CN111453767A - Porous SnO2Micron sheet, preparation method thereof and application of micron sheet to positive electrode of lead-carbon battery - Google Patents
Porous SnO2Micron sheet, preparation method thereof and application of micron sheet to positive electrode of lead-carbon battery Download PDFInfo
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- CN111453767A CN111453767A CN202010272015.9A CN202010272015A CN111453767A CN 111453767 A CN111453767 A CN 111453767A CN 202010272015 A CN202010272015 A CN 202010272015A CN 111453767 A CN111453767 A CN 111453767A
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- 229910052799 carbon Inorganic materials 0.000 title claims abstract description 44
- 238000002360 preparation method Methods 0.000 title claims abstract description 16
- XOLBLPGZBRYERU-UHFFFAOYSA-N tin dioxide Chemical compound O=[Sn]=O XOLBLPGZBRYERU-UHFFFAOYSA-N 0.000 claims abstract description 42
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 39
- 229920000036 polyvinylpyrrolidone Polymers 0.000 claims abstract description 14
- 235000013855 polyvinylpyrrolidone Nutrition 0.000 claims abstract description 14
- 239000002244 precipitate Substances 0.000 claims abstract description 13
- 239000001267 polyvinylpyrrolidone Substances 0.000 claims abstract description 12
- 238000010438 heat treatment Methods 0.000 claims abstract description 8
- KHMOASUYFVRATF-UHFFFAOYSA-J tin(4+);tetrachloride;pentahydrate Chemical compound O.O.O.O.O.Cl[Sn](Cl)(Cl)Cl KHMOASUYFVRATF-UHFFFAOYSA-J 0.000 claims abstract description 8
- 238000001354 calcination Methods 0.000 claims abstract description 5
- 238000001035 drying Methods 0.000 claims description 21
- 235000019441 ethanol Nutrition 0.000 claims description 11
- 239000007772 electrode material Substances 0.000 claims description 4
- 239000007774 positive electrode material Substances 0.000 claims description 4
- 238000001816 cooling Methods 0.000 claims description 3
- 238000001914 filtration Methods 0.000 claims description 3
- 239000000843 powder Substances 0.000 claims description 3
- 238000003756 stirring Methods 0.000 claims description 3
- 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
- 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
- 238000004519 manufacturing process Methods 0.000 claims 1
- 238000000034 method Methods 0.000 abstract description 13
- 239000000654 additive Substances 0.000 abstract description 10
- 230000000996 additive effect Effects 0.000 abstract description 10
- 239000000463 material Substances 0.000 abstract description 7
- 239000002904 solvent Substances 0.000 abstract description 4
- 238000001704 evaporation Methods 0.000 abstract description 2
- 238000011031 large-scale manufacturing process Methods 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
- 239000002253 acid Substances 0.000 description 7
- 238000012360 testing method Methods 0.000 description 7
- 239000011248 coating agent Substances 0.000 description 6
- 238000000576 coating method Methods 0.000 description 6
- 239000003792 electrolyte Substances 0.000 description 6
- 239000011505 plaster Substances 0.000 description 6
- 239000010405 anode material Substances 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
- 238000007599 discharging Methods 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
- 230000005540 biological transmission Effects 0.000 description 3
- 238000004146 energy storage Methods 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
- 238000002156 mixing Methods 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
- 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
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- 238000001994 activation Methods 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 238000009826 distribution Methods 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 238000003860 storage Methods 0.000 description 2
- 239000011149 active material Substances 0.000 description 1
- 230000003321 amplification Effects 0.000 description 1
- 239000003575 carbonaceous material Substances 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 229910003460 diamond Inorganic materials 0.000 description 1
- 239000010432 diamond Substances 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000012983 electrochemical energy storage Methods 0.000 description 1
- 230000002708 enhancing effect Effects 0.000 description 1
- 238000002474 experimental method Methods 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
- 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
- 238000011056 performance test Methods 0.000 description 1
- 230000010287 polarization Effects 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 238000010248 power generation Methods 0.000 description 1
- 239000002243 precursor Substances 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 230000002035 prolonged effect Effects 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 230000019635 sulfation Effects 0.000 description 1
- 238000005670 sulfation reaction Methods 0.000 description 1
- VZGDMQKNWNREIO-UHFFFAOYSA-N tetrachloromethane Chemical compound ClC(Cl)(Cl)Cl VZGDMQKNWNREIO-UHFFFAOYSA-N 0.000 description 1
- 238000012546 transfer Methods 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
-
- 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
-
- B01J35/33—
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- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N33/00—Investigating or analysing materials by specific methods not covered by groups G01N1/00 - G01N31/00
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- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N33/00—Investigating or analysing materials by specific methods not covered by groups G01N1/00 - G01N31/00
- G01N33/48—Biological material, e.g. blood, urine; Haemocytometers
-
- 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
- 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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- 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
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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
- H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
- H01M4/624—Electric conductive fillers
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2002/00—Crystal-structural characteristics
- C01P2002/70—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data
- C01P2002/72—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data by d-values or two theta-values, e.g. as X-ray diagram
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/01—Particle morphology depicted by an image
- C01P2004/04—Particle morphology depicted by an image obtained by TEM, STEM, STM or AFM
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
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- C01P2006/40—Electric properties
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
Abstract
The invention relates to a porous SnO2 micron sheet, a preparation method thereof and application thereof in a lead-carbon battery anode.The method comprises the steps of directly dissolving tin tetrachloride pentahydrate and polyvinylpyrrolidone in ethanol at room temperature to obtain white precipitate, and evaporating and recovering the ethanol solvent; then heating the white precipitate in a muffle furnace and calcining for 2h at 500 ℃ to obtain the porous SnO2Micron sheet. The preparation process is simple, the solvent can be recycled, and the method is suitable for large-scale production. The material obtained by the invention is used as the additive of the positive electrode of the lead-carbon battery, and the energy performance and the power performance can be obviously improved.
Description
Technical Field
The invention provides porous SnO2A large-scale preparation method of micron sheets belongs 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 effective utilization rate of the active material of the positive electrode of the lead-carbon battery, the low power performance of the positive electrode, and the like. For example, in the processes of quick charging and quick discharging in wind and solar power generation energy storage, the positive electrode of the lead-carbon battery is influenced by the increase of the resistance of the polar plate and the diffusion resistance of the internal electrolyte, so that the discharge capacity of the battery is greatly limited. Therefore, the additive capable of improving the effective utilization rate of the positive active material is selected, and the power performance and the discharge capacity of the battery can be greatly improved. The tin dioxide is a material which is relatively stable in the lead-carbon battery and has certain conductivity, and researches have been carried out at present to find that the tin dioxide has the effect of improving the conductivity of a positive electrode plate, so that the performance of the positive electrode is greatly improved. However, to date, they have not been designed to have a better conducting network built and their porosity used for lead carbonA battery positive electrode additive. Therefore, the tin dioxide is designed into a micron-sized porous material, and the structure of the tin dioxide can further improve the capability of enhancing a conductive network and storing acid so as to improve the mass transfer capability. On the other hand, the preparation of porous, large-size SnO2 is generally carried out by hydrothermal method and the like at present, which is not very suitable for large-scale preparation for practical application to a lead-carbon battery positive electrode. Therefore, the invention provides a simple and convenient method capable of large-scale preparation to prepare porous SnO2Micron sheet. The process mainly comprises the steps of directly dissolving tin tetrachloride pentahydrate and polyvinylpyrrolidone into ethanol at room temperature to obtain white precipitate, and evaporating and recovering the ethanol solvent; then heating the white precipitate in a muffle furnace and calcining for 2h at 500 ℃ to obtain the porous SnO2Micron sheet. The preparation process is simple, the solvent can be recycled, and the method is suitable for large-scale production. The lead-carbon battery anode can be used as an additive, and the energy performance and the power performance can be obviously improved.
The invention content is as follows:
aiming at the problems of the existing lead-carbon battery anode, the invention provides a porous tin dioxide micron sheet suitable for large-scale preparation, and the porous tin dioxide micron sheet is used as a lead-carbon battery anode additive, and the high-stability porous tin dioxide micron sheet has excellent conductivity and porosity, so that the current distribution capability of the lead-carbon battery anode plate can be effectively improved, and the storage and transmission performance of internal electrolyte can be improved.
The technical scheme of the invention is as follows:
porous SnO2The preparation method of the micron sheet comprises the following steps:
(1) adding polyvinylpyrrolidone into absolute ethyl alcohol, and stirring for dissolving, wherein; polyvinylpyrrolidone: the mass ratio of the ethanol is 1-10: 100;
(2) adding tin tetrachloride pentahydrate into the solution to obtain a white precipitate, wherein the mass ratio of polyvinylpyrrolidone to tin tetrachloride pentahydrate is 1: 0.1-5;
(3) filtering the white precipitate solution, and recovering ethanol for reuse;
(4) drying the white precipitate in an oven at the temperature of 60-120 ℃ for 3-8 h;
(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 porous SnO2Micron sheet.
Porous SnO2The micron sheet is obtained by the preparation method.
The porous SnO2The application of the micron sheet in the positive electrode of the lead-carbon battery.
The porous SnO2The mass ratio of the micron sheet to the positive active material of the lead-carbon battery is 0.1-5%.
The positive electrode of the lead-carbon battery is the obtained positive electrode of the lead-carbon battery.
The porous SnO2The micron sheet is applied in other fields of optical and electrochemical materials.
The porous SnO2The micron sheet is applied to the fields of electro-catalysts, biosensors, lithium ion battery electrode materials, sodium ion battery electrode materials and photosensitivity.
Compared with the prior art, the invention has the following advantages:
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. The porous tin dioxide micron sheet is selected as the lead-carbon battery anode additive, and the lead-carbon battery anode additive has the characteristics of conductivity and porosity, so that the current distribution in the anode plate can be improved, and the storage and transmission performance of electrolyte can be improved; in the discharging process, certain conductivity of the positive plate can be always kept, and concentration polarization of positive reaction can be reduced, so that the discharging capacity can be improved, the cycle life can be prolonged, and the aim of improving the discharging capacity and the power performance of the lead-carbon battery can be finally achieved.
Description of the drawings:
FIGS. 1(a) and (b) are respectively the products prepared in example 1 of the present inventionPorous SnO2TEM and XRD images of the microsheet material.
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) Adding polyvinylpyrrolidone into ethanol according to a certain mass ratio, and stirring for dissolving, wherein the polyvinylpyrrolidone is prepared by mixing polyvinylpyrrolidone with ethanol; polyvinylpyrrolidone: 2:100 of ethanol;
(2) adding a certain mass of tin tetrachloride pentahydrate into the ethanol solution of the PVP to obtain a white precipitate, wherein the mass ratio of the PVP to the tin tetrachloride pentahydrate is 1: 1;
(3) filtering the white precipitate solution, and recovering ethanol for reuse;
(4) drying the white precipitate in an oven at the temperature of 80 ℃ for 5 hours;
(5) heating the dried powder to 400 ℃ in a muffle furnace at the heating rate of 1 ℃/min, keeping the temperature for 1h for calcining, and naturally cooling to obtain porous SnO2Micron sheet.
Example 2
(1) Commercial positive lead powder was mixed with the porous SnO prepared in example 12Mixing the micron sheet 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) Commercial positive lead powder was mixed with the porous SnO prepared in example 12Mixing the micron sheet additive in a stirrer for 2 hours according to a mass ratio of 100:1 to obtain the required lead-carbon battery positive electrode 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 porous SnO prepared in example 1 of the present invention2TEM and XRD images of the microtablets obtained on a transmission electron microscope instrument and image of model JSM-2100F (JEO L) and a Rigaku D/MAX2550 instrument, respectively, as shown in FIGS. 1(a) and (b).
As is apparent from FIG. 1(a), the resulting material has a sheet-like porous structure, and FIG. 1(b) confirms that the material obtained by the present method has a sheet-like porous structureThe resulting carbon composite does contain SnO2Substances corresponding to standard cards numbered 77-0451. The above results illustrate that the resulting material is porous SnO2Micron sheet.
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.
It can be seen from FIG. 2 that porous SnO is added2The specific discharge capacity of the test lead-carbon batteries with micron sheets (example 2 and example 3) under different multiplying powers is obviously higher than that of the test lead-carbon battery without the porous SnO2 micron sheet (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.
It can be seen from FIG. 3 that porous SnO is added2Test lead-carbon batteries of micron sheets (examples 2 and 3) have higher SnO than without the addition of porous SnO2Test of the micro-sheets the lead-carbon battery (comparative example 1) has a specific discharge capacity and still has a good capacity retention.
Claims (7)
1. Porous SnO2The preparation method of the micron sheet is characterized by comprising the following steps:
(1) adding polyvinylpyrrolidone into absolute ethyl alcohol, and stirring for dissolving, wherein; polyvinylpyrrolidone: the mass ratio of the ethanol is 1-10: 100;
(2) adding tin tetrachloride pentahydrate into the solution to obtain a white precipitate, wherein the mass ratio of polyvinylpyrrolidone to tin tetrachloride pentahydrate is 1: 0.1-5;
(3) filtering the white precipitate solution, and recovering ethanol for reuse;
(4) drying the white precipitate in an oven at the temperature of 60-120 ℃ for 3-8 h;
(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 porous SnO2Micron sheet.
2. Porous SnO2A micron sheet, which is obtained by the production process according to claim 1.
3. A porous SnO according to claim 22The application of the micron sheet in the positive electrode of the lead-carbon battery.
4. A porous SnO according to claim 32The application of the micron sheet on the positive electrode of the lead-carbon battery is characterized in that the porous SnO2The mass ratio of the micron sheet to the positive active material of the lead-carbon battery is 0.1-5%.
5. 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 3 or 4.
6. A porous SnO according to claim 22The micron sheet is applied in other fields of optical and electrochemical materials.
7. A porous SnO according to claim 62The micron sheet 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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| CN109179491A (en) * | 2018-11-09 | 2019-01-11 | 五邑大学 | A kind of fast-growth SnO2The method of nanometer sheet |
| CN110606503A (en) * | 2019-09-16 | 2019-12-24 | 安徽师范大学 | Gold-modified porous tin dioxide micro-nanosheet composite material and preparation method and application thereof |
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| CN109179491A (en) * | 2018-11-09 | 2019-01-11 | 五邑大学 | A kind of fast-growth SnO2The method of nanometer sheet |
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