CN111453765A - Porous carbon-loaded ultra-small SnO2Nano particle composite material and preparation method and application thereof - Google Patents
Porous carbon-loaded ultra-small SnO2Nano particle composite material and preparation method and application thereof Download PDFInfo
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- 229910052799 carbon Inorganic materials 0.000 title claims abstract description 92
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 55
- 238000002360 preparation method Methods 0.000 title claims abstract description 16
- 239000002131 composite material Substances 0.000 title claims description 32
- 239000002245 particle Substances 0.000 title abstract description 14
- XOLBLPGZBRYERU-UHFFFAOYSA-N SnO2 Inorganic materials O=[Sn]=O XOLBLPGZBRYERU-UHFFFAOYSA-N 0.000 claims abstract description 31
- 238000001035 drying Methods 0.000 claims abstract description 23
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N EtOH Substances CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 10
- 238000002156 mixing Methods 0.000 claims abstract description 7
- 238000001354 calcination Methods 0.000 claims abstract description 5
- 238000001914 filtration Methods 0.000 claims abstract description 5
- 239000002105 nanoparticle Substances 0.000 claims description 28
- 238000010438 heat treatment Methods 0.000 claims description 6
- 239000002244 precipitate Substances 0.000 claims description 5
- 239000007772 electrode material Substances 0.000 claims description 4
- 235000007164 Oryza sativa Nutrition 0.000 claims description 3
- 239000013543 active substance Substances 0.000 claims description 3
- 238000001816 cooling Methods 0.000 claims description 3
- 239000010903 husk Substances 0.000 claims description 3
- 239000000203 mixture Substances 0.000 claims description 3
- 239000000843 powder Substances 0.000 claims description 3
- 235000009566 rice Nutrition 0.000 claims description 3
- FWPIDFUJEMBDLS-UHFFFAOYSA-L tin(II) chloride dihydrate Chemical compound O.O.Cl[Sn]Cl FWPIDFUJEMBDLS-UHFFFAOYSA-L 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
- 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
- 238000001291 vacuum drying Methods 0.000 claims description 2
- 240000007594 Oryza sativa Species 0.000 claims 1
- 238000004519 manufacturing process Methods 0.000 claims 1
- 238000000034 method Methods 0.000 abstract description 14
- 238000000151 deposition Methods 0.000 abstract description 10
- 239000000654 additive Substances 0.000 abstract description 9
- 230000000996 additive effect Effects 0.000 abstract description 9
- 230000008021 deposition Effects 0.000 abstract description 6
- 239000000463 material Substances 0.000 abstract description 4
- 229910021626 Tin(II) chloride Inorganic materials 0.000 abstract description 2
- XLYOFNOQVPJJNP-ZSJDYOACSA-N heavy water Substances [2H]O[2H] XLYOFNOQVPJJNP-ZSJDYOACSA-N 0.000 abstract description 2
- 239000011159 matrix material Substances 0.000 abstract description 2
- 238000002844 melting Methods 0.000 abstract description 2
- 230000008018 melting Effects 0.000 abstract description 2
- AXZWODMDQAVCJE-UHFFFAOYSA-L tin(II) chloride (anhydrous) Chemical compound [Cl-].[Cl-].[Sn+2] AXZWODMDQAVCJE-UHFFFAOYSA-L 0.000 abstract description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 18
- 230000000052 comparative effect Effects 0.000 description 11
- YADSGOSSYOOKMP-UHFFFAOYSA-N lead dioxide Inorganic materials O=[Pb]=O YADSGOSSYOOKMP-UHFFFAOYSA-N 0.000 description 7
- 238000012360 testing method Methods 0.000 description 7
- 239000002253 acid Substances 0.000 description 6
- 239000010405 anode material Substances 0.000 description 6
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- 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
- 238000004070 electrodeposition Methods 0.000 description 4
- 239000007774 positive electrode material Substances 0.000 description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 4
- 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
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- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 150000001875 compounds Chemical class 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
- 238000007599 discharging Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000012983 electrochemical energy storage Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 238000003837 high-temperature calcination Methods 0.000 description 1
- 238000001027 hydrothermal synthesis Methods 0.000 description 1
- 229910010272 inorganic material Inorganic materials 0.000 description 1
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- 239000011882 ultra-fine particle Substances 0.000 description 1
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G19/00—Compounds of tin
- C01G19/02—Oxides
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- 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
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/14—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of germanium, tin or lead
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- 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
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- B01J35/33—Electric or magnetic properties
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- 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
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- C01B32/00—Carbon; Compounds thereof
- C01B32/05—Preparation or purification of carbon not covered by groups C01B32/15, C01B32/20, C01B32/25, C01B32/30
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- 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
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- 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
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- H01M10/054—Accumulators with insertion or intercalation of metals other than lithium, e.g. with magnesium or aluminium
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- 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
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- 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
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- 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
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- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
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- H01M4/02—Electrodes composed of, or comprising, active material
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- C01P2004/80—Particles consisting of a mixture of two or more inorganic phases
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Abstract
The invention provides a method for preparing ultra-small SnO particles by taking porous carbon as a matrix2And preparation thereofA method and an application thereof. In this structure, ultra small particles of SnO2Directly anchored on the porous carbon, thereby effectively depositing PbO as a deposition site during the charging of the positive electrode2. And large-sized porous carbon as PbO after deposition2The core of the network, thus constructing a continuous network of charged products. The preparation method mainly comprises the following steps: firstly, the porous carbon is degassed and then mixed with a certain amount of SnCl2·2H2O mixing, melting and impregnating in a vacuum oven at a certain temperature, taking out, filtering off excessive SnCl by using ethanol2·2H2And O, drying and directly calcining in a muffle furnace to obtain the required additive. The preparation process provided by the invention is simple, and the cycle performance of the battery can be obviously improved by using the material obtained by the invention as the lead-carbon battery anode additive.
Description
Technical Field
The invention provides porous carbon supported ultra-small SnO2A simple preparation method of nano particles and application thereof belong 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.
With the circulation, the active material of the positive electrode is gradually changed into independent large particles from a fine porous structureAn active substance. 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. It is well known that cycling of a lead carbon battery is a process of electrodeposition. Due to SnO2And PbO2Is an isomorphous compound, so SnO2Is an effective electrodeposition method for PbO2Which is easily done in electrodeposition. However, directly in SnO2It is very difficult to deposit a fine network structure on large particles. Thus, SnO using ultra-small particles2Can control PbO2The morphology after deposition is still small particle size. Furthermore, ultra-small particle SnO2Has very large surface energy, and thus is isomorphous to the electrodeposition of PbO2Is more advantageous. And large-sized porous carbon as PbO after deposition2The core of the network, thus constructing a continuous network of charged products. But the ultra-small particle size SnO is directly prepared2Is very difficult, and generally requires hydrothermal methods and the like, which are difficult to scale up and are not favorable for practical use. There is a need to find a simple and convenient method for preparing SnO having an ultra-small particle size2. The invention provides a simple preparation method for preparing ultrafine particle SnO2 by using porous carbon as a matrix. In this structure, ultra small particles of SnO2Directly anchored to the porous carbon, thereby allowing efficient deposition of PbO as a deposition site during charging of the positive electrode2The function of (1). The preparation method mainly comprises the following steps: firstly, the porous carbon is degassed and then mixed with a certain amount of SnCl2·2H2O mixing, melting and impregnating in a vacuum oven at a certain temperature, taking out, filtering off excessive SnCl by using ethanol2·2H2And O, drying and directly calcining in a muffle furnace to obtain the required additive. The preparation process provided by the invention is simple, and has great potential in aspects of large-scale production, application to popularization of commercial batteries 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 anode of the existing lead-carbon battery, the invention provides a porous carbon loaded ultra-small SnO which can be simply prepared2The 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 make PbO during charging2Effective deposition on ultra-small SnO2On nanoparticles, thus, fine PbO2The network structure continues to be formed, and the large grain of the positive active material, namely softening and shedding are relieved.
The technical scheme of the invention is as follows:
porous carbon-loaded ultra-small SnO2The preparation method of the nano particle composite material comprises the following steps:
(1) vacuum drying the porous carbon at 100-150 ℃ for 4-8 h;
(2) mixing tin dichloride dihydrate with the porous carbon in the step (1) in a mass ratio of 1-10: 1;
(3) placing the mixture obtained in the step (2) in a vacuum oven, wherein the temperature is 60-90 ℃, and keeping for 4-12 hours;
(4) filtering the white precipitate obtained in the step (3) by using ethanol, and drying the white precipitate in an oven at the temperature of 60-120 ℃ for 3-8 hours;
(5) heating the dried powder to 300-600 ℃ in a muffle furnace at a heating rate of 1-10 ℃/min, keeping the temperature for 0.1-2 h, calcining, and naturally cooling to obtain the porous carbon supported ultra-small SnO2A nanoparticle composite.
In the step (1), the porous carbon is rice hull carbon, coconut shell carbon or ordered mesoporous carbon.
Porous carbon-loaded ultra-small SnO2The nanoparticle composite material is obtained by the preparation method.
Porous carbon-loaded ultra-small SnO2The application of the nano particle composite material in the lead-carbon battery electrode.
Porous carbon-loaded ultra-small SnO2Application of nano particle composite material to lead-carbon battery electrode, and application of porous carbon loaded ultra-small SnO2 nano particle composite material to lead-carbon battery positive electrodeThe mass ratio of the added polar active substance is 0.1-5%.
6. A lead-carbon battery, wherein the positive electrode of the lead-carbon battery is the positive electrode of the lead-carbon battery obtained in claim 4 or 5.
Porous carbon-loaded ultra-small SnO2The nano particle composite material is applied to the fields of other optical and electrochemical materials.
Porous carbon-loaded ultra-small SnO2The 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:
the preparation technology provided by the invention is simple. The precursor can be obtained at normal temperature, and the high-temperature calcination in a muffle furnace is relatively easy 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 SnO2The nano particle composite material is used as a lead-carbon battery positive electrode additive, and can enable PbO to be generated in the charging process2Effective deposition on ultra-small SnO2Large size porous carbon on nanoparticles as post-deposition PbO2The core of the network, thus constructing a continuous network of charged products. The fine PbO2 network structure relieves the large grain of the positive active material, namely softening and dropping, and finally achieves the purpose of improving the performance of the lead-carbon battery.
Description of the drawings:
FIGS. 1(a) and (b) are respectively a porous carbon supported ultra-small SnO prepared in example 1 of the present invention2TEM images and XRD images of the nanoparticle composites.
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 4 mol/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 5 mol/L, and performing a battery performance test after a formation process.
Example 1
(1) The rice husk charcoal was dried under vacuum at 150 ℃ for 6 h.
(2) Mixing tin dichloride dihydrate with the porous carbon in the step (1) in a mass ratio of 3: 1;
(3) putting the mixture obtained in the step (2) into a vacuum oven, and keeping the temperature at 60 ℃ for 6 hours;
(4) filtering the white precipitate with ethanol, and drying in an oven at 60 deg.C for 8 hr;
(5) heating the dried powder to 400 ℃ in a muffle furnace at the heating rate of 2 ℃/min, keeping the temperature for 1h for calcining, and naturally cooling to obtain the porous carbon-loaded ultra-small SnO2A nanoparticle composite material.
Example 2
(1) Commercial positive lead powder and the porous carbon prepared in example 1 loaded with ultra-small SnO2Mixing 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 4 mol/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 5 mol/L, and performing an activation process to test the performance of the battery.
Example 3
(1) The commercial anode lead powder and the porous carbon prepared in the example 1 are loaded with the ultra-small SnO2Mixing the nano particle composite material additive in a stirrer for 2 hours according to the mass ratio of 100:1 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 4 mol/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 5 mol/L, and performing an activation process to test the performance of the battery.
Test examples
Experimental example 1 is porous carbon supported ultra-small SnO prepared in inventive example 12TEM and XRD images of the nanoparticle composite material were obtained on a JSM-2100F (JEO L) type transmission electron microscope instrument and image and a Rigaku D/MAX2550 type instrument, respectively, as shown in FIGS. 1(a) and (b).
It is evident from fig. 1(a) that the both carry particles mostly around 5nm in size. FIG. 1(b) confirms that the carbon composite obtained by the present method indeed contains SnO2Substances corresponding to standard cards numbered 77-0451.
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 the addition of carbon/SnO2The specific discharge capacity of the lead-carbon battery (example 2 and example 3) for the test of the composite is obviously higher than that of the lead-carbon battery without adding carbon/SnO under different multiplying powers2Test of 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/SnO was added2Test lead-carbon batteries of composites (examples 2 and 3) have higher than no added carbon/SnO2Testing of the composites the lead carbon batteries (comparative example 1) had specific discharge capacity and still had good capacity retention.
Claims (8)
1. Porous carbon-loaded ultra-small SnO2The preparation method of the nano particle composite material is characterized by comprising the following steps:
(1) vacuum drying the porous carbon at 100-150 ℃ for 4-8 h;
(2) mixing tin dichloride dihydrate with the porous carbon in the step (1) in a mass ratio of 1-10: 1;
(3) placing the mixture obtained in the step (2) in a vacuum oven, wherein the temperature is 60-90 ℃, and keeping for 4-12 hours;
(4) filtering the white precipitate obtained in the step (3) by using ethanol, and drying the white precipitate in an oven at the temperature of 60-120 ℃ for 3-8 hours;
(5) heating the dried powder to 300-600 ℃ in a muffle furnace at a heating rate of 1-10 ℃/min, keeping the temperature for 0.1-2 h, calcining, and naturally cooling to obtain the porous carbon supported ultra-small SnO2A nanoparticle composite.
2. The porous carbon supported ultra-small SnO as claimed in claim 12The preparation method of the nano particle composite material is characterized by comprising the following steps: step (1)) The porous carbon is rice husk carbon, coconut husk carbon or ordered mesoporous carbon.
3. Porous carbon-loaded ultra-small SnO2A nanoparticle composite material obtained by the production method according to any one of claims 1 to 2.
4. The porous carbon supported ultra-small SnO as claimed in claim 32The application of the nano particle composite material in the lead-carbon battery electrode.
5. The porous carbon supported ultra-small SnO as claimed in claim 42The application of the nano particle composite material on the lead-carbon battery electrode is characterized in that: the porous carbon supported ultra-small SnO2The nano particle composite material is added into the positive active substance of the lead-carbon battery in a mass ratio of 0.1-5%.
6. A lead-carbon battery, characterized in that the positive electrode of the lead-carbon battery is the positive electrode of the lead-carbon battery obtained in claim 4 or 5.
7. The porous carbon supported ultra-small SnO as claimed in claim 22The nano particle composite material is applied to the fields of other optical and electrochemical materials.
8. The porous carbon supported ultra-small SnO of claim 72The 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.
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