CN118016837A - Low-hydrogen-evolution composite carbon material and preparation method thereof, lead-acid battery cathode and lead-acid battery - Google Patents
Low-hydrogen-evolution composite carbon material and preparation method thereof, lead-acid battery cathode and lead-acid battery Download PDFInfo
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- CN118016837A CN118016837A CN202410100082.0A CN202410100082A CN118016837A CN 118016837 A CN118016837 A CN 118016837A CN 202410100082 A CN202410100082 A CN 202410100082A CN 118016837 A CN118016837 A CN 118016837A
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- 239000002131 composite material Substances 0.000 title claims abstract description 49
- 239000003575 carbonaceous material Substances 0.000 title claims abstract description 43
- 239000002253 acid Substances 0.000 title claims abstract description 22
- 238000002360 preparation method Methods 0.000 title claims abstract description 15
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims abstract description 44
- 239000007788 liquid Substances 0.000 claims abstract description 37
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 36
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims abstract description 32
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 31
- 239000001257 hydrogen Substances 0.000 claims abstract description 31
- 229910052799 carbon Inorganic materials 0.000 claims abstract description 29
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 26
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims abstract description 25
- 159000000009 barium salts Chemical class 0.000 claims abstract description 22
- 229910052757 nitrogen Inorganic materials 0.000 claims abstract description 16
- 238000005245 sintering Methods 0.000 claims abstract description 16
- 239000004964 aerogel Substances 0.000 claims abstract description 13
- 239000006185 dispersion Substances 0.000 claims abstract description 13
- 230000008014 freezing Effects 0.000 claims abstract description 11
- 238000007710 freezing Methods 0.000 claims abstract description 11
- 239000002904 solvent Substances 0.000 claims abstract description 9
- 239000013078 crystal Substances 0.000 claims abstract description 8
- 238000004108 freeze drying Methods 0.000 claims abstract description 8
- 239000000725 suspension Substances 0.000 claims abstract description 8
- 238000001035 drying Methods 0.000 claims abstract description 7
- 238000005406 washing Methods 0.000 claims abstract description 6
- IWOUKMZUPDVPGQ-UHFFFAOYSA-N barium nitrate Chemical compound [Ba+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O IWOUKMZUPDVPGQ-UHFFFAOYSA-N 0.000 claims description 18
- 238000000034 method Methods 0.000 claims description 10
- 238000003756 stirring Methods 0.000 claims description 10
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 9
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 9
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 9
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 9
- 239000000654 additive Substances 0.000 claims description 9
- 239000003960 organic solvent Substances 0.000 claims description 8
- 230000000996 additive effect Effects 0.000 claims description 6
- AYJRCSIUFZENHW-UHFFFAOYSA-L barium carbonate Chemical compound [Ba+2].[O-]C([O-])=O AYJRCSIUFZENHW-UHFFFAOYSA-L 0.000 claims description 6
- 229920002472 Starch Polymers 0.000 claims description 4
- ITHZDDVSAWDQPZ-UHFFFAOYSA-L barium acetate Chemical compound [Ba+2].CC([O-])=O.CC([O-])=O ITHZDDVSAWDQPZ-UHFFFAOYSA-L 0.000 claims description 4
- 229920002678 cellulose Polymers 0.000 claims description 4
- 239000001913 cellulose Substances 0.000 claims description 4
- 238000006243 chemical reaction Methods 0.000 claims description 4
- 238000004519 manufacturing process Methods 0.000 claims description 4
- 239000012046 mixed solvent Substances 0.000 claims description 4
- 239000008107 starch Substances 0.000 claims description 4
- 235000019698 starch Nutrition 0.000 claims description 4
- ISFLYIRWQDJPDR-UHFFFAOYSA-L barium chlorate Chemical compound [Ba+2].[O-]Cl(=O)=O.[O-]Cl(=O)=O ISFLYIRWQDJPDR-UHFFFAOYSA-L 0.000 claims description 3
- 238000000926 separation method Methods 0.000 claims description 3
- TZCXTZWJZNENPQ-UHFFFAOYSA-L barium sulfate Chemical compound [Ba+2].[O-]S([O-])(=O)=O TZCXTZWJZNENPQ-UHFFFAOYSA-L 0.000 abstract description 26
- 239000000463 material Substances 0.000 abstract description 11
- 239000011148 porous material Substances 0.000 abstract description 7
- WABPQHHGFIMREM-UHFFFAOYSA-N lead(0) Chemical compound [Pb] WABPQHHGFIMREM-UHFFFAOYSA-N 0.000 description 29
- 230000000052 comparative effect Effects 0.000 description 23
- 230000015572 biosynthetic process Effects 0.000 description 7
- 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 6
- 239000006230 acetylene black Substances 0.000 description 6
- QVQLCTNNEUAWMS-UHFFFAOYSA-N barium oxide Chemical compound [Ba]=O QVQLCTNNEUAWMS-UHFFFAOYSA-N 0.000 description 6
- 239000012153 distilled water Substances 0.000 description 6
- 239000000835 fiber Substances 0.000 description 6
- 239000004021 humic acid Substances 0.000 description 6
- 239000004615 ingredient Substances 0.000 description 6
- 229920005610 lignin Polymers 0.000 description 6
- 239000011505 plaster Substances 0.000 description 6
- 238000012360 testing method Methods 0.000 description 6
- 239000008367 deionised water Substances 0.000 description 4
- 229910021641 deionized water Inorganic materials 0.000 description 4
- 239000003792 electrolyte Substances 0.000 description 4
- 238000002156 mixing Methods 0.000 description 4
- 230000008569 process Effects 0.000 description 4
- 239000002994 raw material Substances 0.000 description 4
- 238000001878 scanning electron micrograph Methods 0.000 description 4
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- 239000011248 coating agent Substances 0.000 description 3
- 238000000576 coating method Methods 0.000 description 3
- 238000011065 in-situ storage Methods 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- 230000009467 reduction Effects 0.000 description 3
- 230000019635 sulfation Effects 0.000 description 3
- 238000005670 sulfation reaction Methods 0.000 description 3
- 238000001291 vacuum drying Methods 0.000 description 3
- UDVDGNKGDSYMAO-UHFFFAOYSA-H S(=O)(=O)([O-])[O-].[Ba+2].[C+4].S(=O)(=O)([O-])[O-].S(=O)(=O)([O-])[O-] Chemical compound S(=O)(=O)([O-])[O-].[Ba+2].[C+4].S(=O)(=O)([O-])[O-].S(=O)(=O)([O-])[O-] UDVDGNKGDSYMAO-UHFFFAOYSA-H 0.000 description 2
- DBERGLNNXHLATL-UHFFFAOYSA-N [Ba].[C] Chemical compound [Ba].[C] DBERGLNNXHLATL-UHFFFAOYSA-N 0.000 description 2
- 238000010306 acid treatment Methods 0.000 description 2
- 239000013543 active substance Substances 0.000 description 2
- 229910052788 barium Inorganic materials 0.000 description 2
- DSAJWYNOEDNPEQ-UHFFFAOYSA-N barium atom Chemical compound [Ba] DSAJWYNOEDNPEQ-UHFFFAOYSA-N 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 238000004140 cleaning Methods 0.000 description 2
- 238000004146 energy storage Methods 0.000 description 2
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- 238000003837 high-temperature calcination Methods 0.000 description 2
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- 239000011159 matrix material Substances 0.000 description 2
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- 238000012986 modification Methods 0.000 description 2
- 230000003647 oxidation Effects 0.000 description 2
- 238000007254 oxidation reaction Methods 0.000 description 2
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 2
- 229910021642 ultra pure water Inorganic materials 0.000 description 2
- 239000012498 ultrapure water Substances 0.000 description 2
- 229910001369 Brass Inorganic materials 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 239000011149 active material Substances 0.000 description 1
- 230000006978 adaptation Effects 0.000 description 1
- 238000004220 aggregation Methods 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- 239000000956 alloy Substances 0.000 description 1
- 229910045601 alloy Inorganic materials 0.000 description 1
- 239000006183 anode active material Substances 0.000 description 1
- 239000010951 brass Substances 0.000 description 1
- 238000003763 carbonization Methods 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- 230000008025 crystallization Effects 0.000 description 1
- 230000001351 cycling effect Effects 0.000 description 1
- 230000003111 delayed effect Effects 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 239000003365 glass fiber Substances 0.000 description 1
- PIJPYDMVFNTHIP-UHFFFAOYSA-L lead sulfate Chemical compound [PbH4+2].[O-]S([O-])(=O)=O PIJPYDMVFNTHIP-UHFFFAOYSA-L 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
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- 238000010899 nucleation Methods 0.000 description 1
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- 239000002245 particle Substances 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- OTYBMLCTZGSZBG-UHFFFAOYSA-L potassium sulfate Chemical compound [K+].[K+].[O-]S([O-])(=O)=O OTYBMLCTZGSZBG-UHFFFAOYSA-L 0.000 description 1
- 229910052939 potassium sulfate Inorganic materials 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 238000007789 sealing Methods 0.000 description 1
- 238000007086 side reaction Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
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- 238000001075 voltammogram Methods 0.000 description 1
Landscapes
- Battery Electrode And Active Subsutance (AREA)
Abstract
The invention provides a preparation method of a low hydrogen evolution composite carbon material, which comprises the following steps: dispersing a carbon source and barium salt in a solvent to obtain a dispersion; transferring the dispersion liquid into an environment containing liquid nitrogen, and freezing to enable ice crystals in the suspension liquid to vertically grow from bottom to top, so as to obtain a unidirectionally oriented gel skeleton; freeze-drying the unidirectional gel skeleton to obtain aerogel; sintering aerogel in inert atmosphere to obtain an intermediate; dispersing the intermediate into water, reacting with sulfuric acid solution, washing, solid-liquid separating and drying to obtain the low hydrogen evolution composite carbon material BaSO 4 @C. The preparation method can obtain the three-dimensional conductive lead composite material with high porosity and high active surface area, and the barium sulfate is uniformly distributed on the surface and inside the pores of the three-dimensional porous carbon, and the material is applied to the negative electrode of the lead-acid battery, can well improve the hydrogen evolution phenomenon of the negative electrode of the lead-acid battery, maintains higher electrochemical active surface area, and remarkably improves the specific capacity and the rapid charge and discharge performance of the battery.
Description
Technical Field
The invention belongs to the technical field of lead-acid batteries, and particularly relates to modification of a negative electrode of a lead-acid battery.
Background
Lead acid batteries are well established in automotive and industrial applications and have been successfully used in a variety of energy storage applications, such as uninterruptible power supplies, telecommunications and solar photovoltaic applications. Lead acid batteries are a good rechargeable energy storage solution due to their low cost, safety, wide availability, manufacturing basis and significant recovery efficiency. Lead-acid batteries are operated under partial charge state cycling conditions in many situations, but in practical applications, it is generally required that the battery can be operated under high-rate partial charge states, the operation conditions can accelerate sulfation of the anode, cause a large amount of anode active substances to aggregate, and thus lead to failure of the anode active substances, and meanwhile, high-rate discharge can accelerate hydrogen evolution reaction of the anode, resulting in side reactions of electrolyte.
The carbon-containing material is added into the anode active material to improve the conductivity of the active material and increase the electrochemical active surface area, so that the formation of irreversible lead sulfate is effectively delayed, but the carbon material has certain reduction performance, and after being added into the anode, the carbon material can cause the reduction of hydrogen evolution overpotential of the anode, so that the hydrogen evolution rate is accelerated.
Disclosure of Invention
Aiming at the technical problems, the invention aims to provide a low-hydrogen-evolution composite carbon material, a preparation method thereof, a lead-acid battery cathode and a lead-acid battery.
To achieve the above object, the present invention proposes the following solution:
The invention provides a preparation method of a low-hydrogen evolution composite carbon material, which comprises the following steps:
(1) Dispersing a carbon source and barium salt in a solvent to obtain a dispersion;
(2) Transferring the dispersion liquid into an environment containing liquid nitrogen, and freezing to enable ice crystals in the suspension liquid to vertically grow from bottom to top, so as to obtain a unidirectionally oriented gel skeleton;
(3) Freeze-drying the unidirectional gel skeleton to obtain aerogel; sintering the aerogel in an inert atmosphere to obtain an intermediate;
(4) Dispersing the intermediate into water, reacting with sulfuric acid solution, washing the obtained product, performing solid-liquid separation and drying to obtain the low-hydrogen evolution composite carbon material BaSO 4 @C.
Preferably, in the step (1), the mass ratio of the barium salt to the carbon source is 1.5-3:1.
Preferably, in step (1), the carbon source is starch and/or cellulose.
Preferably, in step (1), the barium salt is a cleavable barium salt; the barium salt is one or more than two of barium chlorate, barium nitrate, barium acetate and barium carbonate.
Preferably, in the step (1), the solvent is water or a mixed solvent of water and an organic solvent; the organic solvent is one or more of methanol, ethanol, acetic acid and acetone.
Preferably, in the step (3), the sintering temperature is 450-550 ℃; the sintering time is 3-6 hours.
Preferably, step (2) includes: transferring the container filled with the dispersion liquid into a mould filled with liquid nitrogen, wherein a heat conducting sheet or a heat conducting table extending out of the liquid nitrogen liquid level is arranged in the mould, and the container is placed on the heat conducting sheet or the heat conducting table for freezing.
Preferably, in step (4), the reaction is carried out with stirring; further preferably, the stirring speed is 800 to 1200rpm.
Preferably, in the step (4), the density of the sulfuric acid solution is 1.3-1.5 g/mL.
The invention also provides a low-hydrogen evolution composite carbon material which is prepared by adopting the preparation method.
The invention also provides a lead-acid battery anode, which comprises an anode additive, wherein the anode additive adopts the low-hydrogen evolution composite carbon material.
The invention also provides a lead-acid battery comprising the negative electrode.
Compared with the prior art, the invention has the following beneficial effects:
The invention adopts a dispersing-freezing-freeze drying process to disperse and form a uniform mixing and distributing state of a carbon source and barium salt, then utilizes freezing to realize the stop motion of the two substance dispersing states, removes a solvent through freeze drying to prepare aerogel with the carbon source and the barium salt uniformly dispersed, then sinters under a non-oxidizing atmosphere to obtain a composite carbon material with the barium oxide uniformly loaded on the surface and the pores of the three-dimensional porous carbon, and then reacts the composite carbon material with sulfuric acid solution to obtain the composite carbon material with the barium sulfate uniformly loaded on the surface and the pores of the three-dimensional porous carbon. The preparation method can obtain the three-dimensional conductive lead composite material with high porosity and high active surface area, the material is applied to the negative electrode of the lead-acid battery, the hydrogen evolution phenomenon of the negative electrode of the lead-acid battery can be well improved, the composite carbon material can disperse PbSO 4 particles in the electrochemical circulation process, the irreversible crystallization of the lead-acid negative electrode can be reduced in the electrochemical circulation process so as to avoid causing great reduction of the active surface area, the higher electrochemical active surface area is maintained, and further the longer cycle life is provided. The adjustable porous structure of carbon can provide active sites for nucleation of lead, provide a framework for growth of lead branches, remarkably improve specific capacity and rapid charge and discharge performance of the battery, and greatly improve cycle stability of the battery and cycle life under high-rate partial charge state.
Drawings
In order to more clearly illustrate the embodiments of the present invention or the technical solutions in the prior art, the drawings that are required in the embodiments or the description of the prior art will be briefly described, and it is obvious that the drawings in the following description are some embodiments of the present invention, and other drawings may be obtained according to these drawings without inventive effort for a person skilled in the art.
FIG. 1 is an SEM image of a BaSO 4 @ C composite material prepared in example 1.
FIG. 2 is an SEM image of a BaSO 4 @ C composite made in example 3.
Fig. 3 is a graph showing the hydrogen evolution rate of the negative electrode obtained in example 4, comparative example 4 and comparative example 5.
Fig. 4 is a schematic HRPSoC cycle diagram of the negative electrode assembled batteries obtained in example 4, comparative example 4 and comparative example 5 at a magnification of 1C.
Detailed Description
A preparation method of a low hydrogen evolution carbon material comprises the following steps:
(1) Dispersing a carbon source and barium salt in a solvent to obtain a dispersion liquid;
(2) Transferring the dispersion liquid into an environment containing liquid nitrogen, and freezing to enable ice crystals in the suspension liquid to vertically grow from bottom to top, so as to obtain a unidirectionally oriented gel skeleton;
(3) Freeze-drying the unidirectional gel skeleton to obtain aerogel; sintering the aerogel in an inert atmosphere to obtain an intermediate;
(4) Dispersing the intermediate into water, reacting with sulfuric acid solution, washing the obtained product, performing solid-liquid separation and drying to obtain the low hydrogen evolution carbon material BaSO 4 @C.
According to the invention, the single-orientation gel skeleton uniformly dispersed with barium salt is prepared by a freezing method, and then carbonization and sulfation are carried out to obtain the in-situ prepared BaSO 4 @C composite material, the composite material obtained by the method can effectively improve the dispersibility of BaSO 4 in a three-dimensional porous carbon material, improve active sites, avoid the aggregation of barium sulfate, and enable the carbon skeleton to grow orderly, so that the carbon skeleton with more excellent structure and pore structure is obtained, and the performance is improved; and the pore structure of the carbon material in the structure increases the active surface area of the carbon material, thereby being beneficial to constructing a three-dimensional conductive network structure by the composite material.
The preparation method can form a three-dimensional porous carbon matrix rich in pore structures in situ, has high specific active surface area, provides a framework and more active sites for the growth load of lead, and the barium sulfate is uniformly loaded on the surface and in pores of the three-dimensional porous carbon matrix through in-situ growth, so that the barium sulfate has strong binding force with carbon, and can be combined with carbon to form a firm lead-carbon conductive network.
In some preferred embodiments, in the step (1), the mass ratio of the barium salt to the carbon source is 1.5-3:1, for example, 1.5:1, 1.8:1, 2.0:1, 2.2:1, 2.5:1, 2.8:1, 3:1, etc.
In a part of preferred embodiments, in step (1), the carbon source is starch and/or cellulose.
In a partially preferred embodiment, in step (1), the barium salt is a cleavable barium salt; the barium salt is one or more than two of barium chlorate, barium nitrate, barium acetate and barium carbonate.
In a part of preferred embodiments, in the step (1), the solvent is water or a mixed solvent of water and an organic solvent. The organic solvent is one or two of methanol, ethanol, acetic acid and acetone. When the solvent is a mixed solvent of water and an organic solvent, the volume ratio of the water to the organic solvent in the mixture is 7-9:1.
In some embodiments, in step (1), the dispersing may be performed in a conventional manner, for example, under the action of mechanical force such as stirring and/or ultrasound.
In a partially preferred embodiment, in the step (3), the sintering temperature is 450 to 550 ℃, such as 450 ℃, 480 ℃, 500 ℃, 520 ℃, 550 ℃; the sintering time is 3-6 h, such as 3h, 3.5h, 4h, 4.5h, 5h, 5.5h, 6h and the like.
In a partially preferred embodiment, step (2) comprises: transferring the container filled with the dispersion liquid into a mould filled with liquid nitrogen, wherein a heat conducting sheet or a heat conducting table extending out of the liquid nitrogen liquid level is arranged in the mould, and the container is placed on the heat conducting sheet or the heat conducting table for freezing.
In a partially preferred embodiment, in step (4), the reaction is carried out with stirring. Further preferably, the stirring speed is 800 to 1200rpm, for example, 800rpm, 850rpm, 900rpm, 950rpm, 1000rpm, 1050rpm, 1100rpm, 1150rpm, 1200rpm, etc.
In some preferred embodiments, in the step (4), the density of the sulfuric acid solution is 1.3-1.5 g/mL.
In a part of preferred embodiments, in step (4), the drying is vacuum drying.
In some preferred embodiments, the heat conducting fin or the heat conducting platform is made of a heat conducting metal, such as copper or brass alloy.
Some specific embodiments provide a low hydrogen evolution carbon material, which is prepared by the preparation method.
Some embodiments also provide a lead-acid battery negative electrode, comprising a negative electrode additive, wherein the negative electrode additive adopts the low hydrogen evolution carbon material.
Some embodiments also provide a lead-acid battery comprising the foregoing negative electrode.
The invention will be described more fully hereinafter with reference to the accompanying drawings and preferred embodiments in order to facilitate an understanding of the invention, but the scope of the invention is not limited to the following specific embodiments.
Unless defined otherwise, all technical and scientific terms used hereinafter have the same meaning as commonly understood by one of ordinary skill in the art. The terminology used herein is for the purpose of describing particular embodiments only and is not intended to be limiting of the scope of the present invention.
Unless otherwise specifically indicated, the various raw materials, reagents, instruments, equipment and the like used in the present invention are commercially available or may be prepared by existing methods.
Example 1
The preparation method of the BaSO 4 @C composite material comprises the following steps:
step one: 1g of cellulose, 2g of barium nitrate and 80 mL parts of deionized water are dispersed and stirred uniformly.
Step two: preparing a unidirectionally oriented gel skeleton: placing a container filled with suspension into a mould filled with liquid nitrogen, transferring the container filled with the dispersion into the mould filled with liquid nitrogen, wherein a heat conduction table extending out of the liquid nitrogen liquid level is arranged in the mould, and the container is placed on the heat conduction table to promote the ice crystals in the suspension to vertically grow from bottom to top.
Step three: and (5) freeze-drying after the freezing is finished to obtain the aerogel.
Step four: sintering the aerogel at 500 ℃ under an inert atmosphere for 4.5 h to obtain the barium-rich oxide barium carbon material.
Step five: dispersing the carbon material rich in the barium oxide obtained in the step four into 200g of ultrapure water, adding a sulfuric acid solution with the density of 1.4 g/cm 3 into the carbon material, magnetically stirring the mixture at a high speed under the condition of 1200 and rpm, washing and suction-filtering the obtained product, transferring the obtained solid into a vacuum drying box, and drying the solid at 80 ℃ for 24 hours to obtain the barium sulfate carbon composite material with low hydrogen evolution.
An SEM image of the BaSO 4 @c composite material prepared in example 1 is shown in fig. 1, and it can be seen from the image that barium sulfate crystals are uniformly dispersed on a carbon three-dimensional porous structure in the composite material obtained by high-temperature calcination and sulfuric acid treatment of a carbon source and barium salt.
Comparative example 1
Comparative example 1 differs from example 1 in that the addition of barium nitrate was omitted in step one, and the single, unsupported, three-dimensional porous structure carbon material was obtained in step four.
Example 2
(1) The raw material BaSO 4 @C composite material in this example was the BaSO 4 @C composite material prepared in example 1.
(2) The ingredients required by the negative electrode lead plaster are carried out and proportioned according to a conventional formula, wherein the required ingredients are as follows: 80% of lead powder, 1.41 g/mL of sulfuric acid solution, barium sulfate, lignin, humic acid, short fibers, distilled water, acetylene black and BaSO 4 @C material, wherein the mass of the sulfuric acid solution is 6% of the mass of the lead powder; the mass of the barium sulfate is 1% of the mass of the lead powder; the lignin mass is 0.8% of the lead powder mass; the mass of humic acid is 0.5% of the mass of lead powder; the mass of the short fiber is 0.02% of the mass of the lead powder; the mass of distilled water is 8% of the mass of lead powder; the mass of the acetylene black is 2% of the mass of the lead powder; the mass of the BaSO 4 @ C material is 1% of the mass of the lead powder.
(3) Mixing lead powder and additives to obtain the lead paste with apparent density of 4.1 g/cm 3.
(4) And coating the prepared negative electrode lead plaster on a negative electrode grid, and carrying out conventional curing and formation to obtain a negative electrode plate.
Comparative example 2
Comparative example 2 differs from example 2 in that the single unsupported three-dimensional porous structure carbon material prepared in comparative example 1 was used in comparative example 2 instead of the BaSO 4 @c composite material in example 2.
Example 3
The preparation method of the BaSO 4 @C composite material comprises the following steps:
step one: 1g of starch, 2g of barium nitrate and 80 mL parts of deionized water are dispersed and stirred uniformly.
Step two: preparing a unidirectionally oriented gel skeleton: placing a container filled with suspension into a mould filled with liquid nitrogen, transferring the container filled with the dispersion into the mould filled with liquid nitrogen, wherein a heat conduction table extending out of the liquid nitrogen liquid level is arranged in the mould, and the container is placed on the heat conduction table to promote the ice crystals in the suspension to vertically grow from bottom to top.
Step three: and (5) freeze-drying after the freezing is finished to obtain the aerogel.
Step four: sintering the aerogel at 500 ℃ under an inert atmosphere for 4.5 h to obtain the barium-rich oxide barium carbon material.
Step five: dispersing the carbon material rich in the barium oxide obtained in the step four into 200g of ultrapure water, adding a sulfuric acid solution with the density of 1.4 g/cm 3 into the carbon material, magnetically stirring the mixture at a high speed and a stirring speed of 1000rpm, washing and suction-filtering the obtained product, transferring the obtained solid into a vacuum drying box, and drying the solid at 80 ℃ for 24 hours to obtain the barium carbon sulfate composite material with low hydrogen evolution.
An SEM image of the BaSO 4 @C composite material prepared in example 3 is shown in fig. 2, and it can be seen from the image that barium sulfate crystals are uniformly dispersed on a carbon three-dimensional porous structure in a composite material obtained by high-temperature calcination and sulfuric acid treatment of a carbon source and barium salt.
Comparative example 3
Comparative example 3 differs from example 3 in that the addition of barium nitrate was omitted in step one, and in step four, a single, unsupported, three-dimensional porous structure carbon material was obtained.
Example 4
(1) The raw material BaSO 4 @c composite material in this example was BaSO 4 @c composite material prepared in example 3.
(2) The ingredients required by the negative electrode lead plaster are carried out and proportioned according to a conventional formula, wherein the required ingredients are as follows: lead powder with the oxidation degree of 75%, 1.41 g/mL sulfuric acid solution, barium sulfate, lignin, humic acid, short fibers, distilled water, acetylene black and BaSO 4 @C material, wherein the mass of the sulfuric acid solution is 6% of the mass of the lead powder; the mass of the barium sulfate is 1% of the mass of the lead powder; the lignin mass is 0.8% of the lead powder mass; the mass of humic acid is 0.5% of the mass of lead powder; the mass of the short fiber is 0.02% of the mass of the lead powder; the mass of distilled water is 8% of the mass of lead powder; the mass of the acetylene black is 2% of the mass of the lead powder; the mass of the BaSO 4 @C material is 1.0% of that of the lead powder.
(3) Mixing lead powder and additives to obtain the lead paste with apparent density of 4.1 g/cm 3.
(4) And coating the prepared negative electrode lead plaster on a negative electrode grid, and carrying out conventional curing and formation to obtain a negative electrode plate.
Example 5
This example differs from example 1 only in that the amount of barium nitrate used is 1.5g.
Example 6
This example differs from example 1 only in that the amount of barium nitrate used is 3g.
Example 7
The difference between this example and example 1 is that (1) the barium salt is barium acetate and (2) in step (4), the sintering temperature is 550℃and the sintering time is 3 hours.
Example 8
The difference between this example and example 1 is that in step (4), the sintering temperature was 450℃and the sintering time was 6 hours.
Comparative example 4
The difference between this comparative example and example 4 is that in this comparative example, the single unsupported three-dimensional porous structure carbon material prepared in comparative example 3 was used instead of the BaSO 4 @c composite material in example 4.
Comparative example 5
The difference between comparative example 5 and example 4 is that no BaSO 4 @c was added, and the other was the same as example 4.
The ingredients required by the negative electrode lead plaster are carried out and proportioned according to a conventional formula, wherein the required ingredients are as follows: lead powder with the oxidation degree of 75%, 1.41 g/mL sulfuric acid solution, barium sulfate, lignin, humic acid, short fibers, distilled water and acetylene black, wherein the mass of the sulfuric acid solution is 6% of the mass of the lead powder; the mass of the barium sulfate is 1% of the mass of the lead powder; the lignin mass is 0.8% of the lead powder mass; the mass of humic acid is 0.5% of the mass of lead powder; the mass of the short fiber is 0.02% of the mass of the lead powder; the mass of distilled water is 8% of the mass of lead powder; the mass of the acetylene black is 2% of the mass of the lead powder;
Mixing lead powder and additives to obtain a paste, wherein the apparent density of the lead paste is about 4.1 g/cm 3;
and coating the prepared negative electrode lead plaster on a negative electrode grid, and carrying out conventional curing and formation to obtain a negative electrode plate.
Hydrogen evolution rate test: the cured negative electrode plate is used as a working electrode, a 2X 2cm 2 platinum sheet electrode is used as a counter electrode, hg/Hg 2SO4/K2SO4 is used as a reference electrode, and a traditional three-electrode system is assembled for LSV test. Electrochemical testing of all cells was performed in 1.28 g/mL sulfuric acid solution. LSV was detected at a scan rate of 5 mV/s in the range-1.60V to-1.00V.
Fig. 3 is a graph showing the hydrogen evolution rate of a test material using a Linear Sweep Voltammogram (LSV), comparing an electrode added with BaSO 4 @c composite material (example 4) with an electrode added with a single unsupported carbon three-dimensional porous structure material (comparative example 4) and without any addition (comparative example 5), and showing that the hydrogen evolution overpotential of an electrode added with BaSO 4 @c composite material is significantly higher than that of an electrode added with a single unsupported three-dimensional porous structure carbon material.
The battery assembly includes:
And (3) formation: and (3) using glass fiber (AGM) as a separator, assembling the cured negative plate and two standard positive plates, putting the assembled negative plate and the two standard positive plates into a battery mold, adding 1.28 g/mL sulfuric acid as electrolyte, disassembling the battery after the formation is completed in a conventional manner, reserving the negative plate, and cleaning by using deionized water to obtain the negative electrode cooked plate. And after the three standard negative plates and the two standard positive plates are assembled, placing the assembled plates into a battery mold, adding 1.28 g/mL sulfuric acid as electrolyte, disassembling the battery after the formation is completed in a conventional manner, reserving the positive plates, and cleaning the positive plates by using deionized water to obtain the positive cooked plate.
Assembling a battery: and (3) assembling the prepared negative electrode cooked polar plate and the two positive electrode cooked polar plates, putting the assembled positive electrode cooked polar plates and the two positive electrode cooked polar plates into a battery mould, adding 1.28g/mL sulfuric acid as electrolyte, sealing to obtain the battery, and then performing high-rate rapid charge-discharge (HRPSC) test.
High-rate rapid charge and discharge (HRPSOC) test: fig. 4 simulates a HRPSoC cycle schematic at 1C rate for a battery of example 4 with an electrode assembly with a BaSO 4 @c composite material added, with an electrode assembly with a single, non-loaded, three-dimensional porous structure carbon material added in comparative example 4, and with an electrode assembly without any material added in comparative example 5. (HRPSOC) the test method is as follows: (1) The battery was fully charged at 0.1C rate and then discharged to a 50% state of charge (SoC) at 1C rate. (2) And the charge/discharge cycle charges for 15 seconds at 1C rate, stands for 5 seconds, discharges for 15 seconds at 1C rate, and stands for 5 seconds. The battery voltage was measured at the end of each charge and discharge process, and the cycle ended when the discharge cutoff voltage or charge termination voltage was 1.7V or 2.9V.
The results show that: the battery assembled with the electrode (example 4) added with BaSO 4 @c composite material had a cycle number up to 4697 times, which was 1029 times higher than the battery assembled with the electrode (comparative example 4) of a single non-loaded carbon three-dimensional porous structure material (3669). The BaSO 4 @C composite material is added to effectively inhibit sulfation of the electrode under high-rate rapid charge and discharge.
The foregoing is merely a preferred embodiment of the present invention and it should be noted that modifications and adaptations to those skilled in the art may be made without departing from the principles of the present invention, which are intended to be comprehended within the scope of the present invention.
Claims (10)
1. The preparation method of the low-hydrogen evolution composite carbon material is characterized by comprising the following steps of:
(1) Dispersing a carbon source and barium salt in a solvent to obtain a dispersion;
(2) Transferring the dispersion liquid into an environment containing liquid nitrogen, and freezing to enable ice crystals in the suspension liquid to vertically grow from bottom to top, so as to obtain a unidirectionally oriented gel skeleton;
(3) Freeze-drying the unidirectional gel skeleton to obtain aerogel; sintering the aerogel in an inert atmosphere to obtain an intermediate;
(4) Dispersing the intermediate into water, reacting with sulfuric acid solution, washing the obtained product, performing solid-liquid separation and drying to obtain the low-hydrogen evolution composite carbon material BaSO 4 @C.
2. The method for preparing a low hydrogen evolution composite carbon material according to claim 1, wherein in the step (1), the mass ratio of the barium salt to the carbon source is 1.5-3:1.
3. The method of producing a low hydrogen evolution composite carbon material according to claim 1, wherein in the step (1), the carbon source is starch and/or cellulose;
in step (1), the barium salt is a cleavable barium salt; the barium salt is one or more than two of barium chlorate, barium nitrate, barium acetate and barium carbonate.
4. The method for producing a low hydrogen evolution carbon composite material according to claim 1, wherein in the step (1), the solvent is water or a mixed solvent of water and an organic solvent; the organic solvent is one or more of methanol, ethanol, acetic acid and acetone.
5. The method for preparing a low hydrogen evolution composite carbon material according to claim 1, wherein in the step (3), the sintering temperature is 450-550 ℃; the sintering time is 3-6 hours.
6. The method for producing a low hydrogen evolution composite carbon material according to claim 1, wherein the step (2) comprises: transferring the container filled with the dispersion liquid into a mould filled with liquid nitrogen, wherein a heat conducting sheet or a heat conducting table extending out of the liquid nitrogen liquid level is arranged in the mould, and the container is placed on the heat conducting sheet or the heat conducting table for freezing.
7. The method for producing a low hydrogen evolution composite carbon material according to claim 6, wherein in the step (4), the reaction is performed under stirring; the stirring speed is 800-1200 rpm;
In the step (4), the density of the sulfuric acid solution is 1.3-1.5 g/mL.
8. A low hydrogen evolution composite carbon material, characterized in that it is prepared by the preparation method according to any one of claims 1 to 7.
9. A lead acid battery negative electrode comprising a negative electrode additive, wherein the negative electrode additive is the low hydrogen evolution composite carbon material of claim 8.
10. A lead acid battery comprising the negative electrode of claim 9.
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