CN103035894B - Method for preparing composite modified material for lead carbon superbattery - Google Patents
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- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
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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 the method for a kind of low-temperature growth plumbous charcoal superbattery composite modification material.
(2) background technology
In recent years, there is a kind of novel battery in electrokinetic cell field---plumbous charcoal superbattery, it is traditional lead acid accumulator and the combination of ultracapacitor, have that lead acid accumulator is with low cost, the feature of high safety, good stability concurrently, and 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, is also the upgrading of lead-charcoal Asymmetric Supercapacitor.Plumbous charcoal superbattery is with the advantage of its uniqueness, and have a wide range of applications in electrical source of power field space, in particular for hybrid battery electrical automobile.Since CSIR O etc. proposes and prepares plumbous charcoal superbattery, all in the research in this field of positive carrying out in world wide.In recent years, China also had a lot of scholar to carry out the research of this aspect.
Plumbous charcoal superbattery positive pole adopts anode plate for lead acid accumulator, and 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 plumbous charcoal.Consider the production technology adopting lead acid accumulator maturation, in plumbous charcoal, mixed type superbattery causes and pays close attention to widely and study.For type superbattery mixed in plumbous charcoal, Carbon Materials adds in lead plaster with the content of the form of additive, more than 10 times common additives.So the key of this research is the preparation of the porous carbon material being suitable for plumbous charcoal superbattery.
Shuangdeng Science & Technology Development Academy Co., Ltd., Nanjing City proposes a kind of containing the plumbous carbon superbattery of activated carbon negative electrode and the method for preparation thereof in patent CN 101764263 A, and the battery deeper cavity life-span reaches more than 1800 times.The people such as the Chen Hongyu of South China Normal University propose a kind of preparation method of the plumbous charcoal super accumulator containing plumbous carbon composite in patent CN 102072744 A, and plumbous carbon composite is prepared by electrodeposition process.Harbin Institute of Technology king hall dragon waits people in patent CN 102306784A, propose a kind of preparation method with the modified activated carbon of high overpotential of hydrogen evolution, is by liberation of hydrogen inhibitor In
2o
3, Ga
2o
3etc. joining in active carbon; And in patent CN 102201575 A, propose the preparation method of a kind of lead sulfate-graphene combination electrode material and lead-acid battery cathode thereof.
The present invention proposes the material modified method of a kind of low-temperature growth plumbous charcoal superbattery high efficiency composition.Adopt Carbon Materials or carbon composite, wherein carbon composite is 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 ensureing high specific capacitance, improve overpotential of hydrogen evolution, conductivity and the adhesion with lead plaster, thus solve common Carbon Materials for cause in lead plaster change into time negative plate bubble, the problem such as active material loosely comes off, the too early liberation of hydrogen of battery cathode.The plumbous charcoal superbattery of the composite modification material adopting the present invention to prepare, 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 is to provide the method for the composite modified Carbon Materials of the plumbous charcoal superbattery of a kind of low-temperature growth high-performance, and Carbon Materials or carbon composite, through the plumbous and solid plumbous process of absorption leaching, obtain being compounded with Pb (OH)
2or PbCO
3modified Activated Carbon material, and low-temperature decomposition (reaction) to obtain plumbous charcoal superbattery PbO support type high efficiency composition material modified.Preparation technology's low-temperature environment-friendly of the present invention, the plumbous charcoal adhesion of composite modification material is strong, good conductivity, excellent electrochemical performance.
The technical solution used in the present invention is:
The invention provides the method for a kind of low-temperature growth plumbous charcoal superbattery composite modification material, described method is: it is 50 ~ 500g/L(preferably 100 ~ 300 g/L that high-area carbon is joined concentration by (1)) dissoluble lead saline solution in Homogeneous phase mixing, in described dissoluble lead saline solution, the mass ratio of lead salt and high-area carbon is 0.5 ~ 5:1(preferably 1 ~ 2.5:1), add metal soluble-salt again, then after under 25 ~ 40kHz condition, ultrasonic wave disperses 1 ~ 2h, at 15 ~ 60 DEG C, 6 ~ 24h(preferably 25 ~ 30 DEG C is stirred under 100 ~ 1200r/min condition, 12 ~ 24h is stirred) under 500 ~ 800 r/min conditions, suction filtration, obtain filter cake a, described high-area carbon is Carbon Materials or carbon composite, described Carbon Materials is the mixing of one or more arbitrary proportions in active carbon, expanded graphite or nano carbon fiber, described carbon composite be active carbon with acetylene black with the preferred 1:0.1 of mass ratio 1: 0.05 ~ 0.2() mix after under phosphatizing common re-activation be composited, metal in described metal soluble-salt is the mixing of one or more arbitrary proportions in bismuth, indium or tin, (2) the filter cake a that step (1) obtains is joined in solid lead solution, 15 ~ 60 DEG C, stir under 100 ~ 1200r/min condition 1 ~ 5h(preferably 25 ~ 30 DEG C, stir 3 ~ 5h under 150 ~ 300r/min condition), suction filtration, obtain filter cake b, be after neutrality by filter cake b washed with de-ionized water to pH value, freeze-day with constant temperature 1 ~ 5h(preferably 80 ~ 120 DEG C of drying 3 ~ 5h at 50 ~ 120 DEG C), and then constant temperature places 1 ~ 5h(preferably 200 ~ 300 DEG C of constant temperature placement 3 ~ 5h at 150 ~ 300 DEG C), namely obtain described plumbous charcoal superbattery composite modification material after being cooled to room temperature, described solid lead solution is the one in sodium hydrate aqueous solution, potassium hydroxide aqueous solution, aqueous sodium carbonate, wet chemical, ammoniacal liquor, ammonium carbonate solution.
Further, in the described dissoluble lead saline solution of step (1), lead salt is the one in plumbi nitras, lead acetate, lead citrate, sulfamic acid lead.
Further, the mass ratio of the described metal soluble-salt of step (1) and high-area carbon is 0.1 ~ 5: 100(preferred 1 ~ 5:100).
Further, step (1) described carbon composite is prepared as follows: by active carbon and acetylene black with mass ratio 1: 0.05 ~ 0.2 Homogeneous phase mixing, then add volumetric concentration 15 ~ 75%(preferably 55% ~ 65%) phosphate aqueous solution, under 25 ~ 40kHz condition after ultrasonic wave dispersion 30 ~ 60min, then at 15 ~ 50 DEG C, 6 ~ 24h(preferably 25 ~ 30 DEG C is stirred under 100 ~ 1200r/min condition, 12 ~ 24h is stirred) under 1000 ~ 1200 r/min, suction filtration, get filter cake c dry 5 ~ 10h(preferably dry 5 ~ 7h at 80 ~ 100 DEG C at 50 ~ 100 DEG C), again at 500 ~ 800 DEG C of calcination 1 ~ 5h(preferably 700 ~ 800 DEG C of calcination 1 ~ 3h), deionized water is spent to pH value to neutral after being cooled to room temperature, suction filtration, get filter cake d at 50 ~ 100 DEG C of drying 5 ~ 10h, namely described carbon composite is obtained, the volumetric usage of described phosphate aqueous solution counts 1 ~ 20mL/g(preferably 10 ~ 15 mL/g with quality of activated carbon).
Further, step (1) described high-area carbon is that active carbon, expanded graphite, nano carbon fiber or active carbon and acetylene black are with preferred 1:0.1 ~ 0.15 of mass ratio 1:0.05 ~ 0.2() composite material prepared.
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 indium acetate.More preferably the mixing of bismuth nitrate, indium nitrate or nitric acid tin and the mass ratioes such as indium nitrate.
Further, the mass concentration of the described solid lead solution of step (2) is 15 ~ 30%(preferably 15 ~ 20%).
Further, the volumetric usage of the described solid lead solution of step (2) counts 1 ~ 50mL/g(preferably 4 ~ 5 mL/g with high-area carbon quality).
Adopt the plumbous charcoal superbattery composite modification material of the present invention's acquisition as negative electrode active material component, to join in lead oxide powder after Homogeneous phase mixing, ECDC cream, be coated with cream, solidification, dry obtain negative green plate, then through to be internalized into or tank formation mode obtains corresponding lead carbon battery through assembling.Then adopt high magnification partial state of charge loop test mode to test, that is: at 40 DEG C, for complete completely charged lead carbon battery, first with 2C constant-current discharge 60s, leave standstill 10s, then with 2.5V constant voltage charge 60s, maximum current is no more than 2C, leaves standstill 10s.As a circulation, stop when final voltage reaches 1.75V.This process is the situation that simulation lead carbon battery runs in mixed power electric car.
Granularity of activated carbon of the present invention is 100 ~ 500 orders, and specific area is 500 ~ 3000m
2; Expanded graphite dimensions length is 0.5 ~ 100 μm; 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 present invention's plumbous charcoal superbattery composite modification material is obtained by reacting by low-temperature decomposition, and only generate non-toxic gas CO in reaction
2, H
2o, NH
3deng, avoid lead steam that high temperature sintering causes, CO, NO
2deng the pollution of pernicious gas to environment, environmental protection, simultaneously compared to traditional method, as lead ion absorption then direct 500 ~ 900 DEG C of pyrolysiss, reduces energy consumption; Carbon composite raw materials is cheap in addition, preparation process environmental friendliness;
(2) the present invention mainly obtains the composite modification material of load P bO, wherein the PbO particle of load little, not easily reunite, can effectively be distributed in the hole of Carbon Materials, negative plate plumbous charcoal adhesion be strong.
(3) " active carbon/acetylene black " composite material is by active carbon, the common re-activation of acetylene black, and improve the hole of Carbon Materials on the one hand, improve effective ratio area, compared to independent Carbon Materials, specific capacity improves 1 ~ 2 times; Re-activation facilitates the compound of active carbon and acetylene black on the other hand, improves conductivity and the stability thereof of composite modification material.
(4) composite modification material of the present invention is under the prerequisite ensureing electric capacity, improves the overpotential of hydrogen evolution of self significantly.Experimental result shows, compared to unmodified active carbon, overpotential of hydrogen evolution can improve more than 100mV.Experiment shows, adopt plumbous charcoal superbattery prepared by this Modified Activated Carbon material, negative plate is non-foaming, charge-discharge performance good.
(5) the plumbous charcoal superbattery adopting 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 reaches more than 80,000 times, and compared to conventional lead acid battery, performance improves clearly, is suitable for mixed power electric car.
(4) accompanying drawing explanation
Fig. 1: the negative pole obtained by composite modification material in embodiment 1 experiences the linear sweep voltametry curve comparison figure of electrochemical reaction process with the negative pole obtained by normal activated carbon, square (■) curve represents untreated active carbon, and triangle (▲) curve table shows composite modification material;
Fig. 2: SEM figure (amplifying 100,000 times) of untreated active carbon in embodiment 1;
Fig. 3: SEM figure (amplifying 100,000 times) of composite modified active carbon in embodiment 1.
(5) embodiment
Below in conjunction with specific embodiment, the present invention is described further, but protection scope of the present invention is not limited in this.
Embodiment 1
(1) the 200 order active carbons getting 20g Shanghai Jingchun Industrial Co., Ltd. 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 DEG C, under 800r/min, stir 12h, vacuum filtration, obtains the active carbon filter cake 26.7g being adsorbed with lead ion and modified ion (bismuth).
(2) filter cake that step (1) obtains is joined 100mL, mass concentration is the ammonia spirit of 20%, at 25 DEG C, stir 3h with 200r/min speed, vacuum filtration, obtain lead hydroxide and the composite modified active carbon filter cake of bismuth hydroxide, repeatedly clean to pH value weakly acidic pH with deionized water, then by filter cake freeze-day with constant temperature 5h at 80 DEG C, and then at 200 DEG C of temperature, constant temperature keeps 3h, namely obtains the composite modified active carbon 23.4g of plumbous charcoal superbattery after being cooled to room temperature (25 DEG C).
(3) Performance Detection:
A, hydrogen-evolution overpotential is tested: the preparation obtained with step (2) plumbous charcoal superbattery composite modification material is for raw material, Homogeneous phase mixing is compared with the quality of " Carbon Materials: conductive agent: PVDF(NMP)=8:1:1 ", be coated on surface on the Titanium base of polishing, 70 DEG C of dry 5h, obtain test electrode, being placed in proportion is 1.28g/mL aqueous sulfuric acid, on electrochemical workstation CHI660D, carry out linear sweep voltametry test, linear sweep voltametry curve as shown in Figure 1, wherein AC represents untreated activated carbon electrodes, HC is the electrode adopting modified active Carbon Materials to prepare, result shows, the overpotential of hydrogen evolution of modified activated carbon HC is apparently higher than untreated active carbon AC.
B, surface microstructure are tested: get the composite modification material that step (1) activated carbon raw material used and step (2) obtain respectively and carry out SEM surface microstructure sign, the results are shown in Figure 2 and Fig. 3, show to pass through modification, activated carbon surface is compounded with short grained lead compound, improve plumbous charcoal adhesion, the pore structure on surface also there occurs significant change simultaneously.
C, battery testing: the composite modification material obtained by step (2), to close cream at 50 DEG C after the mass ratio of " material modified: lead oxide powder=1: 50 " mixing, then lead plaster is evenly coated on lead-antimony alloy grid, at 50 DEG C, solidify 24h under 98% relative humidities, then through 80 DEG C of dry 12h, obtain lead carbon battery and bear green plate, this green plate is carried out changing into and assembling further, after activated and supplementary electricity, makes plumbous charcoal superbattery.Then document (L.T.Lam is adopted, 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) in battery high magnification partial state of charge cyclic test method, carry out cycle performance of battery test, namely at 40 DEG C, for complete completely charged lead carbon battery, first with 2C constant-current discharge 60s, leave standstill 10s, again with 2.5V constant voltage charge 60s, maximum current is no more than 2C, leave standstill 10s, as a circulation, stop when final voltage reaches 1.75V.High magnification partial state of charge cycle life reaches 80330 circulations.First 1C charging is carried out to each simulated battery, and then 1C electric discharge, calculate respective discharging efficiency, found that the discharging efficiency of common batteries is 56.1%, the discharging efficiency of lead carbon battery is 83.7%.
Embodiment 2
(1) expanded graphite being 50 μm by homemade for 20g size average length joins 200mL, in the lead citrate solution of 180g/L, mix, add nitric acid tin 0.1g, indium nitrate 0.1g, with 30kHz ultrasonic wave dispersion 1h, then at 30 DEG C, 500r/min stirs 24h, and vacuum filtration obtains being adsorbed with the expanded graphite filter cake 25.4g of lead ion and tin, bismuth ion.
(2) filter cake that step (1) obtains is joined 100mL, mass concentration is the aqueous sodium carbonate of 18%, 30 DEG C, stir 4h under 300r/min, vacuum filtration obtains being compounded with the expanded graphite filter cake of ceruse and carbonic acid tin, carbonic acid indium, it is neutral for repeatedly cleaning to pH value with deionized water, then by filter cake 80 DEG C of freeze-day with constant temperature 5h, and then 250 DEG C 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) getting the homemade size average length of 20g is that the nano carbon fiber of 500nm joins 200mL, in the lead acetate solution of 200g/L, mix, add bismuth acetate 0.2g, ultrasonic wave dispersion 1h under 30kHz, then at 25 DEG C, 800r/min stirs 12h, and vacuum filtration obtains the active carbon filter cake 25.5g being adsorbed with lead ion and modified ion.
(2) filter cake that step (1) obtains is joined 100mL, mass concentration is the sodium hydroxide solution of 15%, 25 DEG C, stir 3h under 250r/min, vacuum filtration obtains the nano carbon fiber filter cake of lead hydroxide and bismuth hydroxide modification, deionized water is washed till filtrate pH weakly acidic pH, then by filter cake 120 DEG C of freeze-day with constant temperature 5h, and then 200 DEG C of constant temperature place 3h, namely obtain the high efficiency composition modified activated carbon 22.7g being compounded with lead oxide and modifying oxide after being cooled to room temperature.
Cell manufacturing 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) the 200 order active carbons getting the production of 20g Shanghai Jingchun Industrial Co., Ltd. join in 200mL, 200g/L sulfamic acid lead solution and mix, add bismuth acetate 0.2g, ultrasonic wave dispersion 1h under 30kHz, then at 30 DEG C, stir 20h under 700r/min, the active carbon filter cake of lead ion and modified ion after vacuum filtration, must be adsorbed with.
(2) filter cake that step (1) obtains is joined 100mL, mass concentration is the solution of potassium carbonate of 20%, 25 DEG C, stir 5h under 200r/min, vacuum filtration obtains the active carbon filter cake being inlaid with ceruse and waltherite, deionized water is washed till filtrate pH for neutral, then by filter cake 120 DEG C of freeze-day with constant temperature 5h, and then 300 DEG C of constant temperature place 3h, namely obtain doped with lead oxide and the high efficiency composition modified activated carbon 23.2g modifying oxide after being cooled to room temperature.
Cell manufacturing 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) 200 order active carbons that 20g Shanghai Jingchun Industrial Co., Ltd. produces are got and the acetylene black that 2g average grain diameter is about 50nm is mixed in 500mL large beaker, then in beaker, 250mL is added, the phosphate aqueous solution of volumetric concentration 65%, 30min is disperseed under 40kHz ultrasonic wave, at 25 DEG C, 1000r/min stirs 24h, 80 DEG C of dry 7h after suction filtration, be placed in high temperature furnace 800 DEG C of calcination 1.5h, after being cooled to room temperature, washed with de-ionized water is to pH value weakly acidic pH, suction filtration, get filter cake at 80 DEG C of dry 7h, namely obtain " active carbon/acetylene black " composite material 21.2g.
Corresponding electrode is prepared according to the method preparing activated carbon electrodes in embodiment 1 respectively with the mass ratio of " active carbon: acetylene black: PVDF(NMP)=8:1:1 ", " active carbon/acetylene black: PVDF(NMP)=9:1 ", the total consumption of two arrays of electrodes material is identical, and adopt the electrochemical system in embodiment 1, electrochemical workstation CHI 660D carries out constant current charge-discharge test, the ratio capacitance of activated carbon electrodes is 135.3F/g as calculated, and the ratio capacitance 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 1g bismuth nitrate simultaneously, 1h is disperseed under 30kHz ultrasonic wave, then 25 DEG C, 500r/min stirs 24h, vacuum filtration obtains " active carbon/acetylene black " the composite material filter cake being adsorbed with lead ion and bismuth ion.Filter cake is joined 100mL, mass concentration is the potassium hydroxide aqueous solution of 15%, 25 DEG C, 200r/min stirs 3h, vacuum filtration obtains " active carbon/acetylene black " the composite material filter cake being compounded with lead hydroxide and bismuth hydroxide, pH value weakly acidic pH is washed till with deionized water, then by filter cake 80 DEG C of freeze-day with constant temperature 5h, and then 200 DEG C 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 plumbous charcoal superbattery prepared by above-mentioned efficient " active carbon/acetylene black/lead oxide " composite modification material, cell manufacturing process and method of testing are with embodiment 1, and high magnification partial state of charge cycle-index reaches 85360 times, is suitable for mixed type power vehicle.Compared to conventional accumulators, the 2C overcharging resisting electricity time is long, and the discharging efficiency of lead carbon battery is 85.1%.
Embodiment 6
(1) phosphate aqueous solution volumetric concentration used changes 55% into, 60min is disperseed under 30kHz ultrasonic wave, at 30 DEG C, 1200r/min stirs 12h, after filter cake 100 DEG C of dry 5h, 700 DEG C of calcination 3h, all the other steps, with the step (1) of embodiment 5, obtain " active carbon/acetylene black " composite material 22.1g.
(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, with 30kHz ultrasonic wave dispersion 30min, then at 25 DEG C, stir 12h under 800r/min, vacuum filtration obtains " active carbon/acetylene black " the composite material filter cake being adsorbed with lead ion and bismuth ion.Filter cake is joined the sal volatile that 100mL mass concentration is 20%, at 30 DEG C, 4h is stirred under 150r/min, vacuum filtration obtains " active carbon/acetylene black " the composite material filter cake being compounded with ceruse and carbonic acid indium, it is neutral for repeatedly cleaning to pH value with deionized water, then by filter cake 100 DEG C of dry 5h, and then 250 DEG C 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.
Cell manufacturing 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 preparation method for plumbous charcoal superbattery composite modification material, is characterized in that described method is:
(1) high-area carbon being joined concentration is Homogeneous phase mixing in the dissoluble lead saline solution of 50 ~ 500g/L, in described dissoluble lead saline solution, the mass ratio of lead salt and high-area carbon is 0.5 ~ 5:1, add metal soluble-salt again, then after under 25 ~ 40kHz condition, ultrasonic wave disperses 1 ~ 2h, 15 ~ 60 DEG C, stir 6 ~ 24h under 100 ~ 1200r/min condition, suction filtration, obtains filter cake a; Described high-area carbon is Carbon Materials or carbon composite, described Carbon Materials is the mixing of one or more arbitrary proportions in active carbon, expanded graphite or nano carbon fiber, and described carbon composite is that after active carbon mixes with mass ratio 1:0.05 ~ 0.2 with acetylene black, under phosphatizing, common re-activation is composited; Metal in described metal soluble-salt is the mixing of one or more arbitrary proportions in bismuth, indium or tin;
(2) the filter cake a that step (1) obtains is joined in solid lead solution, 15 ~ 60 DEG C, stir 1 ~ 5h under 100 ~ 1200r/min condition, suction filtration, obtain filter cake b, be after neutrality by filter cake b washed with de-ionized water to pH value, freeze-day with constant temperature 1 ~ 5h at 50 ~ 120 DEG C, and then at 150 ~ 300 DEG C, constant temperature places 1 ~ 5h, namely obtains described plumbous charcoal superbattery composite modification material after being cooled to room temperature; Described solid lead solution is the one in sodium hydrate aqueous solution, potassium hydroxide aqueous solution, aqueous sodium carbonate, wet chemical, ammonia spirit, ammonium carbonate solution.
2. the preparation method of plumbous charcoal superbattery composite modification material as claimed in claim 1, is characterized in that in the described dissoluble lead saline solution of step (1), lead salt is the one in plumbi nitras, lead acetate, lead citrate, sulfamic acid lead.
3. the preparation method of plumbous charcoal superbattery composite modification material as claimed in claim 1, is characterized in that the mass ratio of the described metal soluble-salt of step (1) and high-area carbon is 0.1 ~ 5: 100.
4. the preparation method of plumbous charcoal superbattery composite modification material as claimed in claim 1, it is characterized in that step (1) described carbon composite is prepared as follows: by active carbon and acetylene black with mass ratio 1: 0.05 ~ 0.2 Homogeneous phase mixing, then the phosphate aqueous solution of volumetric concentration 15 ~ 75% is added, ultrasonic wave dispersion 30 ~ 60min under 25 ~ 40kHz condition, then at 15 ~ 50 DEG C, 6 ~ 24h is stirred under 100 ~ 1200r/min condition, suction filtration, get filter cake c dry 5 ~ 10h at 50 ~ 100 DEG C, again at 500 ~ 800 DEG C of calcination 1 ~ 5h, deionized water is spent to pH value to neutral after being cooled to room temperature, suction filtration, get filter cake d at 50 ~ 100 DEG C of drying 5 ~ 10h, namely described carbon composite is obtained, the volumetric usage of described phosphate aqueous solution counts 1 ~ 20mL/g with quality of activated carbon.
5. the preparation method of plumbous charcoal superbattery composite modification material as claimed in claim 1, is characterized in that step (1) described high-area carbon is the composite material that after active carbon, expanded graphite, nano carbon fiber or active carbon mix with mass ratio 1: 0.1 ~ 0.15 with acetylene black, under phosphatizing prepared by common re-activation.
6. the preparation method of plumbous charcoal superbattery composite modification material as claimed in claim 1, is characterized in that 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 indium acetate.
7. the preparation method of plumbous charcoal superbattery composite modification material as claimed in claim 1, is characterized in that the described solid lead solution mass concentration of step (2) is 15 ~ 30%.
8. the preparation method of plumbous charcoal superbattery composite modification material as claimed in claim 7, is characterized in that the volumetric usage of the described solid lead solution of step (2) counts 1 ~ 50mL/g with high-area carbon quality.
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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 |
| CN106299256B (en) * | 2016-11-11 | 2019-06-18 | 华南师范大学 | The preparation method of lead graphene battery negative plate |
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| CN109841798A (en) * | 2017-11-28 | 2019-06-04 | 中国科学院大连化学物理研究所 | A kind of lead carbon battery cathode and its preparation and application |
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