CN106953098B - High-capacity long-life lead-carbon battery cathode and manufacturing method thereof - Google Patents
High-capacity long-life lead-carbon battery cathode and manufacturing method thereof Download PDFInfo
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- 229910052799 carbon Inorganic materials 0.000 title claims abstract description 49
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 15
- 229910021389 graphene Inorganic materials 0.000 claims abstract description 135
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 93
- PAYRUJLWNCNPSJ-UHFFFAOYSA-N Aniline Chemical compound NC1=CC=CC=C1 PAYRUJLWNCNPSJ-UHFFFAOYSA-N 0.000 claims abstract description 70
- 229920000767 polyaniline Polymers 0.000 claims abstract description 66
- 239000000243 solution Substances 0.000 claims abstract description 64
- 238000003756 stirring Methods 0.000 claims abstract description 60
- ROOXNKNUYICQNP-UHFFFAOYSA-N ammonium persulfate Chemical compound [NH4+].[NH4+].[O-]S(=O)(=O)OOS([O-])(=O)=O ROOXNKNUYICQNP-UHFFFAOYSA-N 0.000 claims abstract description 58
- 229910001870 ammonium persulfate Inorganic materials 0.000 claims abstract description 29
- 239000003929 acidic solution Substances 0.000 claims abstract description 26
- 238000000034 method Methods 0.000 claims abstract description 23
- 238000002360 preparation method Methods 0.000 claims abstract description 18
- 239000002131 composite material Substances 0.000 claims abstract description 17
- 238000001035 drying Methods 0.000 claims abstract description 10
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 74
- 239000000203 mixture Substances 0.000 claims description 53
- 239000002070 nanowire Substances 0.000 claims description 49
- 239000011259 mixed solution Substances 0.000 claims description 42
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 35
- TZCXTZWJZNENPQ-UHFFFAOYSA-L barium sulfate Chemical compound [Ba+2].[O-]S([O-])(=O)=O TZCXTZWJZNENPQ-UHFFFAOYSA-L 0.000 claims description 30
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 28
- VLTRZXGMWDSKGL-UHFFFAOYSA-N perchloric acid Chemical compound OCl(=O)(=O)=O VLTRZXGMWDSKGL-UHFFFAOYSA-N 0.000 claims description 28
- 239000000835 fiber Substances 0.000 claims description 22
- WABPQHHGFIMREM-UHFFFAOYSA-N lead(0) Chemical compound [Pb] WABPQHHGFIMREM-UHFFFAOYSA-N 0.000 claims description 22
- 239000011505 plaster Substances 0.000 claims description 20
- 239000002253 acid Substances 0.000 claims description 17
- 239000011248 coating agent Substances 0.000 claims description 15
- 238000000576 coating method Methods 0.000 claims description 15
- QJZYHAIUNVAGQP-UHFFFAOYSA-N 3-nitrobicyclo[2.2.1]hept-5-ene-2,3-dicarboxylic acid Chemical compound C1C2C=CC1C(C(=O)O)C2(C(O)=O)[N+]([O-])=O QJZYHAIUNVAGQP-UHFFFAOYSA-N 0.000 claims description 14
- 238000004108 freeze drying Methods 0.000 claims description 14
- 239000004021 humic acid Substances 0.000 claims description 14
- 229920005610 lignin Polymers 0.000 claims description 14
- 238000005406 washing Methods 0.000 claims description 14
- 239000008367 deionised water Substances 0.000 claims description 12
- 229910021641 deionized water Inorganic materials 0.000 claims description 12
- 239000002994 raw material Substances 0.000 claims description 12
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 10
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 8
- 229910017604 nitric acid Inorganic materials 0.000 claims description 8
- 230000003647 oxidation Effects 0.000 claims description 7
- 238000007254 oxidation reaction Methods 0.000 claims description 7
- 239000002244 precipitate Substances 0.000 claims description 7
- 238000011065 in-situ storage Methods 0.000 claims description 5
- 238000006116 polymerization reaction Methods 0.000 claims description 5
- 239000000126 substance Substances 0.000 claims description 5
- 239000004677 Nylon Substances 0.000 claims description 4
- 229920004933 Terylene® Polymers 0.000 claims description 4
- 229920001778 nylon Polymers 0.000 claims description 4
- 239000005020 polyethylene terephthalate Substances 0.000 claims description 4
- 229920002972 Acrylic fiber Polymers 0.000 claims description 3
- 230000002378 acidificating effect Effects 0.000 claims description 2
- 238000005119 centrifugation Methods 0.000 claims description 2
- 239000003999 initiator Substances 0.000 claims description 2
- 239000000178 monomer Substances 0.000 claims description 2
- 230000010355 oscillation Effects 0.000 claims description 2
- 230000007935 neutral effect Effects 0.000 claims 1
- 230000019635 sulfation Effects 0.000 abstract description 6
- 238000005670 sulfation reaction Methods 0.000 abstract description 6
- 239000000654 additive Substances 0.000 abstract description 5
- 230000000996 additive effect Effects 0.000 abstract description 5
- 239000006185 dispersion Substances 0.000 abstract description 4
- 239000007773 negative electrode material Substances 0.000 abstract description 4
- 238000011031 large-scale manufacturing process Methods 0.000 abstract description 2
- 230000003139 buffering effect Effects 0.000 abstract 1
- 238000009210 therapy by ultrasound Methods 0.000 abstract 1
- 239000007788 liquid Substances 0.000 description 6
- 238000007599 discharging Methods 0.000 description 5
- 239000006228 supernatant Substances 0.000 description 5
- 238000001132 ultrasonic dispersion Methods 0.000 description 5
- 239000003990 capacitor Substances 0.000 description 4
- 239000000463 material Substances 0.000 description 4
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000011049 filling Methods 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- 239000001257 hydrogen Substances 0.000 description 2
- 239000002114 nanocomposite Substances 0.000 description 2
- 229920000742 Cotton Polymers 0.000 description 1
- 239000006230 acetylene black Substances 0.000 description 1
- 239000013543 active substance Substances 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000007580 dry-mixing Methods 0.000 description 1
- 239000003792 electrolyte Substances 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000002708 enhancing effect Effects 0.000 description 1
- 239000003365 glass fiber Substances 0.000 description 1
- 238000011068 loading method Methods 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 229920006389 polyphenyl polymer Polymers 0.000 description 1
- 230000002035 prolonged effect Effects 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 238000005303 weighing Methods 0.000 description 1
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
- H01M4/624—Electric conductive fillers
- H01M4/625—Carbon or graphite
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
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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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Abstract
The invention provides a lead-carbon battery cathode with high capacity and long service life and a manufacturing method thereof, and relates to a preparation method of a polyaniline/graphene composite material, which is applied to the lead-carbon battery cathode. Firstly, carrying out ultrasonic treatment on an acidic solution of graphene to obtain a graphene dispersion solution, then adding aniline into the graphene dispersion solution, uniformly stirring under an ice bath condition, adding an acidic solution of ammonium persulfate, continuously stirring for 12-26 h, centrifuging, and drying to obtain the polyaniline/graphene composite material. The polyaniline/graphene composite material is used as a negative electrode additive of a lead-carbon battery, can improve the conductivity of a negative plate, inhibit the sulfation of a lead negative electrode, and remarkably improve the HRPSoC cycle life and the negative electrode active material utilization rate of the lead-carbon battery. The polyaniline/graphene composite material can play a role in shunting and buffering large current, and the charge acceptance of the lead-carbon battery is remarkably improved. The method has the advantages of simple process, convenient operation, low production cost and easy large-scale production.
Description
Technical Field
The invention relates to the technical field of lead-carbon batteries, in particular to a polyaniline/graphene composite material and application thereof as a negative electrode material of a lead-carbon battery.
Background
Lead-carbon batteries have become one of the most interesting technologies for researchers at home and abroad. The lead-carbon battery is a novel super battery, and integrates a lead-acid battery and a super capacitor: the advantages of instantaneous high-capacity charging of the super capacitor and the specific energy of the lead-acid battery are brought into play, and the super capacitor has good charging and discharging performance. However, the traditional lead-acid battery is often in failure due to serious sulfation of the negative active material, and the cycle life is greatly reduced. The polyaniline/graphene nano composite material is introduced into the negative electrode of the lead-carbon battery, so that the conductivity of the negative plate can be improved, the sulfation of the negative electrode is inhibited, the HRPSoC cycle life of the lead-carbon battery and the utilization rate of the negative active material are improved, and the polyaniline/graphene nano composite material is a capacitor material, so that the current can be shunted, the large current can be buffered, and the charge acceptance of the lead-carbon battery is improved.
The existing preparation method of the modified lead-carbon battery cathode, such as the patent of application number CN201310316549.7 "a graphene dispersion liquid modified lead-acid battery cathode lead paste and its preparation method", discloses a method comprising: weighing lead powder, fiber, acetylene black and barium sulfate, putting the weighed materials into a paste mixer for dry mixing, adding the dispersed graphene dispersion liquid into the paste mixer, adding sulfuric acid, mixing uniformly, measuring the apparent density, adding water according to the measured apparent density, wherein the apparent density is controlled to be 4.0 +/-0.5 g/cm3. Coating the lead plaster on a negative plate grid, curing to obtain a raw negative electrode, assembling a lead-acid battery by using a commercial raw positive electrode and glass fiber cotton as a diaphragm, and filling the lead-acid battery with the filling density of 1.325g/cm3The sulfuric acid aqueous solution is used as electrolyte, the battery is subjected to internal formation, and a charging and discharging test is carried out by using a blue charging and discharging machine with the range of 5V 10A. According to the method, the modified graphene is doped in the negative lead paste, so that the problem that the graphene is difficult to be fully dispersed in active substances is solved to a certain extent, the graphene can fully exert the advantages of the graphene, the conductive capability of the negative plate is improved, the charge acceptance of the negative plate is improved, the specific energy of the lead-acid battery is increased, and the sulfation of the negative plate is reduced. However, the graphene used as a negative electrode additive of a lead-carbon battery in the patent still has some disadvantages, and the main disadvantages are: the hydrogen evolution overpotential of the graphene is low, and the problem of hydrogen evolution of the negative electrode is aggravated by adding the graphene, so that the lead-acid storage battery is seriously dehydrated, the maintenance-free performance is reduced, and the service life is greatly shortened.
Disclosure of Invention
The invention aims to overcome the defects and shortcomings of the prior art and provide a lead-carbon battery cathode with high capacity and long service life and a manufacturing method thereof, wherein the polyaniline/graphene composite material and the preparation method thereof are used for the cathode of the lead-carbon battery. The polyaniline/graphene composite material is prepared by a simple and effective method, the process is simple, and the obtained polyaniline/graphene composite material is structurally characterized in that polyaniline is loaded on the surface of graphene in a nanowire array form, and the charge acceptance, the multiplying power discharge capacity and the discharge capacity of a negative plate can be remarkably improved by adding the polyaniline/graphene composite material; meanwhile, the sulfation of the lead cathode can be inhibited, the water loss is inhibited, and the service life of the lead-carbon battery is prolonged.
The technical route of the invention is as follows: the polyaniline/graphene composite material is prepared by taking graphene and aniline as raw materials through a chemical in-situ polymerization method, and is structurally characterized in that polyaniline is erected on the surface of the graphene in a nanowire array mode, and then the prepared polyaniline/graphene composite material is used as a lead-carbon battery cathode additive to prepare the high-capacity and long-life lead-carbon battery cathode.
The invention provides a method for manufacturing a high-capacity long-life lead-carbon battery cathode, which is characterized by comprising the following steps of:
(1) the lead-carbon battery cathode with high capacity and long service life comprises the following components in percentage by mass: 65-85% of lead powder, 0.1-2% of polyaniline/graphene composite material, 0.5-1% of barium sulfate, 5-9% of sulfuric acid, 0.2-1% of humic acid, 0.05-2% of short fiber, 0-1.2% of lignin and 9-13% of water;
wherein: the oxidation degree of the lead powder is 70-77%;the polyaniline/graphene composite material is graphene And aniline as raw material, and loading the polyaniline nanowire array synthesized by chemical in-situ polymerization method on the surface of graphene, namely polyphenyl Amine nanowiresArray @ graphene; the density of the sulfuric acid is 1.1-1.49g/cm3(ii) a The short fiber is one or more of nylon, acrylic fiber or terylene.
(2) Pouring the lead powder, barium sulfate, humic acid, short fibers and lignin into a beaker according to the mass ratio in the step (1), and stirring for 5-10 min to obtain a mixture A;
(3) dispersing the polyaniline nanowire array @ graphene in deionized water according to the mass ratio in the step (1), and stirring for 3-10 min to obtain a mixture B;
(4) adding the mixture A into the mixture B, and stirring for 5-15 min to obtain a mixture C;
(5) adding sulfuric acid (added within 5 min) according to the mass ratio in the step (1) into the mixture C, stirring for 5-25 min, and controlling the temperature of the mixture not to exceed 60 ℃;
(6)uniformly stirring the mixture treated by the sulfuric acid, and controlling the apparent density of the lead paste to be 3.5-4.5 g/ml and lead Apparent density of paste is controlled by deionized waterObtaining lead paste of the negative electrode of the lead-carbon battery;
(7) uniformly coating the prepared lead plaster on a negative plate grid to prepare a negative plate, wherein the mass of the coating plaster is 10-20 g;
(8) curing the prepared negative plate for 24-60 hours at the humidity of 50-100% and the temperature of 30-70 ℃, and then drying for 15-30 hours at the temperature of 40-70 ℃.
According to the method of claim 1, wherein,the invention relates to a polyaniline nanowire array @ grapheneThe method is characterized in that:
(1) the polyaniline nanowire array @ graphene as claimed in claim 1, which is structurally characterized in that polyaniline is erected on the surface of graphene in a nanowire array form, and the preparation method thereof is characterized in that the polyaniline nanowire array @ graphene is synthesized by a chemical in-situ polymerization method in an acidic medium by taking graphene and aniline as raw materials and ammonium persulfate as an initiator, wherein the raw materials comprise the following components in percentage by mass and volume:
the mass ratio of aniline to graphene is 1: 1-20: 1;
the mass-volume ratio of the graphene to the acidic solution is 0.01-0.12 g: 100 ml;
the mass volume ratio of the ammonium persulfate to the acidic solution is 0.1-4.5 g: 100 ml;
wherein: the graphene is one or two of graphene oxide and reduced graphene oxide;
the purity of the aniline is 88-99%;
the acid solution is one or more of perchloric acid solution, hydrochloric acid solution, sulfuric acid solution and nitric acid solution, wherein the concentration of the acid solution is 0.01-2.0 mol/L;
(2)the preparation method of the polyaniline nanowire array @ graphene as claimed in claim 1, which comprises the following specific steps The method comprises the following steps:adding graphene into the prepared acidic solution according to the mass-volume ratio of the graphene to the acidic solution in the step (1), carrying out ultrasonic oscillation on the mixture, adding absolute ethyl alcohol into the obtained solution, placing the solution in an ice bath, and stirring for 20-40 min to obtain a mixed solution A;
(3) under the ice-bath stirring condition, adding an aniline monomer into the mixed solution A according to the mass ratio of aniline and graphene obtained in the step (1), and mechanically stirring for 20-40 min to obtain a mixed solution B;
(4) preparing an acidic solution of ammonium persulfate according to the mass-to-volume ratio of the ammonium persulfate to the acidic solution in the step (1), adding the acidic solution into the mixed solution B, and continuously stirring and reacting for 12-26 h under an ice bath condition to obtain a mixed solution C;
(5) centrifuging the mixed solution C prepared in the step (4), collecting precipitate, repeatedly washing with the solution,until the upper layer centrifugate reaches neutralityObtaining a residue;
the centrifugal rotating speed is 2000-5000 r/min, each time of centrifugation is 3-15 min, and the used washing solution is one or two of deionized water and absolute ethyl alcohol.
(6) And (5) carrying out freeze drying on the residue prepared in the step (5) to obtain the polyaniline nanowire array @ graphene.
The temperature of the freeze drying is-50 to-80 ℃, the vacuum degree is 1 to 20Pa, and the drying time is 12 to 24 hours.
After the technical scheme is adopted, the invention mainly has the following effects:
the invention uses polyaniline nanowire array @ graphene with a novel structure as a negative electrode additive of the lead-carbon battery, thereby obviously reducing the sulfation of the lead-carbon battery under the high-rate working condition, prolonging the service life of the lead-carbon battery, reducing water loss, enhancing the maintenance-free performance and prolonging the service life of the lead-carbon battery.
The polyaniline nanowire array @ graphene is used as the negative electrode additive of the lead-carbon battery, and the polyaniline nanowire array @ graphene has good conductivity and pseudocapacitance characteristics, is strong in structural stability, has a remarkable shunting effect under the condition of high-current charging and discharging, and remarkably improves the charging acceptance, high-rate working performance and charging and discharging capacity of the lead-carbon battery.
3, the preparation method of the polyaniline nanowire array @ graphene is simple, low in energy consumption, safe and reliable in production process, low in production cost and easy for large-scale production.
Detailed Description
The present invention will be further described with reference to the following specific embodiments.
Example 1
A method for manufacturing a high-capacity long-life lead-carbon battery cathode comprises the following specific steps:
1. the lead-carbon battery cathode with high capacity and long service life comprises the following components in percentage by mass: 81% of lead powder, 0.1% of polyaniline nanowire array @ graphene, 0.7% of barium sulfate, 6% of sulfuric acid, 0.2% of humic acid, 1% of short fibers, 1% of lignin and 10% of water;
wherein: the oxidation degree of the lead powder is 75%; the density of the sulfuric acid is 1.38g/cm3(ii) a The short fiber is nylon.
2. Pouring the lead powder, barium sulfate, humic acid, short fibers and lignin into a beaker according to the mass ratio in the step 1, and stirring for 5min to obtain a mixture A;
3. dispersing the polyaniline nanowire array @ graphene in deionized water according to the mass ratio in the step 1, and stirring for 10min to obtain a mixture B;
4. adding the mixture A into the mixture B, and stirring for 10min to obtain a mixture C;
5. adding sulfuric acid according to the mass ratio in the step 1 into the mixture C, controlling the time for adding the sulfuric acid within 5min, and stirring for 20 min;
6.the mixture treated by the sulfuric acid is stirred evenly and the apparent density of the lead plaster is controlled to be 4.3g/mlObtaining lead paste of the negative electrode of the lead-carbon battery;
7. uniformly coating the prepared lead plaster on a negative plate grid to prepare a negative plate, wherein the mass of the coating plaster is about 18 g;
8. the prepared negative plate is cured for 48 hours under the conditions of humidity of 80% and temperature of 30 ℃, and then dried for 24 hours under the condition of temperature of 50 ℃.
The preparation method of the polyaniline nanowire array @ graphene comprises the following specific steps:
1. the polyaniline nanowire array @ graphene comprises the following raw materials in percentage by mass and volume:
the mass ratio of aniline to graphene is 15: 1;
the mass-to-volume ratio of the graphene to the acidic solution is 0.06 g: 100 ml;
the mass-volume ratio of the ammonium persulfate to the acidic solution is 1.5 g: 100 ml;
wherein: the graphene is reduced graphene oxide; the purity of the aniline is 98%; the acid solution is a perchloric acid solution, and the concentration of the perchloric acid solution is 0.1 mol/L;
2. the preparation method of the polyaniline nanowire array @ graphene comprises the following steps: adding graphene into a prepared perchloric acid solution according to the mass volume ratio of the graphene to the perchloric acid solution in the step 1, performing ultrasonic dispersion for 60min, and stirring in an ice bath for 40min to obtain a mixed solution A;
3. under the ice-bath stirring condition, adding aniline into the mixed solution A according to the mass ratio of aniline to graphene in the step 1, and mechanically stirring for 30min to obtain a mixed solution B;
4. adding ammonium persulfate into the prepared perchloric acid solution according to the mass-volume ratio of the ammonium persulfate to the perchloric acid solution in the step 1, adding the ammonium persulfate into the mixed solution B, and continuously stirring and reacting for 24 hours under the ice bath condition to obtain a mixed solution C;
5. centrifuging the mixed solution C prepared in the step 4, collecting precipitate, repeatedly washing with the solution,up to The supernatant centrifugate reaches neutralityObtaining a residue, wherein the washing liquid is absolute ethyl alcohol, the centrifugal rotating speed is 2000r/min, and the centrifugal time is 10 min;
6. and (3) carrying out freeze drying on the residue prepared in the step (5) to obtain the polyaniline nanowire array @ graphene, wherein the conditions of freeze drying are-70 ℃, 15Pa and 24h of drying time.
Example 2
A method for manufacturing a high-capacity long-life lead-carbon battery cathode comprises the following specific steps:
1. the lead-carbon battery cathode with high capacity and long service life comprises the following components in percentage by mass: 77% of lead powder, 0.4% of polyaniline nanowire array @ graphene, 0.4% of barium sulfate, 8% of sulfuric acid, 0.9% of humic acid, 1.5% of short fibers, 0.8% of lignin and 11% of water;
wherein: the oxidation degree of the lead powder is 72%; the density of the sulfuric acid is 1.18g/cm3(ii) a The short fiber is terylene.
2. Pouring the lead powder, barium sulfate, humic acid, short fibers and lignin into a beaker according to the mass ratio in the step 1, and stirring for 10min to obtain a mixture A;
3. dispersing the polyaniline nanowire array @ graphene in deionized water according to the mass ratio in the step 1, and stirring for 5min to obtain a mixture B;
4. adding the mixture A into the mixture B, and stirring for 8min to obtain a mixture C;
5. adding sulfuric acid according to the mass ratio in the step 1 into the mixture C, controlling the time for adding the sulfuric acid within 5min, and stirring for 10 min;
6.the mixture treated by the sulfuric acid is stirred evenly and the apparent density of the lead plaster is controlled to be 3.5g/mlObtaining lead paste of the negative electrode of the lead-carbon battery;
7. uniformly coating the prepared lead plaster on a negative plate grid to prepare a negative plate, wherein the mass of the coating plaster is about 12 g;
8. the negative plate prepared above was cured at a humidity of 90% and a temperature of 45 ℃ for 36 hours, and then dried at a temperature of 45 ℃ for 16 hours.
The preparation method of the polyaniline nanowire array @ graphene comprises the following specific steps:
1. the polyaniline nanowire array @ graphene comprises the following raw materials in percentage by mass and volume:
the mass ratio of aniline to graphene is 5: 1;
the mass-to-volume ratio of the graphene to the acidic solution is 0.10 g: 100 ml;
the mass volume ratio of the ammonium persulfate to the acidic solution is 0.3 g: 20ml of the solution;
wherein: the graphene is graphene oxide; the aniline purity is 92%; the acid solution is hydrochloric acid solution, and the concentration of the hydrochloric acid solution is 1 mol/L;
2. the preparation method of the polyaniline nanowire array @ graphene comprises the following steps: adding graphene into the prepared hydrochloric acid solution according to the mass volume ratio of the graphene to the hydrochloric acid solution in the step 1, performing ultrasonic dispersion for 60min, and stirring in an ice bath for 40min to obtain a mixed solution A;
3. under the ice-bath stirring condition, adding aniline into the mixed solution A according to the mass ratio of aniline to graphene in the step 1, and mechanically stirring for 30min to obtain a mixed solution B;
4. adding ammonium persulfate into the prepared hydrochloric acid solution according to the mass-volume ratio of the ammonium persulfate to the hydrochloric acid solution in the step 1, adding the ammonium persulfate into the mixed solution B, and continuously stirring and reacting for 24 hours under the ice bath condition to obtain a mixed solution C;
5. centrifuging the mixed solution C prepared in the step 4, collecting precipitate, repeatedly washing with the solution,up to The supernatant centrifugate reaches neutralityObtaining a residue, wherein the washing liquid is absolute ethyl alcohol, the centrifugal rotating speed is 2000r/min, and the centrifugal time is 10 min;
6. and (3) carrying out freeze drying on the residue prepared in the step (5) to obtain the polyaniline nanowire array @ graphene, wherein the conditions of freeze drying are-70 ℃, 15Pa and 24h of drying time.
Example 3
A method for manufacturing a high-capacity long-life lead-carbon battery cathode comprises the following specific steps:
1. the lead-carbon battery cathode with high capacity and long service life comprises the following components in percentage by mass: 82% of lead powder, 1% of polyaniline nanowire array @ graphene, 0.6% of barium sulfate, 5.3% of sulfuric acid, 0.9% of humic acid, 0.8% of short fibers, 0.4% of lignin and 9% of water;
wherein: the oxidation degree of the lead powder is 76%; the density of the sulfuric acid is 1.24g/cm3(ii) a The short fiber is acrylic fiber.
2. Pouring the lead powder, barium sulfate, humic acid, short fibers and lignin into a beaker according to the mass ratio in the step 1, and stirring for 8min to obtain a mixture A;
3. dispersing the polyaniline nanowire array @ graphene in deionized water according to the mass ratio in the step 1, and stirring for 6min to obtain a mixture B;
4. adding the mixture A into the mixture B, and stirring for 12min to obtain a mixture C;
5. adding sulfuric acid according to the mass ratio in the step 1 into the mixture C, controlling the time for adding the sulfuric acid within 5min, and stirring for 15 min;
6.the mixture treated by the sulfuric acid is stirred evenly and the apparent density of the lead plaster is controlled to be 4.0g/mlObtaining lead paste of the negative electrode of the lead-carbon battery;
7. uniformly coating the prepared lead plaster on a negative plate grid to prepare a negative plate, wherein the mass of the coating plaster is about 15 g;
8. the negative plate prepared above was cured at a humidity of 95% and a temperature of 60 ℃ for 55 hours, and then dried at a temperature of 60 ℃ for 26 hours.
The preparation method of the polyaniline nanowire array @ graphene comprises the following specific steps:
1. the polyaniline nanowire array @ graphene comprises the following raw materials in percentage by mass and volume:
the mass ratio of the aniline to the graphene is 10: 1;
the mass-to-volume ratio of the graphene to the acidic solution is 0.04 g: 100 ml;
the mass-volume ratio of the ammonium persulfate to the acidic solution is 4.0 g: 100 ml;
wherein: the graphene is reduced graphene oxide; the aniline purity is 95%; the acid solution is a perchloric acid solution, and the concentration of the perchloric acid solution is 1.5 mol/L.
2. The preparation method of the polyaniline nanowire array @ graphene comprises the following steps: adding graphene into a prepared perchloric acid solution according to the mass volume ratio of the graphene to the perchloric acid solution in the step 1, performing ultrasonic dispersion for 45min, adding 10ml of absolute ethyl alcohol into the system, placing the absolute ethyl alcohol in an ice bath, and stirring for 35min to obtain a mixed solution A;
3. under the ice-bath stirring condition, adding aniline into the mixed solution A according to the mass ratio of aniline to graphene in the step 1, and mechanically stirring for 30min to obtain a mixed solution B;
4. adding ammonium persulfate into the prepared perchloric acid solution according to the mass-volume ratio of the ammonium persulfate to the perchloric acid solution in the step 1, adding the ammonium persulfate into the mixed solution B, and continuously stirring and reacting for 12 hours under the ice bath condition to obtain a mixed solution C;
5. centrifuging the mixed solution C prepared in the step 4, collecting precipitate, repeatedly washing with the solution,up to The supernatant centrifugate reaches neutralityObtaining a residue, wherein the washing solution is deionized water, the centrifugal rotation speed is 5000r/min, and the centrifugal time is 3 min;
6. and (3) carrying out freeze drying on the residue prepared in the step (5) to obtain the polyaniline nanowire array @ graphene, wherein the freeze drying condition is-75 ℃, 20Pa, and the drying time is 18 h.
Example 4
A method for manufacturing a high-capacity long-life lead-carbon battery cathode comprises the following specific steps:
1. the lead-carbon battery cathode with high capacity and long service life comprises the following components in percentage by mass: 80% of lead powder, 1.5% of polyaniline nanowire array @ graphene, 0.5% of barium sulfate, 5% of sulfuric acid, 0.5% of humic acid, 1.8% of short fibers, 0.7% of lignin and 10% of water;
wherein: the oxidation degree of the lead powder is 72%; the density of the sulfuric acid is 1.32g/cm3(ii) a The short fiber is terylene.
2. Pouring the lead powder, barium sulfate, humic acid, short fibers and lignin into a beaker according to the mass ratio in the step 1, and stirring for 6min to obtain a mixture A;
3. dispersing the polyaniline nanowire array @ graphene in deionized water according to the mass ratio in the step 1, and stirring for 12min to obtain a mixture B;
4. adding the mixture A into the mixture B, and stirring for 10min to obtain a mixture C;
5. adding sulfuric acid according to the mass ratio in the step 1 into the mixture C, controlling the time for adding the sulfuric acid within 5min, and stirring for 20 min;
6.the mixture treated by the sulfuric acid is stirred evenly and the apparent density of the lead plaster is controlled to be 3.7g/mlObtaining lead paste of the negative electrode of the lead-carbon battery;
7. uniformly coating the prepared lead plaster on a negative plate grid to prepare a negative plate, wherein the mass of the coating plaster is about 16 g;
8. the negative plate prepared in the above way is cured for 40h under the conditions of humidity of 90% and temperature of 50 ℃, and then dried for 24h under the condition of temperature of 45 ℃.
The preparation method of the polyaniline nanowire array @ graphene comprises the following specific steps:
1. the polyaniline nanowire array @ graphene comprises the following raw materials in percentage by mass and volume:
the mass ratio of aniline to graphene is 12.5: 1;
the mass-to-volume ratio of the graphene to the acidic solution is 0.05: 100 ml;
the mass-volume ratio of the ammonium persulfate to the acidic solution is 2.0 g: 100 ml;
wherein: the graphene is graphene oxide; the aniline purity is 96%; the acid solution is a nitric acid solution, and the concentration of the nitric acid solution is 0.5 mol/L;
2. the preparation method of the polyaniline nanowire array @ graphene comprises the following steps: adding graphene into the prepared nitric acid solution according to the mass volume ratio of the graphene to the nitric acid solution in the step 1, performing ultrasonic dispersion for 30min, and stirring in an ice bath for 30min to obtain a mixed solution A;
3. under the ice-bath stirring condition, adding aniline into the mixed solution A according to the mass ratio of aniline to graphene in the step 1, and mechanically stirring for 25min to obtain a mixed solution B;
4. adding ammonium persulfate into the prepared nitric acid solution according to the mass-volume ratio of the ammonium persulfate to the nitric acid solution in the step 1, adding the ammonium persulfate into the mixed solution B, and continuously stirring and reacting for 25 hours under the ice bath condition to obtain a mixed solution C;
5. centrifuging the mixed solution C prepared in the step 4, collecting precipitate, repeatedly washing with the solution,up to The supernatant centrifugate reaches neutralityObtaining a residue, wherein the washing liquid is absolute ethyl alcohol, the centrifugal rotating speed is 4000r/min, and the centrifugal time is 3 min;
6. and (3) carrying out freeze drying on the residue prepared in the step (5) to obtain the polyaniline nanowire array @ graphene, wherein the conditions of freeze drying are-77 ℃ and 10Pa, and the drying time is 18 h.
Example 5
A method for manufacturing a high-capacity long-life lead-carbon battery cathode comprises the following specific steps:
1. the lead-carbon battery cathode with high capacity and long service life comprises the following components in percentage by mass: 76% of lead powder, 0.8% of polyaniline nanowire array @ graphene, 0.7% of barium sulfate, 8% of sulfuric acid, 0.5% of humic acid, 1.5% of short fibers, 0.5% of lignin and 12% of water;
wherein: the oxidation degree of the lead powder is 74%; the density of the sulfuric acid is 1.3g/cm3(ii) a The short fiber is nylon;
2. pouring the lead powder, barium sulfate, humic acid, short fibers and lignin into a beaker according to the mass ratio in the step 1, and stirring for 8min to obtain a mixture A;
3. dispersing the polyaniline nanowire array @ graphene in deionized water according to the mass ratio in the step 1, and stirring for 10min to obtain a mixture B;
4. adding the mixture A into the mixture B, and stirring for 10min to obtain a mixture C;
5. adding sulfuric acid according to the mass ratio in the step 1 into the mixture C, controlling the time for adding the sulfuric acid within 5min, and stirring for 20 min;
6.the mixture treated by the sulfuric acid is stirred evenly and the apparent density of the lead plaster is controlled to be 3.7g/mlObtaining lead paste of the negative electrode of the lead-carbon battery;
7. uniformly coating the prepared lead plaster on a negative plate grid to prepare a negative plate, wherein the mass of the coating plaster is about 13 g;
8. the negative plate prepared above was cured at 55 ℃ for 30h at 96% humidity and then dried at 60 ℃ for 20 h.
The preparation method of the polyaniline nanowire array @ graphene comprises the following specific steps:
1. the polyaniline nanowire array @ graphene comprises the following raw materials in percentage by mass and volume:
the mass ratio of aniline to graphene is 7.5: 1;
the mass-to-volume ratio of the graphene to the acidic solution is 0.03 g: 100 ml;
the mass volume ratio of the ammonium persulfate to the acidic solution is 0.2 g: 100 ml;
wherein: the graphene is reduced graphene oxide; the aniline purity is 93%; the acid solution is a hydrochloric acid solution, and the concentration of the hydrochloric acid solution is 0.05 mol/L;
2. the preparation method of the polyaniline nanowire array @ graphene comprises the following steps: adding graphene into the prepared hydrochloric acid solution according to the mass volume ratio of the graphene to the hydrochloric acid solution in the step 1, performing ultrasonic dispersion for 20min, and stirring in an ice bath for 30min to obtain a mixed solution A;
3. under the ice-bath stirring condition, adding aniline into the mixed solution A according to the mass ratio of aniline to graphene in the step 1, and mechanically stirring for 30min to obtain a mixed solution B;
4. adding ammonium persulfate into the prepared hydrochloric acid solution according to the mass-volume ratio of the ammonium persulfate to the hydrochloric acid solution in the step 1, adding the ammonium persulfate into the mixed solution B, and continuously stirring and reacting for 24 hours under the ice bath condition to obtain a mixed solution C;
5. centrifuging the mixed solution C prepared in the step 4, collecting precipitate, repeatedly washing with the solution,up to The supernatant centrifugate reaches neutralityObtaining a residue, wherein the washing liquid is absolute ethyl alcohol, the centrifugal rotating speed is 4500r/min, and the centrifugal time is 4 min;
6. and (3) carrying out freeze drying on the residue prepared in the step (5) to obtain the polyaniline nanowire array @ graphene, wherein the conditions of freeze drying are-78 ℃ and 5Pa, and the drying time is 20 h.
Claims (2)
1. A method for manufacturing a high-capacity long-life lead-carbon battery cathode is characterized by comprising the following steps:
(1) the lead-carbon battery cathode with high capacity and long service life comprises the following components in percentage by mass: 65-85% of lead powder, 0.1-2% of polyaniline/graphene composite material, 0.5-1% of barium sulfate, 5-9% of sulfuric acid, 0.2-1% of humic acid, 0.05-2% of short fiber, 0-1.2% of lignin and 9-13% of water;
wherein: the oxidation degree of the lead powder is 70-77%; the polyaniline/graphene composite material is characterized in that a polyaniline nanowire array synthesized by taking graphene and aniline as raw materials through a chemical in-situ polymerization method is loaded on the surface of the graphene, namely the polyaniline nanowire array @ graphene; the density of the sulfuric acid is 1.1-1.49g/cm3(ii) a The short fiber is one or more of nylon, acrylic fiber or terylene;
(2) pouring the lead powder, barium sulfate, humic acid, short fibers and lignin into a beaker according to the mass ratio in the step (1), and stirring for 5-10 min to obtain a mixture A;
(3) dispersing the polyaniline nanowire array @ graphene in deionized water according to the mass ratio in the step (1), and stirring for 3-10 min to obtain a mixture B;
(4) adding the mixture A into the mixture B, and stirring for 5-15 min to obtain a mixture C;
(5) adding sulfuric acid according to the mass ratio in the step (1) into the mixture C, stirring for 5-25 min within 5min, and controlling the temperature of the mixture not to exceed 60 ℃;
(6) uniformly stirring the mixture treated by the sulfuric acid, and controlling the apparent density of the lead paste to be 3.5-4.5 g/ml, wherein the apparent density of the lead paste is controlled by deionized water to obtain the lead paste of the negative electrode of the lead-carbon battery;
(7) uniformly coating the prepared lead plaster on a negative plate grid to prepare a negative plate, wherein the mass of the coating plaster is 10-20 g;
(8) curing the prepared negative plate for 24-60 hours at the humidity of 50-100% and the temperature of 30-70 ℃, and then drying for 15-30 hours at the temperature of 40-70 ℃.
2. The method for manufacturing the negative electrode of the lead-carbon battery with high capacity and long service life according to claim 1, wherein the method for preparing the polyaniline/graphene composite material specifically comprises the following steps:
the graphene/aniline composite material is synthesized by taking graphene and aniline as raw materials and ammonium persulfate as an initiator in an acidic medium through a chemical in-situ polymerization method, and comprises the following raw materials in percentage by mass:
the mass ratio of aniline to graphene is 1: 1-20: 1;
the mass-volume ratio of the graphene to the acidic solution is 0.01-0.12 g: 100 ml;
the mass volume ratio of the ammonium persulfate to the acidic solution is 0.1-4.5 g: 100 ml;
wherein: the graphene is one or two of graphene oxide and reduced graphene oxide;
the purity of the aniline is 88-99%;
the acid solution is one or more of perchloric acid solution, hydrochloric acid solution, sulfuric acid solution and nitric acid solution, wherein the concentration of the acid solution is 0.01-2.0 mol/L;
the preparation method comprises the following specific steps:
(2.1) adding graphene into the prepared acidic solution according to the mass-volume ratio of the graphene to the acidic solution, carrying out ultrasonic oscillation on the mixture, adding absolute ethyl alcohol into the obtained solution, placing the obtained solution in an ice bath, and stirring for 20-40 min to obtain a mixed solution A;
(2.2) under the ice-bath stirring condition, adding an aniline monomer into the mixed solution A according to the mass ratio of aniline to graphene in the step (2.1), and mechanically stirring for 20-40 min to obtain a mixed solution B;
(2.3) preparing an acidic solution of ammonium persulfate according to the mass-volume ratio of the ammonium persulfate to the acidic solution, adding the acidic solution into the mixed solution B, and continuously stirring and reacting for 12-26 h under the ice bath condition to obtain a mixed solution C;
(2.4) centrifuging the mixed solution C prepared in the step (2.3), collecting precipitate, and repeatedly washing with the solution until the upper layer centrifugate is neutral to obtain residue;
the centrifugal rotating speed is 2000-5000 r/min, each time of centrifugation is 3-15 min, and the used washing solution is one or two of deionized water and absolute ethyl alcohol;
(2.5) carrying out freeze drying on the residue prepared in the step (2.4) to obtain a polyaniline nanowire array @ graphene;
the temperature of the freeze drying is-50 to-80 ℃, the vacuum degree is 1 to 20Pa, and the drying time is 12 to 24 hours.
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