CN102903895B - Electrode material for super lead acid battery, preparation method of electrode material and method for preparing cathode of super lead acid battery by using electrode material - Google Patents
Electrode material for super lead acid battery, preparation method of electrode material and method for preparing cathode of super lead acid battery by using electrode material Download PDFInfo
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- CN102903895B CN102903895B CN201210394944.2A CN201210394944A CN102903895B CN 102903895 B CN102903895 B CN 102903895B CN 201210394944 A CN201210394944 A CN 201210394944A CN 102903895 B CN102903895 B CN 102903895B
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/13—Energy storage using capacitors
Abstract
The invention provides an electrode material for a super lead acid battery, a preparation method of the electrode material and a method for preparing a cathode of the super lead acid battery by using the electrode material, and relates to an electrode material, a preparation method thereof and preparation of a cathode of a battery. The problem that the working electric potential of a porous carbon electrode of the conventional super-capacitor is greatly different from that of a cathode of a lead acid battery is solved. The electrode material for the super lead acid battery consists of a porous carbon material and a modified material. The preparation method comprises the following steps of: preparing the modified material into a solution; mixing the solution and the porous carbon material; adding dilute sulphuric acid in the mixture; and filtering and drying the mixture to obtain the electrode material, or mechanically mixing the modified material and the porous carbon material to obtain the electrode material. The method for preparing the cathode of the super lead acid battery comprises the following steps of: manufacturing the electrode material into an electrode plate; parallelly connecting the electrode plate and a cathode of a lead acid battery; or mixing the electrode material and the material of the lead acid battery, and preparing the mixture into an electrode so as to obtain the cathode of the super lead acid battery. The initial working electric potential and the hydrogen precipitation electric potential of an electrode for the super lead acid battery are similar to those of the lead acid battery; and the electrode can be used for super lead acid batteries or super-capacitors.
Description
The application is that application number is 201110067111.0, the applying date is that denomination of invention is that on 03 18th, 2011, denomination of invention are for the electrode material of lead-acid ultra-battery, its preparation method and utilize it to prepare the divisional application of the application for a patent for invention of the method for lead-acid ultra-battery negative pole.
Technical field
The present invention relates to prepare the method for battery cathode.
Background technology
By electrode of super capacitor and various all or part of mixing of cell type electrode, forming asymmetric ultracapacitor or superbattery has become a new developing direction.Particularly the porous carbon electrodes of ultracapacitor is embedded to the lead-acid ultra-battery of formation based on super capacitor in VRLA (VRLA) battery, for the electrical source of power of hybrid electric vehicle, can make be enhanced about more than once the useful life of VRLA (VRLA) battery.The superbattery that the porous carbon electrodes simple combination of existing lead-acid battery electrode and super capacitor can not be formed in same monomer, because be generally-0.7V of the initial work potential (vs.Hg/Hg of the electric discharge of the porous carbon electrodes of ultracapacitor
2sO
4), be generally-0.99V of the initial work potential of the electric discharge (vs.Hg/Hg of lead-acid battery negative pole
2sO
4),, there is notable difference in differ-0.3V of the work potential scope～-0.4V between the porous carbon electrodes of capacitor and lead-acid battery negative pole, this species diversity can cause electric discharge commitment, the porous carbon electrodes of capacitor can not with plumbous negative pole co-operation; And the electromotive force that the hydrogen of porous carbon materials electrode is separated out is only-1.1V that this will cause, in the time of approaching charging latter stage, producing more hydrogen, and then after causing battery long-time running, electrolyte is dry gradually.
Summary of the invention
The present invention will solve work potential scope between the porous carbon electrodes of existing super capacitor and lead-acid battery negative pole to differ larger, cause the technical problem of super capacitor electrode cisco unity malfunction in lead-acid ultra-battery, and the method for preparing battery cathode for the electrode material of lead-acid ultra-battery of utilizing is provided.
Electrode material for lead-acid ultra-battery of the present invention is to be made up of the material modified of 20%～80% porous carbon materials and 20%～80% by mass percentage, and wherein material modified is PbSO
4, or material modified be by mass percentage by 90%～99% PbSO
4with 1%～10% BaSO
4composition, or material modified be by mass percentage by 90%～99% PbSO
4with 1%～10% CaSO
4composition, or be material modified by mass percentage by 80.2%～99.8% PbSO
4, 0.1%～9.9% BaSO
4with 0.1%～9.9% CaSO
4composition.
The preparation method of the above-mentioned electrode material for lead-acid ultra-battery carries out according to the following steps: one, first take the soluble-salt of porous carbon materials and material modified metallic element, make the quality of the sulfate that this metallic element is corresponding account for 20%～80% of porous carbon materials and sulfate quality sum; The soluble-salt of the metallic element two, step 1 being taken is mixed with the aqueous solution that concentration of metal ions is 0.1mol/L～2.0mol/L, obtains the salting liquid of metallic element; The salting liquid of the metallic element that the porous carbon materials three, step 1 being taken and step 2 obtain adds in container, mixes, then supersonic oscillations 1h～12h; Four, measure the dilute sulfuric acid that enough concentration is 0.1mol/L～2.0mol/L, dilute sulfuric acid is joined in the container described in step 3, stir 30min～40min, then suction filtration, it is 5～6 that the filter cake obtaining is washed with distilled water to pH value; Five, refilter, it is dry 20h～24h in the baking oven of 110 DEG C～120 DEG C that the solid formation obtaining is placed on to temperature, obtains the electrode material for lead-acid ultra-battery; Wherein material modified described in step 1 is PbSO
4, or material modified be by mass percentage by 90%～99% PbSO
4with 1%～10% BaSO
4composition, or material modified be by mass percentage by 90%～99% PbSO
4with 1%～10% CaSO
4composition, or be material modified by mass percentage by 80.2%～99.8% PbSO
4, 0.1%～9.9% BaSO
4with 0.1%～9.9% CaSO
4composition.
Electrode material for lead-acid ultra-battery of the present invention can also be by mass percentage by 20%～80% porous carbon materials and 80%～20% material modified composition, wherein material modified is micron order Pb powder, or material modified be by mass percentage by 90%～99% micron order Pb powder and 1%～10%BaSO
4composition, or material modified be by mass percentage by 90%～99% micron order Pb powder and 1%～10%CaSO
4composition, or material modified be by mass percentage by 80.2%～99.8% micron order Pb powder, 0.1%～9.9% BaSO
4with 0.1%～9.9% CaSO
4composition.
The preparation method of the above-mentioned electrode material for lead-acid ultra-battery carries out according to the following steps: take by mass percentage the material modified of 20%～80% porous carbon materials and 80%～20%, and by porous carbon materials and material modified joining in mixing tank, be to mix 5h～24h under the condition of 50 revs/min～800 revs/min at rotating speed, obtain the electrode material for lead-acid ultra-battery; Wherein said material modified be micron order Pb powder, or material modified be by mass percentage by 90%～99% micron order Pb powder and 1%～10%BaSO
4composition, or material modified be by mass percentage by 90%～99% micron order Pb powder and 1%～10%CaSO
4composition, or material modified be by mass percentage by 80.2%～99.8% micron order Pb powder, 0.1%～9.9% BaSO
4with 0.1%～9.9% CaSO
4composition.
The method that utilization of the present invention is prepared lead-acid ultra-battery negative pole for the electrode material of lead-acid ultra-battery is carried out according to the following steps: one, take by mass percentage 64%～81% the electrode material for lead-acid ultra-battery, 10%～15% acetylene black, 2%～3% sodium carboxymethylcellulose, 4%～8% ptfe emulsion and 3%～8% distilled water; Three, the electrode material for lead-acid ultra-battery and the acetylene black that step 1 are taken pack mixing tank into, be to mix 5h～8h under 50 revs/min～800 revs/min conditions at rotating speed, then the ptfe emulsion that adds successively distilled water that step 1 takes, sodium carboxymethyl cellulose solution prepared by step 2 and step 1 to take, stir 0.2h～2.0h, obtain lotion; Four, lotion step 3 being obtained is coated on lead-acid battery grid, being coated with cream thickness is 0.1mm～3.0mm, then being placed on temperature is the drying baker inner drying 24h～48h of 50 DEG C～70 DEG C, then changes into according to the chemical synthesizing method of VRLA battery negative pole, obtains battery lead plate; Five, the battery lead plate of being prepared by step 4 is in parallel with lead-acid battery negative pole, obtains lead-acid ultra-battery negative pole.
The method that utilization of the present invention is prepared lead-acid ultra-battery negative pole for the electrode material of lead-acid ultra-battery can also be carried out according to the following steps: take by mass percentage the lead-acid battery negative material of 1%～50% the electrode material for lead-acid ultra-battery and 50%～99% and mix, then be prepared into negative pole according to the method for preparing VRLA battery negative pole, obtain lead-acid ultra-battery negative pole.
The present invention is by modifying element soluble-salt solution impregnation for porous carbon materials, make metal ion enter into porous carbon materials, then carry out sulfation, obtain the material modified novel carbon-based composite electrode material forming with porous carbon materials, or carry out mechanical mixture by material modified with porous carbon materials, by material modified modification, making the electrode material for lead-acid ultra-battery of the present invention is 1.25～1.35g/cm in density
3h
2sO
4the electromotive force that in solution, hydrogen is separated out is-1.5V～-1.4V (vs.Hg/Hg
2sO
4), under the same conditions, the electromotive force that the hydrogen of lead-acid battery negative pole is separated out is-1.5V, thus the electromotive force that the hydrogen of the known electrode material for lead-acid ultra-battery of the present invention is separated out is suitable with lead-acid battery negative pole.While charging latter stage, the hydrogen amount of separating out on electrode is suitable with the hydrogen amount of separating out on lead-acid battery negative pole, can not cause the dry of electrolyte; The initial work potential of the electric discharge of the electrode material for lead-acid ultra-battery of the present invention is-0.96V～-0.98V, approaches with the initial work potential-0.99V of the electric discharge of lead-acid battery negative pole.Because the initial work potential of electric discharge of electrode of the present invention is suitable with lead-acid battery negative pole with the evolution or deposition potential of hydrogen, can not make the electrolyte dry-out of battery, can ensure that superbattery normally works.
The preparation method of the electrode material for lead-acid ultra-battery of the present invention is simple, the electrode material stable performance of preparation, no matter be to be first prepared into battery lead plate for the electrode material of lead-acid ultra-battery, and then the interior parallel lead-acid ultra-battery negative pole of formation in parallel with lead-acid battery negative pole, or the internal-mixing lead-acid ultra-battery negative pole of preparation after the electrode material for lead-acid ultra-battery and the negative material of lead-acid battery are directly mixed, the lead-acid ultra-battery forming with the positive pole of VRLA (VRLA) battery, for the electrical source of power of hybrid electric vehicle, can make improve 1～2 times the useful life of VRLA (VRLA) battery.
Electrode material for lead-acid ultra-battery of the present invention not only can be for the preparation of the electrode of lead-acid ultra-battery, can also be for the preparation of the electrode of ultracapacitor.
Brief description of the drawings
Fig. 1 is the constant current charge-discharge curve chart of the lead-acid ultra-battery negative pole of embodiment 67 preparations; Fig. 2 is lead-acid ultra-battery negative pole, common plumbic acid battery cathode and the electrode potential of porous carbon negative pole and the graph of a relation of liberation of hydrogen speed of embodiment 67 preparations, in figure
represent the electrode potential of lead-acid ultra-battery negative pole and the relation of liberation of hydrogen speed,
represent the electrode potential of common plumbic acid battery cathode and the relation of liberation of hydrogen speed,
represent the electrode potential of porous carbon negative pole and the relation of liberation of hydrogen speed.
Embodiment
Embodiment one: the electrode material for lead-acid ultra-battery of present embodiment is to be made up of the material modified of 20%～80% porous carbon materials and 20%～80% by mass percentage, wherein material modified is PbSO
4, or material modified be by mass percentage by 90%～99% PbSO
4with 1%～10% BaSO
4composition, or material modified be by mass percentage by 90%～99% PbSO
4with 1%～10% CaSO
4composition, or be material modified by mass percentage by 80.2%～99.8% PbSO
4, 0.1%～9.9% BaSO
4with 0.1%～9.9% CaSO
4composition.
The electrode material for lead-acid ultra-battery in present embodiment is material modified and compound porous carbon materials, material modified is sulfate, by material modified modification, making the electrode material for lead-acid ultra-battery of present embodiment is 1.25～1.35g/cm in density
3h
2sO
4the electromotive force that in solution, hydrogen is separated out is-1.5V～-1.4V (vs.Hg/Hg
2sO
4), under the same conditions, the electromotive force that the hydrogen of lead-acid battery negative pole is separated out is-1.5V, thus the electromotive force that the hydrogen of the electrode material for lead-acid ultra-battery of known present embodiment is separated out is suitable with lead-acid battery negative pole.While charging latter stage, the hydrogen amount of separating out on electrode is suitable with the hydrogen amount of separating out on lead-acid battery negative pole, can not cause the dry of electrolyte; The initial work potential of the electric discharge of the electrode material for lead-acid ultra-battery of present embodiment is-0.96V～-0.98V, approaches with the initial work potential-0.99V of the electric discharge of lead-acid battery negative pole.The initial work potential of the electric discharge of electrode prepared by the electrode material of present embodiment is suitable with lead-acid battery negative pole with the evolution or deposition potential of hydrogen, can superbattery normally be worked.
Embodiment two: present embodiment is different from embodiment one: be to be formed by the material modified of 25%～75% porous carbon materials and 25%～75% by mass percentage for the electrode material of lead-acid ultra-battery.Other is identical with embodiment one.
Embodiment three: present embodiment is different from embodiment one: be to be formed by the material modified of 50% porous carbon materials and 50% by mass percentage for the electrode material of lead-acid ultra-battery.Other is identical with embodiment one.
Embodiment four: present embodiment is different from one of embodiment one to three: material modified by mass percentage by 91%～98% PbSO
4with 2%～9% BaSO
4combination.Other is identical with one of embodiment one to three.
Embodiment five: present embodiment is different from one of embodiment one to three: material modified by mass percentage by 95% PbSO
4with 5% BaSO
4combination.Other is identical with one of embodiment one to three.
Embodiment six: present embodiment is different from one of embodiment one to three: material modified by mass percentage by 92%～98% PbSO
4with 2%～8% CaSO
4combination.Other is identical with one of embodiment one to three.
Embodiment seven: present embodiment is different from one of embodiment one to three: material modified by mass percentage by 96% PbSO
4with 4% CaSO
4combination.Other is identical with one of embodiment one to three.
Embodiment eight: present embodiment is different from one of embodiment one to three: material modified by mass percentage by 81%～99% PbSO
4, 0.5%～9.5% BaSO
4with 0.5%～9.5% CaSO
4combination.Other is identical with one of embodiment one to three.
Embodiment nine: present embodiment is different from one of embodiment one to eight: porous carbon materials is active carbon, activated carbon fiber, activated carbon felt, mesoporous carbon or carbon nano-tube.Other is identical with one of embodiment one to eight.
Embodiment ten: the preparation method of the electrode material for lead-acid ultra-battery of present embodiment carries out according to the following steps: one, first take soluble-salt and the porous carbon materials of material modified metallic element, make the quality of the sulfate that this metallic element is corresponding account for 20%～80% of porous carbon materials and sulfate quality sum; The soluble-salt of the metallic element two, step 1 being taken is mixed with the aqueous solution that concentration of metal ions is 0.1mol/L～2.0mol/L, obtains the salting liquid of metallic element; The salting liquid of the metallic element that the porous carbon materials three, step 1 being taken and step 2 obtain adds in container, mixes, then supersonic oscillations 1h～12h; Four, measure the dilute sulfuric acid that enough concentration is 0.1mol/L～2.0mol/L, dilute sulfuric acid is joined in the container described in step 3, stir 30min～40min, then suction filtration, it is 5～6 that the filter cake obtaining is washed with distilled water to pH value; Five, refilter, it is dry 20h～24h in the baking oven of 110 DEG C～120 DEG C that the solid formation obtaining is placed on to temperature, obtains the electrode material for lead-acid ultra-battery; Wherein material modified described in step 1 is PbSO
4, or material modified be by mass percentage by 90%～99% PbSO
4with 1%～10% BaSO
4composition, or material modified be by mass percentage by 90%～99% PbSO
4with 1%～10% CaSO
4composition, or be material modified by mass percentage by 80.2%～99.8% PbSO
4, 0.1%～9.9% BaSO
4with 0.1%～9.9% CaSO
4composition.
Modifying element soluble-salt solution impregnation for porous carbon materials in present embodiment, make metal ion enter into porous carbon materials, then carry out sulfation, obtain the material modified novel carbon-based composite electrode material forming with porous carbon materials, by material modified modification, making the electrode material for lead-acid ultra-battery of present embodiment is 1.25～1.35g/cm in density
3h
2sO
4the electromotive force that in solution, hydrogen is separated out is-1.5V～-1.4V (vs.Hg/Hg
2sO
4), under the same conditions, the electromotive force that the hydrogen of lead-acid battery negative pole is separated out is-1.5V, thus the electromotive force that the hydrogen of the electrode material for lead-acid ultra-battery of known present embodiment is separated out is suitable with lead-acid battery negative pole.While charging latter stage, the hydrogen amount of separating out on electrode is suitable with the hydrogen amount of separating out on lead-acid battery negative pole, can not cause the dry of electrolyte; The initial work potential of the electric discharge of the electrode material for lead-acid ultra-battery of present embodiment is-0.96V～-0.98V, approaches with the initial work potential-0.99V of the electric discharge of lead-acid battery negative pole.The initial work potential of the electric discharge of electrode prepared by the electrode material of present embodiment is suitable with lead-acid battery negative pole with the evolution or deposition potential of hydrogen, can superbattery normally be worked.
Embodiment 11: present embodiment is different from embodiment ten: material modified by mass percentage by 91%～98% PbSO described in step 1
4with 2%～9% BaSO
4composition.Other is identical with embodiment ten.
Embodiment 12: present embodiment is different from embodiment ten: material modified by mass percentage by 95% PbSO described in step 1
4with 5% BaSO
4composition.Other is identical with embodiment ten.
Embodiment 13: present embodiment is different from embodiment ten: material modified by mass percentage by 92%～98% PbSO described in step 1
4with 2%～8% CaSO
4composition.Other is identical with embodiment ten.
Embodiment 14: present embodiment is different from embodiment ten: material modified by mass percentage by 96% PbSO described in step 1
4with 4% CaSO
4composition.Other is identical with embodiment ten.
Embodiment 15: present embodiment is different from embodiment ten: material modified by mass percentage by 81%～99% PbSO described in step 1
4, 0.5%～9.5% BaSO
4with 0.5%～9.5% CaSO
4composition.Other is identical with embodiment ten.
Embodiment 16: present embodiment is different from embodiment ten: material modified by mass percentage by 90% PbSO described in step 1
4, 5% BaSO
4with 5% CaSO
4composition.Other is identical with embodiment ten.
Embodiment 17: present embodiment is different from one of embodiment ten to 16: the quality of the sulfate that material modified middle metallic element in step 1 is corresponding accounts for 25%～75% of porous carbon materials and sulfate quality sum.Other is identical with one of embodiment ten to 16.
Embodiment 18: present embodiment is different from one of embodiment ten to 16: the quality of the sulfate that material modified middle metallic element in step 1 is corresponding accounts for 50% of porous carbon materials and sulfate quality sum.Other is identical with one of embodiment ten to 16.
Embodiment 19: present embodiment is different from one of embodiment ten to 18: in the salting liquid of the metallic element in step 2, concentration of metal ions is 0.3mol/L～1.7mol/L.Other is identical with one of embodiment ten to 18.
Embodiment 20: present embodiment is different from one of embodiment ten to 18: in the salting liquid of the metallic element in step 2, concentration of metal ions is 1.0mol/L.Other is identical with one of embodiment ten to 18.
Embodiment 21: present embodiment is different from one of embodiment ten to 20: supersonic oscillations 2h～10h in step 3.Other is identical with one of embodiment ten to 20.
In present embodiment, the object of supersonic oscillations is to make metallic element salting liquid fully and evenly be impregnated into the surface of porous carbon materials and the inside in hole.
Embodiment 22: present embodiment is different from one of embodiment ten to 20: supersonic oscillations 5h in step 3.Other is identical with one of embodiment ten to 20.
Embodiment 23: present embodiment is different from one of embodiment ten to 22: in step 4, the concentration of enough dilute sulfuric acids is 0.3mol/L～1.5mol/L.Other is identical with one of embodiment ten to 22.
In present embodiment, " enough " refers to that the molal quantity of the sulfate ion in dilute sulfuric acid is more than or equal to the molal quantity of metal ion in the salting liquid of metallic element, make metal ion be transformed into sulfate and be deposited on inside porous carbon materials and face and hole, unnecessary sulfate ion can be removed by washing step afterwards.
Embodiment 24: present embodiment is different from one of embodiment ten to 22: in step 4, the concentration of dilute sulfuric acid is 1.0mol/L.Other is identical with one of embodiment ten to 22.
Embodiment 25: present embodiment is different from one of embodiment ten to 24: adding the mixing time after dilute sulfuric acid in step 4 is 32min～38min, it is 5.2～5.8 that the filter cake after suction filtration is washed with distilled water to pH value.Other is identical with one of embodiment ten to 24.
Embodiment 26: present embodiment is different from one of embodiment ten to 24: be 35min by the mixing time after dilute sulfuric acid in step 4, it is 5.5 that the filter cake after suction filtration is washed with distilled water to pH value.Other is identical with one of embodiment ten to 24.
In the filter cake obtaining in the step 4 of present embodiment, contain the sulfate of porous carbon materials and modified metal.
Embodiment 27: present embodiment is different from one of embodiment ten to 26: in step 5, the baking temperature of solid formation is 112 DEG C～118 DEG C, be 21h～23h drying time.Other is identical with one of embodiment ten to 26.
Embodiment 28: present embodiment is different from one of embodiment ten to 26: in step 5, the baking temperature of solid formation is 115 DEG C, be 22h drying time.Other is identical with one of embodiment ten to 26.
Embodiment 29: present embodiment is different from one of embodiment ten to 28: the porous carbon materials in step 1 is active carbon, activated carbon fiber, activated carbon felt, mesoporous carbon or carbon nano-tube.Other is identical with one of embodiment ten to 28.
Embodiment 30: the electrode material for lead-acid ultra-battery of present embodiment can also be by mass percentage by 20%～80% porous carbon materials and 80%～20% material modified composition, wherein material modified is micron order Pb powder, or material modified be by mass percentage by 90%～99% micron order Pb powder and 1%～10%BaSO
4composition, or material modified be by mass percentage by 90%～99% micron order Pb powder and 1%～10%CaSO
4composition, or material modified be by mass percentage by 80.2%～99.8% micron order Pb powder, 0.1%～9.9% BaSO
4with 0.1%～9.9% CaSO
4composition.
Embodiment 31: what present embodiment was different from embodiment 30 is for the electrode material of lead-acid ultra-battery by mass percentage by 20%～80% porous carbon materials and 80%～20% material modified composition.Other is identical with embodiment 30.
Embodiment 32: what present embodiment was different from embodiment 30 is for the electrode material of lead-acid ultra-battery by mass percentage by 60% porous carbon materials and 40% material modified composition.Other is identical with embodiment 30.
Embodiment 33: it is material modified by mass percentage by 91%～98% micron order Pb powder and 2%～9% BaSO that what present embodiment was different from one of embodiment 30 to 32 is
4composition.Other is identical with one of embodiment 30 to 32.
Embodiment 34: it is material modified by mass percentage by 95% micron order Pb powder and 5% BaSO that what present embodiment was different from one of embodiment 30 to 32 is
4composition.Other is identical with one of embodiment 30 to 32.
Embodiment 35: it is material modified by mass percentage by 92%～98% micron order Pb powder and 2%～8% CaSO that what present embodiment was different from one of embodiment 30 to 32 is
4composition.Other is identical with one of embodiment 30 to 32.
Embodiment 36: it is material modified by mass percentage by 96% micron order Pb powder and 4% CaSO that what present embodiment was different from one of embodiment 30 to 32 is
4composition.Other is identical with one of embodiment 30 to 32.
Embodiment 37: what present embodiment was different from one of embodiment 30 to 32 is material modified by mass percentage by 81%～99% micron order Pb powder, 0.5%～9.5% BaSO
4with 0.5%～9.5% CaSO
4composition.Other is identical with one of embodiment 30 to 32.
Embodiment 38: what present embodiment was different from one of embodiment 30 to 32 is material modified by mass percentage by 90% micron order Pb powder, 5.0% BaSO
4with 5.0% CaSO
4composition.Other is identical with one of embodiment 30 to 32.
Embodiment 39: the preparation method of the electrode material for lead-acid ultra-battery of present embodiment carries out according to the following steps: take by mass percentage the material modified of 20%～80% porous carbon materials and 80%～20% and by porous carbon materials and the material modified mixing tank that joins, be to mix 5h～24h under the condition of 50 revs/min～800 revs/min at rotating speed, obtain the electrode material for lead-acid ultra-battery; Wherein said material modified be micron order Pb powder, or material modified be by mass percentage by 90%～99% micron order Pb powder and 1%～10%BaSO
4composition, or material modified be by mass percentage by 90%～99% micron order Pb powder and 1%～10%CaSO
4composition, or material modified be by mass percentage by 80.2%～99.8% micron order Pb powder, 0.1%～9.9% BaSO
4with 0.1%～9.9% CaSO
4composition.
Present embodiment is carried out mechanical mixture by material modified with porous carbon materials, obtain the material modified electrode material for lead-acid ultra-battery forming with porous carbon materials, interact with porous carbon materials by material modified, making the electrode material for lead-acid ultra-battery of present embodiment is 1.25～1.35g/cm in density
3h
2sO
4the electromotive force that in solution, hydrogen is separated out is-1.5V～-1.4V (vs.Hg/Hg
2sO
4), under the same conditions, the electromotive force that the hydrogen of lead-acid battery negative pole is separated out is-1.5V, thus the electromotive force that the hydrogen of the electrode material for lead-acid ultra-battery of known present embodiment is separated out is suitable with lead-acid battery negative pole.While charging latter stage, the hydrogen amount of separating out on electrode is suitable with the hydrogen amount of separating out on lead-acid battery negative pole, can not cause the dry of electrolyte; The initial work potential of the electric discharge of the electrode material for lead-acid ultra-battery of present embodiment is-0.96V～-0.98V, approaches with the initial work potential-0.99V of the electric discharge of lead-acid battery negative pole.The initial work potential of the electric discharge of the electrode material for lead-acid ultra-battery of present embodiment is suitable with lead-acid battery negative pole with the evolution or deposition potential of hydrogen, can superbattery normally be worked.
Embodiment 40: present embodiment is different from embodiment 39: take by mass percentage the material modified of 25%～75% porous carbon materials and 25%～75%.Other is identical with embodiment 39.
Embodiment 41: present embodiment is different from embodiment 39: take by mass percentage the material modified of 50% porous carbon materials and 50%.Other is identical with embodiment 39.
Embodiment 42: present embodiment is different from one of embodiment 39 to 41: the rotating speed of mixing tank is 100 revs/min～700 revs/min, and incorporation time is 8h～20h.Other is identical with one of embodiment 39 to 41.
Embodiment 43: present embodiment is different from one of embodiment 39 to 41: the rotating speed of mixing tank is 400 revs/min, incorporation time is 15h.Other is identical with one of embodiment 39 to 41.
Embodiment 44: present embodiment is different from one of embodiment 39 to 43: material modified by mass percentage by 90%～99% micron order Pb powder and 2%～8% BaSO
4composition.Other is identical with one of embodiment 39 to 43.
Embodiment 45: present embodiment is different from one of embodiment 39 to 43: material modified by mass percentage by 95% micron order Pb powder and 5% BaSO
4composition.
Embodiment 46: it is material modified by mass percentage by 90%～99% micron order Pb powder and 2%～8% CaSO that what present embodiment was different from one of embodiment 39 to 43 is
4composition.Other is identical with one of embodiment 39 to 43.
Embodiment 47: it is material modified by mass percentage by 95% micron order Pb powder and 5% CaSO that what present embodiment was different from one of embodiment 39 to 43 is
4composition.Other is identical with one of embodiment 39 to 43.
Embodiment 48: what present embodiment was different from one of embodiment 39 to 43 is material modified by mass percentage by 82%～99% micron order Pb powder, 0.5%～9.0% BaSO
4with 0.5%～9.0% CaSO
4composition.Other is identical with one of embodiment 39 to 43.
Embodiment 49: what present embodiment was different from one of embodiment 39 to 43 is material modified by mass percentage by 90% micron order Pb powder, 5.0% BaSO
4with 5.0% CaSO
4composition.Other is identical with one of embodiment 39 to 43.
Embodiment 50: what present embodiment was different from one of embodiment 30 to 38 is that described porous carbon materials is activated carbon or carbon nano-tube.Other is identical with one of embodiment 30 to 38.
Embodiment 51: the method that the utilization of present embodiment is prepared lead-acid ultra-battery negative pole for the electrode material of lead-acid ultra-battery is carried out according to the following steps: take by mass percentage 64%～81% the electrode material for lead-acid ultra-battery, 10%～15% acetylene black, 2%～3% sodium carboxymethylcellulose, 4%～8% ptfe emulsion and 3%～8% distilled water; Two, it is 1%～5% the aqueous solution that sodium carboxymethylcellulose step 1 being taken is mixed with concentration; Three, the electrode material for lead-acid ultra-battery and the acetylene black that step 1 are taken pack mixing tank into, be to mix 5h～8h under 50 revs/min～800 revs/min conditions at rotating speed, then the ptfe emulsion that adds successively distilled water that step 1 takes, sodium carboxymethyl cellulose solution prepared by step 2 and step 1 to take, stir 0.2h～2.0h, obtain lotion; Four, lotion step 3 being obtained is coated on lead-acid battery grid, being coated with cream thickness is 0.1mm～3.0mm, then being placed on temperature is the drying baker inner drying 24h～48h of 50 DEG C～70 DEG C, then changes into according to the chemical synthesizing method of VRLA battery negative pole, obtains battery lead plate; Five, the battery lead plate of being prepared by step 4 is in parallel with lead-acid battery negative pole, obtains lead-acid ultra-battery negative pole.
Ptfe emulsion described in present embodiment step 1 is commercially available prod.
Present embodiment is to utilize to be first prepared into battery lead plate for the electrode material of lead-acid ultra-battery, and then the interior parallel lead-acid ultra-battery negative pole of formation in parallel with lead-acid battery negative pole, the lead-acid ultra-battery of composition has following chemical property, in the electrolyte of lead-acid battery, namely density is 1.25～1.35g/cm
3h
2sO
4in solution, H
2approach-1.5V～-1.4V (vs.Hg/Hg of the electromotive force of separating out
2sO
4), suitable with lead-acid battery negative pole; The initial work potential of the electric discharge of this lead-acid ultra-battery negative pole is-0.98V～0.96V, with lead-acid battery negative pole-0.99V approach, in the time of charging latter stage, hydrogen precipitation rate is suitable with plumbic acid negative pole, lead-acid ultra-battery can normally be worked, electrode performance prepared by present embodiment is stable, form the lead-acid ultra-battery based on super capacitor with VRLA (VRLA) battery, be used as the electrical source of power of hybrid electric vehicle, can make improve 1～2 times the useful life of VRLA (VRLA) battery.
Embodiment 52: present embodiment is different from embodiment 51: take by mass percentage 68.4%～80.6% the electrode material for lead-acid ultra-battery, 11%～14% acetylene black, 2.2%～2.8% sodium carboxymethylcellulose, 4.2%～7.8% ptfe emulsion and 4%～7% distilled water in step 1.Other is identical with embodiment 51.
Embodiment 53: present embodiment is different from embodiment 51: take by mass percentage 75.5% the electrode material for lead-acid ultra-battery, 12% acetylene black, 2.5% sodium carboxymethylcellulose, 5% ptfe emulsion and 5% distilled water in step 1.Other is identical with embodiment 51.
Embodiment 54: present embodiment is different from one of embodiment 51 to 53: in step 2, the concentration of sodium carboxymethyl cellulose solution is 1.5%～4.5%.Other is identical with one of embodiment 51 to 53.
Embodiment 55: present embodiment is different from one of embodiment 51 to 53: in step 2, the concentration of sodium carboxymethyl cellulose solution is 3%.Other is identical with one of embodiment 51 to 53.
Embodiment 56: present embodiment is different from one of embodiment 51 to 55: in step 3, the rotating speed of mixing tank is 100 revs/min～700 revs/min, and incorporation time is 5.5h～7.5h.Other is identical with one of embodiment 51 to 55.
Embodiment 57: present embodiment is different from one of embodiment 51 to 55: in step 3, the rotating speed of mixing tank is 400 revs/min, incorporation time is 6.5h.Other is identical with one of embodiment 51 to 55.
Embodiment 58: present embodiment is different from one of embodiment 51 to 57: being coated with cream thickness in step 4 is 0.2mm～2.5mm.Other is identical with one of embodiment 51 to 57.
Embodiment 59: present embodiment is different from one of embodiment 51 to 57: be coated with cream thickness 1.0mm in step 4.Other is identical with one of embodiment 51 to 57.
Embodiment 60: present embodiment is different from one of embodiment 51 to 57: the baking temperature that has been coated with the lead-acid battery grid of lotion in step 4 is 55 DEG C～65 DEG C, and be 26h～45h drying time.Other is identical with one of embodiment 51 to 57.
Embodiment 61: present embodiment is different from one of embodiment 51 to 59: the baking temperature that has been coated with the lead-acid battery grid of lotion in step 4 is 60 DEG C, be 36h drying time.Other is identical with one of embodiment 51 to 59.
Embodiment 62: present embodiment is different from one of embodiment 51 to 59: the baking temperature that has been coated with the lead-acid battery grid of lotion in step 4 is 60 DEG C, be 36h drying time.Other is identical with one of embodiment 51 to 59.
Embodiment 63: present embodiment is different from one of embodiment 51 to 59: the chemical synthesizing method of the VRLA battery negative pole in step 4 carries out according to the following steps: a, first at 5A/cm
2galvanostatic conditions under the 1min that charges, then leave standstill 15min; B, with 2.5A/cm
2constant current charge 1h, then with 4A/cm
2constant current charge 10h, then leave standstill 10min; C, with 3.5A/cm
2constant current charge 6h, then with 3A/cm
2constant current charge 5h, finally with 1.5A/cm
2constant current charge 1h, completes changing into of negative plate VRLA battery negative pole.Other is identical with one of embodiment 51 to 59.
Embodiment 64: the method that the utilization of present embodiment is prepared lead-acid ultra-battery negative pole for the electrode material of lead-acid ultra-battery is carried out according to the following steps: take by mass percentage the lead-acid battery negative material of 1%～50% the electrode material for lead-acid ultra-battery and 50%～99% and mix, then be prepared into negative pole according to the method for preparing VRLA battery negative pole, obtain lead-acid ultra-battery negative pole.
The internal-mixing lead-acid ultra-battery negative pole that present embodiment is prepared after the electrode material for lead-acid ultra-battery and the negative material of lead-acid battery are directly mixed, there is following chemical property, in the electrolyte of lead-acid battery, namely density is 1.25～1.35g/cm
3h
2sO
4in solution, H
2approach-1.5V～-1.4V (vs.Hg/Hg of the electromotive force of separating out
2sO
4), suitable with lead-acid battery negative pole; The initial work potential of the electric discharge of this lead-acid ultra-battery negative pole is-0.98V～0.96V, with lead-acid battery negative pole-0.99V approach, in the time of charging latter stage, hydrogen precipitation rate is suitable with plumbic acid negative pole, lead-acid ultra-battery can normally be worked, electrode performance prepared by the present invention is stable, form the lead-acid ultra-battery based on super capacitor with VRLA (VRLA) battery, be used as the electrical source of power of hybrid electric vehicle, can make improve 1～2 times the useful life of VRLA (VRLA) battery.
Embodiment 65: what present embodiment was different from embodiment 64 is takes 5%～45% the electrode material for lead-acid ultra-battery and 55%～95% lead-acid battery negative material by mass percentage.Other is identical with embodiment 64.
Embodiment 66: what present embodiment was different from embodiment 64 is takes 30% the electrode material for lead-acid ultra-battery and 70% lead-acid battery negative material by mass percentage.Other is identical with embodiment 64.
Embodiment 67: the preparation method of the electrode material for lead-acid ultra-battery of present embodiment carries out according to the following steps: one, first take 8.5g plumbi nitras, 0.7g barium nitrate and 3g activated carbon; Two, plumbi nitras step 1 being taken and barium nitrate join in 20mL distilled water, are mixed with mixing salt solution; Three, the mixing salt solution that activated carbon step 1 being taken and step 2 obtain adds in container, mixes, then supersonic oscillations 1h; Four, measure the dilute sulfuric acid that 30mL concentration is 1.0mol/L, dilute sulfuric acid is joined in the container described in step 3, stir 30min, then suction filtration obtains the filter cake that comprises porous carbon materials and modified metal sulfate, and it is 6 that filter cake is washed with distilled water to pH value again; Five, filter, it is dry 24h in the baking oven of 115 DEG C that the solid formation obtaining is placed on to temperature, obtains the electrode material for lead-acid ultra-battery.
The electrode material for lead-acid ultra-battery that present embodiment obtains is by mass percentage by 26.3% activated carbon and 73.7% material modified composition, and wherein material modified is by mass percentage by 92.56% PbSO
4with 7.44% BaSO
4composition.
The electrode material for lead-acid ultra-battery that present embodiment is obtained is prepared the method for lead-acid ultra-battery negative pole and is carried out according to the following steps: one, take by mass percentage 80% the electrode material for lead-acid ultra-battery, 10% acetylene black, 2.5% sodium carboxymethylcellulose, 4.5% ptfe emulsion and 3% distilled water; Two, it is 3% the aqueous solution that sodium carboxymethylcellulose step 1 being taken is mixed with concentration; Three, the electrode material for lead-acid ultra-battery and the acetylene black that step 1 are taken pack mixing tank into, under rotating speed 500rpm condition, mix 7h, then add successively the distilled water that step 1 takes, sodium carboxymethyl cellulose solution and ptfe emulsion prepared by step 2, stir 1.0h, obtain lotion; Four, lotion step 3 being obtained is coated on lead-acid battery grid, is coated with cream thickness 2.5mm, is then placed on temperature and is the drying baker inner drying 36h of 60 DEG C, then changes into, and the condition of changing into is 5A/cm
2the 1min that charges under galvanostatic conditions, then leaves standstill 15min, continues with 2.5A/cm
2constant current charge 1h, and then with 4A/cm
2constant current charge 10h, then leave standstill 10min, afterwards again with 3.5A/cm
2constant current charge 6h, with 3A/cm
2constant current charge 5h, finally with 1.5A/cm
2constant current charge 1h, the battery lead plate that obtains changing into; Five, the battery lead plate after changing into and lead-acid battery negative pole carry out interior in parallelly, obtain lead-acid ultra-battery negative pole.
The interior parallel lead-acid ultra-battery negative pole that present embodiment is obtained and VRLA battery positive plate form lead-acid ultra-battery, and the electrolyte of this battery is that density is 1.25～1.35g/cm
3h
2sO
4solution, test the constant current charge-discharge curve of this lead-acid ultra-battery negative pole as shown in Figure 1, as seen from Figure 1, the initial work potential of the electric discharge of lead-acid ultra-battery negative pole prepared by present embodiment is-0.96V, approach with the initial work potential-0.99V of lead-acid battery negative pole, lower than the initial work potential-0.72V of porous carbon materials.
The lead-acid ultra-battery negative pole that prepared by present embodiment obtain present embodiment and VRLA battery positive plate form lead-acid ultra-battery, and the electrolyte of this battery is that density is 1.25～1.35g/cm
3h
2sO
4solution, test hydrogen precipitation rate, common plumbic acid battery cathode and porous carbon negative pole are tested to hydrogen precipitation rate under identical condition simultaneously, the lead-acid ultra-battery negative pole obtaining, common plumbic acid battery cathode and the electrode potential of porous carbon negative pole and the relation of liberation of hydrogen speed as shown in Figure 2, in figure
represent the electrode potential of lead-acid ultra-battery negative pole and the relation of liberation of hydrogen speed,
represent the electrode potential of common plumbic acid battery cathode and the relation of liberation of hydrogen speed,
represent the electrode potential of porous carbon negative pole and the relation of liberation of hydrogen speed, as can be seen from Figure 2, the H of lead-acid ultra-battery negative pole
2approach-1.5V (vs.Hg/Hg of the electromotive force of separating out
2sO
4), suitable with common plumbic acid battery cathode, lower than the H of porous carbon negative pole
2the electromotive force (1.1V) of separating out, in the time of charging latter stage, hydrogen precipitation rate is suitable with plumbic acid negative pole, can not cause the dry of battery electrolyte.
Embodiment 68: the preparation method of the electrode material for lead-acid ultra-battery of present embodiment carries out according to the following steps: one, first take 8.5g plumbi nitras, 0.7g barium nitrate and 3g activated carbon; Two, plumbi nitras step 1 being taken and barium nitrate join in 20mL distilled water, are mixed with mixing salt solution; Three, the mixing salt solution that activated carbon step 1 being taken and step 2 obtain adds in container, mixes, then supersonic oscillations 1h; Four, measure the dilute sulfuric acid that 30mL concentration is 1.0mol/L, dilute sulfuric acid is joined in the container described in step 3, stir 30min, then suction filtration obtains the filter cake that comprises porous carbon materials and modified metal sulfate, and it is 5 that filter cake is washed with distilled water to pH value again; Five, filter, it is dry 24h in the baking oven of 120 DEG C that solid formation is placed on to temperature, obtains the electrode material for lead-acid ultra-battery.
The electrode material for lead-acid ultra-battery that present embodiment obtains is by mass percentage by approximately 26.3% activated carbon and 73.7% material modified composition, is wherein by mass percentage by 92.56% PbSO
4with 7.44% BaSO
4combination.
The method of utilizing the electrode material for lead-acid ultra-battery that present embodiment obtains to prepare lead-acid ultra-battery negative pole is carried out according to the following steps: take electrode material, 78.76g spongy lead powder, 0.06g polypropene staple, 0.62g barium sulfate, 0.16g lignin, 0.20g humic acid, the 0.20g acetylene black of 20g for lead-acid ultra-battery, and mix, and be placed in mixing tank and be dry mixed and close 5min, then add 10g distilled water to be stirred to and mix, then add 1.4g/cm
3h
2sO
4solution 8g, is stirred to and mixes, and obtains creme, and creme is coated on lead-acid battery grid, is coated with cream thickness 2mm, is then placed on temperature and is the drying baker inner drying 36h of 70 DEG C, then changes into, and the condition of changing into is 5A/cm
2the 1min that charges under galvanostatic conditions, then leaves standstill 15min, continues with 2.5A/cm
2constant current charge 1h, and then with 4A/cm
2constant current charge 10h, then leave standstill 10min, afterwards again with 3.5A/cm
2constant current charge 6h, with 3A/cm
2constant current charge 5h, finally with 1.5A/cm
2constant current charge 1h, obtains changing into end, obtains lead-acid ultra-battery negative pole.
By the lead-acid ultra-battery that obtains internal-mixing lead-acid ultra-battery negative pole directly and VRLA battery positive plate forms, the electrolyte of this battery is that density is 1.25～1.35g/cm
3h
2sO
4solution, the performance of testing this battery is as follows:
The H of lead-acid ultra-battery negative pole
2the electromotive force of separating out is-1.5V (vs.Hg/Hg
2sO
4), suitable with common plumbic acid battery cathode, lower than the H of porous carbon negative pole
2the electromotive force (1.1V) of separating out; The initial work potential of the electric discharge of this lead-acid ultra-battery negative pole is-0.96V to be-0.99V, lower than the initial work potential-0.72V of porous carbon materials with the initial work potential of lead-acid battery negative pole.In the time of charging latter stage, hydrogen precipitation rate is suitable with lead-acid battery negative pole, can not cause the dry of battery electrolyte.
Embodiment 69: the preparation method of the electrode material for lead-acid ultra-battery of present embodiment carries out according to the following steps: take by mass percentage the micron order Pb powder of 60% activated carbon and 40% and activated carbon and micron order Pb are joined to mixing tank, under rotating speed 600rpm condition, mix 8h, obtain the electrode material for lead-acid ultra-battery.
Electrode material for lead-acid ultra-battery prepared by present embodiment is made up of micron order Pb powder and activated carbon.
The method of utilizing the electrode material for lead-acid ultra-battery prepared by present embodiment to prepare the negative pole of lead-acid ultra-battery is carried out according to the following steps: one, take by mass percentage 80% the electrode material for lead-acid ultra-battery, 10% acetylene black, 2.5 sodium carboxymethylcellulose, 4.5% ptfe emulsion and 3% distilled water; Two, it is 5% the aqueous solution that sodium carboxymethylcellulose step 1 being taken is mixed with concentration; Three, the electrode material for lead-acid ultra-battery and the acetylene black that step 1 are taken pack mixing tank into, under rotating speed 500rpm condition, mix 7h, then add successively the distilled water that step 1 takes, sodium carboxymethyl cellulose solution and ptfe emulsion prepared by step 2, stir 1.0h, obtain lotion; Four, lotion step 3 being obtained is coated on lead-acid battery grid, is coated with cream thickness 3mm, is then placed on temperature and is the drying baker inner drying 48h of 70 DEG C, then changes into, and the condition of changing into is 5A/cm
2the 1min that charges under galvanostatic conditions, then leaves standstill 15min, continues with 2.5A/cm
2constant current charge 1h, and then with 4A/cm
2constant current charge 10h, then leave standstill 10min, afterwards again with 3.5A/cm
2constant current charge 6h, with 3A/cm
2constant current charge 5h, finally with 1.5A/cm
2constant current charge 1h, the battery lead plate that obtains changing into; Five, step 4 is obtained change into after battery lead plate and lead-acid battery negative pole carry out interior in parallelly, obtain the negative plate of lead-acid ultra-battery.
The interior parallel lead-acid ultra-battery negative plate obtaining and VRLA battery positive plate are formed to lead-acid ultra-battery, and the electrolyte of this battery is that density is 1.25～1.35g/cm
3h
2sO
4solution, the performance of testing this battery is as follows:
The H of the negative pole of super capacitor lead-acid battery
2the electromotive force of separating out is-1.5V (vs.Hg/Hg
2sO
4), suitable with common plumbic acid battery cathode, lower than the H of porous carbon negative pole
2the electromotive force (1.1V) of separating out; The initial work potential of the electric discharge of this novel composite electrode material is-0.96V to be-0.99V, lower than the initial work potential-0.72V of porous carbon materials with the initial work potential of lead-acid battery negative pole.In the time of charging latter stage, hydrogen precipitation rate is suitable with plumbic acid negative pole, can not cause the dry of battery electrolyte.
Embodiment 70: the preparation method of the electrode material for lead-acid ultra-battery of present embodiment carries out according to the following steps: take by mass percentage the micron order Pb powder of 60% activated carbon and 40% and activated carbon and micron order Pb are joined to mixing tank, under rotating speed 500rpm condition, mix 6h, obtain the electrode material for lead-acid ultra-battery.
Electrode material for lead-acid ultra-battery prepared by present embodiment is made up of micron order Pb powder and activated carbon.
The method of the negative pole of preparing lead-acid ultra-battery for the electrode material of lead-acid ultra-battery is carried out according to the following steps: take electrode material, 78.76g spongy lead powder, 0.06g polypropene staple, 0.62g barium sulfate, 0.16g lignin, 0.20g humic acid, the 0.20g acetylene black of 20g for lead-acid ultra-battery, being placed in mixing tank is dry mixed and closes 5min, add 10g distilled water to be stirred to and mix, then add 1.4g/cm
3h
2sO
4solution 8g, is stirred to and mixes, and obtains creme, and creme is coated on lead-acid battery grid, is coated with cream thickness 2mm, is then placed on temperature and is the drying baker inner drying 24h of 60 DEG C, then changes into, and the condition of changing into is 5A/cm
2the 1min that charges under galvanostatic conditions, then leaves standstill 15min, continues with 2.5A/cm
2constant current charge 1h, and then with 4A/cm
2constant current charge 10h, then leave standstill 10min, afterwards again with 3.5A/cm
2constant current charge 6h, with 3A/cm
2constant current charge 5h, finally with 1.5A/cm
2constant current charge 1h, completes and changes into, and obtains the negative pole of lead-acid ultra-battery.
The negative pole of the internal-mixing lead-acid ultra-battery obtaining is direct and VRLA battery positive plate forms lead-acid ultra-battery, the electrolyte of this battery is that density is 1.25～1.35g/cm
3h
2sO
4solution, the performance of testing this battery is as follows:
The H of lead-acid ultra-battery negative pole
2the electromotive force of separating out is-1.5V (vs.Hg/Hg
2sO
4), suitable with common plumbic acid battery cathode, lower than the H of porous carbon negative pole
2the electromotive force (1.1V) of separating out; The initial work potential of the electric discharge of the negative pole of this lead-acid ultra-battery is-0.96V to be-0.99V, lower than the initial work potential-0.72V of porous carbon materials with the initial work potential of common plumbic acid battery cathode.In the time of charging latter stage, hydrogen precipitation rate is suitable with plumbic acid negative pole, can not cause the dry of electrolyte.
Claims (1)
1. utilize the method for preparing lead-acid ultra-battery negative pole for the electrode material of lead-acid ultra-battery, it is characterized in that utilizing the method for preparing lead-acid ultra-battery negative pole for the electrode material of lead-acid ultra-battery to carry out according to the following steps: one, take by mass percentage 75.5%～81% the electrode material for lead-acid ultra-battery, 10%～12% acetylene black, 2%～2.5% sodium carboxymethylcellulose, 4%～5% ptfe emulsion and 3%～5% distilled water; Two, it is 1%～5% the aqueous solution that sodium carboxymethylcellulose step 1 being taken is mixed with concentration; Three, the electrode material for lead-acid ultra-battery and the acetylene black that step 1 are taken pack mixing tank into, be to mix 5h～8h under 50 revs/min～800 revs/min conditions at rotating speed, then the ptfe emulsion that adds successively distilled water that step 1 takes, sodium carboxymethyl cellulose solution prepared by step 2 and step 1 to take, stir 0.2h～2.0h, obtain lotion; Four, lotion step 3 being obtained is coated on lead-acid battery grid, being coated with cream thickness is 0.1mm～3.0mm, then being placed on temperature is the drying baker inner drying 24h～48h of 50 DEG C～70 DEG C, then changes into according to the chemical synthesizing method of VRLA battery negative pole, obtains battery lead plate; Five, the battery lead plate of being prepared by step 4 is in parallel with lead-acid battery negative pole, obtains lead-acid ultra-battery negative pole;
The preparation method of the electrode material for lead-acid ultra-battery described in step 1 carries out according to the following steps: take by mass percentage the material modified of 20%～80% porous carbon materials and 80%～20% and by porous carbon materials and the material modified mixing tank that joins, be to mix 5h～24h under the condition of 50 revs/min～800 revs/min at rotating speed, obtain the electrode material for lead-acid ultra-battery; Wherein material modified is micron order Pb powder, or material modified be by mass percentage by 90%～99% micron order Pb powder and 1%～10%BaSO
4composition, or material modified be by mass percentage by 90%～99% micron order Pb powder and 1%～10%CaSO
4composition, or material modified be by mass percentage by 80.2%～99.8% micron order Pb powder, 0.1%～9.9% BaSO
4with 0.1%～9.9% CaSO
4composition;
The chemical synthesizing method of the VRLA battery negative pole in step 4 carries out according to the following steps: a, first at 5A/cm
2galvanostatic conditions under the 1min that charges, then leave standstill 15min; B, with 2.5A/cm
2constant current charge 1h, then with 4A/cm
2constant current charge 10h, then leave standstill 10min; C, with 3.5A/cm
2constant current charge 6h, then with 3A/cm
2constant current charge 5h, finally with 1.5A/cm
2constant current charge 1h, completes changing into of lead-acid ultra-battery negative pole.
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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 |
| CN108550799A (en) * | 2018-06-11 | 2018-09-18 | 四会市恒星智能科技有限公司 | Negative material and preparation method thereof for low-loss lead-acid battery |
| CN110212195A (en) * | 2019-06-21 | 2019-09-06 | 天能电池(芜湖)有限公司 | A kind of carbon material surface modification mode of reduction lead carbon battery capacitor electric discharge and active material discharge potential difference |
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| CN101556997A (en) * | 2009-05-25 | 2009-10-14 | 长兴昌盛电气有限公司 | Super battery plate |
| CN101719420A (en) * | 2009-11-06 | 2010-06-02 | 苏州大学 | Super capacitance storage battery |
| CN101969149A (en) * | 2010-09-25 | 2011-02-09 | 张天任 | Mixed cathode diachylon of superbattery and preparation method thereof |
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