CN109860730B - Preparation method of lead-acid battery negative electrode composite material additive - Google Patents
Preparation method of lead-acid battery negative electrode composite material additive Download PDFInfo
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- 239000002253 acid Substances 0.000 title claims abstract description 41
- 239000002131 composite material Substances 0.000 title claims abstract description 33
- 239000000654 additive Substances 0.000 title claims abstract description 31
- 230000000996 additive effect Effects 0.000 title claims abstract description 31
- 238000002360 preparation method Methods 0.000 title claims abstract description 9
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 claims abstract description 37
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 32
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 29
- 229910002804 graphite Inorganic materials 0.000 claims abstract description 28
- 239000010439 graphite Substances 0.000 claims abstract description 28
- 239000011787 zinc oxide Substances 0.000 claims abstract description 24
- 238000000034 method Methods 0.000 claims abstract description 22
- 239000000017 hydrogel Substances 0.000 claims abstract description 19
- 238000006243 chemical reaction Methods 0.000 claims abstract description 15
- 239000008367 deionised water Substances 0.000 claims abstract description 14
- 229910021641 deionized water Inorganic materials 0.000 claims abstract description 14
- 239000000843 powder Substances 0.000 claims abstract description 11
- 238000001027 hydrothermal synthesis Methods 0.000 claims abstract description 10
- 238000009210 therapy by ultrasound Methods 0.000 claims abstract description 10
- 238000004108 freeze drying Methods 0.000 claims abstract description 8
- 238000007710 freezing Methods 0.000 claims abstract description 6
- 230000008014 freezing Effects 0.000 claims abstract description 6
- 239000000243 solution Substances 0.000 claims description 47
- 238000003756 stirring Methods 0.000 claims description 14
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 9
- 238000001035 drying Methods 0.000 claims description 7
- WABPQHHGFIMREM-UHFFFAOYSA-N lead(0) Chemical compound [Pb] WABPQHHGFIMREM-UHFFFAOYSA-N 0.000 claims description 7
- QAOWNCQODCNURD-UHFFFAOYSA-N sulfuric acid Substances OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 7
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims description 6
- 238000003760 magnetic stirring Methods 0.000 claims description 6
- 239000011259 mixed solution Substances 0.000 claims description 6
- 229910021382 natural graphite Inorganic materials 0.000 claims description 6
- 238000005406 washing Methods 0.000 claims description 6
- JIAARYAFYJHUJI-UHFFFAOYSA-L zinc dichloride Chemical compound [Cl-].[Cl-].[Zn+2] JIAARYAFYJHUJI-UHFFFAOYSA-L 0.000 claims description 6
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 3
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims description 3
- 239000007864 aqueous solution Substances 0.000 claims description 3
- 238000005119 centrifugation Methods 0.000 claims description 3
- 238000001816 cooling Methods 0.000 claims description 3
- 238000010438 heat treatment Methods 0.000 claims description 3
- 239000005457 ice water Substances 0.000 claims description 3
- 238000002156 mixing Methods 0.000 claims description 3
- 230000010355 oscillation Effects 0.000 claims description 3
- 239000000376 reactant Substances 0.000 claims description 3
- 238000002604 ultrasonography Methods 0.000 claims description 3
- 239000011592 zinc chloride Substances 0.000 claims description 3
- 235000005074 zinc chloride Nutrition 0.000 claims description 3
- PIJPYDMVFNTHIP-UHFFFAOYSA-L lead sulfate Chemical compound [PbH4+2].[O-]S([O-])(=O)=O PIJPYDMVFNTHIP-UHFFFAOYSA-L 0.000 description 7
- TZCXTZWJZNENPQ-UHFFFAOYSA-L barium sulfate Chemical compound [Ba+2].[O-]S([O-])(=O)=O TZCXTZWJZNENPQ-UHFFFAOYSA-L 0.000 description 6
- 239000000203 mixture Substances 0.000 description 5
- 239000003792 electrolyte Substances 0.000 description 4
- 239000003292 glue Substances 0.000 description 4
- 239000002245 particle Substances 0.000 description 4
- 238000003466 welding Methods 0.000 description 4
- 238000007789 sealing Methods 0.000 description 3
- 229920005552 sodium lignosulfonate Polymers 0.000 description 3
- 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 description 2
- 229910052924 anglesite Inorganic materials 0.000 description 2
- 239000011248 coating agent Substances 0.000 description 2
- 238000000576 coating method Methods 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 239000000835 fiber Substances 0.000 description 2
- 238000011049 filling Methods 0.000 description 2
- 239000004021 humic acid Substances 0.000 description 2
- 230000002035 prolonged effect Effects 0.000 description 2
- 238000005507 spraying Methods 0.000 description 2
- 230000019635 sulfation Effects 0.000 description 2
- 238000005670 sulfation reaction Methods 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- KEQXNNJHMWSZHK-UHFFFAOYSA-L 1,3,2,4$l^{2}-dioxathiaplumbetane 2,2-dioxide Chemical compound [Pb+2].[O-]S([O-])(=O)=O KEQXNNJHMWSZHK-UHFFFAOYSA-L 0.000 description 1
- 229920001732 Lignosulfonate Polymers 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 1
- 239000011149 active material Substances 0.000 description 1
- 239000013543 active substance Substances 0.000 description 1
- 238000004891 communication Methods 0.000 description 1
- 230000002860 competitive effect Effects 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000005370 electroosmosis Methods 0.000 description 1
- 238000007667 floating Methods 0.000 description 1
- 230000006870 function Effects 0.000 description 1
- 229910021389 graphene Inorganic materials 0.000 description 1
- 230000002427 irreversible effect Effects 0.000 description 1
- 238000012423 maintenance Methods 0.000 description 1
- 230000003446 memory effect Effects 0.000 description 1
- 239000007773 negative electrode material Substances 0.000 description 1
- 239000006259 organic additive Substances 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 230000027756 respiratory electron transport chain Effects 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
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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 preparation method of a lead-acid battery cathode composite material additive, which comprises the following steps of firstly preparing graphite oxide GO by adopting an improved Hummers' method; then preparing spherical zinc oxide S-ZnO powder by adopting a one-step hydrothermal method; dissolving the prepared graphite oxide in deionized water, and performing ultrasonic treatment to fully disperse the graphite oxide; adding the prepared spherical zinc oxide S-ZnO powder into the prepared solution, and continuing ultrasonic treatment; transferring the treated solution into a reaction kettle, and reacting for a period of time at high temperature in an oven to obtain cylindrical RGO/S-ZnO hydrogel; and transferring the obtained RGO/S-ZnO hydrogel into a sample tube, freezing the sample tube in a refrigerator for a period of time, and performing freeze drying treatment to obtain the RGO/S-ZnO composite material. The composite material prepared by the method can be used as an additive to increase the specific surface area and porosity of the lead-acid storage battery plate, and improve the capacity and cycle life of the battery.
Description
Technical Field
The invention relates to the technical field of lead-acid storage batteries, in particular to a preparation method of a composite material additive for a negative electrode of a lead-acid battery.
Background
The lead-acid battery has the advantages of low cost, rich raw materials, wide working temperature range, convenience in floating charge and no memory effect, the remarkable advantages enable the lead-acid battery to be widely applied to the industries of electric power, communication, computers and the like, and in addition, the valve-controlled lead-acid battery has good sealing performance and no leakage, the complicated problem of maintenance is avoided, and the lead-acid battery is promoted to be popular with people in the industry in the field of electric automobiles. When the lead-acid storage battery is operated under the condition of HRPSoC, the discharge product of the negative electrode is large-particle PbSO4Crystals due to HSO in the electrolyte at high rate4 －The reaction consumption rate is far greater than the diffusion rate, so that a large amount of lead sulfate is easily accumulated on the surface of the negative plate. And because the larger lead sulfate particles have less solubility in the electrolyte, this is during chargingThe lead sulfate is difficult to participate in the reaction, only a small part of the lead sulfate is reduced into the spongy lead, and the reversibility of the battery is poor. PbSO on the surface of the negative plate after repeated charge-discharge cycles4Continuously accumulating to form compact sulfate layer, reducing porosity and electron transfer rate of the plate, and not benefiting HSO4 －The lead is diffused into the pole plate to contact and react with the active lead, so that the utilization rate of the active material lead cannot be brought into full play, the capacity of the negative electrode is reduced, and the battery fails in advance. It can be seen that the main factor of failure of lead-acid batteries under the HRPSoC operating regime is the irreversible sulfation of the negative plate.
To address this problem, the prior art solution takes measures to add an additive to the negative electrode active material: barium sulfate, organic additives such as lignin and sodium lignosulfonate, etc., which, although improving the performance of the batteries, still remain unsolved, the most fatal sulfation problem.
Disclosure of Invention
The invention aims to provide a preparation method of a lead-acid battery negative electrode composite material additive, the composite material prepared by the method can be used as the additive to increase the specific surface area of a lead-acid battery plate, a conductive network is formed in a battery negative plate, the conductive performance and the active substance utilization rate of the plate are improved, and the effects of improving the battery capacity and prolonging the HRPSoC cycle life are achieved.
The purpose of the invention is realized by the following technical scheme:
a method of preparing a lead-acid battery negative composite additive, the method comprising:
and 6, transferring the obtained RGO/S-ZnO hydrogel to a sample tube, freezing the sample tube in a refrigerator for a period of time, and performing freeze drying treatment to obtain the RGO/S-ZnO composite material.
The process of the step 1 specifically comprises the following steps:
firstly, adding 1-2 g of natural graphite into 30-60 mL of natural graphite in a volume ratio of 1: 9 concentrated phosphoric acid: mixing concentrated sulfuric acid with the solution, and stirring uniformly in an ice bath;
then 6-8g KMnO is slowly added into the mixed solution4Reacting for 2-3h at 0-4 ℃, then heating to 50 ℃, and reacting for 12h by magnetic stirring;
adding 46-100 mL of ice water, and continuing to react for 20-30 min;
then adding 15-25 mL of 3-5 wt.% H into the reaction solution2O2Standing for 2-3h until the solution is yellow, and then performing centrifugal washing operation by using a dilute HCl solution and deionized water to obtain graphite oxide hydrogel;
adding a proper amount of deionized water into the obtained graphite oxide hydrogel, and carrying out ice bath ultrasound for 2 hours until the graphite oxide hydrogel is uniformly dispersed;
and then, the graphite oxide GO is placed in a refrigerator to be frozen for 24 hours, and is frozen and dried for 48 hours to obtain graphite oxide GO.
The process of the step 2 specifically comprises the following steps:
firstly, 3.0g of sodium hydroxide is put into a 100mL beaker, and 30mL of water is added to be fully dissolved, and the solution is marked as A solution;
then 1.36g of zinc chloride is weighed and poured into a 50mL beaker, 20mL of water is added for dissolving, and the solution is marked as B solution;
then dropwise adding the solution B into the solution A under magnetic stirring, and reacting for 40min to obtain a clear solution;
then adding a pre-prepared HC1 aqueous solution to adjust the alkalinity of the clear solution to 11-11.5, and stirring for 20 min;
transferring the mixed solution into a hydrothermal reaction kettle with the capacity of 100mL, and putting the reaction kettle into a constant-temperature drying oven to react for 12 hours at the temperature of 80 ℃;
after hydrothermal reaction, naturally cooling the obtained reactant to room temperature, and carrying out ultrasonic oscillation and centrifugation treatment;
and then washing the mixture by using deionized water and absolute ethyl alcohol for three times respectively, and freeze-drying the mixture for 24 hours to obtain white spherical zinc oxide S-ZnO powder.
The composite material is used as an additive of a negative plate of a lead-acid storage battery, wherein: the weight percentage of the composite material is 0.5-2.0% of the lead powder content in the negative plate of the lead-acid storage battery.
According to the technical scheme provided by the invention, the composite material is used as an additive, so that the specific surface area of the lead-acid storage battery pole plate can be increased, the conductivity of the pole plate can be improved, the cycle product of the battery is more uniform, the particle size of lead sulfate is effectively reduced, the conversion efficiency of the lead sulfate to negative lead is improved, and the HRPSoC cycle life of the battery in the HEV is prolonged. Thereby improving the competitive advantage of the lead-acid storage battery in the market.
Drawings
In order to more clearly illustrate the technical solutions of the embodiments of the present invention, the drawings needed to be used in the description of the embodiments are briefly introduced below, and it is obvious that the drawings in the following description are only some embodiments of the present invention, and it is obvious for those skilled in the art to obtain other drawings based on the drawings without creative efforts.
Fig. 1 is a schematic flow chart of a preparation method of a lead-acid battery negative electrode composite material additive provided by an embodiment of the invention.
Detailed Description
The technical solutions in the embodiments of the present invention are clearly and completely described below with reference to the drawings in the embodiments of the present invention, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments of the present invention without making any creative effort, shall fall within the protection scope of the present invention.
The following embodiments of the present invention will be further described in detail with reference to the accompanying drawings, and fig. 1 is a schematic flow chart of a preparation method of a lead-acid battery negative electrode composite material additive provided by the embodiments of the present invention, where the method includes:
in the step, the specific preparation process is as follows:
firstly, adding 1-2 g of natural graphite into 30-60 mL of natural graphite in a volume ratio of 1: 9 concentrated phosphoric acid: mixing concentrated sulfuric acid with the solution, and stirring uniformly in an ice bath;
then 6-8g KMnO is slowly added into the mixed solution4Reacting for 2-3h at 0-4 ℃, then heating to 50 ℃, and reacting for 12h by magnetic stirring;
adding 46-100 mL of ice water, and continuing to react for 20-30 min;
then adding 15-25 mL of 3-5 wt.% H into the reaction solution2O2Standing for 2-3h until the solution is yellow, and then performing centrifugal washing operation by using a dilute HCl solution and deionized water to obtain graphite oxide hydrogel;
adding a proper amount of deionized water into the obtained graphite oxide hydrogel, and carrying out ice bath ultrasound for 2 hours until the graphite oxide hydrogel is uniformly dispersed;
and then, the graphite oxide GO is placed in a refrigerator to be frozen for 24 hours, and is frozen and dried for 48 hours to obtain graphite oxide GO.
in the step, the specific process is as follows:
firstly, 3.0g of sodium hydroxide is put into a 100mL beaker, and 30mL of water is added to be fully dissolved, and the solution is marked as A solution;
then 1.36g of zinc chloride is weighed and poured into a 50mL beaker, 20mL of water is added for dissolving, and the solution is marked as B solution;
then dropwise adding the solution B into the solution A under magnetic stirring, and reacting for 40min to obtain a clear solution;
then adding a pre-prepared HC1 aqueous solution to adjust the alkalinity of the clear solution to 11-11.5, and stirring for 20 min;
transferring the mixed solution into a hydrothermal reaction kettle with the capacity of 100mL, and putting the reaction kettle into a constant-temperature drying oven to react for 12 hours at the temperature of 80 ℃;
after hydrothermal reaction, naturally cooling the obtained reactant to room temperature, and carrying out ultrasonic oscillation and centrifugation treatment;
and then washing the mixture by using deionized water and absolute ethyl alcohol for three times respectively, and freeze-drying the mixture for 24 hours to obtain white spherical zinc oxide S-ZnO powder.
in the step, graphite oxide can be dissolved in 40mL of deionized water to prepare a solution with the mass concentration of 2g/L, and ultrasonic treatment is carried out for 2 hours to fully disperse GO;
in this step, the time of the ultrasonic treatment may be 1 hour;
in this step, the solution can be transferred to a 100mL reaction vessel and reacted in an oven at a high temperature of 180 ℃ for 12 hours to obtain a cylindrical RGO/S-ZnO hydrogel.
And 6, transferring the obtained RGO/S-ZnO hydrogel to a sample tube, freezing the sample tube in a refrigerator for a period of time, and performing freeze drying treatment to obtain the RGO/S-ZnO composite material.
In the step, the RGO/S-ZnO hydrogel can be transferred to a sample tube and is frozen in a refrigerator for 12 hours, and then is frozen and dried for 48 hours to obtain the RGO/S-ZnO composite material.
Furthermore, the RGO/S-ZnO composite material can be used as an additive of a negative plate of the lead-acid storage battery, and the weight percentage of the composite material is 0.5-2.0% of the content of lead powder in the negative plate of the lead-acid storage battery.
The performance of the composite material as an additive is described in detail in the following specific examples, wherein the weight percentage of the additive added in the example is 0.5-2% of the lead powder content in the negative plate formula of the storage battery, and the specific examples include two cases:
1) blank group (0%): when the negative plate of the lead-acid storage battery is prepared, no additive is added, specifically, 3 g of lead powder, 0.024 g of barium sulfate, 0.027g of humic acid, 0.0045 g of sodium lignosulphonate and 0.0024 g of short fibers are put into a paste mixer to be mixed for 3-5 minutes, then water with the formula amount is added to be mixed uniformly for 10 minutes, then dilute sulfuric acid with the formula amount is added within 15-30 minutes, lead paste is continuously stirred while adding acid, the lead paste is stirred for 10-15 minutes after adding acid, the temperature of the paste is ensured not to be higher than 60 ℃ in the stirring process, the apparent density is measured 5 minutes before the paste is discharged, the process specification requirement is met, if the temperature is higher, proper water can be added for regulation, and if the temperature is lower than the specification, the stirring time can be properly prolonged.
Coating a plate, spraying acid, drying the surface, curing for not less than 48 hours at 63 ℃ under the condition that the relative humidity is 92%, and drying for 36 hours to ensure that the free lead and the water content meet the requirements of process specifications to obtain a raw negative plate;
then assembling a 2V small-sized seal valve controlled lead-acid battery, welding, sealing a battery cover by glue, adding a rubber ring welding terminal, dripping color glue, filling acid, and forming and charging to obtain a finished battery; the test was then conducted as a comparative example.
2) Additive package (0.5 w%, 1.0 w%, 1.5 w% and 2.0 w%): when a negative plate of a lead-acid storage battery is prepared, the RGO/S-ZnO composite material prepared by the invention is added as an additive, and specifically, 3 g of lead powder, 0.024 g of barium sulfate, 0.027g of humic acid, 0.0045 g of sodium lignosulfonate and 0.0024 g of short fiber are added, and 0.5%, 1.0%, 1.5% and 2.0% of the content of the lead powder are respectively added into the RGO/S-ZnO composite material. Stirring for 3-5 minutes to uniformly mix, adding water with the formula amount, stirring for 10min, adding dilute sulfuric acid with the formula amount within 10-12 min, adding acid while continuously stirring the lead paste, adding the acid, then stirring for 10-15 min, ensuring that the temperature of the paste is not higher than 60 ℃ in the stirring process, measuring the apparent density 5min before the paste is discharged, and meeting the process specified requirements, if the apparent density is higher, adding appropriate amount of water for regulation, and if the apparent density is lower than the specified value, properly prolonging the stirring time.
Coating a plate, spraying acid, drying the surface, curing for not less than 48 hours at 63 ℃ under the condition that the relative humidity is 92%, and drying for 36 hours to ensure that the free lead and the water content meet the requirements of process specifications, thereby obtaining a raw negative plate; then assembling a 2V small-sized valve-controlled battery, welding, sealing the battery cover by glue, adding a rubber ring welding terminal, dripping color glue, filling acid, and forming and charging to obtain a finished battery; the test was then conducted as a comparative example. The electrochemical performance of the cells obtained under the five conditions described above [ blank (0%), additive (0.5 w%, 1.0 w%, 1.5 w% and 2.0 w%) ]wastested,
| battery with a battery cell | Specific capacity of first discharge (mAh/g) | HRPSoC cycle life (time) |
| Blank group 0% | 106.4 | 7210 |
| 0.5 w% of additive | 109.5 | 12397 |
| Additive 1.0 w% | 128.35 | 19158 |
| Additive 1.5 w% | 125.7 | 15920 |
| 2.0 w% of additive | 116.2 | 11354 |
As shown in table 1, the first discharge specific capacity and the HRPSoC cycle life are compared: TABLE 1
From the results in Table 1, it can be seen that: the composite material additive improves the first discharge specific capacity of the lead-acid battery and prolongs the HRPSoC cycle life, so that the RGO/S-ZnO composite material can be used as the negative plate additive of the lead-acid battery.
It is noted that those skilled in the art will recognize that embodiments of the present invention are not described in detail herein.
In conclusion, the specific surface area and the porosity of the lead-acid storage battery plate can be increased by using the composite material as the additive, the additive forms a conductive network in the battery negative plate, so that the battery cycle product is more uniform, PbSO4 can be fully reduced, and the generation of large-particle lead sulfate is avoided. In addition, zinc oxide in the composite material can be dissolved in electrolyte, so that a channel similar to a mesopore can be formed between graphene layers, the porosity of a polar plate is increased, the composite material has the function of storing the electrolyte, and the composite material is equivalent to an electroosmosis pump.
The above description is only for the preferred embodiment of the present invention, but the scope of the present invention is not limited thereto, and any changes or substitutions that can be easily conceived by those skilled in the art within the technical scope of the present invention are included in the scope of the present invention. Therefore, the protection scope of the present invention shall be subject to the protection scope of the claims.
Claims (2)
1. A preparation method of a lead-acid battery negative electrode composite material additive is characterized by comprising the following steps:
step 1, firstly, preparing graphite oxide GO by adopting an improved Hummers' method;
the process of the step 1 specifically comprises the following steps:
firstly, adding 1-2 g of natural graphite into 30-60 mL of natural graphite in a volume ratio of 1: 9 concentrated phosphoric acid: mixing concentrated sulfuric acid with the solution, and stirring uniformly in an ice bath;
then 6-8g of KMnO is added into the mixed solution4Reacting for 2-3h at 0-4 ℃, then heating to 50 ℃, and reacting for 12h by magnetic stirring;
adding 46-100 mL of ice water, and continuing to react for 20-30 min;
then adding 15-25 mL of 3-5 wt.% H into the reaction solution2O2Until the solution is yellow, then carrying out centrifugal washing operation by using a dilute HCl solution and deionized water to obtain graphite oxide hydrogel;
adding deionized water into the obtained graphite oxide hydrogel, and carrying out ice bath ultrasound for 2 hours until the graphite oxide hydrogel is uniformly dispersed;
then placing the graphite oxide GO in a refrigerator for freezing for 24h, and then carrying out freeze drying for 48h to obtain graphite oxide GO;
step 2, preparing spherical zinc oxide S-ZnO powder by adopting a one-step hydrothermal method; the specific process is as follows:
firstly, 3.0g of sodium hydroxide is put into a 100mL beaker, and 30mL of water is added to be fully dissolved, and the solution is marked as A solution;
then 1.36g of zinc chloride is weighed and poured into a 50mL beaker, 20mL of water is added for dissolving, and the solution is marked as B solution;
then dropwise adding the solution B into the solution A under magnetic stirring, and reacting for 40min to obtain a clear solution;
then adding a pre-prepared HC1 aqueous solution to adjust the alkalinity of the clear solution to 11-11.5, and stirring for 20 min;
transferring the mixed solution into a hydrothermal reaction kettle with the capacity of 100mL, and putting the reaction kettle into a constant-temperature drying oven to react for 12 hours at the temperature of 80 ℃;
after hydrothermal reaction, naturally cooling the obtained reactant to room temperature, and carrying out ultrasonic oscillation and centrifugation treatment;
washing with deionized water and absolute ethyl alcohol for three times respectively, and freeze-drying for 24h to obtain white spherical zinc oxide S-ZnO powder;
step 3, dissolving the graphite oxide prepared in the step 1 in deionized water, and performing ultrasonic treatment to fully disperse the graphite oxide;
step 4, adding the spherical zinc oxide S-ZnO powder prepared in the step 2 into the prepared solution, and continuing ultrasonic treatment;
step 5, transferring the solution treated in the step 4 into a reaction kettle, and reacting in an oven at a high temperature for a period of time to obtain cylindrical RGO/S-ZnO hydrogel; specifically, the reaction is carried out for 12 hours in an oven at the high temperature of 180 ℃;
step 6, transferring the obtained RGO/S-ZnO hydrogel to a sample tube, freezing the sample tube in a refrigerator for a period of time, and then carrying out freeze drying treatment to obtain an RGO/S-ZnO composite material; in particular to a freezing treatment in a refrigerator for 12 h.
2. The method for preparing the negative electrode composite material additive of the lead-acid battery according to claim 1, wherein the composite material is used as an additive of a negative plate of the lead-acid battery, and the method comprises the following steps:
the weight percentage of the composite material is 0.5-2.0% of the lead powder content in the negative plate of the lead-acid storage battery.
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| CN107188164A (en) * | 2017-07-11 | 2017-09-22 | 济南大学 | A kind of preparation method of rGO/ZnO tiny balloons |
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2018
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| CN102760867A (en) * | 2012-07-25 | 2012-10-31 | 哈尔滨工业大学 | Superbattery polar plate containing grapheme-based hydrogel, preparation method thereof and lead acid superbattery assembled thereby |
| WO2016064532A1 (en) * | 2014-10-22 | 2016-04-28 | Cabot Corporation | Carbon additives for negative electrodes |
| CN106159275A (en) * | 2016-06-24 | 2016-11-23 | 华南师范大学 | A kind of preparation method of polar plate of lead acid storage battery additive |
| CN106374118A (en) * | 2016-10-14 | 2017-02-01 | 济南大学 | ZnO/rGO composite material with efficient electro-catalysis oxygen reduction performance |
| CN107188164A (en) * | 2017-07-11 | 2017-09-22 | 济南大学 | A kind of preparation method of rGO/ZnO tiny balloons |
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