CN112133914A - Porous carbon-loaded ultra-small PbSO4Nano particle composite material, preparation thereof and application thereof in lead carbon battery anode - Google Patents
Porous carbon-loaded ultra-small PbSO4Nano particle composite material, preparation thereof and application thereof in lead carbon battery anode Download PDFInfo
- Publication number
- CN112133914A CN112133914A CN202010271981.9A CN202010271981A CN112133914A CN 112133914 A CN112133914 A CN 112133914A CN 202010271981 A CN202010271981 A CN 202010271981A CN 112133914 A CN112133914 A CN 112133914A
- Authority
- CN
- China
- Prior art keywords
- porous carbon
- carbon
- small
- lead
- pbso
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
- 229910052799 carbon Inorganic materials 0.000 title claims abstract description 82
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 55
- 239000002131 composite material Substances 0.000 title claims abstract description 29
- 238000002360 preparation method Methods 0.000 title claims abstract description 15
- 239000002245 particle Substances 0.000 title abstract description 17
- 229910052924 anglesite Inorganic materials 0.000 claims abstract description 30
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims abstract description 26
- 238000001914 filtration Methods 0.000 claims abstract description 16
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 16
- 238000003756 stirring Methods 0.000 claims abstract description 10
- 239000007864 aqueous solution Substances 0.000 claims abstract description 8
- RLJMLMKIBZAXJO-UHFFFAOYSA-N lead nitrate Chemical compound [O-][N+](=O)O[Pb]O[N+]([O-])=O RLJMLMKIBZAXJO-UHFFFAOYSA-N 0.000 claims abstract description 8
- 239000002105 nanoparticle Substances 0.000 claims description 27
- ROOXNKNUYICQNP-UHFFFAOYSA-N ammonium persulfate Chemical compound [NH4+].[NH4+].[O-]S(=O)(=O)OOS([O-])(=O)=O ROOXNKNUYICQNP-UHFFFAOYSA-N 0.000 claims description 10
- 239000000243 solution Substances 0.000 claims description 9
- KEQXNNJHMWSZHK-UHFFFAOYSA-L 1,3,2,4$l^{2}-dioxathiaplumbetane 2,2-dioxide Chemical compound [Pb+2].[O-]S([O-])(=O)=O KEQXNNJHMWSZHK-UHFFFAOYSA-L 0.000 claims description 7
- 229910001870 ammonium persulfate Inorganic materials 0.000 claims description 5
- 238000006243 chemical reaction Methods 0.000 claims description 5
- 239000000126 substance Substances 0.000 claims description 5
- 235000007164 Oryza sativa Nutrition 0.000 claims description 4
- 239000007772 electrode material Substances 0.000 claims description 4
- 235000009566 rice Nutrition 0.000 claims description 4
- 239000013543 active substance Substances 0.000 claims description 3
- 239000000706 filtrate Substances 0.000 claims description 3
- 235000013162 Cocos nucifera Nutrition 0.000 claims description 2
- 244000060011 Cocos nucifera Species 0.000 claims description 2
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 claims description 2
- 206010034972 Photosensitivity reaction Diseases 0.000 claims description 2
- FKNQFGJONOIPTF-UHFFFAOYSA-N Sodium cation Chemical compound [Na+] FKNQFGJONOIPTF-UHFFFAOYSA-N 0.000 claims description 2
- 239000012295 chemical reaction liquid Substances 0.000 claims description 2
- 150000001875 compounds Chemical class 0.000 claims description 2
- 239000010411 electrocatalyst Substances 0.000 claims description 2
- 239000006181 electrochemical material Substances 0.000 claims description 2
- 229910001416 lithium ion Inorganic materials 0.000 claims description 2
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 claims description 2
- 230000003287 optical effect Effects 0.000 claims description 2
- 230000036211 photosensitivity Effects 0.000 claims description 2
- 229910001415 sodium ion Inorganic materials 0.000 claims description 2
- 240000007594 Oryza sativa Species 0.000 claims 1
- 238000000034 method Methods 0.000 abstract description 13
- 238000000151 deposition Methods 0.000 abstract description 9
- 239000000654 additive Substances 0.000 abstract description 8
- 230000000996 additive effect Effects 0.000 abstract description 8
- 230000008021 deposition Effects 0.000 abstract description 7
- 239000000463 material Substances 0.000 abstract description 4
- 230000021523 carboxylation Effects 0.000 abstract description 2
- 238000006473 carboxylation reaction Methods 0.000 abstract description 2
- 238000011031 large-scale manufacturing process Methods 0.000 abstract description 2
- 238000001035 drying Methods 0.000 description 18
- 230000000052 comparative effect Effects 0.000 description 11
- 238000012360 testing method Methods 0.000 description 8
- 239000002253 acid Substances 0.000 description 6
- 239000010405 anode material Substances 0.000 description 6
- 239000011248 coating agent Substances 0.000 description 6
- 238000000576 coating method Methods 0.000 description 6
- 239000011505 plaster Substances 0.000 description 6
- PIJPYDMVFNTHIP-UHFFFAOYSA-L lead sulfate Chemical group [PbH4+2].[O-]S([O-])(=O)=O PIJPYDMVFNTHIP-UHFFFAOYSA-L 0.000 description 5
- 230000015572 biosynthetic process Effects 0.000 description 4
- 239000008367 deionised water Substances 0.000 description 4
- 229910021641 deionized water Inorganic materials 0.000 description 4
- 241000209094 Oryza Species 0.000 description 3
- 239000004698 Polyethylene Substances 0.000 description 3
- 239000003792 electrolyte Substances 0.000 description 3
- 239000004744 fabric Substances 0.000 description 3
- WABPQHHGFIMREM-UHFFFAOYSA-N lead(0) Chemical compound [Pb] WABPQHHGFIMREM-UHFFFAOYSA-N 0.000 description 3
- 239000004745 nonwoven fabric Substances 0.000 description 3
- -1 polyethylene Polymers 0.000 description 3
- 229920000573 polyethylene Polymers 0.000 description 3
- 239000007774 positive electrode material Substances 0.000 description 3
- 238000005096 rolling process Methods 0.000 description 3
- 239000008399 tap water Substances 0.000 description 3
- 235000020679 tap water Nutrition 0.000 description 3
- 238000005406 washing Methods 0.000 description 3
- 238000003917 TEM image Methods 0.000 description 2
- 238000001994 activation Methods 0.000 description 2
- 239000011149 active material Substances 0.000 description 2
- 230000002776 aggregation Effects 0.000 description 2
- 235000013339 cereals Nutrition 0.000 description 2
- 239000003610 charcoal Substances 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 238000007599 discharging Methods 0.000 description 2
- 238000004146 energy storage Methods 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 239000010903 husk Substances 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- 238000001556 precipitation Methods 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- 238000005054 agglomeration Methods 0.000 description 1
- 238000004220 aggregation Methods 0.000 description 1
- 230000003321 amplification Effects 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 239000003575 carbonaceous material Substances 0.000 description 1
- 238000009388 chemical precipitation Methods 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 230000001351 cycling effect Effects 0.000 description 1
- 229910003460 diamond Inorganic materials 0.000 description 1
- 239000010432 diamond Substances 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000012983 electrochemical energy storage Methods 0.000 description 1
- 238000004070 electrodeposition Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 230000001939 inductive effect Effects 0.000 description 1
- 229910010272 inorganic material Inorganic materials 0.000 description 1
- 239000011147 inorganic material Substances 0.000 description 1
- 230000014759 maintenance of location Effects 0.000 description 1
- 238000003199 nucleic acid amplification method Methods 0.000 description 1
- FWFGVMYFCODZRD-UHFFFAOYSA-N oxidanium;hydrogen sulfate Chemical compound O.OS(O)(=O)=O FWFGVMYFCODZRD-UHFFFAOYSA-N 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 230000019635 sulfation Effects 0.000 description 1
- 238000005670 sulfation reaction Methods 0.000 description 1
Images
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
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- B01J27/02—Sulfur, selenium or tellurium; Compounds thereof
- B01J27/053—Sulfates
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/30—Catalysts, in general, characterised by their form or physical properties characterised by their physical properties
- B01J35/33—Electric or magnetic properties
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/40—Catalysts, in general, characterised by their form or physical properties characterised by dimensions, e.g. grain size
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/08—Heat treatment
- B01J37/10—Heat treatment in the presence of water, e.g. steam
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y30/00—Nanotechnology for materials or surface science, e.g. nanocomposites
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B32/00—Carbon; Compounds thereof
- C01B32/05—Preparation or purification of carbon not covered by groups C01B32/15, C01B32/20, C01B32/25, C01B32/30
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G21/00—Compounds of lead
- C01G21/20—Sulfates
-
- 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
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/052—Li-accumulators
- H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
-
- 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
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/054—Accumulators with insertion or intercalation of metals other than lithium, e.g. with magnesium or aluminium
-
- 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
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
- H01M4/624—Electric conductive fillers
- H01M4/625—Carbon or graphite
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
- H01M4/628—Inhibitors, e.g. gassing inhibitors, corrosion inhibitors
-
- 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
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Organic Chemistry (AREA)
- Materials Engineering (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Manufacturing & Machinery (AREA)
- Inorganic Chemistry (AREA)
- Physics & Mathematics (AREA)
- Nanotechnology (AREA)
- Composite Materials (AREA)
- Condensed Matter Physics & Semiconductors (AREA)
- General Physics & Mathematics (AREA)
- Crystallography & Structural Chemistry (AREA)
- Thermal Sciences (AREA)
- Battery Electrode And Active Subsutance (AREA)
Abstract
The invention provides a porous carbon-loaded ultra-small PbSO4Nano particleA sub-composite material, a method for preparing the same and applications thereof. In this structure, the ultra-small particles PbSO4Directly anchored on the porous carbon, thereby effectively depositing PbSO as a deposition site during anode discharge4. The preparation method mainly comprises the following steps: firstly, carrying out carboxylation treatment on porous carbon, then dissolving the porous carbon in lead nitrate aqueous solution with certain concentration, stirring at certain temperature, filtering with water, and then filtering with sulfuric acid to obtain the porous carbon-loaded ultra-small PbSO4Particles. The preparation process provided by the invention is simple, and has great potential in the aspects of large-scale production, commercial battery popularization and the like. The material obtained by the invention is used as the anode additive of the lead-carbon battery, and the cycle performance of the battery can be obviously improved.
Description
Technical Field
The invention provides a porous carbon-loaded ultra-small PbSO4Nanoparticles, a preparation method and application thereof, belonging to the technical field of inorganic material preparation.
Technical Field
Since the invention and the application of the lead-acid battery, the lead-acid battery occupies a very important position in the field of electrochemical energy storage by virtue of the ultrahigh cost performance, the recyclable materials, the excellent performance and the like. However, with the development of the current society and science and technology, the application scenarios of the electrochemical energy client are greatly changed, such as the appearance of new fields of wind and light energy storage, start and stop, and the like, and new opportunities and challenges are brought to the lead-acid battery. In order to meet this opportunity, lead-acid batteries have been further developed, and thus lead-carbon batteries have been born. At present, lead-carbon batteries mainly refer to that a proper carbon material is added into a negative electrode of a traditional lead-acid battery or the lead negative electrode is completely replaced by a carbon electrode and the like and then is combined with a traditional positive electrode. The lead-carbon battery effectively improves the rapid sulfation phenomenon of the cathode of the traditional lead-acid battery, prolongs the cycle life of the lead-carbon battery, and is further suitable for new application scenes such as wind-solar energy storage, start-stop and the like.
However, in the research on the positive electrode of the lead-carbon battery, the development of the lead-carbon battery is still restricted by the short cycle life of the positive electrode of the lead-carbon battery. For example, in the deep charging and deep discharging process of the lead-carbon battery for the electric vehicle, the anode of the lead-carbon battery is gradually softened and falls off along with the circulation of the polar plate, so that the service life of the battery is greatly limited.
As the cycle proceeds, the active material of the positive electrode gradually changes from a fine porous structure to a separate large-particle active material. Larger particles are gradually separated from the positive electrode plate, so that the positive electrode is softened and falls off. Therefore, the aggregation of the positive active material is inhibited and a certain fine network structure is kept in circulation, and a great relieving effect is generated on the failure of the positive active material. Therefore, reasonably inducing the deposition of the lead sulfate and relieving the large-grained agglomeration of the lead sulfate is a very reasonable strategy for improving the cycle life of the positive electrode. It is well known that cycling of a lead carbon battery is a process of electrodeposition. The deposition of lead sulfate during discharge generally follows an electron transfer-chemical precipitation process. Precipitation generally occurs more easily on the seed crystal, so that the precipitation of lead sulfate can be induced by ultra-small lead sulfate particles, and finally PbSO can be controlled4The morphology after deposition is still small particle size. Furthermore, very small particle PbSO4Has a very large surface energy and is therefore more advantageous for the deposition of PbSO 4. And the large-sized porous carbon serves as a core of the PbSO4 network after deposition, thereby constructing a continuous network structure of discharge products. The invention provides a method for preparing ultra-small particle PbSO by taking porous carbon as a substrate4The simple preparation method. In this structure, the ultra-small particles PbSO4Directly anchored on the porous carbon, thereby effectively depositing PbSO as a deposition site during anode discharge4. The preparation method mainly comprises the following steps: firstly, carrying out carboxylation treatment on porous carbon, then dissolving the porous carbon in lead nitrate aqueous solution with certain concentration, stirring at certain temperature, filtering with water, and then filtering with sulfuric acid to obtain the porous carbon-loaded ultra-small PbSO4Particles. The preparation process provided by the invention is simple, and has great potential in the aspects of large-scale production, commercial battery popularization and the like. The material obtained by the invention is used as the anode additive of the lead-carbon battery, and the cycle performance of the battery can be obviously improved.
The invention content is as follows:
aiming at the problems of the positive electrode of the existing lead-carbon battery, the invention providesA porous carbon supported ultra-small PbSO which can be simply prepared4The method of the nano particle composite material and the application of the nano particle composite material as the additive of the positive electrode of the lead-carbon battery. The material can effectively deposit PbSO4 in ultra-small PbSO during discharge4On the nanoparticles, therefore, a fine PbSO4 network structure continues to be formed, and the large grain of the positive electrode active material, namely softening and shedding, is relieved.
The technical scheme of the invention is as follows:
porous carbon-loaded ultra-small PbSO4The preparation method of the nano particle composite material is characterized by comprising the following steps:
(1) dissolving porous carbon in 2-8 mol/L ammonium persulfate aqueous solution at 10-90 ℃, and stirring for 4-8 h; the mass ratio of the porous carbon to the ammonium persulfate aqueous solution is 1: 15-25;
(2) filtering the solution obtained in the step (1), placing the solution in an oven, and keeping the temperature at 60-90 ℃ for 4-12 h;
(3) dissolving the dried substance obtained in the step (2) in water with the mass of 20-30 times, adding a certain mass of lead nitrate, keeping the temperature of 10-90 ℃ and the stirring state, and keeping stirring reaction for 2-8 hours; wherein the mass ratio of the lead nitrate to the dried substance is 1-10: 1;
(4) taking out the reaction liquid, filtering with water, filtering with 0.05-0.5 mol/L sulfuric acid aqueous solution, and finally filtering with a large amount of water;
(5) putting the obtained filtrate in an oven, keeping the temperature at 60-90 ℃ for 4-12 h; thus obtaining the porous carbon supported ultra-small PbSO4 nano particle compound.
In the step (1), the porous carbon is rice hull carbon, coconut shell carbon or ordered mesoporous carbon.
Porous carbon-loaded ultra-small PbSO4The nano particle composite material is prepared by the method.
Porous carbon-loaded ultra-small PbSO4The application of the nano particle composite material in the positive electrode of the lead-carbon battery.
The porous carbon supported ultra-small PbSO4The nano particle composite material is used as the positive active substance of the lead-carbon batteryThe mass ratio of the additive is 0.05-3%.
The porous carbon supported ultra-small PbSO4The nano particle composite material is applied to the fields of other optical and electrochemical materials.
The porous carbon supported ultra-small PbSO4The nano particle composite material is applied to the fields of electro-catalysts, biosensors, lithium ion battery electrode materials, sodium ion battery electrode materials and photosensitivity.
Has the advantages that: compared with the prior art, the invention has the following advantages:
the preparation technology provided by the invention is simple. The whole reaction is carried out in a water bath at the temperature of not higher than 100 ℃, so the operation is easier to realize. The method is more suitable for industrial amplification operation. The simple preparation method provides a foundation for really applying the lead-carbon battery positive electrode as an additive. Selective porous carbon loaded ultra-small PbSO4The nano particle composite material is used as a lead-carbon battery positive electrode additive, and can ensure that PbSO can be generated in the discharging process4Effectively deposited on the ultra-small PbSO4 nano-particles, and the large-sized porous carbon serves as the core of the deposited PbSO4 network, thereby constructing a continuous network structure of discharge products. Fine PbSO4The network structure relieves the large grain of the positive active substance, namely softening and dropping, and finally achieves the purpose of improving the performance of the lead-carbon battery.
Description of the drawings:
FIG. 1 shows that the porous carbon prepared in example 1 of the present invention supports ultra-small PbSO4TEM images of the nanoparticle composite;
fig. 2 is a comparative histogram of capacities of lead-carbon batteries prepared in comparative example 1, example 2 and example 3 of the present invention at different discharge rates.
The horizontal grid histogram is comparative example 1, and the vertical grid histogram and the cross grid are the capacity values of example 2 and example 3, respectively.
Fig. 3 is a graph showing the discharge capacity of the lead-carbon batteries prepared in comparative example 1, example 2 and example 3 of the present invention as a function of the number of times of discharge at a discharge current of 0.5C.
Where the triangle is comparative example 1 and the diamond and circle are shown as example 2 and example 3, respectively.
The specific implementation mode is as follows:
the invention will be further illustrated by the following figures and detailed description of embodiments, which are not to be construed as limiting the invention to the examples.
In the following examples, these examples are only for illustrating the present invention and are not intended to limit the scope of the present invention. Experimental procedures without specific conditions noted in the following examples, generally according to conditions conventional in the art or as recommended by the manufacturer; the raw materials, reagents and the like used are, unless otherwise specified, those commercially available from the conventional markets and the like. Any insubstantial changes and substitutions made by those skilled in the art based on the present invention are intended to be covered by the claims.
Comparative example 1
(1) 100g of commercial anode lead powder is put into a stirrer, 11.5g of deionized water is added into the stirrer to be ground uniformly, and 8.8g of deionized water with the density of 1.41g/cm is added3The sulfuric acid is uniformly mixed to obtain pre-coating lead plaster, the lead plaster is uniformly coated on a grid to prepare a green plate (with the length of 7cm and the width of 4cm), and the coating mass is 22 +/-0.5 g. Then wrapping the green plate with non-woven cloth and rolling with a polyethylene rod.
(2) Removing the wrapped non-woven fabric, drying the raw pole plate in a drying box with the relative humidity of more than or equal to 98% and the temperature of 65 ℃ for 24 hours, drying in a common drying box with the temperature of 60 ℃ for 24 hours, and taking out to obtain the cooked pole plate.
(3) And (3) after the prepared cooked polar plate is subjected to a formation process in sulfuric acid with the concentration of 4mol/L, washing the polar plate for 2 hours by using tap water, and drying the polar plate for 24 hours in a common drying oven at the temperature of 60 ℃.
(4) And (3) assembling the positive plate obtained in the step (4) and two negative plates with the same specification into a battery, wherein the electrolyte is sulfuric acid with the concentration of 5mol/L, and performing a battery performance test after a formation process.
Example 1
(1) 10g of rice husk charcoal was dissolved in 200mL of an 8mol/L aqueous ammonium persulfate solution at 20 ℃ and stirred for 8 hours.
(2) Filtering the solution obtained in the step (1), placing the solution in an oven, keeping the temperature at 60 ℃ for 12 hours;
(3) dissolving the dried substance obtained in the step (2) in 200mL of water, adding a certain mass of lead nitrate, keeping the temperature at 60 ℃ and stirring, and keeping stirring for reaction for 4 hours; wherein the mass ratio of the lead nitrate to the porous carbon is 2: 1;
(4) the reaction solution was taken out and filtered. Filtering with water, then filtering with 0.05mol/L sulfuric acid water solution, and finally filtering with a large amount of water.
(5) Placing the obtained filtrate in an oven at 60 deg.C for 12 hr; thus obtaining the porous carbon-loaded ultra-small PbSO4A nanoparticle composite.
Example 2
(1) The commercial anode lead powder and the rice husk charcoal prepared in example 1 are loaded with ultra-small PbSO4Mixing the nano particle composite material additive in a stirrer according to a mass ratio of 100:0.5 for 2 hours to obtain the required lead-carbon battery anode material;
(2) 100g of the obtained anode material is put into a stirrer, 11.5g of deionized water is added into the stirrer to be ground uniformly, and 8.8g of the ground anode material with the density of 1.41g/cm is added3The sulfuric acid is uniformly mixed to obtain pre-coating lead plaster, the lead plaster is uniformly coated on a grid to prepare a green plate (with the length of 7cm and the width of 4cm), and the coating mass is 22 +/-0.5 g. Then wrapping the green plate with non-woven cloth and rolling with a polyethylene rod.
(3) Removing the wrapped non-woven fabric, drying the raw pole plate in a drying box with the relative humidity of more than or equal to 98% and the temperature of 65 ℃ for 24 hours, drying in a common drying box with the temperature of 60 ℃ for 24 hours, and taking out to obtain the cooked pole plate.
(4) And (3) after the prepared cooked polar plate is subjected to a formation process in sulfuric acid with the concentration of 4mol/L, washing the polar plate for 2 hours by using tap water, and drying the polar plate for 24 hours in a common drying oven at the temperature of 60 ℃.
(5) And (3) assembling the positive plate obtained in the step (4) and two negative plates with the same specification into a battery, wherein the electrolyte is sulfuric acid with the concentration of 5mol/L, and performing an activation process to test the performance of the battery.
Example 3
(1) Commercial positive lead powder was prepared as in example 2Porous carbon supported ultra-small PbSO4Mixing the nano particle composite material additive in a stirrer according to a mass ratio of 100:0.8 for 2 hours to obtain the required lead-carbon battery anode material;
(2) 100g of the obtained anode material is put into a stirrer, 11.5g of deionized water is added into the stirrer to be ground uniformly, and 8.8g of the ground anode material with the density of 1.41g/cm is added3The sulfuric acid is uniformly mixed to obtain pre-coating lead plaster, the lead plaster is uniformly coated on a grid to prepare a green plate (with the length of 7cm and the width of 4cm), and the coating mass is 22 +/-0.5 g. Then wrapping the green plate with non-woven cloth and rolling with a polyethylene rod.
(3) Removing the wrapped non-woven fabric, drying the raw pole plate in a drying box with the relative humidity of more than or equal to 98% and the temperature of 65 ℃ for 24 hours, drying in a common drying box with the temperature of 60 ℃ for 24 hours, and taking out to obtain the cooked pole plate.
(4) And (3) after the prepared cooked polar plate is subjected to a formation process in sulfuric acid with the concentration of 4mol/L, washing the polar plate for 2 hours by using tap water, and drying the polar plate for 24 hours in a common drying oven at the temperature of 60 ℃.
(5) And (3) assembling the positive plate obtained in the step (4) and two negative plates with the same specification into a battery, wherein the electrolyte is sulfuric acid with the concentration of 5mol/L, and performing an activation process to test the performance of the battery.
Test examples
Test example 1 porous carbon-supported PbSO prepared in inventive example 14TEM image of the nanoparticle composite material obtained on JSM-2100F (JEOL) type transmission electron microscope instrument, as shown in FIG. 1.
It is apparent from FIG. 1 that a large amount of black PbSO is supported on the porous carbon4Small particles.
Experimental example 2 is a comparative histogram of capacities of lead-carbon batteries prepared in comparative example 1, example 2 and example 3 of the present invention at different discharge rates, as shown in fig. 2. The charging condition is that the constant current is charged to 2.35V at 0.2C, and then the constant voltage is kept at 2.35V until the current is reduced to 15 mA; the discharge conditions were such that the discharge voltage was 1.75V at each discharge rate.
From FIG. 2 it can be seen that carbon/PbSO was added4Testing of small particle composites lead-carbon batteries (examples 2 and 3) specific discharge capacities at different ratesAre obviously higher than that of the carbon/PbSO which is not added4Test of small particle composite lead carbon batteries (comparative example 1).
Experimental example 3 is a graph showing the discharge capacity of the lead-carbon batteries prepared in comparative example 1, example 2 and example 3 of the present invention as a function of the number of times of discharge at a discharge current of 0.5C, as shown in fig. 3. The charging condition is that the constant current is charged to 2.35V at 0.2C, and then the constant voltage is kept at 2.35V until the current is reduced to 15 mA; the discharge was carried out under a discharge rate of 0.5C until the voltage became 1.75V, and the discharge was successively cycled.
From FIG. 3 it can be seen that carbon/PbSO was added4Test lead-carbon batteries of small particle composites (examples 2 and 3) have higher performance than the batteries without added carbon/PbSO4Test of small particle composites lead carbon batteries (comparative example 1) have a specific discharge capacity and still have a good capacity retention.
Claims (7)
1. Porous carbon-loaded ultra-small PbSO4The preparation method of the nano particle composite material is characterized by comprising the following steps:
(1) dissolving porous carbon in 2-8 mol/L ammonium persulfate aqueous solution at 10-90 ℃, and stirring for 4-8 h; the mass ratio of the porous carbon to the ammonium persulfate aqueous solution is 1: 15-25;
(2) filtering the solution obtained in the step (1), placing the solution in an oven, and keeping the temperature at 60-90 ℃ for 4-12 h;
(3) dissolving the dried substance obtained in the step (2) in water with the mass of 20-30 times, adding a certain mass of lead nitrate, keeping the temperature of 10-90 ℃ and the stirring state, and keeping stirring reaction for 2-8 hours; wherein the mass ratio of the lead nitrate to the dried substance is 1-10: 1;
(4) taking out the reaction liquid, filtering with water, filtering with 0.05-0.5 mol/L sulfuric acid aqueous solution, and finally filtering with a large amount of water;
(5) putting the obtained filtrate in an oven, keeping the temperature at 60-90 ℃ for 4-12 h; thus obtaining the porous carbon supported ultra-small PbSO4 nano particle compound.
2. The porous carbon supported ultra-small P as claimed in claim 1bSO4The preparation method of the nano particle composite material is characterized by comprising the following steps: in the step (1), the porous carbon is rice hull carbon, coconut shell carbon or ordered mesoporous carbon.
3. Porous carbon-loaded ultra-small PbSO4Nanoparticle composite material, characterized by being obtained by the preparation process according to claim 1 or 2.
4. The porous carbon-supported ultra-small PbSO as in claim 34The application of the nano particle composite material in the positive electrode of the lead-carbon battery.
5. The porous carbon-supported ultra-small PbSO as in claim 44The application of the nano particle composite material in the positive electrode of the lead-carbon battery is characterized in that the porous carbon loads ultra-small PbSO4The nano particle composite material is added into the positive active substance of the lead-carbon battery in a mass ratio of 0.05-3%.
6. The porous carbon supported ultra-small PbSO as in claim 34The nano particle composite material is applied to the fields of other optical and electrochemical materials.
7. The porous carbon supported ultra-small PbSO as in claim 64The nano particle composite material is applied to the fields of electro-catalysts, biosensors, lithium ion battery electrode materials, sodium ion battery electrode materials and photosensitivity.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202010271981.9A CN112133914A (en) | 2020-04-09 | 2020-04-09 | Porous carbon-loaded ultra-small PbSO4Nano particle composite material, preparation thereof and application thereof in lead carbon battery anode |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202010271981.9A CN112133914A (en) | 2020-04-09 | 2020-04-09 | Porous carbon-loaded ultra-small PbSO4Nano particle composite material, preparation thereof and application thereof in lead carbon battery anode |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN112133914A true CN112133914A (en) | 2020-12-25 |
Family
ID=73850364
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202010271981.9A Pending CN112133914A (en) | 2020-04-09 | 2020-04-09 | Porous carbon-loaded ultra-small PbSO4Nano particle composite material, preparation thereof and application thereof in lead carbon battery anode |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN112133914A (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN117352739A (en) * | 2023-11-09 | 2024-01-05 | 昆明理工大学 | Preparation method of additive capable of effectively inhibiting irreversible sulfation of negative electrode |
Citations (13)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103066248A (en) * | 2012-12-21 | 2013-04-24 | 中南大学 | Method for chemical doping of plumbum (Pb) on surface of cathode carbon material used for ultrabattery |
| CN104659350A (en) * | 2015-02-26 | 2015-05-27 | 中南大学 | Method for secondary modification of surface of active carbon material for super battery |
| CN104685674A (en) * | 2012-09-28 | 2015-06-03 | 卡博特公司 | Active material compositions comprising high surface area carbonaceous materials |
| CN105895918A (en) * | 2014-12-16 | 2016-08-24 | 北京科技大学 | Negative electrode active material additive for lead storage battery |
| CN106463726A (en) * | 2014-06-10 | 2017-02-22 | 卡博特公司 | Electrode compositions comprising carbon additives |
| CN107579240A (en) * | 2017-09-20 | 2018-01-12 | 吉林省凯禹电化学储能技术发展有限公司 | A kind of preparation method of C-base composte material for lead carbon battery negative pole |
| CN107845777A (en) * | 2016-09-21 | 2018-03-27 | 中国科学院大连化学物理研究所 | The preparation method of lead carbon battery composite negative pole and its composite negative pole and application |
| CN107949937A (en) * | 2015-07-17 | 2018-04-20 | 卡博特公司 | Oxidized black and the application for lead-acid battery |
| CN108123137A (en) * | 2016-11-26 | 2018-06-05 | 中国科学院大连化学物理研究所 | Part graphitization activated carbon base compound additive and preparation and cathode and application |
| CN109119606A (en) * | 2018-08-02 | 2019-01-01 | 天能电池集团有限公司 | A kind of preparation method and application of nanometer of lead deposit hierarchical porous structure carbon composite |
| CN109698343A (en) * | 2018-12-29 | 2019-04-30 | 南通沃德材料科技有限公司 | A kind of preparation method and application of nanometer of lead deposit hierarchical porous structure carbon composite |
| CN110212172A (en) * | 2019-05-10 | 2019-09-06 | 重庆大学 | A kind of composite material and preparation method of carbon material in-situ deposition nanometer lead crystal grain/lead oxide |
| CN110753673A (en) * | 2018-11-23 | 2020-02-04 | 辽宁星空钠电电池有限公司 | Biomass-based functional group modified sodium ion battery negative electrode material and preparation method and application thereof |
-
2020
- 2020-04-09 CN CN202010271981.9A patent/CN112133914A/en active Pending
Patent Citations (13)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104685674A (en) * | 2012-09-28 | 2015-06-03 | 卡博特公司 | Active material compositions comprising high surface area carbonaceous materials |
| CN103066248A (en) * | 2012-12-21 | 2013-04-24 | 中南大学 | Method for chemical doping of plumbum (Pb) on surface of cathode carbon material used for ultrabattery |
| CN106463726A (en) * | 2014-06-10 | 2017-02-22 | 卡博特公司 | Electrode compositions comprising carbon additives |
| CN105895918A (en) * | 2014-12-16 | 2016-08-24 | 北京科技大学 | Negative electrode active material additive for lead storage battery |
| CN104659350A (en) * | 2015-02-26 | 2015-05-27 | 中南大学 | Method for secondary modification of surface of active carbon material for super battery |
| CN107949937A (en) * | 2015-07-17 | 2018-04-20 | 卡博特公司 | Oxidized black and the application for lead-acid battery |
| CN107845777A (en) * | 2016-09-21 | 2018-03-27 | 中国科学院大连化学物理研究所 | The preparation method of lead carbon battery composite negative pole and its composite negative pole and application |
| CN108123137A (en) * | 2016-11-26 | 2018-06-05 | 中国科学院大连化学物理研究所 | Part graphitization activated carbon base compound additive and preparation and cathode and application |
| CN107579240A (en) * | 2017-09-20 | 2018-01-12 | 吉林省凯禹电化学储能技术发展有限公司 | A kind of preparation method of C-base composte material for lead carbon battery negative pole |
| CN109119606A (en) * | 2018-08-02 | 2019-01-01 | 天能电池集团有限公司 | A kind of preparation method and application of nanometer of lead deposit hierarchical porous structure carbon composite |
| CN110753673A (en) * | 2018-11-23 | 2020-02-04 | 辽宁星空钠电电池有限公司 | Biomass-based functional group modified sodium ion battery negative electrode material and preparation method and application thereof |
| CN109698343A (en) * | 2018-12-29 | 2019-04-30 | 南通沃德材料科技有限公司 | A kind of preparation method and application of nanometer of lead deposit hierarchical porous structure carbon composite |
| CN110212172A (en) * | 2019-05-10 | 2019-09-06 | 重庆大学 | A kind of composite material and preparation method of carbon material in-situ deposition nanometer lead crystal grain/lead oxide |
Non-Patent Citations (1)
| Title |
|---|
| 黄占斌: "《环境科学》", 30 November 2017, 冶金工业出版社 * |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN117352739A (en) * | 2023-11-09 | 2024-01-05 | 昆明理工大学 | Preparation method of additive capable of effectively inhibiting irreversible sulfation of negative electrode |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN112133897B (en) | Method for reducing surface alkali amount of positive electrode material and improving electrochemical performance through wet coating | |
| CN110042503B (en) | MoSe2@ C electrospun hollow nanofiber and preparation method and application thereof | |
| CN107732158A (en) | Lithium ion battery negative electrode preparation method, cathode pole piece and lithium ion battery | |
| CN110817958B (en) | Carbon-coated nano vanadium pentoxide lithium battery positive electrode material and liquid-phase in-situ preparation method thereof | |
| CN103296275A (en) | Carbon-material-coated lead powder composite material and application thereof | |
| CN107464924A (en) | A kind of sheet oxygen defect lithium vanadate anode material and preparation method thereof | |
| CN110197899A (en) | A kind of preparation method of lithium foil | |
| CN112133902A (en) | Sodium metal negative electrode deposition matrix and preparation method and application thereof | |
| CN110790248B (en) | Iron-doped cobalt phosphide microsphere electrode material with flower-shaped structure and preparation method and application thereof | |
| CN113793928A (en) | Modified ternary cathode material and preparation method and application thereof | |
| CN110467170B (en) | High-potential positive electrode material of potassium ion battery and preparation method thereof | |
| CN117673521A (en) | Preparation method and application of aqueous zinc ion battery electrolyte containing organic sulfide additive | |
| CN108281646B (en) | Niobium metal doped fibrous lithium vanadate material and preparation method and application thereof | |
| CN112133914A (en) | Porous carbon-loaded ultra-small PbSO4Nano particle composite material, preparation thereof and application thereof in lead carbon battery anode | |
| WO2024082540A1 (en) | Modified graphene negative electrode material and preparation method therefor, negative electrode sheet, and battery | |
| CN115626637B (en) | Preparation method of carbon/graphene/lithium titanate composite anode material | |
| CN115991505A (en) | Modified ternary positive electrode material and preparation method and application thereof | |
| CN115172693A (en) | Neutral silver-zinc battery positive electrode material and preparation method thereof, and neutral silver-zinc battery | |
| CN111453767B (en) | Porous SnO2Micron sheet, preparation method thereof and application of micron sheet to positive electrode of lead-carbon battery | |
| CN111453765A (en) | Porous carbon-loaded ultra-small SnO2Nano particle composite material and preparation method and application thereof | |
| CN113193191B (en) | Manganous-manganic oxide nanocrystalline @3D honeycomb-shaped hierarchical porous network framework carbon composite material and preparation and application thereof | |
| CN115703633B (en) | Micron-sized embroidered ball-shaped porous carbon material and preparation method and application thereof | |
| CN116885174B (en) | Mixed doped carbon material and use thereof in sodium ion battery material for vehicles | |
| CN115849446B (en) | Copper element doped titanium niobate microsphere anode material and preparation method and application thereof | |
| CN114314644B (en) | Preparation method of SnO2@C-P composite electrode material |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| WD01 | Invention patent application deemed withdrawn after publication | ||
| WD01 | Invention patent application deemed withdrawn after publication |
Application publication date: 20201225 |