CN103035894A - Method for preparing composite modified material for lead carbon superbattery - Google Patents
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- CN103035894A CN103035894A CN2012105537517A CN201210553751A CN103035894A CN 103035894 A CN103035894 A CN 103035894A CN 2012105537517 A CN2012105537517 A CN 2012105537517A CN 201210553751 A CN201210553751 A CN 201210553751A CN 103035894 A CN103035894 A CN 103035894A
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Abstract
The invention discloses a method for preparing a composite modified material for a lead carbon superbattery. The method comprises the following steps: adding a carbon carrier into a soluble lead salt aqueous solution, mixing uniformly, adding metal soluble salt, ultrasonically dispersing, stirring and performing suction filtration to obtain a filter cake a; and adding the filter cake into a solid lead solution, stirring and performing suction filtration to obtain a filter cake b, cleaning the filter cake b with deionized water until the pH value is neutral, segmentally heating and cooling to the room temperature to obtain the composite modified material for the lead carbon superbattery. The composite modified material for the lead carbon superbattery is obtained through low-temperature decomposition reaction, and only non-toxic gases such as CO2, H2O and NH3 are generated in the reaction, so environmental friendliness is achieved and the energy consumption is reduced. PbO particles loaded by the composite modified material are small and difficult to aggregate and can be effectively distributed into holes of a carbon material, so a negative plate has strong lead carbon binding force. The lead carbon superbattery prepared from the composite modified material has excellent charging and discharging performance and excellent cycle life performance.
Description
(1) technical field
The present invention relates to a kind of preparation method of plumbous charcoal superbattery negative pole, particularly a kind of low temperature prepares the method that plumbous charcoal superbattery is used composite modification material.
(2) background technology
In recent years, a kind of novel battery has appearred in the electrokinetic cell field---plumbous charcoal superbattery, it is the combination of traditional lead acid accumulator and ultracapacitor, have that lead acid accumulator is with low cost concurrently, the characteristics of high safety, good stability, and the ultracapacitor specific power large, have extended cycle life, the advantage of safety and environmental protection.Plumbous charcoal superbattery is a kind of optimal design of lead acid accumulator, also is the upgrading of lead-charcoal Asymmetric Supercapacitor.Plumbous charcoal superbattery is with its unique advantage, and the space that has a wide range of applications in the electrical source of power field is in particular for the hybrid battery electrical automobile.Since the proposition such as CSIRO and preparing plumbous charcoal superbattery, in the world wide all in the research in this field of positive carrying out.In recent years, China also had a lot of scholars to carry out the research of this aspect.
The anodal anode plate for lead acid accumulator that adopts of plumbous charcoal superbattery, negative pole has different preparation methods, wherein mainly contains mixed type in stereotype carbon slab independence parallel connection type, plumbous charcoal subregion application type, plumbous charcoal overlapping type and the plumbous charcoal.Consider the production technology that adopts the lead acid accumulator maturation, the interior mixed type superbattery of plumbous charcoal has caused to be paid close attention to widely and studies.For mixed type superbattery in the plumbous charcoal, Carbon Materials is with the form of additive, the content of common additives adds in the lead plaster more than 10 times.So the key of this research is to be suitable for the preparation of the porous carbon material of plumbous charcoal superbattery.
Shuangdeng Science ﹠ Technology Development Academy Co., Ltd., Nanjing City has proposed a kind of plumbous carbon superbattery of activated carbon negative electrode and method of preparation thereof of containing in patent CN 101764263 A, the dark cycle life of battery has reached more than 1800 times.The people such as the Chen Hongyu of South China Normal University have proposed a kind of preparation method who contains the plumbous charcoal super accumulator of plumbous carbon composite in patent CN 102072744 A, plumbous carbon composite is prepared by electrodeposition process.Harbin Institute of Technology king hall dragon waits the people to propose a kind of preparation method with modified activated carbon of high overpotential of hydrogen evolution in patent CN 102306784 A, is with liberation of hydrogen inhibitor In
2O
3, Ga
2O
3Deng joining in the active carbon; And the preparation method of a kind of lead sulfate-graphene combination electrode material and lead-acid battery negative pole thereof proposed in patent CN 102201575 A.
The present invention proposes a kind of low temperature and prepares the plumbous charcoal superbattery material modified method of high efficiency composition.Adopt Carbon Materials or carbon composite, wherein carbon composite is to be obtained by common re-activation by general goods active carbon and acetylene black, by lead, bismuth, tin, the isoionic absorption of indium, the growth of corresponding oxide, the steps such as the removal of impurity obtain composite modification material, on the basis that guarantees high specific capacitance, improved overpotential of hydrogen evolution, conductivity and with the adhesion of lead plaster, thereby the problems such as negative plate bubbles when having solved changing into that common Carbon Materials is used for that lead plaster causes, active material loosely comes off, battery cathode too early liberation of hydrogen.Adopt the plumbous charcoal superbattery of the composite modification material of the present invention's preparation, charge-discharge performance is good, and the circulation of high magnification partial state of charge can reach more than 80,000 times.
(3) summary of the invention
The object of the invention provides a kind of low temperature and prepares the plumbous charcoal superbattery of high-performance with the method for composite modified Carbon Materials, and Carbon Materials or carbon composite soak plumbous and plumbous process admittedly through absorption, obtain being compounded with Pb (OH)
2Or PbCO
3The Modified Activated Carbon material, and low-temperature decomposition (reaction) to obtain plumbous charcoal superbattery material modified with PbO support type high efficiency composition.Preparation technology's low-temperature environment-friendly of the present invention, the plumbous charcoal adhesion of composite modification material is strong, good conductivity, chemical property are good.
The technical solution used in the present invention is:
The invention provides a kind of low temperature and prepare the method that plumbous charcoal superbattery is used composite modification material, described method is: (1) joins concentration with the charcoal carrier is preferred 100 ~ 300 g/L of 50 ~ 500g/L() the dissoluble lead saline solution in evenly mix, the mass ratio of lead salt and charcoal carrier is 0.5 ~ 5:1(preferred 1 ~ 2.5:1) in the described dissoluble lead saline solution, add again the metal soluble-salt, then after ultrasonic wave under 25 ~ 40kHz condition disperses 1 ~ 2h, at 15 ~ 60 ℃, stir preferred 25 ~ 30 ℃ of 6 ~ 24h(under 100 ~ 1200r/min condition, stir 12 ~ 24h) under 500 ~ 800 r/min conditions, suction filtration obtains filter cake a; Described charcoal carrier is Carbon Materials or carbon composite, described Carbon Materials is the mixing of one or more arbitrary proportions in active carbon, expanded graphite or the nano carbon fiber, and described carbon composite is active carbon with acetylene black with the preferred 1:0.1 of 1: 0.05 ~ 0.2(of mass ratio) mix after under phosphatizing common re-activation be composited; Metal in the described metal soluble-salt is the mixing of one or more arbitrary proportions in bismuth, indium or the tin; (2) the filter cake a that step (1) is obtained joins in the solid lead solution, under 15 ~ 60 ℃, 100 ~ 1200r/min condition, stir 1 ~ 5h(and preferably under 25 ~ 30 ℃, 150 ~ 300r/min condition, stir 3 ~ 5h), suction filtration, obtain filter cake b, after filter cake b is neutrality with washed with de-ionized water to pH value, 50 ~ 120 ℃ of preferred 80 ~ 120 ℃ of dryings 3 ~ 5h) of lower freeze-day with constant temperature 1 ~ 5h(, and then place preferred 200 ~ 300 ℃ of constant temperature of 1 ~ 5h(at 150 ~ 300 ℃ of lower constant temperature and place 3 ~ 5h), namely obtain described plumbous charcoal superbattery composite modification material after being cooled to room temperature; Described solid lead solution is a kind of in sodium hydrate aqueous solution, potassium hydroxide aqueous solution, aqueous sodium carbonate, wet chemical, ammoniacal liquor, the ammonium carbonate solution.
Further, lead salt is a kind of in plumbi nitras, lead acetate, lead citrate, the sulfamic acid lead in the described dissoluble lead saline solution of step (1).
Further, the mass ratio of the described metal soluble-salt of step (1) and charcoal carrier is 0.1 ~ 5: 100(preferred 1 ~ 5:100).
Further, the described carbon composite of step (1) prepares as follows: active carbon and acetylene black are evenly mixed with mass ratio 1: 0.05 ~ 0.2, then add volumetric concentration 15 ~ 75%(preferred 55% ~ 65%) phosphate aqueous solution, after ultrasonic wave under 25 ~ 40kHz condition disperses 30 ~ 60min, then at 15 ~ 50 ℃, stir preferred 25 ~ 30 ℃ of 6 ~ 24h(under 100 ~ 1200r/min condition, stir 12 ~ 24h) under 1000 ~ 1200 r/min, suction filtration, get filter cake c in preferred 80 ~ 100 ℃ lower dry 5 ~ 7h) of 50 ~ 100 ℃ of lower dry 5 ~ 10h(, again 500 ~ 800 ℃ of preferred 700 ~ 800 ℃ of calcinations 1 ~ 3h) of calcination 1 ~ 5h(, wash to the pH value extremely neutral with deionized water after being cooled to room temperature, suction filtration, get filter cake d at 50 ~ 100 ℃ of drying 5 ~ 10h, namely obtain described carbon composite; The volumetric usage of described phosphate aqueous solution is counted preferred 10 ~ 15 mL/g of 1 ~ 20mL/g(with quality of activated carbon).
Further, the described charcoal carrier of step (1) is that active carbon, expanded graphite, nano carbon fiber or active carbon and acetylene black are with the preferred 1:0.1 of mass ratio 1:0.05 ~ 0.2(~ 0.15) composite material of preparation.
Further, the described metal soluble-salt of step (1) is the mixing of one or both arbitrary proportions in bismuth nitrate, nitric acid tin, indium nitrate, bismuth acetate, tin acetate or the indium acetate.More preferably bismuth nitrate, indium nitrate or nitric acid tin and the mass ratioes such as indium nitrate mixes.
Further, the mass concentration of the described solid lead solution of step (2) is 15 ~ 30%(preferred 15 ~ 20%).
Further, the volumetric usage of the described solid lead solution of step (2) is counted preferred 4 ~ 5 mL/g of 1 ~ 50mL/g(with charcoal carrier quality).
The plumbous charcoal superbattery that adopts the present invention to obtain uses composite modification material as the negative electrode active material component, join in the lead oxide powder evenly mix after, ECDC cream, be coated with cream, curing, dryly obtain negative green plate, again through be internalized into or outside change into mode and obtain corresponding lead carbon battery through assembling.Then adopt high magnification partial state of charge loop test mode to test, that is: under 40 ℃, for complete completely charged lead carbon battery, first with 2C constant-current discharge 60s, leave standstill 10s, with 2.5V constant voltage charge 60s, maximum current is no more than 2C, leaves standstill 10s again.As a circulation, when reaching 1.75V, final voltage stops.The situation that this process is moved in mixed power electric car for the simulation lead carbon battery.
Granularity of activated carbon of the present invention is 100 ~ 500 orders, and specific area is 500 ~ 3000m
2The expanded graphite dimensions length is 0.5 ~ 100 μ m; The nano carbon fiber dimensions length is 100 ~ 5000nm, and described acetylene black average grain diameter is 10 ~ 500nm.
Filter cake a of the present invention, filter cake b, filter cake c and filter cake d are filter cake, name for ease of differentiation, and letter itself does not have implication.
Compared with prior art, beneficial effect of the present invention is mainly reflected in:
(1) the plumbous charcoal superbattery of the present invention composite modification material is to obtain by the low-temperature decomposition reaction, and only generates non-toxic gas CO in the reaction
2, H
2O, NH
3Deng, the lead steam, CO, the NO that have avoided high temperature sintering to cause
2Deng the pollution of pernicious gas to environment, environmental protection simultaneously than traditional method, is adsorbed then direct 500 ~ 900 ℃ of pyrolysiss such as lead ion, has reduced energy consumption; The carbon composite raw materials is cheap in addition, the preparation process environmental friendliness;
(2) the present invention mainly obtains the composite modification material of load P bO, and wherein the PbO particle of load is little, difficult reunites, and can effectively be distributed in the hole of Carbon Materials, and the plumbous charcoal adhesion of negative plate is strong.
(3) " active carbon/acetylene black " composite material has improved the hole of Carbon Materials on the one hand by active carbon, the common re-activation of acetylene black, has improved effective ratio area, and than independent Carbon Materials, specific capacity has improved 1 ~ 2 times; Re-activation has promoted the compound of active carbon and acetylene black on the other hand, has improved conductivity and the stability thereof of composite modification material.
(4) composite modification material of the present invention has improved the overpotential of hydrogen evolution of self significantly under the prerequisite that guarantees electric capacity.Experimental result shows that than unmodified active carbon, overpotential of hydrogen evolution can improve more than the 100mV.Experiment shows, adopts the plumbous charcoal superbattery of this Modified Activated Carbon material preparation, and negative plate is non-foaming, charge-discharge performance good.
(5) the plumbous charcoal superbattery that adopts this active carbon to prepare, charge-discharge performance is good, and cycle life performance is superior.The circulation of high magnification partial state of charge has reached more than 80,000 times, and than common lead-acid battery, performance improves very obvious, is suitable for mixed power electric car.
(4) description of drawings
The linear potential scanning curve comparison diagram of the negative pole that is made by composite modification material among Fig. 1: the embodiment 1 and the negative pole experience electrochemical reaction process that is made by common active carbon, the square (■) curve represent the active carbon that is untreated, triangle (▲) curve table give instructions in reply close material modified;
The SEM figure (amplifying 100,000 times) of active carbon is untreated among Fig. 2: the embodiment 1;
The SEM of composite modified active carbon figure (amplifying 100,000 times) among Fig. 3: the embodiment 1.
(5) embodiment
The present invention is described further below in conjunction with specific embodiment, but protection scope of the present invention is not limited in this.
(1) the 200 order active carbons of getting the brilliant pure Industrial Co., Ltd. in 20g Shanghai join 200mL, in the plumbi nitras aqueous solution of 180g/L, mix, add bismuth nitrate 0.2g, in 30kHz supersonic oscillations instrument, disperse 1h, then at 25 ℃, stir 12h under the 800r/min, vacuum filtration obtains the active carbon filter cake 26.7g that absorption has lead ion and modified ion (bismuth).
(2) filter cake that step (1) is obtained joins 100mL, mass concentration is 20% ammonia spirit, under 25 ℃, stir 3h with 200r/min speed, vacuum filtration obtains the composite modified active carbon filter cake of lead hydroxide and bismuth hydroxide, repeatedly clean to the pH value near neutral with deionized water, then with filter cake in 80 ℃ of lower freeze-day with constant temperature 5h, and then constant temperature keeps 3h under 200 ℃ of temperature, is cooled to namely to obtain plumbous charcoal superbattery after the room temperature (25 ℃) with composite modified active carbon 23.4g.
(3) Performance Detection:
A, hydrogen-evolution overpotential test: the plumbous charcoal superbattery of the preparation composite modification material that obtains take step (2) is as raw material, mass ratio with " Carbon Materials: conductive agent: PVDF(NMP)=8:1:1 " evenly mixes, be coated on the surface through on the titanium matrix of polishing, 70 ℃ of dry 5h, obtain test electrode, placing proportion is the 1.28g/mL aqueous sulfuric acid, on electrochemical workstation CHI 660D, carry out the linear potential sweep test, the linear potential scanning curve as shown in Figure 1, wherein AC represents the activated carbon electrodes that is untreated, HC is for adopting the electrode of modified active Carbon Materials preparation, the result shows that the overpotential of hydrogen evolution of modified activated carbon HC is apparently higher than the active carbon AC that is untreated.
B, surface microstructure test: the composite modification material of getting respectively the acquisition of the used active carbon raw material of step (1) and step (2) carries out the SEM surface microstructure and characterizes, the results are shown in Figure 2 and Fig. 3, show by modification, activated carbon surface is compounded with short grained lead compound, improved plumbous charcoal adhesion, significant variation has also occured in the pore structure on surface simultaneously.
C, battery testing: with the composite modification material of step (2) acquisition, close cream at 50 ℃ after the mass ratio mixing with " material modified: lead oxide powder=1: 50 ", then lead plaster evenly is coated on the lead-antimony alloy grid, at 50 ℃, solidify 24h under the 98% relative humidity condition, again through 80 ℃ of dry 12h, obtain the negative green plate of lead carbon battery, this green plate is changed into and further assembling, make plumbous charcoal superbattery behind the activated and additional electricity.Then adopt document (L.T.Lam, R.Louey, N.P.Haigh, et al. VRLA Ultrabattery for high-rate partial-state-of-charge operation[J]. Journal of Power Sources, 174 (2007): 16 – 29) the battery high magnification partial state of charge cyclic test method in, carry out the cycle performance of battery test, namely under 40 ℃, for complete completely charged lead carbon battery, first with 2C constant-current discharge 60s, leave standstill 10s, with 2.5V constant voltage charge 60s, maximum current is no more than 2C, leaves standstill 10s again, as a circulation, when reaching 1.75V, final voltage stops.High magnification partial state of charge cycle life reaches 80330 circulations.Each simulated battery is carried out first the 1C charging, and then the 1C discharge, calculating discharging efficiency separately, the discharging efficiency that found that common batteries is 56.1%, the discharging efficiency of lead carbon battery is 83.7%.
Embodiment 2
(1) expanded graphite that is 50 μ m with the homemade size average length of 20g joins 200mL, in the lead citrate solution of 180g/L, mix, add nitric acid tin 0.1g, indium nitrate 0.1g, disperse 1h with the 30kHz ultrasonic wave, then under 30 ℃, 500r/min stirs 24h, and vacuum filtration obtains adsorbing lead ion and tin, the expanded graphite filter cake 25.4g of bismuth ion.
(2) filter cake that step (1) is obtained joins 100mL, mass concentration is 18% aqueous sodium carbonate, under 30 ℃, 300r/min, stir 4h, vacuum filtration obtains being compounded with the expanded graphite filter cake of ceruse and carbonic acid tin, carbonic acid indium, it is neutral repeatedly cleaning to the pH value with deionized water, then with 80 ℃ of freeze-day with constant temperature 5h of filter cake, and then 250 ℃ of low temperature keep 5h, namely obtain high efficiency composition modified expanded graphite 22.3g after being cooled to room temperature.
All the other processes are with embodiment 1, and high magnification partial state of charge cycle life reaches 81600 times, and the discharging efficiency of lead carbon battery is 84.3%.
Embodiment 3
(1) nano carbon fiber that to get the homemade size average length of 20g be 500nm joins 200mL, in the lead acetate solution of 200g/L, mix, add bismuth acetate 0.2g, ultrasonic wave disperses 1h under 30kHz, then under 25 ℃, 800r/min stirs 12h, and vacuum filtration obtains adsorbing the active carbon of lead ion and modified ion filter cake 25.5g.
(2) filter cake that step (1) is obtained joins 100mL, mass concentration is 15% sodium hydroxide solution, under 25 ℃, 250r/min, stir 3h, vacuum filtration obtains the nano carbon fiber filter cake of lead hydroxide and bismuth hydroxide modification, it is closely neutral that deionized water is washed till filtrate pH, then with 120 ℃ of freeze-day with constant temperature 5h of filter cake, and then 200 ℃ of constant temperature place 3h, are cooled to the high efficiency composition modified activated carbon 22.7g that namely obtains being compounded with lead oxide and modify oxide after the room temperature.
Battery preparation process and method of testing are with embodiment 1, and high magnification partial state of charge cycle life reaches 80540 times, and the discharging efficiency of lead carbon battery is 82.3%.
Embodiment 4
(1) getting 200 order active carbons that the brilliant pure Industrial Co., Ltd. in 20g Shanghai produces joins in 200mL, the 200g/L sulfamic acid lead solution and mixes, add bismuth acetate 0.2g, ultrasonic wave disperses 1h under 30kHz, then at 30 ℃, stir 20h under the 700r/min, must adsorb behind the vacuum filtration has the active carbon of lead ion and modified ion filter cake.
(2) filter cake that step (1) is obtained joins 100mL, mass concentration is 20% solution of potassium carbonate, under 25 ℃, 200r/min, stir 5h, vacuum filtration obtains being inlaid with the active carbon filter cake of ceruse and waltherite, deionized water is washed till filtrate pH for neutral, then with 120 ℃ of freeze-day with constant temperature 5h of filter cake, and then 300 ℃ of constant temperature place 3h, are cooled to the high efficiency composition modified activated carbon 23.2g that namely obtains being doped with lead oxide and modify oxide after the room temperature.
Battery preparation process and method of testing are with embodiment 1, and high magnification partial state of charge cycle life reaches 78320 times, and the discharging efficiency of lead carbon battery is 81.9%.
Embodiment 5
(1) getting the acetylene black that 200 order active carbons that the brilliant pure Industrial Co., Ltd. in 20g Shanghai produces and 2g average grain diameter be about 50nm is mixed in the 500mL large beaker, then in beaker, add 250mL, the phosphate aqueous solution of volumetric concentration 65%, under the 40kHz ultrasonic wave, disperse 30min, 25 ℃ of lower 1000r/min stir 24h, 80 ℃ of dry 7h behind the suction filtration, place 800 ℃ of calcination 1.5h of high temperature furnace, washed with de-ionized water is near neutral to the pH value after being cooled to room temperature, suction filtration, get filter cake at 80 ℃ of dry 7h, namely obtain " active carbon/acetylene black " composite material 21.2g.
Mass ratio with " active carbon: acetylene black: PVDF(NMP)=8:1:1 ", " active carbon/acetylene black: PVDF(NMP)=9:1 " prepares corresponding electrode according to the method for preparing activated carbon electrodes among the embodiment 1 respectively, the total consumption of two arrays of electrodes material is identical, and the electrochemical system among the employing embodiment 1, carry out the constant current charge-discharge test at electrochemical workstation CHI 660D, the ratio electric capacity of activated carbon electrodes is 135.3F/g as calculated, and the ratio electric capacity of carbon composite electrode is 321.6F/g.
(2) 21.2g " active carbon/acetylene black " composite material is added 200mL, in the lead nitrate solution of 180g/L, add simultaneously the 1g bismuth nitrate, under the 30kHz ultrasonic wave, disperse 1h, then stir 24h at 25 ℃, 500r/min, vacuum filtration obtains adsorbing " active carbon/acetylene black " of lead ion and bismuth ion composite material filter cake.Filter cake is joined 100mL, mass concentration is 15% potassium hydroxide aqueous solution, 25 ℃, 200r/min stir 3h, vacuum filtration obtains being compounded with " active carbon/acetylene black " composite material filter cake of lead hydroxide and bismuth hydroxide, it is near neutral to be washed till the pH value with deionized water, then with 80 ℃ of freeze-day with constant temperature 5h of filter cake, and then 200 ℃ of constant temperature keep 3h, namely obtain efficient " active carbon/acetylene black/lead oxide " composite material 23.8g after being cooled to room temperature.
With the plumbous charcoal superbattery of above-mentioned efficient " active carbon/acetylene black/lead oxide " composite modification material preparation, battery preparation process and method of testing are with embodiment 1, and high magnification partial state of charge cycle-index has reached 85360 times, is suitable for mixed type power vehicle.Than conventional accumulators, the 2C overcharging resisting electricity time is long, and the discharging efficiency of lead carbon battery is 85.1%.
Embodiment 6
(1) used phosphate aqueous solution volumetric concentration changes 55% into, under the 30kHz ultrasonic wave, disperse 60min, under 30 ℃, 1200r/min stirs 12h, behind 100 ℃ of dry 5h of filter cake, 700 ℃ of calcination 3h, all the other steps obtain " active carbon/acetylene black " composite material 22.1g with the step (1) of embodiment 5.
(2) 22.1g " active carbon/acetylene black " composite material is joined 150mL, in the lead acetate solution of 200g/L, mix, add indium acetate 0.1g, disperse 30min with the 30kHz ultrasonic wave, then at 25 ℃, stir 12h under the 800r/min, vacuum filtration obtains adsorbing " active carbon/acetylene black " of lead ion and bismuth ion composite material filter cake.It is 20% sal volatile that filter cake is joined the 100mL mass concentration, at 30 ℃, stir 4h under the 150r/min, vacuum filtration obtains being compounded with " active carbon/acetylene black " composite material filter cake of ceruse and carbonic acid indium, it is neutral repeatedly cleaning to the pH value with deionized water, then with 100 ℃ of dry 5h of filter cake, and then 250 ℃ of constant temperature place 5h, namely obtain efficient " active carbon/acetylene black/lead oxide " composite modification material 23.1g after being cooled to room temperature.
Battery preparation process and method of testing are with embodiment 8, and high magnification partial state of charge cycle life reaches 86370 times, and the discharging efficiency of lead carbon battery is 84.8%.
Claims (8)
1. a plumbous charcoal superbattery is characterized in that described method is with the preparation method of composite modification material:
(1) the charcoal carrier is joined evenly mixing in the dissoluble lead saline solution that concentration is 50 ~ 500g/L, the mass ratio of lead salt and charcoal carrier is 0.5 ~ 5:1 in the described dissoluble lead saline solution, add again the metal soluble-salt, then after ultrasonic wave under 25 ~ 40kHz condition disperses 1 ~ 2h, under 15 ~ 60 ℃, 100 ~ 1200r/min condition, stir 6 ~ 24h, suction filtration obtains filter cake a; Described charcoal carrier is Carbon Materials or carbon composite, described Carbon Materials is the mixing of one or more arbitrary proportions in active carbon, expanded graphite or the nano carbon fiber, described carbon composite be active carbon with after acetylene black is mixed with mass ratio 1:0.05 ~ 0.2 under phosphatizing common re-activation be composited; Metal in the described metal soluble-salt is the mixing of one or more arbitrary proportions in bismuth, indium or the tin;
(2) the filter cake a that step (1) is obtained joins in the solid lead solution, under 15 ~ 60 ℃, 100 ~ 1200r/min condition, stir 1 ~ 5h, suction filtration, obtain filter cake b, after filter cake b is neutrality with washed with de-ionized water to pH value, at 50 ~ 120 ℃ of lower freeze-day with constant temperature 1 ~ 5h, and then place 1 ~ 5h at 150 ~ 300 ℃ of lower constant temperature, namely obtain described plumbous charcoal superbattery composite modification material after being cooled to room temperature; Described solid lead solution is a kind of in sodium hydrate aqueous solution, potassium hydroxide aqueous solution, aqueous sodium carbonate, wet chemical, ammonia spirit, the ammonium carbonate solution.
2. plumbous charcoal superbattery is characterized in that lead salt in the described dissoluble lead saline solution of step (1) is a kind of in plumbi nitras, lead acetate, lead citrate, the sulfamic acid lead with the preparation method of composite modification material as claimed in claim 1.
3. plumbous charcoal superbattery is characterized in that with the preparation method of composite modification material the mass ratio of the described metal soluble-salt of step (1) and charcoal carrier is 0.1 ~ 5: 100 as claimed in claim 1.
As claimed in claim 1 plumbous charcoal superbattery with the preparation method of composite modification material, it is characterized in that the described carbon composite of step (1) prepares as follows: active carbon and acetylene black are evenly mixed with mass ratio 1: 0.05 ~ 0.2, then the phosphate aqueous solution that adds volumetric concentration 15 ~ 75%, ultrasonic wave disperses 30 ~ 60min under 25 ~ 40kHz condition, then at 15 ~ 50 ℃, stir 6 ~ 24h under 100 ~ 1200r/min condition, suction filtration, get filter cake c in 50 ~ 100 ℃ of lower dry 5 ~ 10h, again at 500 ~ 800 ℃ of calcination 1 ~ 5h, wash to the pH value extremely neutral with deionized water after being cooled to room temperature, suction filtration, get filter cake d at 50 ~ 100 ℃ of drying 5 ~ 10h, namely obtain described carbon composite; The volumetric usage of described phosphate aqueous solution is counted 1 ~ 20mL/g with quality of activated carbon.
5. plumbous charcoal superbattery is characterized in that with the preparation method of composite modification material the described charcoal carrier of step (1) is active carbon, expanded graphite, nano carbon fiber or active carbon and acetylene black are mixed rear common re-activation preparation under phosphatizing with mass ratio 1: 0.1 ~ 0.15 composite material as claimed in claim 1.
6. plumbous charcoal superbattery is characterized in that with the preparation method of composite modification material the described metal soluble-salt of step (1) is the mixing of one or both arbitrary proportions in bismuth nitrate, nitric acid tin, indium nitrate, bismuth acetate, tin acetate or the indium acetate as claimed in claim 1.
7. plumbous charcoal superbattery is characterized in that with the preparation method of composite modification material the described solid lead solution mass concentration of step (2) is 15 ~ 30% as claimed in claim 1.
8. plumbous charcoal superbattery is characterized in that with the preparation method of composite modification material the volumetric usage of the described solid lead solution of step (2) is counted 1 ~ 50mL/g with charcoal carrier quality as claimed in claim 7.
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| CN103618089A (en) * | 2013-12-16 | 2014-03-05 | 中国船舶重工集团公司第七一二研究所 | Modified activated carbon as well as preparation method thereof and method for manufacturing carbon negative plate of super lead-acid battery by using modified activated carbon |
| CN104167551A (en) * | 2014-08-11 | 2014-11-26 | 深圳市佰特瑞储能***有限公司 | Preparation method of composite carbon material for lead-carbon super battery |
| CN106159258A (en) * | 2015-04-14 | 2016-11-23 | 郭永千 | The uniform mixing method of lead carbon battery nano-scale carbon |
| CN106299256A (en) * | 2016-11-11 | 2017-01-04 | 华南师范大学 | The preparation method of lead graphene battery negative plate |
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