
obe consumed in the temperature range of C, the content that finally can obtain material with carbon element in composite material is 75.8%, and the content of the nanometer PbO of load is 24.2%.
D, liberation of hydrogen rate test: above-mentioned composite material is made electrode, linear scanning method is utilized to test its liberation of hydrogen speed, and the result that itself and commercial activated carbons obtain is contrasted, curve obtained as shown in Figure 5, wherein red dotted line is active carbon (AC) electrode, and black solid line is PbO@C composite electrode, and result shows, the overpotential of hydrogen evolution of PbO@C composite electrode is apparently higher than activated carbon electrodes, and overpotential of hydrogen evolution improves 150 more than mV.
In order to further illustrate PbO@C composite to the improvement of liberation of hydrogen speed, its current versus time curve under the permanent electromotive forces of-1.4 V can be tested, and the curve that itself and active carbon obtain is contrasted, acquired results as shown in Figure 6, as seen from the figure, PbO@C composite electrode and the liberation of hydrogen electric current of active carbon (AC) electrode when-1.4 V are respectively 20.05 mA and 48.31 mA, the liberation of hydrogen speed of PbO@C composite is far smaller than active carbon, and the result that this and linear scanning method obtain is consistent.
The preparation process of electrode is specially: apply on a current collector by PbO C composite (active carbon), acetylene black, PTFE after being mixed into paste according to a certain percentage, dry and obtain electrode; Then it can be used as work electrode, platinum electrode is to electrode, Hg/Hg
2sO
4electrode is reference electrode, utilizes three-electrode system to complete test.
E, battery performance test: above-mentioned negative plate and business positive plate are assembled into simulated battery, then utilize one to obtain work system that international advanced lead-acid battery federation (ALABC) approves carrys out test battery cycle performance of (HPRSoC) under high magnification partial state of charge, concrete test process is: first use 1 C current discharge to 50% SoC to the battery being full of electricity, then carry out single microcirculation test.Microcirculation work system is: leave standstill 60 s after 2 C current charges 60 s, then use 2 C current discharge 60 s, carries out next microcirculation after leaving standstill 60 s; The voltage of battery is measured in the latter stage of each microcirculation charging and discharging, upper voltage limit for cell setting is 2.83 V, lower limit is 1.83 V, when discharge voltage is lower than 1.83 V or when charging voltage stops battery testing more than during 2.83 V, constitute the charge and discharge cycles test of a unit.Adopt new prestige BTS series battery ability meter, utilize above-mentioned work system, the cycle-index of battery under HPRSoC recording interpolation 1.0% PbO@C composite is 7868 times.
Embodiment 6
(1) adding proportion of the present embodiment PbO@C composite as different from Example 5 becomes 1.5% of lead powder quality, and additive method is identical with embodiment 5 with parameter.
(2) adopt new prestige BTS series battery ability meter, the cycle-index of battery under HPRSoC recording interpolation 1.5% PbO@C composite is 9375 times.
Embodiment 7
(1) adding proportion of the present embodiment PbO@C composite as different from Example 5 becomes 2.0% of lead powder quality, and additive method is identical with embodiment 5 with parameter.
(2) adopt new prestige BTS series battery ability meter, the cycle-index of battery under HPRSoC recording interpolation 2.0% PbO@C composite is 8515 times.
Embodiment 8
(1) adding proportion of the present embodiment PbO@C composite as different from Example 5 becomes 3.0% of lead powder quality, and additive method is identical with embodiment 5 with parameter.
(2) adopt new prestige BTS series battery ability meter, the cycle-index of battery under HPRSoC recording interpolation 3.0% PbO@C composite is 7267 times.
(3) according to the experimental result of embodiment 5 ~ 8, can obtain PbO@C composite coefficient optimum proportion is in the battery 1.5% of lead powder quality, therefore using the interpolation standard of this ratio as several embodiment below, and the battery that the battery and comparative example that add the composite material assembling of this ratio are assembled is carried out the contrast of performance.
Embodiment 9
(1) preparation method of the PbO@C composite of the present embodiment is: the p-aminobenzoic acid of certain mass joins in ethanol by <1>, be heated to 70 ° of C, make it be dissolved in ethanol completely, solution concentration is 3 mol/L; The lead acetate of 0.5 mol/L joins in above-mentioned solution by <2>, constantly stirs in a heated condition, until ethanol all evaporates, obtains white powder; <3> by above-mentioned white powder at N
2under atmosphere, with temperature calcination 2 h of 600 ° of C, obtain the PbO@C composite of black.
(2) batching needed for cathode lead plaster is carried out proportioning according to certain formula, wherein required batching has: oxidizability is the lead powder of 78%; Density is the sulfuric acid solution of 1.4 g/mL; Barium sulfate; Lignin; Humic acid; Short fiber; Distilled water; Acetylene black; Graphite; PbO@C composite.Wherein the adding proportion of PbO@C composite is 1.5% of lead powder quality.
(3) all batchings carried out and cream according to general technique, apparent density of lead paste controls at 4.5 g/cm
3.
(4) above-mentioned obtained cathode lead plaster is coated on negative electrode grid, and is conventionally cured and changes into, obtained composite negative plate.
Embodiment 10
The present embodiment place different from embodiment 9 is that lead salt used becomes plumbi nitras, and calcining heat becomes 550 ° of C, and calcination time becomes 6 h, and all the other are identical with embodiment 9.
Embodiment 11
The present embodiment place different from embodiment 9 is that organic carbon source becomes benzoic acid, and calcining heat becomes 550 ° of C, and calcining heat becomes 12 h, and all the other are identical with embodiment 9.
Embodiment 12
The present embodiment place different from embodiment 9 is that organic carbon source becomes benzoic acid, and lead salt used becomes plumbi nitras, and all the other are identical with embodiment 9.
The effect of patent of the present invention is further illustrated below by two comparative examples.
Comparative example 1
(1) batching needed for cathode lead plaster is carried out proportioning according to certain formula, wherein required batching has: oxidizability is the lead powder of 78%; Density is the sulfuric acid solution of 1.4 g/mL; Barium sulfate; Lignin; Humic acid; Short fiber; Distilled water; Acetylene black; Graphite; Active carbon.Active carbon wherein used is the commercial activated carbons of standard, without any process.
(2) above-mentioned batching carried out and cream according to general technique, apparent density of lead paste controls at 4.2 g/cm
3.
(3) above-mentioned obtained cathode lead plaster is coated on negative electrode grid, and is conventionally cured and changes into, obtained negative plates.
Comparative example 2
(1) batching needed for cathode lead plaster is carried out proportioning according to certain formula, in wherein required batching and comparative example 1, have passed through modification unlike active carbon used.
(2) preparation method of above-mentioned modified activated carbon is: be immersed in by a certain amount of absorbent charcoal material in dissoluble lead salting liquid, stirring is in conjunction with sonic oscillation, lead ion is made to enter into the hole of absorbent charcoal material or in its surface attached, then add excess of ammonia water, after fully stirring, lead ion is precipitated completely, suction filtration, then by fully dry for the filter cake obtained, then calcine under 250 ° of C, obtain the absorbent charcoal material of load P bO.
(3) all batchings carried out and cream according to general technique, apparent density of lead paste controls at 4.2 g/cm
3.
(4) above-mentioned obtained cathode lead plaster is coated on negative electrode grid, and is conventionally cured and changes into, obtained negative plates.
Experiment content
(1) cyclical stability of battery under 0.5 C electric current
The stability of battery in cyclic process is a major criterion of assessment battery performance quality, and the battery that embodiment 6 and comparative example 1, comparative example 2 are assembled is carried out contrast experiment by patent of the present invention.3 Battery packs changed into are carried out charge-discharge test under 0.5 C electric current, and cycle-index is decided to be 200 times, and test result as shown in Figure 7.As can be seen from figure we, the battery cell 1 adding common commercial active carbon circulates the more serious of capacity attenuation after 200 times, although the battery cell 2 adding conventional impregnation modified activated carbon can improve the situation of capacity attenuation a little, but effect is not clearly, and the battery cell 3 adding 1.5% PbO@C composite obviously can improve the capacity attenuation of battery, significantly promote the cyclical stability of battery.
(2) battery cycle performance of (HPRSoC) under high magnification partial state of charge
What the cycle performance of battery under HPRSoC embodied is the ability that battery carries out fast charging and discharging under big current, and this is as one of micro-mixed HEV electrokinetic cell very important standard.That the battery utilizing embodiment 6 and comparative example 1, comparative example 2 to assemble carries out contrast experiment equally.3 Battery packs changed into are full of electricity, then carry out cycle life test with 1 C electric current by after battery discharge to 50% SoC: 2 C charge 60 s, leave standstill 60 s, 2 C discharge 60 s, and leave standstill 60 s, upper voltage limit is 2.83 V, lower limit is 1.83 V, and test result as shown in Figure 8.From figure, we can find out that the cycle-index of battery cell 1 under HPRSoC of adding common commercial active carbon is 3367 times, the cycle-index of battery cell 2 under HPRSoC of adding conventional impregnation modified activated carbon is 6513 times, and the cycle-index of battery cell 3 under HPRSoC of adding 1.5% PbO@C composite is 9375 times, this illustrates that the interpolation of PbO@C composite significantly can promote the cycle life of battery under HPRSoC.
In order to explain the reason that the interpolation of PbO@C composite significantly improves cycle performance of battery, battery battery obtained for embodiment 6 and comparative example 1 obtained different partial circulating charging/discharging voltage curve of (HPRSoC) under high magnification partial state of charge contrasts with the rear negative pole shape appearance figure that circulates.
(1) battery that the battery that embodiment 6 is obtained and comparative example 1 obtain different partial circulating charging/discharging voltage curve comparisons of (HPRSoC) under high magnification partial state of charge: as shown in Figure 9, wherein a figure is battery cell 1, the b figure of interpolation common commercial active carbon is the battery cell 3 adding PbO@C composite.In cyclic process, the end of charge voltage adding the battery cell 3 of PbO@C composite is less than the battery cell 1 adding common commercial active carbon, and the final discharging voltage of cell 3 is greater than cell 1, this illustrates that the interpolation of PbO@C composite can reduce the polarization of negative plate, thus promotes the cycle performance of battery.As can be seen from the contrast of two width figure, it is not very large that the charging voltage of two kinds of batteries changes in different partial circulatings, and the factor really affecting battery cycle life under HPRSoC is discharge voltage.Add the cell 1 of common commercial active carbon in such as a figure, its final discharging voltage drops to 1.8303 V of the 3367th (cell 1 is last) partial circulating from 2.0114 V of the 1st partial circulating; And the final discharging voltage adding cell 3 the 1st partial circulating of PbO@C composite in b figure is 2.05 V, the final discharging voltage of the 3367th partial circulating is 1.9831 V, 6000th time is 1.9134 V, until the final discharging voltage of the 9375th (cell 3 is last) partial circulating is 1.8315 V.It can thus be appreciated that it is more slow that the battery discharge voltage in cyclic process adding PbO@C composite declines, and polarizes less, thus make cycle life longer.
(2) after the circulating battery that the battery that embodiment 6 is obtained and comparative example 1 obtain, negative pole shape appearance figure contrasts: as shown in Figure 10, wherein a figure is negative pole shape appearance figure after the battery cell 1 adding common commercial active carbon circulates, and b figure is negative pole shape appearance figure after the battery cell 3 of interpolation PbO@C composite circulates.As can be seen from the contrast of two width figure, add the battery cell 1 of common commercial active carbon after cycling, polar board surface still can generate the larger PbSO of some particles
4, obviously can also see the existence of activated carbon granule in figure, illustrate that the phenomenon that carbon is separated out has appearred in pole plate in cyclic process, this creates adverse influence to battery performance.And the PbSO of the battery cell 3 adding PbO@C composite after cycling on pole plate
4particle is less, and it is more homogeneous, and not there is carbon granule in polar board surface, this further demonstrates that the PbO in PbO@C composite can carry out electrochemical conversion to Pb in circulating battery process, thus a kind of cross-linked structure can be formed with the Pb in lead plaster, material with carbon element is pinned at lead plaster inside, fundamentally solves the problem that in traditional handicraft, pole plate carbon is separated out, greatly improve the useful life of battery.
Embody rule approach of the present invention is a lot, and the above is only the preferred embodiment of the present invention, should be understood that; for those skilled in the art; under the premise without departing from the principles of the invention, can also make some improvement, these improvement also should be considered as protection scope of the present invention.
Claims (8)
1. a lead-acid battery preparation method for plumbous carbon composite, is characterized in that comprising the following steps:
1) join in ethanol by organic carbon source, be heated to 70 ° of more than C, make it be dissolved in ethanol completely, the molar concentration of solution is 1 ~ 5 mol/L;
2) join in above-mentioned solution by the solubility lead salt of 0.5 mol/L, the mol ratio of organic carbon source and solubility lead salt is 2 ~ 10:1, constantly stirs in a heated condition, until ethanol all evaporates, obtains white powder;
3) by above-mentioned white powder at N
2under atmosphere, with 1 ~ 5
othe heating rate of C/min, at the temperature lower calcination 2 ~ 12h of 550 ~ 600 ° of C, obtains plumbous carbon composite.
2. the lead-acid battery according to claim 1 preparation method of plumbous carbon composite, is characterized in that: the organic carbon source described in step 1) is the organic substance containing benzoic acid group.
3. the lead-acid battery according to claim 1 preparation method of plumbous carbon composite, is characterized in that: step 2) described in solubility lead salt be one in acetate, nitrate, hydrochloride and complex salt containing lead element.
4. one kind comprises the composite negative plate of the plumbous carbon composite of lead-acid battery described in above any one claim, it is characterized in that comprising following component: lead powder, sulfuric acid solution, barium sulfate, lignin, humic acid, short fiber, distilled water, acetylene black, graphite, plumbous carbon composite, wherein, sulfuric acid solution quality is 4% ~ 18% of lead powder quality; Barium sulfate quality is 0.1% ~ 3.0% of lead powder quality; Lignin quality is 0.1% ~ 2.0% of lead powder quality; Humic acid quality is 0.1% ~ 2.0% of lead powder quality; Short fiber quality is 0.01% ~ 0.2% of lead powder quality; Distilled water quality is 5% ~ 20% of lead powder quality; Acetylene black quality is 0.1% ~ 2.5% of lead powder quality; Graphite quality is 0.1% ~ 2.5% of lead powder quality; Plumbous carbon composite quality is 0.5% ~ 10% of lead powder quality.
5. composite negative plate according to claim 4, is characterized in that: described plumbous carbon composite quality is 1% ~ 6% of lead powder quality.
6. composite negative plate according to claim 4, is characterized in that: described plumbous carbon composite quality is 1% ~ 3% of lead powder quality.
7. composite negative plate according to claim 4, is characterized in that: described degree of oxidation of lead powder is 78%.
8. composite negative plate according to claim 4, is characterized in that: described sulfuric acid solution density is 1.4 g/mL.
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