CN117712296A - High-capacity long-service-life lead-carbon battery negative electrode and manufacturing method thereof - Google Patents
High-capacity long-service-life lead-carbon battery negative electrode and manufacturing method thereof Download PDFInfo
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- 229910052799 carbon Inorganic materials 0.000 title claims abstract description 70
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 17
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims abstract description 80
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 68
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims abstract description 47
- 239000001257 hydrogen Substances 0.000 claims abstract description 47
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 47
- TZCXTZWJZNENPQ-UHFFFAOYSA-L barium sulfate Chemical compound [Ba+2].[O-]S([O-])(=O)=O TZCXTZWJZNENPQ-UHFFFAOYSA-L 0.000 claims abstract description 40
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- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 25
- 229920002678 cellulose Polymers 0.000 claims abstract description 20
- 239000001913 cellulose Substances 0.000 claims abstract description 20
- 239000008367 deionised water Substances 0.000 claims abstract description 20
- 229910021641 deionized water Inorganic materials 0.000 claims abstract description 20
- WABPQHHGFIMREM-UHFFFAOYSA-N lead(0) Chemical compound [Pb] WABPQHHGFIMREM-UHFFFAOYSA-N 0.000 claims abstract description 20
- YDEXUEFDPVHGHE-GGMCWBHBSA-L disodium;(2r)-3-(2-hydroxy-3-methoxyphenyl)-2-[2-methoxy-4-(3-sulfonatopropyl)phenoxy]propane-1-sulfonate Chemical compound [Na+].[Na+].COC1=CC=CC(C[C@H](CS([O-])(=O)=O)OC=2C(=CC(CCCS([O-])(=O)=O)=CC=2)OC)=C1O YDEXUEFDPVHGHE-GGMCWBHBSA-L 0.000 claims abstract description 19
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 30
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims description 28
- 229910052757 nitrogen Inorganic materials 0.000 claims description 15
- 229910021529 ammonia Inorganic materials 0.000 claims description 14
- 238000010277 constant-current charging Methods 0.000 claims description 14
- 239000010453 quartz Substances 0.000 claims description 14
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 14
- 229910000416 bismuth oxide Inorganic materials 0.000 claims description 13
- TYIXMATWDRGMPF-UHFFFAOYSA-N dibismuth;oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[Bi+3].[Bi+3] TYIXMATWDRGMPF-UHFFFAOYSA-N 0.000 claims description 13
- AJNVQOSZGJRYEI-UHFFFAOYSA-N digallium;oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[Ga+3].[Ga+3] AJNVQOSZGJRYEI-UHFFFAOYSA-N 0.000 claims description 13
- 229910001195 gallium oxide Inorganic materials 0.000 claims description 13
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- 238000012360 testing method Methods 0.000 claims description 12
- 238000000034 method Methods 0.000 claims description 9
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- 239000004570 mortar (masonry) Substances 0.000 claims description 7
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- 238000003756 stirring Methods 0.000 claims description 7
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- 238000005670 sulfation reaction Methods 0.000 description 3
- YADSGOSSYOOKMP-UHFFFAOYSA-N dioxolead Chemical group O=[Pb]=O YADSGOSSYOOKMP-UHFFFAOYSA-N 0.000 description 2
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- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
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Classifications
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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 discloses a high-capacity long-life lead-carbon battery negative electrode and a manufacturing method thereof, which relate to the technical field of lead-carbon battery negative electrodes and comprise the following components in parts by weight: 100-110 parts of lead powder, 5-10 parts of active carbon powder, 5-10 parts of nitrogen-doped active carbon powder, 0.12-0.18 part of sodium lignin sulfonate, 0.10-0.12 part of short cellulose, 0.20-0.24 part of barium sulfate, 0.05-0.06 part of hydrogen inhibitor, 0.10-0.12 part of sulfuric acid and 12-16 parts of deionized water. The invention improves the inhibiting effect of the invention on the hydrogen evolution dehydration reaction by changing the surface characteristics of the active carbon material and adding the hydrogen inhibitor, thereby being capable of helping to prolong the service life and the capacity of the negative electrode of the lead-carbon battery prepared by the invention.
Description
Technical Field
The invention relates to the technical field of lead-carbon battery cathodes, in particular to a high-capacity long-service-life lead-carbon battery cathode and a manufacturing method thereof.
Background
Lead-carbon batteries are a new generation of lead-acid batteries. The method solves the common problem of the common valve-controlled lead-acid battery in the energy storage application of new energy automobiles and solar and wind power generation, namely the problem that the battery is invalid due to serious sulfation of the negative electrode when the battery is recycled under the high-rate partial charge condition. Negative characteristics of lead-carbon battery: firstly, the charging is fast, and the charging speed is improved by 8 times; secondly, the discharge power is improved by 3 times; thirdly, the cycle life is prolonged to 6 times, and the cycle charging times are up to 2000 times; fourthly, the cost performance is high, the selling price is improved compared with that of a lead-acid battery, but the service life of the cycle use is greatly prolonged; fifthly, the energy-saving device is safe and stable to use and can be widely applied to various new energy and energy-saving fields. In addition, the lead-carbon battery also exerts the specific energy advantage of the lead-acid battery, and has very good charge-discharge performance, and can be fully charged within 90 minutes (if the lead-acid battery is charged and discharged in this way, the service life of the lead-acid battery is less than 30 times). And due to the addition of carbon (graphene), the sulfation phenomenon of the negative electrode is prevented, and one factor of the failure of the battery is improved.
The lead-carbon battery is a capacitor type lead-acid battery, wherein the positive electrode is lead dioxide, the negative electrode is a lead-carbon composite electrode, and the electrolyte is sulfuric acid solution. Lead-carbon batteries can effectively inhibit sulfation problems of negative electrode active substances by introducing carbon materials with capacitance characteristics, such as graphite, carbon black, activated carbon, carbon nanotubes, graphene and the like, into the negative electrode of the traditional lead-acid battery in an 'internal and' or 'internal mixing' mode, so that the cycle life of the battery is obviously prolonged, and the charge and discharge power of the battery is improved.
At present, high-activity carbon materials are introduced into the negative electrode of the lead-carbon battery, so that besides normal electrode reaction, the surface of the carbon materials also simultaneously performs hydrogen evolution and dehydration side reaction, and the cycle life of the lead-carbon battery is reduced. In order to inhibit the hydrogen evolution dehydration reaction of the negative electrode of the lead-carbon battery, the patent of the prior art publication No. CN110911678B adopts a mode of adding two different hydrogen inhibitors into the lead-carbon battery to inhibit the hydrogen evolution dehydration reaction of the negative electrode of the lead-carbon battery. However, the hydrogen inhibitor added in the technical scheme can only prevent the hydrogen evolution dehydration reaction from being carried out singly from the perspective of improving the hydrogen evolution overpotential of the negative electrode carbon material of the lead-carbon battery, has limited hydrogen inhibition effect and can influence the service life of the lead-carbon battery.
Disclosure of Invention
Aiming at the defects of the prior art, the invention provides the high-capacity long-life lead-carbon battery cathode and the manufacturing method thereof, and the inhibition effect of the invention on the hydrogen evolution dehydration reaction is improved by changing the surface characteristics of the active carbon material and adding the hydrogen inhibitor in a double mode, so that the service life and the capacity of the prepared lead-carbon battery cathode can be prolonged.
In order to achieve the above purpose, the technical scheme adopted by the invention is as follows: the high-capacity long-life lead-carbon battery cathode comprises the following components in parts by weight: 100-110 parts of lead powder, 5-10 parts of active carbon powder, 5-10 parts of nitrogen-doped active carbon powder, 0.12-0.18 part of sodium lignin sulfonate, 0.10-0.12 part of short cellulose, 0.20-0.24 part of barium sulfate, 0.05-0.06 part of hydrogen inhibitor, 0.10-0.12 part of sulfuric acid and 12-16 parts of deionized water.
Preferably, the hydrogen inhibitor comprises gallium oxide and bismuth oxide, and the proportion of the gallium oxide to the bismuth oxide is 1:1.
preferably, the concentration of the sulfuric acid is 1.4g/cm 3 。
The invention also discloses a manufacturing method of the high-capacity long-life lead-carbon battery cathode, which comprises the following steps:
step one, preparing nitrogen-doped activated carbon powder: placing activated carbon powder into a quartz boat, placing the quartz boat into a vacuum tube furnace, introducing mixed gas of nitrogen and ammonia, heating to 900 ℃, preserving heat for 2 hours, and taking out after natural cooling;
grinding lead powder, activated carbon powder, nitrogen-doped activated carbon powder, sodium lignin sulfonate, barium sulfate and inhibitor in a mortar, sieving, uniformly screening, placing in a container, adding deionized water into the container, uniformly stirring, adding short cellulose and sulfuric acid, grinding into paste, coating, and placing the coated polar plate in a concentration of 1.15g/cm 3 Is taken out after being rapidly pickled in sulfuric acid solution;
step three, placing the negative plate subjected to pickling in the step two into a programmable constant temperature and humidity test box for curing treatment;
step four, solidifying the step threeThe concentration of the negative plate is 1.035g/cm 3 Is formed into 52h.
Preferably, in step one, the ratio of nitrogen to ammonia is 1:1.
preferably, the heating rate of the vacuum tube furnace in the first step is 10 ℃/min.
Preferably, in step three, the curing conditions are: curing at 60 deg.C and 100% humidity for 48 hr, and then placing in a forced air drying oven for 24 hr at 60 deg.C.
Preferably, the formation process in step four is as follows: firstly, standing for 2h, then carrying out constant current charging for 1h at 0.05C multiplying power, and then carrying out constant current charging for 20h at 0.1C multiplying power; after standing for 2h, carrying out constant current discharge for 1h at a rate of 0.1C, then carrying out constant current charge for 10h at a rate of 0.1C, carrying out constant current charge for 12h at a rate of 0.2C, and finally carrying out constant current charge for 4h at a rate of 0.1C.
Compared with the prior art, the invention provides the high-capacity long-life lead-carbon battery cathode and the manufacturing method thereof, and the high-capacity long-life lead-carbon battery cathode has the following beneficial effects:
the active carbon and the nitrogen-doped active carbon are added into the negative electrode material of the lead-carbon battery, the surface characteristics of the carbon material are changed by utilizing nitrogen elements, and the electron cloud structure around the carbon is regulated, so that the process of hydrogen evolution dehydration reaction can be hindered, the effect of inhibiting the hydrogen evolution reaction on the surface of the carbon material is achieved, meanwhile, the hydrogen evolution overpotential of the negative electrode of the lead-carbon battery is improved by adding the hydrogen inhibitor, and the effect of further inhibiting the hydrogen evolution dehydration reaction is achieved.
Detailed Description
In order to enable those skilled in the art to better understand the technical solutions of the present invention, the present invention will be described in further detail with reference to specific embodiments.
Example 1
The invention provides a high-capacity long-life lead-carbon battery cathode which is prepared from the following raw materials in parts by weight: 100-110 parts of lead powder, 5-10 parts of active carbon powder, 5-10 parts of nitrogen-doped active carbon powder, 0.12-0.18 part of sodium lignin sulfonate, 0.10-0.12 part of short cellulose, 0.20-0.24 part of barium sulfate, 0.05-0.06 part of hydrogen inhibitor, 0.10-0.12 part of sulfuric acid and 12-16 parts of deionized water;
in the embodiment, 100 parts of lead powder, 5 parts of activated carbon powder, 5 parts of nitrogen-doped activated carbon powder, 0.12 part of sodium lignin sulfonate, 0.10 part of short cellulose, 0.20 part of barium sulfate, 0.05 part of hydrogen inhibitor, 0.10 part of sulfuric acid and 12 parts of deionized water are used;
it should be further noted that the hydrogen inhibitor used in the present invention includes gallium oxide and bismuth oxide, and the ratio of gallium oxide to bismuth oxide is 1:1: sulfuric acid was used at a concentration of 1.4g/cm 3 。
The invention also discloses a manufacturing method of the high-capacity long-life lead-carbon battery cathode, which comprises the following steps:
step one, preparing nitrogen-doped activated carbon powder: placing activated carbon powder into a quartz boat, then placing the quartz boat into a vacuum tube furnace, and introducing mixed gas of nitrogen and ammonia, wherein the ratio of the nitrogen to the ammonia is 1:1, heating to 900 ℃, keeping the temperature for 2 hours at the heating speed of 10 ℃/min in a vacuum tube furnace, and taking out after natural cooling;
grinding lead powder, activated carbon powder, nitrogen-doped activated carbon powder, sodium lignin sulfonate, barium sulfate and inhibitor in a mortar, sieving, uniformly screening, placing in a container, adding deionized water into the container, uniformly stirring, adding short cellulose and sulfuric acid, grinding into paste, coating, and placing the coated polar plate in a concentration of 1.15g/cm 3 Is taken out after being rapidly pickled in sulfuric acid solution;
step three, placing the negative plate subjected to pickling in the step two into a programmable constant temperature and humidity test box for curing treatment: curing for 48 hours at 60 ℃ under the condition of 100% humidity, and then placing the cured materials into a blast drying oven for 24 hours, wherein the temperature is set to be 60 ℃;
fourthly, the negative plate solidified in the third step is processed at the concentration of 1.035g/cm 3 Is formed into 52h in sulfuric acid solution;
the specific operation of the formation is as follows: firstly, standing for 2h, then carrying out constant current charging for 1h at 0.05C multiplying power, and then carrying out constant current charging for 20h at 0.1C multiplying power; after standing for 2h, carrying out constant current discharge for 1h at a rate of 0.1C, then carrying out constant current charge for 10h at a rate of 0.1C, carrying out constant current charge for 12h at a rate of 0.2C, and finally carrying out constant current charge for 4h at a rate of 0.1C.
The negative electrode plate prepared in this example was welded in a lead-carbon battery, and then the battery performance test was performed on the lead-carbon battery, and the test results are shown in table 1 below:
TABLE 1
When the lead-carbon battery in the market is charged with 2C current, only 50% of the electric quantity can be charged; when charged at 3C current, 40% charge was charged in 14 minutes; the lead-carbon battery of the negative plate prepared by the invention can charge more than 50% of electric quantity when being charged by 2C current, and can charge 60% of electric quantity within 14 minutes when being charged by 3C current, mainly because the invention reduces the occurrence of hydrogen evolution and water loss reaction of the negative electrode and improves the charge acceptance of the negative electrode by changing the surface characteristics of the active carbon material and adding the hydrogen inhibitor.
Example 2
The invention provides a high-capacity long-life lead-carbon battery cathode which is prepared from the following raw materials in parts by weight: 100-110 parts of lead powder, 5-10 parts of active carbon powder, 5-10 parts of nitrogen-doped active carbon powder, 0.12-0.18 part of sodium lignin sulfonate, 0.10-0.12 part of short cellulose, 0.20-0.24 part of barium sulfate, 0.05-0.06 part of hydrogen inhibitor, 0.10-0.12 part of sulfuric acid and 12-16 parts of deionized water;
in the embodiment, 102 parts of lead powder, 6 parts of activated carbon powder, 6 parts of nitrogen-doped activated carbon powder, 0.14 part of sodium lignin sulfonate, 0.10 part of short cellulose, 0.20 part of barium sulfate, 0.05 part of hydrogen inhibitor, 0.10 part of sulfuric acid and 13 parts of deionized water are used.
It should be further noted that the hydrogen inhibitor used in the present invention comprises gallium oxide and bismuth oxide in the ratio of1:1: sulfuric acid was used at a concentration of 1.4g/cm 3 。
The invention also discloses a manufacturing method of the high-capacity long-life lead-carbon battery cathode, which comprises the following steps:
step one, preparing nitrogen-doped activated carbon powder: placing activated carbon powder into a quartz boat, then placing the quartz boat into a vacuum tube furnace, and introducing mixed gas of nitrogen and ammonia, wherein the ratio of the nitrogen to the ammonia is 1:1, heating to 900 ℃, keeping the temperature for 2 hours at the heating speed of 10 ℃/min in a vacuum tube furnace, and taking out after natural cooling;
grinding lead powder, activated carbon powder, nitrogen-doped activated carbon powder, sodium lignin sulfonate, barium sulfate and inhibitor in a mortar, sieving, uniformly screening, placing in a container, adding deionized water into the container, uniformly stirring, adding short cellulose and sulfuric acid, grinding into paste, coating, and placing the coated polar plate in a concentration of 1.15g/cm 3 Is taken out after being rapidly pickled in sulfuric acid solution;
step three, placing the negative plate subjected to pickling in the step two into a programmable constant temperature and humidity test box for curing treatment: curing for 48 hours at 60 ℃ under the condition of 100% humidity, and then placing the cured materials into a blast drying oven for 24 hours, wherein the temperature is set to be 60 ℃;
fourthly, the negative plate solidified in the third step is processed at the concentration of 1.035g/cm 3 Is formed into 52h in sulfuric acid solution;
the specific operation of the formation is as follows: firstly, standing for 2h, then carrying out constant current charging for 1h at 0.05C multiplying power, and then carrying out constant current charging for 20h at 0.1C multiplying power; after standing for 2h, carrying out constant current discharge for 1h at a rate of 0.1C, then carrying out constant current charge for 10h at a rate of 0.1C, carrying out constant current charge for 12h at a rate of 0.2C, and finally carrying out constant current charge for 4h at a rate of 0.1C.
The negative electrode plate prepared in this example was welded in a lead-carbon battery, and then the battery performance test was performed on the lead-carbon battery, and the test results are shown in table 2 below:
TABLE 2
When the lead-carbon battery in the market is charged with 2C current, only 50% of the electric quantity can be charged; when charged at 3C current, 40% charge was charged in 14 minutes; the lead-carbon battery of the negative plate prepared by the invention can charge 87% of electric quantity when being charged by 2C current, and can charge 65% of electric quantity within 14 minutes when being charged by 3C current, mainly because the invention reduces the occurrence of hydrogen evolution and water loss reaction of the negative electrode and improves the charge acceptance of the negative electrode by changing the surface characteristics of the active carbon material and adding the hydrogen inhibitor.
Example 3
The invention provides a high-capacity long-life lead-carbon battery cathode which is prepared from the following raw materials in parts by weight: 100-110 parts of lead powder, 5-10 parts of active carbon powder, 5-10 parts of nitrogen-doped active carbon powder, 0.12-0.18 part of sodium lignin sulfonate, 0.10-0.12 part of short cellulose, 0.20-0.24 part of barium sulfate, 0.05-0.06 part of hydrogen inhibitor, 0.10-0.12 part of sulfuric acid and 12-16 parts of deionized water;
in the embodiment, 104 parts of lead powder, 8 parts of activated carbon powder, 8 parts of nitrogen-doped activated carbon powder, 0.14 part of sodium lignin sulfonate, 0.11 part of short cellulose, 0.22 part of barium sulfate, 0.06 part of hydrogen inhibitor, 0.11 part of sulfuric acid and 14 parts of deionized water are used.
It should be further noted that the hydrogen inhibitor used in the present invention includes gallium oxide and bismuth oxide, and the ratio of gallium oxide to bismuth oxide is 1:1 and sulfuric acid is used at a concentration of 1.4g/cm 3 。
The invention also discloses a manufacturing method of the high-capacity long-life lead-carbon battery cathode, which comprises the following steps:
step one, preparing nitrogen-doped activated carbon powder: placing activated carbon powder into a quartz boat, then placing the quartz boat into a vacuum tube furnace, and introducing mixed gas of nitrogen and ammonia, wherein the ratio of the nitrogen to the ammonia is 1:1, heating to 900 ℃, keeping the temperature for 2 hours at the heating speed of 10 ℃/min in a vacuum tube furnace, and taking out after natural cooling;
step two, lead powder, activated carbon powder, nitrogen-doped activated carbon powder and wood are mixedGrinding sodium sulfonate, barium sulfate and inhibitor in mortar, sieving, placing into container, adding deionized water into the container, stirring, adding short cellulose and sulfuric acid, grinding to paste, coating, and making the coated polar plate with concentration of 1.15g/cm 3 Is taken out after being rapidly pickled in sulfuric acid solution;
step three, placing the negative plate subjected to pickling in the step two into a programmable constant temperature and humidity test box for curing treatment: curing for 48 hours at 60 ℃ under the condition of 100% humidity, and then placing the cured materials into a blast drying oven for 24 hours, wherein the temperature is set to be 60 ℃;
fourthly, the negative plate solidified in the third step is processed at the concentration of 1.035g/cm 3 Is formed into 52h in sulfuric acid solution;
the specific operation of the formation is as follows: firstly, standing for 2h, then carrying out constant current charging for 1h at 0.05C multiplying power, and then carrying out constant current charging for 20h at 0.1C multiplying power; after standing for 2h, carrying out constant current discharge for 1h at a rate of 0.1C, then carrying out constant current charge for 10h at a rate of 0.1C, carrying out constant current charge for 12h at a rate of 0.2C, and finally carrying out constant current charge for 4h at a rate of 0.1C.
The negative electrode plate prepared in this example was welded in a lead-carbon battery, and then the battery performance test was performed on the lead-carbon battery, and the test results are shown in table 3 below:
TABLE 3 Table 3
When the lead-carbon battery in the market is charged with 2C current, only 50% of the electric quantity can be charged; when charged at 3C current, 40% charge was charged in 14 minutes; the lead-carbon battery of the negative plate prepared by the invention can charge 87% of electric quantity when being charged by 2C current, and can charge 65% of electric quantity within 14 minutes when being charged by 3C current, mainly because the invention reduces the occurrence of hydrogen evolution and water loss reaction of the negative electrode and improves the charge acceptance of the negative electrode by changing the surface characteristics of the active carbon material and adding the hydrogen inhibitor.
Example 4
The invention provides a high-capacity long-life lead-carbon battery cathode which is prepared from the following raw materials in parts by weight: 100-110 parts of lead powder, 5-10 parts of active carbon powder, 5-10 parts of nitrogen-doped active carbon powder, 0.12-0.18 part of sodium lignin sulfonate, 0.10-0.12 part of short cellulose, 0.20-0.24 part of barium sulfate, 0.05-0.06 part of hydrogen inhibitor, 0.10-0.12 part of sulfuric acid and 12-16 parts of deionized water;
in the embodiment, 106 parts of lead powder, 8 parts of activated carbon powder, 8 parts of nitrogen-doped activated carbon powder, 0.16 part of sodium lignin sulfonate, 0.11 part of short cellulose, 0.22 part of barium sulfate, 0.06 part of hydrogen inhibitor, 0.11 part of sulfuric acid and 15 parts of deionized water are used.
It should be further noted that the hydrogen inhibitor used in the present invention includes gallium oxide and bismuth oxide, and the ratio of gallium oxide to bismuth oxide is 1:1 and sulfuric acid is used at a concentration of 1.4g/cm 3 。
The invention also discloses a manufacturing method of the high-capacity long-life lead-carbon battery cathode, which comprises the following steps:
step one, preparing nitrogen-doped activated carbon powder: placing activated carbon powder into a quartz boat, then placing the quartz boat into a vacuum tube furnace, and introducing mixed gas of nitrogen and ammonia, wherein the ratio of the nitrogen to the ammonia is 1:1, heating to 900 ℃, keeping the temperature for 2 hours at the heating speed of 10 ℃/min in a vacuum tube furnace, and taking out after natural cooling;
grinding lead powder, activated carbon powder, nitrogen-doped activated carbon powder, sodium lignin sulfonate, barium sulfate and inhibitor in a mortar, sieving, uniformly screening, placing in a container, adding deionized water into the container, uniformly stirring, adding short cellulose and sulfuric acid, grinding into paste, coating, and placing the coated polar plate in a concentration of 1.15g/cm 3 Is taken out after being rapidly pickled in sulfuric acid solution;
step three, placing the negative plate subjected to pickling in the step two into a programmable constant temperature and humidity test box for curing treatment: curing for 48 hours at 60 ℃ under the condition of 100% humidity, and then placing the cured materials into a blast drying oven for 24 hours, wherein the temperature is set to be 60 ℃;
step four, the cathode solidified in the step threeThe plate has a concentration of 1.035g/cm 3 Is formed into 52h in sulfuric acid solution;
the specific operation of the formation is as follows: firstly, standing for 2h, then carrying out constant current charging for 1h at 0.05C multiplying power, and then carrying out constant current charging for 20h at 0.1C multiplying power; after standing for 2h, carrying out constant current discharge for 1h at a rate of 0.1C, then carrying out constant current charge for 10h at a rate of 0.1C, carrying out constant current charge for 12h at a rate of 0.2C, and finally carrying out constant current charge for 4h at a rate of 0.1C.
The negative electrode plate prepared in this example was welded in a lead-carbon battery, and then the battery performance test was performed on the lead-carbon battery, and the test results are shown in table 4 below:
TABLE 4 Table 4
When the lead-carbon battery in the market is charged with 2C current, only 50% of the electric quantity can be charged; when charged at 3C current, 40% charge was charged in 14 minutes; the lead-carbon battery of the negative plate prepared by the invention can charge 86% of electric quantity when being charged by 2C current, and can charge 68% of electric quantity within 14 minutes when being charged by 3C current, mainly because the invention reduces the occurrence of hydrogen evolution and water loss reaction of the negative electrode and improves the charge acceptance of the negative electrode by changing the surface characteristics of the active carbon material and adding the hydrogen inhibitor.
Example 5
The invention provides a high-capacity long-life lead-carbon battery cathode which is prepared from the following raw materials in parts by weight: 100-110 parts of lead powder, 5-10 parts of active carbon powder, 5-10 parts of nitrogen-doped active carbon powder, 0.12-0.18 part of sodium lignin sulfonate, 0.10-0.12 part of short cellulose, 0.20-0.24 part of barium sulfate, 0.05-0.06 part of hydrogen inhibitor, 0.10-0.12 part of sulfuric acid and 12-16 parts of deionized water;
in the embodiment, 110 parts of lead powder, 10 parts of active carbon powder, 10 parts of nitrogen-doped active carbon powder, 0.18 part of sodium lignin sulfonate, 0.12 part of short cellulose, 0.24 part of barium sulfate, 0.06 part of hydrogen inhibitor, 0.12 part of sulfuric acid and 16 parts of deionized water are used.
It should be further noted that the present inventionThe hydrogen inhibitor comprises gallium oxide and bismuth oxide, wherein the proportion of the gallium oxide to the bismuth oxide is 1:1, sulfuric acid was used at a concentration of 1.4g/cm 3 。
The invention also discloses a manufacturing method of the high-capacity long-life lead-carbon battery cathode, which comprises the following steps:
step one, preparing nitrogen-doped activated carbon powder: placing activated carbon powder into a quartz boat, then placing the quartz boat into a vacuum tube furnace, and introducing mixed gas of nitrogen and ammonia, wherein the ratio of the nitrogen to the ammonia is 1:1, heating to 900 ℃, keeping the temperature for 2 hours at the heating speed of 10 ℃/min in a vacuum tube furnace, and taking out after natural cooling;
grinding lead powder, activated carbon powder, nitrogen-doped activated carbon powder, sodium lignin sulfonate, barium sulfate and inhibitor in a mortar, sieving, uniformly screening, placing in a container, adding deionized water into the container, uniformly stirring, adding short cellulose and sulfuric acid, grinding into paste, coating, and placing the coated polar plate in a concentration of 1.15g/cm 3 Is taken out after being rapidly pickled in sulfuric acid solution;
step three, placing the negative plate subjected to pickling in the step two into a programmable constant temperature and humidity test box for curing treatment: curing for 48 hours at 60 ℃ under the condition of 100% humidity, and then placing the cured materials into a blast drying oven for 24 hours, wherein the temperature is set to be 60 ℃;
fourthly, the negative plate solidified in the third step is processed at the concentration of 1.035g/cm 3 Is formed into 52h in sulfuric acid solution;
the specific operation of the formation is as follows: firstly, standing for 2h, then carrying out constant current charging for 1h at 0.05C multiplying power, and then carrying out constant current charging for 20h at 0.1C multiplying power; after standing for 2h, carrying out constant current discharge for 1h at a rate of 0.1C, then carrying out constant current charge for 10h at a rate of 0.1C, carrying out constant current charge for 12h at a rate of 0.2C, and finally carrying out constant current charge for 4h at a rate of 0.1C.
The negative electrode plate prepared in this example was welded in a lead-carbon battery, and then the battery performance test was performed on the lead-carbon battery, and the test results are shown in table 5 below:
TABLE 5
When the lead-carbon battery in the market is charged with 2C current, only 50% of the electric quantity can be charged; when charged at 3C current, 40% charge was charged in 14 minutes; the lead-carbon battery of the negative plate prepared by the invention can charge 87% of electric quantity when being charged by 2C current, and can charge 62% of electric quantity within 14 minutes when being charged by 3C current, mainly because the invention reduces the occurrence of hydrogen evolution and water loss reaction of the negative electrode and improves the charge acceptance of the negative electrode by changing the surface characteristics of the active carbon material and adding the hydrogen inhibitor.
The foregoing has shown and described the basic principles and main features of the present invention and the advantages of the present invention. It will be understood by those skilled in the art that the present invention is not limited to the embodiments described above, and that the above embodiments and descriptions are merely illustrative of the principles of the present invention, and various changes and modifications may be made without departing from the spirit and scope of the invention, which is defined in the appended claims.
Claims (8)
1. The utility model provides a high capacity long-life plumbous carbon battery negative pole which characterized in that: comprises the following components in parts by weight: 100-110 parts of lead powder, 5-10 parts of active carbon powder, 5-10 parts of nitrogen-doped active carbon powder, 0.12-0.18 part of sodium lignin sulfonate, 0.10-0.12 part of short cellulose, 0.20-0.24 part of barium sulfate, 0.05-0.06 part of hydrogen inhibitor, 0.10-0.12 part of sulfuric acid and 12-16 parts of deionized water.
2. The high capacity long life lead carbon battery negative electrode of claim 1, wherein: the hydrogen inhibitor comprises gallium oxide and bismuth oxide, wherein the proportion of the gallium oxide to the bismuth oxide is 1:1.
3. the high capacity long life lead carbon battery negative electrode of claim 1, wherein: the concentration of sulfuric acid is 1.4g/cm 3 。
4. A method of making a high capacity long life lead carbon battery negative electrode according to any of claims 1-3, characterized by: the method comprises the following steps:
step one, preparing nitrogen-doped activated carbon powder: placing activated carbon powder into a quartz boat, placing the quartz boat into a vacuum tube furnace, introducing mixed gas of nitrogen and ammonia, heating to 900 ℃, preserving heat for 2 hours, and taking out after natural cooling;
grinding lead powder, activated carbon powder, nitrogen-doped activated carbon powder, sodium lignin sulfonate, barium sulfate and inhibitor in a mortar, sieving, uniformly screening, placing in a container, adding deionized water into the container, uniformly stirring, adding short cellulose and sulfuric acid, grinding into paste, coating, and placing the coated polar plate in a concentration of 1.15g/cm 3 Is taken out after being rapidly pickled in sulfuric acid solution;
step three, placing the negative plate subjected to pickling in the step two into a programmable constant temperature and humidity test box for curing treatment;
fourthly, the negative plate solidified in the third step is processed at the concentration of 1.035g/cm 3 Is formed into 52h.
5. The method for manufacturing the high-capacity long-life lead-carbon battery anode, which is disclosed in claim 4, is characterized in that: in the first step, the ratio of nitrogen to ammonia is 1:1.
6. the method for manufacturing the high-capacity long-life lead-carbon battery anode, which is disclosed in claim 4, is characterized in that: in the first step, the temperature rising speed of the vacuum tube furnace is 10 ℃/min.
7. The method for manufacturing the high-capacity long-life lead-carbon battery anode, which is disclosed in claim 4, is characterized in that: in the third step, the curing conditions are as follows: curing at 60 deg.C and 100% humidity for 48 hr, and then placing in a forced air drying oven for 24 hr at 60 deg.C.
8. The method for manufacturing the high-capacity long-life lead-carbon battery anode, which is disclosed in claim 4, is characterized in that: the formation process in step four is as follows: firstly, standing for 2h, then carrying out constant current charging for 1h at 0.05C multiplying power, and then carrying out constant current charging for 20h at 0.1C multiplying power; after standing for 2h, carrying out constant current discharge for 1h at a rate of 0.1C, then carrying out constant current charge for 10h at a rate of 0.1C, carrying out constant current charge for 12h at a rate of 0.2C, and finally carrying out constant current charge for 4h at a rate of 0.1C.
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