CN113036130B - Carbon material for low-temperature lead-carbon battery and preparation method and application thereof - Google Patents
Carbon material for low-temperature lead-carbon battery and preparation method and application thereof Download PDFInfo
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- CN113036130B CN113036130B CN201911360374.3A CN201911360374A CN113036130B CN 113036130 B CN113036130 B CN 113036130B CN 201911360374 A CN201911360374 A CN 201911360374A CN 113036130 B CN113036130 B CN 113036130B
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- 239000003575 carbonaceous material Substances 0.000 title claims abstract description 138
- 229910052799 carbon Inorganic materials 0.000 title claims abstract description 96
- 238000002360 preparation method Methods 0.000 title claims abstract description 8
- TZCXTZWJZNENPQ-UHFFFAOYSA-L barium sulfate Chemical compound [Ba+2].[O-]S([O-])(=O)=O TZCXTZWJZNENPQ-UHFFFAOYSA-L 0.000 claims abstract description 109
- 150000001721 carbon Chemical class 0.000 claims description 77
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 74
- 239000011505 plaster Substances 0.000 claims description 43
- 238000001035 drying Methods 0.000 claims description 42
- 239000002253 acid Substances 0.000 claims description 40
- 159000000009 barium salts Chemical class 0.000 claims description 37
- 238000000034 method Methods 0.000 claims description 21
- QVQLCTNNEUAWMS-UHFFFAOYSA-N barium oxide Chemical compound [Ba]=O QVQLCTNNEUAWMS-UHFFFAOYSA-N 0.000 claims description 18
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 18
- 238000005245 sintering Methods 0.000 claims description 15
- WABPQHHGFIMREM-UHFFFAOYSA-N lead(0) Chemical compound [Pb] WABPQHHGFIMREM-UHFFFAOYSA-N 0.000 claims description 14
- 239000008367 deionised water Substances 0.000 claims description 11
- 229910021641 deionized water Inorganic materials 0.000 claims description 11
- 239000000654 additive Substances 0.000 claims description 10
- 230000000996 additive effect Effects 0.000 claims description 9
- 239000008139 complexing agent Substances 0.000 claims description 5
- 239000012298 atmosphere Substances 0.000 claims description 2
- 239000002738 chelating agent Substances 0.000 claims description 2
- 230000000536 complexating effect Effects 0.000 claims description 2
- 238000005470 impregnation Methods 0.000 claims description 2
- 230000004048 modification Effects 0.000 claims description 2
- 238000012986 modification Methods 0.000 claims description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 abstract description 24
- 238000002425 crystallisation Methods 0.000 abstract description 6
- 230000008025 crystallization Effects 0.000 abstract description 6
- PIJPYDMVFNTHIP-UHFFFAOYSA-L lead sulfate Chemical compound [PbH4+2].[O-]S([O-])(=O)=O PIJPYDMVFNTHIP-UHFFFAOYSA-L 0.000 abstract description 6
- 229910021393 carbon nanotube Inorganic materials 0.000 abstract description 2
- 239000002041 carbon nanotube Substances 0.000 abstract description 2
- 229910021389 graphene Inorganic materials 0.000 abstract description 2
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 abstract description 2
- 239000000203 mixture Substances 0.000 description 42
- 238000003756 stirring Methods 0.000 description 28
- 238000002156 mixing Methods 0.000 description 19
- 229910021642 ultra pure water Inorganic materials 0.000 description 18
- 239000012498 ultrapure water Substances 0.000 description 18
- IWOUKMZUPDVPGQ-UHFFFAOYSA-N barium nitrate Chemical compound [Ba+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O IWOUKMZUPDVPGQ-UHFFFAOYSA-N 0.000 description 16
- 229920005610 lignin Polymers 0.000 description 13
- 239000002245 particle Substances 0.000 description 10
- 238000012360 testing method Methods 0.000 description 10
- 229910052788 barium Inorganic materials 0.000 description 9
- DSAJWYNOEDNPEQ-UHFFFAOYSA-N barium atom Chemical compound [Ba] DSAJWYNOEDNPEQ-UHFFFAOYSA-N 0.000 description 9
- KCXVZYZYPLLWCC-UHFFFAOYSA-N EDTA Chemical compound OC(=O)CN(CC(O)=O)CCN(CC(O)=O)CC(O)=O KCXVZYZYPLLWCC-UHFFFAOYSA-N 0.000 description 8
- 230000000052 comparative effect Effects 0.000 description 8
- 238000007580 dry-mixing Methods 0.000 description 8
- 239000000843 powder Substances 0.000 description 8
- 238000005096 rolling process Methods 0.000 description 8
- 238000007711 solidification Methods 0.000 description 8
- 230000008023 solidification Effects 0.000 description 8
- 238000005507 spraying Methods 0.000 description 8
- OSGAYBCDTDRGGQ-UHFFFAOYSA-L calcium sulfate Chemical compound [Ca+2].[O-]S([O-])(=O)=O OSGAYBCDTDRGGQ-UHFFFAOYSA-L 0.000 description 7
- 238000009826 distribution Methods 0.000 description 7
- 238000005485 electric heating Methods 0.000 description 7
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 6
- 235000011114 ammonium hydroxide Nutrition 0.000 description 6
- 239000012299 nitrogen atmosphere Substances 0.000 description 6
- 238000007790 scraping Methods 0.000 description 6
- 239000003792 electrolyte Substances 0.000 description 5
- 239000011575 calcium Substances 0.000 description 4
- 239000000463 material Substances 0.000 description 3
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 2
- QPCDCPDFJACHGM-UHFFFAOYSA-N N,N-bis{2-[bis(carboxymethyl)amino]ethyl}glycine Chemical compound OC(=O)CN(CC(O)=O)CCN(CC(=O)O)CCN(CC(O)=O)CC(O)=O QPCDCPDFJACHGM-UHFFFAOYSA-N 0.000 description 2
- 229910052791 calcium Inorganic materials 0.000 description 2
- ZCCIPPOKBCJFDN-UHFFFAOYSA-N calcium nitrate Chemical compound [Ca+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O ZCCIPPOKBCJFDN-UHFFFAOYSA-N 0.000 description 2
- 239000011248 coating agent Substances 0.000 description 2
- 238000000576 coating method Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 229960003330 pentetic acid Drugs 0.000 description 2
- 230000010287 polarization Effects 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 230000019635 sulfation Effects 0.000 description 2
- 238000005670 sulfation reaction Methods 0.000 description 2
- PQHYOGIRXOKOEJ-UHFFFAOYSA-N 2-(1,2-dicarboxyethylamino)butanedioic acid Chemical compound OC(=O)CC(C(O)=O)NC(C(O)=O)CC(O)=O PQHYOGIRXOKOEJ-UHFFFAOYSA-N 0.000 description 1
- 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 1
- 239000006230 acetylene black Substances 0.000 description 1
- WDIHJSXYQDMJHN-UHFFFAOYSA-L barium chloride Chemical compound [Cl-].[Cl-].[Ba+2] WDIHJSXYQDMJHN-UHFFFAOYSA-L 0.000 description 1
- 229910001626 barium chloride Inorganic materials 0.000 description 1
- AYJRCSIUFZENHW-DEQYMQKBSA-L barium(2+);oxomethanediolate Chemical compound [Ba+2].[O-][14C]([O-])=O AYJRCSIUFZENHW-DEQYMQKBSA-L 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- BRPQOXSCLDDYGP-UHFFFAOYSA-N calcium oxide Chemical compound [O-2].[Ca+2] BRPQOXSCLDDYGP-UHFFFAOYSA-N 0.000 description 1
- ODINCKMPIJJUCX-UHFFFAOYSA-N calcium oxide Inorganic materials [Ca]=O ODINCKMPIJJUCX-UHFFFAOYSA-N 0.000 description 1
- 239000000292 calcium oxide Substances 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- SZDRZMKKMAXBHS-UHFFFAOYSA-L disodium 2-(1,2-dicarboxyethylamino)butanedioate Chemical compound N(C(C(=O)O)CC(=O)O)C(C(=O)[O-])CC(=O)[O-].[Na+].[Na+] SZDRZMKKMAXBHS-UHFFFAOYSA-L 0.000 description 1
- 238000004146 energy storage Methods 0.000 description 1
- 230000008014 freezing Effects 0.000 description 1
- 238000007710 freezing Methods 0.000 description 1
- 239000004021 humic acid Substances 0.000 description 1
- 229940080260 iminodisuccinate Drugs 0.000 description 1
- 238000010348 incorporation Methods 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 238000011068 loading method Methods 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 238000013508 migration Methods 0.000 description 1
- 230000005012 migration Effects 0.000 description 1
- MGFYIUFZLHCRTH-UHFFFAOYSA-N nitrilotriacetic acid Chemical compound OC(=O)CN(CC(O)=O)CC(O)=O MGFYIUFZLHCRTH-UHFFFAOYSA-N 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
Classifications
-
- 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
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/06—Lead-acid accumulators
-
- 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
- H01M4/14—Electrodes for lead-acid accumulators
- H01M4/16—Processes of manufacture
- H01M4/20—Processes of manufacture of pasted electrodes
-
- 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
Abstract
The invention discloses a carbon material, a preparation method and application thereof. The nano barium sulfate is loaded on the surface of the carbon material, and can provide a large number of lead sulfate crystallization sites at the end stage of battery discharge by using the nano barium sulfate as the negative electrode of the lead-carbon battery, so that the discharge capacity of the battery at low temperature is improved, and the charge acceptance of the lead-carbon battery at low temperature is also improved. The preparation method of the carbon material provided by the invention is suitable for various porous carbon-based materials including active carbon, graphene, carbon nano-tubes, ordered mesoporous carbon materials and the like. The lead-carbon battery prepared by the carbon material can still maintain excellent battery performance under the low temperature condition of minus 40 ℃ to 0 ℃, and the application field of the lead-carbon battery is expanded.
Description
Technical Field
The invention belongs to the technical field of battery energy storage, and particularly relates to a carbon material, a preparation method and application thereof.
Background
The lead-carbon battery is a novel lead-acid battery using carbon material as negative electrode additive, and is characterized by long cycle life, high safety, mature production technology and low cost. The lead-carbon battery reduces the sulfation problem of the traditional lead-acid battery to a certain extent by adding the carbon material into the negative electrode, thereby obviously prolonging the cycle life of the battery.
However, the incorporation of carbon materials also results in lead-carbon batteries having significantly lower low temperature capacities than lead-acid batteries under the same conditions. The main reasons for the low-temperature capacity of the lead-carbon battery are as follows: under the low-temperature condition, the reduction of the sulfuric acid concentration of the electrolyte can raise the freezing point temperature of the electrolyte, so that the migration speed of electrolyte ions is reduced, and the concentration polarization of the electrode is increased. The increase of the concentration polarization of the negative electrode can lead the terminal voltage of the lead-carbon battery to reach the discharge termination voltage in advance in the discharge process, so that the electric quantity discharged by the battery is reduced to some extent.
The concentration of the electrolyte is increased, and although the low-temperature discharge capacity of the lead-carbon battery can be improved to a certain extent, the sulfation of the electrode can be accelerated, and the charge-discharge cycle life of the battery is obviously reduced. The route for improving the low-temperature capacity exertion of the lead-carbon battery by simply increasing the concentration of the electrolyte is not feasible.
Disclosure of Invention
In order to solve the technical problems, the invention provides a carbon material suitable for an internal mixing type lead-carbon battery, and particularly provides a carbon material, a preparation method and application thereof, and a large number of nano barium sulfate crystal nuclei are loaded on the surface of the carbon material, so that a large number of lead sulfate crystallization sites can be provided at the end stage of battery discharge by a battery cathode, and the low-temperature discharge capacity of the battery is improved.
In order to achieve the above purpose, the technical scheme adopted by the invention is as follows:
in one aspect of the invention, a carbon material is provided, the carbon material comprising a carbon-based material, the carbon-based material supporting nano barium sulfate on the surface.
Optionally, the content of the nano barium sulfate is 0.1-99% of the total mass of the carbon material.
Optionally, the particle size range of the nano barium sulfate is 0.1-500 nm.
Optionally, the carbon material is a carbon material for a low temperature lead carbon battery.
In another aspect of the present invention, there is provided a method for preparing a carbon material, including at least:
complexing the barium salt with a complexing agent to obtain a barium salt complex;
and modifying the carbon-based material by adopting a barium salt complex to obtain the modified carbon material rich in nano barium sulfate.
Optionally, the dosage of the barium salt accounts for 1-65% of the total mass of the barium salt and the carbon-based material;
the barium salt is water-soluble barium salt;
the complexing agent is an aminopolycarboxylic acid chelating agent.
Specifically, the amount of the barium salt is independently selected from 1%, 30.9%, 47.2%, 57.3%, 64.2%, 65% of the total mass of the barium salt and the carbon-based material.
The barium salt may be selected from barium salts other than barium sulfate, barium carbonate, such as barium nitrate, barium chloride, etc., and preferably, barium nitrate is used in the present invention.
The complexing agent can be selected from any one of ethylenediamine tetraacetic acid (EDTA), disodium Iminodisuccinate (IDS), diethylenetriamine pentaacetic acid (DTPA) and aminotriacetic acid (NTA).
Optionally, modifying the carbon-based material with a barium salt complex comprises at least:
adding the carbon-based material into the barium salt complex for impregnation to obtain a modified carbon material rich in the barium salt complex;
sintering the modified carbon material rich in the barium salt complex to obtain a modified carbon material rich in barium oxide;
and (3) reacting the modified carbon material rich in the barium oxide with sulfuric acid solution to obtain the modified carbon material rich in nano barium sulfate.
Optionally, the process of obtaining the modified carbon material enriched in the barium salt complex and the modified carbon material enriched in nano barium sulfate at least comprises the following steps:
drying the modified carbon material rich in the barium salt complex and the modified carbon material rich in the nano barium sulfate;
the drying temperature is 80-120 ℃.
The lower limit of the drying temperature is independently selected from 80 ℃, 90 ℃, 95 ℃, 100 ℃ and 110 ℃; the upper limit of the drying temperature is independently selected from 90 ℃, 100 ℃, 110 ℃, 115 ℃ and 120 ℃.
The drying time can be determined according to the dryness of the product, and the free water in the product is removed.
Optionally, the sintering is specifically:
and sintering the modified carbon material rich in the barium salt complex for 1-5 h at 600-900 ℃ under the protection of atmosphere.
The lower limit of the sintering temperature is independently selected from 600 ℃, 650 ℃, 700 ℃, 750 ℃ and 800 ℃; the upper limit of the drying temperature is independently selected from 650 ℃, 750 ℃, 800 ℃, 850 ℃ and 900 ℃.
The sintering time is independently selected from 1h, 2h, 3h, 4h and 5h.
Alternatively, the sulfuric acid solution has a density of 1.05 to 1.5g/cm 3 ；
The mass of the sulfuric acid in the sulfuric acid solution is 11-37 percent of the total mass of the barium salt and the carbon-based material
The amount of sulfuric acid solution determines the loading of nano barium sulfate in the modified carbon material, thereby affecting the discharge capacity of the battery. Too little sulfuric acid solution is added, so that nano barium sulfate is generated too little, enough lead sulfate crystallization sites cannot be generated on the negative electrode, and the effect of improving the discharge capacity of the battery cannot be achieved; otherwise, the content of nano barium sulfate is not increased continuously due to excessive sulfuric acid solution, so that the resource waste is caused.
Specifically, the sulfuric acid dosage is independently selected from 11%, 18.50%, 25.90%, 34.88% and 37% of the total mass of the barium salt and the carbon-based material; in the specific embodiment of the invention, the density is 1.275g/cm at 25 DEG C 3 The dosage of the sulfuric acid solution is more than 30 percent of the total mass of the barium salt and the carbon-based material, and the dosage of the sulfuric acid solution is independently selected from 50 percent, 70 percent, 94.25 percent and 100 percent of the total mass of the barium salt and the carbon-based material.
The invention provides a low-temperature lead-carbon battery negative electrode lead plaster, which comprises any one of the carbon materials and at least one of the carbon materials obtained by the method;
the negative electrode lead plaster comprises the following components: 100 parts of lead powder, 0.1 to 10 parts of additive, 0.01 to 100 parts of carbon material, 10 to 21 parts of deionized water and 4 to 100 parts of sulfuric acid solution;
the density of the sulfuric acid solution is 1.1-1.4 g/cm 3 。
Specifically, in the negative electrode lead paste, at least one of common lead paste additives such as lignin, humic acid and the like is adopted as the additive, and the lower limit of the content of the additive is independently selected from 0.1 part by weight, 2 parts by weight, 5 parts by weight and 8 parts by weight; the upper limit of the content of the additive is independently selected from 0.2 weight part, 4 weight parts, 6 weight parts and 9 weight parts.
In the negative electrode lead plaster, the lower limit of the content of the carbon material is independently selected from 0.01 weight part, 12.6 weight parts, 19.5 weight parts and 50 weight parts; the upper limit of the content of the carbon material is independently selected from 16.2 parts by weight, 23.4 parts by weight, 70 parts by weight and 100 parts by weight.
In the negative electrode lead plaster, the lower limit of the content of deionized water is independently selected from 10 parts by weight, 12.5 parts by weight, 15.5 parts by weight and 17 parts by weight; the upper limit of the content of the carbon material is independently selected from 11 parts by weight, 14 parts by weight, 19 parts by weight, 21 parts by weight.
In the negative electrode lead plaster, the lower limit of the content of the sulfuric acid solution is independently selected from 4 parts by weight, 8.5 parts by weight, 20 parts by weight and 50 parts by weight; the upper limit of the content of the carbon material is independently selected from 10 parts by weight, 25 parts by weight, 70 parts by weight and 100 parts by weight.
In a fourth aspect of the invention, a low-temperature lead-carbon battery is provided, and a battery negative electrode is coated with the negative electrode lead plaster.
The invention has the beneficial effects that:
1. the nano barium sulfate is loaded on the surface of the carbon material and is used for the negative electrode of the lead-carbon battery, and a large number of lead sulfate crystallization sites can be provided at the end stage of battery discharge, so that the discharge capacity of the battery at low temperature is improved.
2. The carbon material with the nano barium sulfate loaded on the surface is doped into the negative electrode of the lead-carbon battery, so that the charge acceptance of the lead-carbon battery at low temperature can be improved.
3. The preparation method of the carbon material provided by the invention is suitable for various porous carbon-based materials including active carbon, graphene, carbon nano-tubes, ordered mesoporous carbon materials and the like.
4. The lead-carbon battery prepared by the carbon material can still maintain excellent battery performance under the low temperature condition of minus 40 ℃ to 0 ℃, and the application field of the lead-carbon battery is expanded.
Detailed Description
The present invention is described in detail below with reference to examples.
Unless otherwise specified, the starting materials in the examples were purchased commercially and used without treatment; the instrument and equipment are recommended to use parameters by manufacturers.
In the examples, the normal temperature and low temperature discharge capacity test of the lead carbon battery was performed using a blue charge-discharge meter.
In the embodiment, the method for detecting the particle size distribution of the nano barium sulfate on the modified carbon material comprises the following steps: and fully sintering the carbon additive loaded with the barium sulfate in an air environment at 600 ℃, removing carbon particles in the mixture, and testing the particle size distribution of the sintered product by adopting a laser particle size analyzer.
Example 1
1. Preparing a modified carbon material rich in nano barium sulfate:
(1) Preparing a solution A: 9.072g of ethylenediamine tetraacetic acid is added into 200g of ultrapure water, 17.384g of ammonia water with the concentration of 25% -28% is added, and the solution is fully stirred until the solution becomes clear and transparent.
(2) Preparing a solution B: 8.06g of barium nitrate was taken and sufficiently dissolved in 750g of ultrapure water, followed by adding 18g of activated carbon to the solution and stirring appropriately.
(3) Pouring the solution A into the solution B, and fully stirring and mixing. Transferring the obtained mixture into an electric heating drying oven, drying at 80 ℃ for 24 hours, and removing free water in the mixture to obtain the modified carbon material rich in EDTA-Ba complex.
(4) Transferring the modified carbon material rich in the EDTA-Ba complex obtained in the step (3) into a tube furnace, and sintering for 5 hours at 600 ℃ in a nitrogen atmosphere to obtain the modified carbon material rich in the barium oxide.
(5) Dispersing the modified carbon material of the barium-rich oxide obtained in the step (4) into 200g of ultra-pure water, and adding 13.03g of a barium-rich oxide having a density of 1.275g/cm thereto 3 The mixture is magnetically stirred at high speed, the obtained product is transferred into an electric heating drying oven and dried for 24 hours at 80 ℃ to obtain the product rich in nanometerThe modified carbon material of barium sulfate was designated as sample C1.
The sample C1 is sintered and detected, and the result shows that the particle size distribution of the nano barium sulfate is in the range of 0.1-500 nm.
2. Preparing a lead-carbon battery cathode:
(1) Taking 100 parts by weight of lead powder, 0.2 part by weight of lignin and 12.6 parts by weight of modified carbon material rich in nano barium sulfate, pouring the materials into a container of a paste mixer, dry-mixing for 3 minutes, and fully and uniformly mixing the components to obtain a mixture;
(2) 15.5 parts by weight of deionized water is weighed, added into the mixture obtained in the step (1) rapidly under slow stirring of powder for 2 minutes, stirred for 3 minutes continuously, and then added slowly with the density of 1.4g/cm 3 8.5 parts by weight of sulfuric acid solution, the whole acid adding time is controlled within 5 minutes, and the stirring is continued for 13 minutes after the sulfuric acid solution is completely added, so that the lead-carbon battery negative electrode lead paste is obtained. The temperature in the lead plaster and the container in the process of mixing the lead plaster is not more than 65 ℃, the temperature of the lead plaster is not more than 40 ℃, and the apparent density of the lead plaster is controlled to be 3.6-4.4 g/cm 3 。
(3) And (3) scraping the lead-carbon battery negative electrode lead paste obtained in the step (2) on a negative electrode grid, rolling and acid spraying, then placing the negative electrode lead paste into a high-low temperature box with controllable humidity for solidification and drying, solidifying for 36 hours under the condition that the temperature is 45 ℃ and the relative humidity is 95%, and then drying for 9 hours at 85 ℃ to obtain the lead-carbon battery negative electrode.
3. And (3) assembling the lead-carbon battery cathode prepared in the step (2) and the lead-acid battery anode into the lead-carbon battery with the capacity of 2V5.2 Ah.
And after the assembled lead-carbon battery is formed, testing the discharge capacity at low temperature and low temperature. The discharge capacity of the lead-carbon battery reaches 4.27Ah at the temperature of minus 10 ℃.
Example 2
1. Preparing a modified carbon material rich in nano barium sulfate:
(1) Preparing a solution A: 18.144g of ethylenediamine tetraacetic acid is added into 200g of ultrapure water, 36.764g of ammonia water with the concentration of 25% -28% is added, and the solution is fully stirred until the solution becomes clear and transparent.
(2) Preparing a solution B: 16.12g of barium nitrate was taken and sufficiently dissolved in 750g of ultrapure water, followed by adding 18g of activated carbon to the solution and stirring appropriately.
(3) Pouring the solution A into the solution B, and fully stirring and mixing. Transferring the obtained mixture into an electrothermal drying oven, drying at 120 ℃ for 24 hours, and removing free water in the mixture to obtain the modified carbon material rich in EDTA-Ba complex.
(4) Transferring the modified carbon material rich in the EDTA-Ba complex obtained in the step (3) into a tube furnace, and sintering at 700 ℃ for 5 hours in a nitrogen atmosphere to obtain the modified carbon material rich in the barium oxide.
(5) Dispersing the modified carbon material of the barium-rich oxide obtained in the step (4) into 200g of ultra-pure water, and adding thereto 23.88g of a barium-rich oxide having a density of 1.275g/cm 3 The mixture was magnetically stirred at high speed, and the resulting product was transferred to an electric drying oven and dried at 120C for 24 hours to obtain a modified carbon material rich in nano barium sulfate, designated sample C1.
The sample C1 is sintered and detected, and the result shows that the particle size distribution of the nano barium sulfate is in the range of 0.1-500 nm.
2. Preparing a lead-carbon battery cathode:
(1) Taking 100 parts by weight of lead powder, 0.2 part by weight of lignin and 16.2 parts by weight of modified carbon material rich in nano barium sulfate, pouring the lead powder, the lignin and the modified carbon material into a container of a paste mixer, and dry-mixing for 5 minutes to fully and uniformly mix the components to obtain a mixture;
(2) 15.5 parts by weight of deionized water is weighed, added into the mixture obtained in the step (1) rapidly under slow stirring of powder for 3 minutes, stirred for 6 minutes continuously, and then added slowly with the density of 1.4g/cm 3 8.5 parts by weight of sulfuric acid solution, controlling the whole acid adding time within 10 minutes, and continuously stirring for 20 minutes after the sulfuric acid solution is completely added to obtain the lead-carbon battery negative electrode lead plaster. The temperature in the lead plaster and the container in the process of mixing the lead plaster is not more than 65 ℃, the temperature of the lead plaster is not more than 40 ℃, and the apparent density of the lead plaster is controlled to be 3.6-4.4 g/cm 3 。
(3) And (3) scraping the lead-carbon battery negative electrode lead paste obtained in the step (2) on a negative electrode grid, rolling and acid spraying, then placing the negative electrode lead paste into a high-low temperature box with controllable humidity for solidification and drying, solidifying for 36 hours under the condition that the temperature is 45 ℃ and the relative humidity is 95%, and then drying for 9 hours at 85 ℃ to obtain the lead-carbon battery negative electrode.
3. And (3) assembling the lead-carbon battery cathode prepared in the step (2) and the lead-acid battery anode into the lead-carbon battery with the capacity of 2V5.2 Ah.
And after the assembled lead-carbon battery is formed, testing the discharge capacity at low temperature and low temperature. The discharge capacity of the lead-carbon battery reaches 4.20Ah at the temperature of minus 10 ℃.
Example 3
1. The steps are to prepare modified carbon material rich in nano barium sulfate:
(1) Preparing a solution A: 27.216g of ethylenediamine tetraacetic acid is added into 200g of ultrapure water, 52.148g of ammonia water with the concentration of 25% -28% is added, and the solution is fully stirred until the solution becomes clear and transparent.
(2) Preparing a solution B: 24.18g of barium nitrate was taken and sufficiently dissolved in 750g of ultrapure water, followed by adding 18g of activated carbon to the solution and stirring appropriately.
(3) Pouring the solution A into the solution B, and fully stirring and mixing. Transferring the obtained mixture into an electric heating drying oven, drying at 100deg.C for 24 hr, and removing free water to obtain modified carbon material rich in EDTA-Ba complex.
(4) Transferring the modified carbon material rich in the EDTA-Ba complex obtained in the step (3) into a tube furnace, and sintering at 800 ℃ for 5 hours in a nitrogen atmosphere to obtain the modified carbon material rich in the barium oxide.
(5) Dispersing the modified carbon material of the barium-rich oxide obtained in the step (4) into 200g of ultra-pure water, and adding thereto 39.76g of a modified carbon material having a density of 1.275g/cm 3 The mixture was magnetically stirred at high speed, and the resulting product was transferred to an electric drying oven and dried at 100C for 24 hours to obtain a modified carbon material rich in nano barium sulfate, designated sample C1.
The sample C1 is sintered and detected, and the result shows that the particle size distribution of the nano barium sulfate is in the range of 0.1-500 nm.
2. Preparing a lead-carbon battery cathode:
(1) Taking 100 parts by weight of lead powder, 0.2 part by weight of lignin and 19.8 parts by weight of modified carbon material rich in nano barium sulfate, pouring the lead powder, the lignin and the modified carbon material into a container of a paste mixer, and dry-mixing for 4 minutes to fully and uniformly mix the components to obtain a mixture;
(2) 15.5 parts by weight of deionized water is weighed, added into the mixture obtained in the step (1) rapidly under slow stirring of powder for 2 minutes, stirred for 4 minutes continuously, and then added slowly with the density of 1.4g/cm 3 8.5 parts by weight of sulfuric acid solution, the whole acid adding time is controlled within 7 minutes, and stirring is continued for 15 minutes after the sulfuric acid solution is completely added, so that the lead-carbon battery negative electrode lead paste is obtained. The temperature in the lead plaster and the container in the process of mixing the lead plaster is not more than 65 ℃, the temperature of the lead plaster is not more than 40 ℃, and the apparent density of the lead plaster is controlled to be 3.6-4.4 g/cm 3 。
(3) And (3) scraping the lead-carbon battery negative electrode lead paste obtained in the step (2) on a negative electrode grid, rolling and acid spraying, then placing the negative electrode lead paste into a high-low temperature box with controllable humidity for solidification and drying, solidifying for 36 hours under the condition that the temperature is 45 ℃ and the relative humidity is 95%, and then drying for 9 hours at 85 ℃ to obtain the lead-carbon battery negative electrode.
3. And (3) assembling the lead-carbon battery cathode prepared in the step (2) and the lead-acid battery anode into the lead-carbon battery with the capacity of 2V5.2 Ah.
And after the assembled lead-carbon battery is formed, testing the discharge capacity at low temperature and low temperature. The discharge capacity of the lead-carbon battery reaches 4.35Ah at the temperature of minus 10 ℃.
Example 4
1. Preparing a modified carbon material rich in nano barium sulfate:
(1) Preparing a solution A: 36.287g of ethylenediamine tetraacetic acid is added into 200g of ultrapure water, 69.212g of ammonia water with the concentration of 25% -28% is added, and the solution is fully stirred until the solution becomes clear and transparent.
(2) Preparing a solution B: 32.24g of barium nitrate was taken and sufficiently dissolved in 750g of ultrapure water, followed by adding 18g of activated carbon to the solution and stirring appropriately.
(3) Pouring the solution A into the solution B, and fully stirring and mixing. Transferring the obtained mixture into an electrothermal drying oven, drying at 110 ℃ for 24 hours, and removing free water in the mixture to obtain the modified carbon material rich in EDTA-Ba complex.
(4) Transferring the modified carbon material rich in the EDTA-Ba complex obtained in the step (3) into a tube furnace, and sintering for 5 hours at 900 ℃ in a nitrogen atmosphere to obtain the modified carbon material rich in the barium oxide.
(5) Dispersing the modified carbon material of the barium-rich oxide obtained in the step (4) into 200g of ultra-pure water, and adding thereto 50.24g of a barium-rich oxide having a density of 1.275g/cm 3 The mixture was magnetically stirred at high speed, and the resulting product was transferred to an electric drying oven and dried at 110C for 24 hours to obtain a modified carbon material rich in nano barium sulfate, designated sample C1.
The sample C1 is sintered and detected, and the result shows that the particle size distribution of the nano barium sulfate is in the range of 0.1-500 nm.
2. Preparing a lead-carbon battery cathode:
(1) Taking 100 parts by weight of lead powder, 0.2 part by weight of lignin and 23.4 parts by weight of modified carbon material rich in nano barium sulfate, pouring the materials into a container of a paste mixer, dry-mixing for 3 minutes, and fully and uniformly mixing the components to obtain a mixture;
(2) 15.5 parts by weight of deionized water is weighed, added into the mixture obtained in the step (1) rapidly under slow stirring of powder for 3 minutes, stirred for 5 minutes continuously, and then added slowly with the density of 1.4g/cm 3 8.5 parts by weight of sulfuric acid solution, the whole acid adding time is controlled within 9 minutes, and the stirring is continued for 17 minutes after the sulfuric acid solution is completely added, so that the lead-carbon battery negative electrode lead paste is obtained. The temperature in the lead plaster and the container in the process of mixing the lead plaster is not more than 65 ℃, the temperature of the lead plaster is not more than 40 ℃, and the apparent density of the lead plaster is controlled to be 3.6-4.4 g/cm 3 ；
(3) And (3) scraping the lead-carbon battery negative electrode lead paste obtained in the step (2) on a negative electrode grid, rolling and acid spraying, then placing the negative electrode lead paste into a high-low temperature box with controllable humidity for solidification and drying, solidifying for 36 hours under the condition that the temperature is 45 ℃ and the relative humidity is 95%, and then drying for 9 hours at 85 ℃ to obtain the lead-carbon battery negative electrode.
3. And (3) assembling the lead-carbon battery cathode prepared in the step (2) and the lead-acid battery anode into the lead-carbon battery with the capacity of 2V5.2 Ah.
And after the assembled lead-carbon battery is formed, testing the discharge capacity at low temperature and low temperature. The discharge capacity of the lead-carbon battery reaches 4.22Ah at the temperature of minus 10 ℃.
Comparative example 1
1. Preparing a lead-carbon battery cathode:
(1) Taking 100 parts by weight of lead powder, 1.2 parts by weight of additive (barium sulfate and 0.2 part by weight of lignin) and 1.0 part by weight of unmodified carbon material, pouring the materials into a container of a paste mixing machine, and dry-mixing for 5 minutes to fully and uniformly mix the components to obtain a mixture;
(2) 15.5 parts by weight of deionized water is weighed, added into the mixture obtained in the step (1) rapidly under slow stirring of powder for 3 minutes, stirred for 6 minutes continuously, and then added slowly with the density of 1.4g/cm 3 8.5 parts by weight of sulfuric acid solution, controlling the whole acid adding time within 10 minutes, and continuously stirring for 20 minutes after the sulfuric acid solution is completely added to obtain the lead-carbon battery negative electrode lead plaster. The temperature in the lead plaster and the container in the process of mixing the lead plaster is not more than 65 ℃, the temperature of the lead plaster is not more than 40 ℃, and the apparent density of the lead plaster is controlled to be 3.6-4.4 g/cm 3 。
(3) And (3) directly coating the lead-carbon battery negative electrode lead paste obtained in the step (2) on a negative electrode grid, rolling and acid spraying, then placing the lead-carbon battery negative electrode lead paste into a high-low temperature box with controllable humidity for solidification and drying, solidifying for 36 hours under the condition that the temperature is 45 ℃ and the relative humidity is 95%, and then drying for 9 hours at 85 ℃ to obtain the lead-carbon battery negative electrode.
2. And (3) assembling the lead-carbon battery cathode prepared in the step (1) and the lead-acid battery anode into the lead-carbon battery with the capacity of 2V5.2 Ah.
And after the assembled lead-carbon battery is formed, testing the discharge capacity at low temperature and low temperature. In comparative example 2, a conventional carbon material is doped in the lead-carbon battery, nano barium sulfate is not loaded on the surface of the carbon material, and the discharge capacity of the lead-carbon battery is only 3.96Ah at the temperature of minus 10 ℃; in example 2, the discharge capacity of the lead-carbon battery doped with the modified carbon material supporting nano barium sulfate was 4.22 under the same conditions. .
Comparative example 2
1. Preparing a lead-acid battery cathode:
(1) Taking 100 parts by weight of lead powder, 1.2 parts by weight of additive (barium sulfate and 0.2 part by weight of lignin) and 0.2 part by weight of acetylene black, pouring the mixture into a paste mixing machine container, and dry-mixing the mixture for 5 minutes to fully and uniformly mix the components to obtain a mixture;
(2) 15.5 parts by weight of deionized water is weighed, added into the mixture obtained in the step (1) rapidly under slow stirring of powder for 3 minutes, stirred for 6 minutes continuously, and then added slowly with the density of 1.4g/cm 3 8.5 parts by weight of sulfuric acid solution, the whole acid adding time is controlled within 10 minutes, and stirring is continued for 20 minutes after the sulfuric acid solution is completely added, so that the lead-acid battery negative electrode lead paste is obtained. The temperature in the lead plaster and the container in the process of mixing the lead plaster is not more than 65 ℃, the temperature of the lead plaster is not more than 40 ℃, and the apparent density of the lead plaster is controlled to be 3.6-4.4 g/cm 3 。
(3) And (3) directly coating the lead-acid battery negative electrode lead paste obtained in the step (2) on a negative electrode grid, rolling and acid spraying, then placing the lead-acid battery negative electrode lead paste into a high-low temperature box with controllable humidity for solidification and drying, solidifying for 36 hours under the condition that the temperature is 45 ℃ and the relative humidity is 95%, and then drying for 9 hours at 85 ℃ to obtain the lead-acid battery negative electrode.
2. And (3) assembling the lead-acid battery with the cathode and the anode of the lead-acid battery prepared in the step (1) to obtain the lead-acid battery with the capacity of 2V5.2 Ah.
After the assembled lead-acid battery is completed, a low-temperature and low-temperature discharge capacity test is performed. In comparison with example 2, the lead-acid battery had a discharge capacity of 4.11Ah at-10 ℃, while in example 2, the lead-acid battery doped with the modified carbon material loaded with nano barium sulfate had a discharge capacity of 4.22 under the same conditions.
Comparative example 3
1. Preparing a modified carbon material rich in nano calcium sulfate:
(1) Preparing a solution A: 36.287g of ethylenediamine tetraacetic acid is added into 200g of ultrapure water, 69.212g of ammonia water with the concentration of 25% -28% is added, and the solution is fully stirred until the solution becomes clear and transparent.
(2) Preparing a solution B: 32.24g of calcium nitrate was taken and sufficiently dissolved in 750g of ultrapure water, followed by adding 18g of activated carbon to the solution and stirring appropriately.
(3) Pouring the solution A into the solution B, and fully stirring and mixing. Transferring the obtained mixture into an electric heating drying oven, drying at 110 ℃ for 24 hours, and removing free water in the mixture to obtain the modified carbon material rich in EDTA-Ca complex.
(4) Transferring the modified carbon material rich in the EDTA-Ca complex obtained in the step (3) into a tube furnace, and sintering for 5 hours at 900 ℃ in a nitrogen atmosphere to obtain the modified carbon material rich in calcium oxide.
(5) Dispersing the modified carbon material of the calcium-enriched oxide obtained in the step (4) into 200g of ultrapure water, and adding thereto 50.24g of a calcium-enriched oxide having a density of 1.275g/cm 3 The mixture is magnetically stirred at high speed, the obtained product is transferred into an electric heating drying oven, and dried for 24 hours at 110 ℃ to obtain the modified carbon material rich in nano calcium sulfate.
2. Preparing a lead-carbon battery cathode:
(1) Taking 100 parts by weight of lead powder, 0.2 part by weight of lignin and 23.4 parts by weight of modified carbon material rich in nano calcium sulfate, pouring the lead powder, the lignin and the modified carbon material into a container of a paste mixer, and dry-mixing for 3 minutes to fully and uniformly mix the components to obtain a mixture;
(2) 15.5 parts by weight of deionized water is weighed, added into the mixture obtained in the step (1) rapidly under slow stirring of powder for 3 minutes, stirred for 5 minutes continuously, and then added slowly with the density of 1.4g/cm 3 8.5 parts by weight of sulfuric acid solution, the whole acid adding time is controlled within 9 minutes, and the stirring is continued for 17 minutes after the sulfuric acid solution is completely added, so that the lead-carbon battery negative electrode lead paste is obtained. The temperature in the lead plaster and the container in the process of mixing the lead plaster is not more than 65 ℃, the temperature of the lead plaster is not more than 40 ℃, and the apparent density of the lead plaster is controlled to be 3.6-4.4 g/cm 3 ；
(3) And (3) scraping the lead-carbon battery negative electrode lead paste obtained in the step (2) on a negative electrode grid, rolling and acid spraying, then placing the negative electrode lead paste into a high-low temperature box with controllable humidity for solidification and drying, solidifying for 36 hours under the condition that the temperature is 45 ℃ and the relative humidity is 95%, and then drying for 9 hours at 85 ℃ to obtain the lead-carbon battery negative electrode.
3. And (3) assembling the lead-carbon battery cathode prepared in the step (2) and the lead-acid battery anode into the lead-carbon battery with the capacity of 2V5.2 Ah.
And after the assembled lead-carbon battery is formed, testing the discharge capacity at low temperature and low temperature. Compared with example 4, the discharge capacity of the lead-carbon battery doped with the modified carbon material loaded with nano-calcium sulfate in the comparative example is 3.77Ah at the temperature of minus 10 ℃, while the discharge capacity of the lead-carbon battery doped with the modified carbon material loaded with nano-barium sulfate in example 4 is 4.22Ah under the same condition.
Comparative example 4
1. Preparing a modified carbon material rich in barium sulfate:
(1) Preparing a solution A: 18.144g of ethylenediamine tetraacetic acid is added into 200g of ultrapure water, 36.764g of ammonia water with the concentration of 25% -28% is added, and the solution is fully stirred until the solution becomes clear and transparent.
(2) Preparing a solution B: 16.12g of barium nitrate was taken and sufficiently dissolved in 750g of ultrapure water, followed by adding 18g of activated carbon to the solution and stirring appropriately.
(3) Pouring the solution A into the solution B, and fully stirring and mixing. Transferring the obtained mixture into an electric heating drying oven, drying at 80-120 ℃ for 24 hours, and removing free water in the mixture to obtain the modified carbon material rich in EDTA-Ba complex.
(4) Transferring the modified carbon material rich in the EDTA-Ba complex obtained in the step (3) into a tube furnace, and sintering at 700 ℃ for 5 hours in a nitrogen atmosphere to obtain the modified carbon material rich in the barium oxide.
(5) Dispersing the modified carbon material of the barium-rich oxide obtained in the step (4) into 200g of ultra-pure water, and adding thereto 8.06g of a barium-rich oxide having a density of 1.275g/cm 3 The mixture is magnetically stirred at high speed, the obtained product is transferred into an electric heating drying box and dried for 24 hours at 80-120 ℃ to obtain a modified carbon material rich in nano barium sulfate, which is marked as a sample C1.
The sample C1 is sintered and detected, and the result shows that the particle size distribution of the nano barium sulfate is in the range of 0.1-500 nm.
2. Preparing a lead-carbon battery cathode:
(1) Taking 100 parts by weight of lead powder, 0.2 part by weight of lignin and 16.2 parts by weight of modified carbon material rich in nano barium sulfate, pouring the lead powder, the lignin and the modified carbon material into a container of a paste mixer, and dry-mixing for 5 minutes to fully and uniformly mix the components to obtain a mixture;
(2) 15.5 parts by weight of deionized water is weighed, added into the mixture obtained in the step (1) rapidly under slow stirring of powder for 3 minutes, stirred for 6 minutes continuously, and then added slowly with the density of 1.4g/cm 3 8.5 parts by weight of sulfuric acid solution, controlling the whole acid adding time within 10 minutes, and continuously stirring for 20 minutes after the sulfuric acid solution is completely added to obtain the lead-carbon battery negative electrode lead plaster. The temperature in the lead plaster and the container in the process of mixing the lead plaster is not more than 65 ℃, the temperature of the lead plaster is not more than 40 ℃, and the apparent density of the lead plaster is controlled to be 3.6-4.4 g/cm 3 。
(3) And (3) scraping the lead-carbon battery negative electrode lead paste obtained in the step (2) on a negative electrode grid, rolling and acid spraying, then placing the negative electrode lead paste into a high-low temperature box with controllable humidity for solidification and drying, solidifying for 36 hours under the condition that the temperature is 45 ℃ and the relative humidity is 95%, and then drying for 9 hours at 85 ℃ to obtain the lead-carbon battery negative electrode.
3. And (3) assembling the lead-carbon battery cathode prepared in the step (2) and the lead-acid battery anode into the lead-carbon battery with the capacity of 2V5.2 Ah.
And after the assembled lead-carbon battery is formed, testing the discharge capacity at low temperature and low temperature. In comparative example 2, after the addition amount of sulfuric acid is reduced (the use amount of sulfuric acid solution is less than 30% of the total mass of barium nitrate and active carbon), nano barium sulfate loaded on the surface of a carbon material is reduced, and the discharge capacity of the lead-carbon battery is 3.86Ah at the temperature of minus 10 ℃; under the same conditions, in example 2, the discharge capacity of the lead-carbon battery doped with the modified carbon material loaded with nano barium sulfate was 4.22Ah.
The discharge capacities of the batteries in the examples of the present invention and the comparative examples at-10 ℃ are shown below:
as can be seen from the table above, compared with the common lead-carbon battery, the lead-carbon battery provided by the invention has obviously improved discharge capacity at-10 ℃ and is higher than the discharge capacity of the common lead-acid battery. Therefore, the modified carbon material rich in nano barium sulfate is doped into the negative electrode, so that the discharge capacity of the negative electrode of the lead-carbon battery at low temperature is improved, and the application field of the lead-carbon battery is expanded. The invention verifies the addition of nano barium sulfate by changing the doping raw materials and the dosage, and can increase the crystallization site of lead sulfate, thereby improving the discharge capacity of the battery, but other raw materials cannot realize the technical effects. In addition, the addition of nano barium sulfate determines the increase of lead sulfate crystallization sites in the battery, thereby directly affecting the discharge capacity of the battery.
The foregoing description is only a few examples of the present application and is not intended to limit the present application in any way, and although the present application is disclosed in the preferred examples, it is not intended to limit the present application, and any person skilled in the art may make some changes or modifications to the disclosed technology without departing from the scope of the technical solution of the present application, and the technical solution is equivalent to the equivalent embodiments.
Claims (8)
1. A preparation method of a carbon material is characterized in that,
the carbon material comprises a carbon-based material, and nano barium sulfate is loaded on the surface of the carbon-based material;
the method at least comprises the following steps:
complexing the barium salt with a complexing agent to obtain a barium salt complex;
modifying the carbon-based material by adopting the barium salt complex to obtain a carbon material rich in nano barium sulfate;
the modification of the carbon-based material with the barium salt complex at least comprises:
adding the carbon-based material into the barium salt complex for impregnation to obtain a modified carbon material rich in the barium salt complex;
sintering the modified carbon material rich in the barium salt complex to obtain a modified carbon material rich in barium oxide;
and (3) reacting the modified carbon material rich in the barium oxide with sulfuric acid solution to obtain the modified carbon material rich in nano barium sulfate.
2. The method according to claim 1, wherein,
the content of the nano barium sulfate is 0.1-99% of the total mass of the carbon material.
3. The method according to claim 1, wherein,
the dosage of the barium salt accounts for 1-65% of the total mass of the barium salt and the carbon-based material;
the barium salt is water-soluble barium salt;
the complexing agent is an aminopolycarboxylic acid chelating agent.
4. The method according to claim 1, wherein,
the process for obtaining the modified carbon material rich in the barium salt complex and the modified carbon material rich in nano barium sulfate at least comprises the following steps:
drying the modified carbon material rich in the barium salt complex and the modified carbon material rich in nano barium sulfate;
the drying temperature is 80-120 ℃.
5. The method according to claim 1, wherein,
the sintering is specifically as follows:
and sintering the modified carbon material rich in the barium salt complex for 1-5 h at 600-900 ℃ under the protection of atmosphere.
6. The method according to claim 1, wherein,
the density of the sulfuric acid solution is 1.05-1.5 g/cm 3 ；
The mass of sulfuric acid in the sulfuric acid solution is 11% -37% of the total mass of the barium salt and the carbon-based material.
7. A low-temperature lead-carbon battery negative electrode lead plaster is characterized in that,
at least one of the carbon materials prepared by the method according to any one of claims 1-6;
the negative electrode lead plaster comprises the following components: 100 parts of lead powder, 0.1-10 parts of additive, 0.01-100 parts of carbon material for the low-temperature lead-carbon battery, 10-21 parts of deionized water and 4-100 parts of sulfuric acid solution.
8. A low-temperature lead-carbon battery is characterized in that,
the battery negative electrode is coated with the negative electrode lead paste of claim 7.
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