CN115286034B - Preparation method of basic lead sulfate material, basic lead sulfate material and application - Google Patents
Preparation method of basic lead sulfate material, basic lead sulfate material and application Download PDFInfo
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- CN115286034B CN115286034B CN202210791736.XA CN202210791736A CN115286034B CN 115286034 B CN115286034 B CN 115286034B CN 202210791736 A CN202210791736 A CN 202210791736A CN 115286034 B CN115286034 B CN 115286034B
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- 239000000463 material Substances 0.000 title claims abstract description 35
- PIJPYDMVFNTHIP-UHFFFAOYSA-L lead sulfate Chemical compound [PbH4+2].[O-]S([O-])(=O)=O PIJPYDMVFNTHIP-UHFFFAOYSA-L 0.000 title claims abstract description 28
- 238000002360 preparation method Methods 0.000 title claims abstract description 14
- 238000001354 calcination Methods 0.000 claims abstract description 28
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims abstract description 22
- 238000000034 method Methods 0.000 claims abstract description 22
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 14
- 229910052799 carbon Inorganic materials 0.000 claims abstract description 14
- 239000002253 acid Substances 0.000 claims abstract description 11
- -1 saccharide compound Chemical class 0.000 claims abstract description 9
- 238000002156 mixing Methods 0.000 claims abstract description 8
- 239000002994 raw material Substances 0.000 claims abstract description 6
- 239000011248 coating agent Substances 0.000 claims abstract description 4
- 238000000576 coating method Methods 0.000 claims abstract description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 3
- 239000012298 atmosphere Substances 0.000 claims description 13
- 239000007789 gas Substances 0.000 claims description 12
- 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
- 238000004321 preservation Methods 0.000 claims description 6
- WQZGKKKJIJFFOK-GASJEMHNSA-N Glucose Natural products OC[C@H]1OC(O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-GASJEMHNSA-N 0.000 claims description 5
- 150000001720 carbohydrates Chemical class 0.000 claims description 5
- 239000008103 glucose Substances 0.000 claims description 5
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 4
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 4
- 230000035484 reaction time Effects 0.000 claims description 4
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 3
- 235000014633 carbohydrates Nutrition 0.000 claims description 3
- 239000007772 electrode material Substances 0.000 claims description 3
- 239000007788 liquid Substances 0.000 claims description 3
- 239000001301 oxygen Substances 0.000 claims description 3
- 229910052760 oxygen Inorganic materials 0.000 claims description 3
- OWEGMIWEEQEYGQ-UHFFFAOYSA-N 100676-05-9 Natural products OC1C(O)C(O)C(CO)OC1OCC1C(O)C(O)C(O)C(OC2C(OC(O)C(O)C2O)CO)O1 OWEGMIWEEQEYGQ-UHFFFAOYSA-N 0.000 claims description 2
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 claims description 2
- HEBKCHPVOIAQTA-QWWZWVQMSA-N D-arabinitol Chemical compound OC[C@@H](O)C(O)[C@H](O)CO HEBKCHPVOIAQTA-QWWZWVQMSA-N 0.000 claims description 2
- WQZGKKKJIJFFOK-QTVWNMPRSA-N D-mannopyranose Chemical compound OC[C@H]1OC(O)[C@@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-QTVWNMPRSA-N 0.000 claims description 2
- 229930091371 Fructose Natural products 0.000 claims description 2
- 239000005715 Fructose Substances 0.000 claims description 2
- RFSUNEUAIZKAJO-ARQDHWQXSA-N Fructose Chemical compound OC[C@H]1O[C@](O)(CO)[C@@H](O)[C@@H]1O RFSUNEUAIZKAJO-ARQDHWQXSA-N 0.000 claims description 2
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 2
- LKDRXBCSQODPBY-AMVSKUEXSA-N L-(-)-Sorbose Chemical compound OCC1(O)OC[C@H](O)[C@@H](O)[C@@H]1O LKDRXBCSQODPBY-AMVSKUEXSA-N 0.000 claims description 2
- GUBGYTABKSRVRQ-PICCSMPSSA-N Maltose Natural products O[C@@H]1[C@@H](O)[C@H](O)[C@@H](CO)O[C@@H]1O[C@@H]1[C@@H](CO)OC(O)[C@H](O)[C@H]1O GUBGYTABKSRVRQ-PICCSMPSSA-N 0.000 claims description 2
- 229920002472 Starch Polymers 0.000 claims description 2
- CZMRCDWAGMRECN-UGDNZRGBSA-N Sucrose Chemical compound O[C@H]1[C@H](O)[C@@H](CO)O[C@@]1(CO)O[C@@H]1[C@H](O)[C@@H](O)[C@H](O)[C@@H](CO)O1 CZMRCDWAGMRECN-UGDNZRGBSA-N 0.000 claims description 2
- 229930006000 Sucrose Natural products 0.000 claims description 2
- 229910052786 argon Inorganic materials 0.000 claims description 2
- WQZGKKKJIJFFOK-VFUOTHLCSA-N beta-D-glucose Chemical compound OC[C@H]1O[C@@H](O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-VFUOTHLCSA-N 0.000 claims description 2
- GUBGYTABKSRVRQ-QUYVBRFLSA-N beta-maltose Chemical compound OC[C@H]1O[C@H](O[C@H]2[C@H](O)[C@@H](O)[C@H](O)O[C@@H]2CO)[C@H](O)[C@@H](O)[C@@H]1O GUBGYTABKSRVRQ-QUYVBRFLSA-N 0.000 claims description 2
- 229910002091 carbon monoxide Inorganic materials 0.000 claims description 2
- 239000001913 cellulose Substances 0.000 claims description 2
- 229920002678 cellulose Polymers 0.000 claims description 2
- 239000001307 helium Substances 0.000 claims description 2
- 229910052734 helium Inorganic materials 0.000 claims description 2
- SWQJXJOGLNCZEY-UHFFFAOYSA-N helium atom Chemical compound [He] SWQJXJOGLNCZEY-UHFFFAOYSA-N 0.000 claims description 2
- 239000001257 hydrogen Substances 0.000 claims description 2
- 229910052739 hydrogen Inorganic materials 0.000 claims description 2
- HEBKCHPVOIAQTA-UHFFFAOYSA-N meso ribitol Natural products OCC(O)C(O)C(O)CO HEBKCHPVOIAQTA-UHFFFAOYSA-N 0.000 claims description 2
- 229910052757 nitrogen Inorganic materials 0.000 claims description 2
- 239000008107 starch Substances 0.000 claims description 2
- 235000019698 starch Nutrition 0.000 claims description 2
- 239000005720 sucrose Substances 0.000 claims description 2
- 239000002245 particle Substances 0.000 abstract description 9
- 238000005054 agglomeration Methods 0.000 abstract description 3
- 230000002776 aggregation Effects 0.000 abstract description 3
- 239000000654 additive Substances 0.000 abstract description 2
- 230000000996 additive effect Effects 0.000 abstract description 2
- 238000010335 hydrothermal treatment Methods 0.000 abstract description 2
- 230000000052 comparative effect Effects 0.000 description 7
- 239000013078 crystal Substances 0.000 description 4
- 239000011505 plaster Substances 0.000 description 4
- 238000003756 stirring Methods 0.000 description 4
- 239000002243 precursor Substances 0.000 description 3
- 239000000243 solution Substances 0.000 description 3
- 239000007864 aqueous solution Substances 0.000 description 2
- 239000012299 nitrogen atmosphere Substances 0.000 description 2
- 239000002667 nucleating agent Substances 0.000 description 2
- 239000007774 positive electrode material Substances 0.000 description 2
- 229910052924 anglesite Inorganic materials 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000004146 energy storage Methods 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 125000002791 glucosyl group Chemical group C1([C@H](O)[C@@H](O)[C@H](O)[C@H](O1)CO)* 0.000 description 1
- 238000003837 high-temperature calcination Methods 0.000 description 1
- 230000001771 impaired effect Effects 0.000 description 1
- OCWMFVJKFWXKNZ-UHFFFAOYSA-L lead(2+);oxygen(2-);sulfate Chemical compound [O-2].[O-2].[O-2].[Pb+2].[Pb+2].[Pb+2].[Pb+2].[O-]S([O-])(=O)=O OCWMFVJKFWXKNZ-UHFFFAOYSA-L 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 230000006911 nucleation Effects 0.000 description 1
- 238000010899 nucleation Methods 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 238000005245 sintering Methods 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 238000005728 strengthening Methods 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
Classifications
-
- 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
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/14—Electrodes for lead-acid accumulators
- H01M4/16—Processes of manufacture
-
- 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
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/10—Particle morphology extending in one dimension, e.g. needle-like
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/60—Particles characterised by their size
- C01P2004/61—Micrometer sized, i.e. from 1-100 micrometer
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2006/00—Physical properties of inorganic compounds
- C01P2006/40—Electric properties
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2006/00—Physical properties of inorganic compounds
- C01P2006/80—Compositional purity
-
- 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)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Manufacturing & Machinery (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Inorganic Chemistry (AREA)
- Battery Electrode And Active Subsutance (AREA)
Abstract
The application discloses a preparation method of a basic lead sulfate material, the basic lead sulfate material and application thereof, comprising the following steps: (1) Will contain PbSO 4 Mixing the raw materials of sugar and water, and performing hydrothermal treatment to obtain carbon-coated PbSO 4 The method comprises the steps of carrying out a first treatment on the surface of the (2) Coating carbon with PbSO 4 Mixing with PbO and dilute sulfuric acid, preserving heat, calcining I and II, and obtaining the basic lead sulfate material. By using the preparation method, agglomeration and growth of the 4BS particles in the calcination process can be blocked by adding the saccharide compound. The basic lead sulfate prepared by the method has small particles and high purity, can be used as a positive electrode additive of a lead-acid battery, and can enhance the strength of a positive electrode plate. And the preparation method of the basic lead sulfate material is simple and can be prepared in batch.
Description
Technical Field
The application belongs to the technical field of electrode materials, and particularly relates to a preparation method of a basic lead sulfate material, the basic lead sulfate material and application.
Background
Softening and stripping of the positive electrode is one of the main causes of failure of lead acid batteries. In the manufacturing process of the lead-acid battery, the positive electrode material is converted into tribasic lead sulfate (3 PbO.PbSO during the curing process 4 Abbreviated as 3 BS) and tetrabasic lead sulphate (4 pbo.pbso4, abbreviated as 4 BS). Compared with 3BS,4BS, the lead paste has thicker crystal grains, can play a role in strengthening the lead paste structure in the positive plate, lightens the problems of softening and falling off of the positive electrode, and prolongs the charge-discharge cycle life of the battery. 4BS crystals are pre-added into the lead plaster, and can be used as a nucleating agent in the curing process, so that the nucleation speed of 4BS is increased, more positive electrode materials are induced to be converted into 4BS, and the crystal growth and the content of 4BS in the lead plaster are promoted to be increased. The preparation of 4BS crystals by a high-temperature sintering method has received a great deal of attention by virtue of low cost and high yield. However, in the high-temperature calcination process, due to agglomeration and particle growth, the prepared 4BS particles tend to be too large, and have poor dispersibility in the lead plaster, so that the effect of the lead plaster nucleating agent is seriously impaired. Therefore, there is a need forA preparation method of small-particle high-purity basic lead sulfate material is provided.
Disclosure of Invention
In order to solve the technical problems, the application provides a basic lead sulfate material.
According to one aspect of the present application, there is provided a method of preparing a basic lead sulphate material comprising the steps of:
(1) Will contain PbSO 4 Mixing the raw materials of the carbohydrate and water, and reacting to obtain the carbon-coated PbSO 4 ；
(2) Coating the carbon-coated PbSO obtained in (1) 4 Mixing with PbO and sulfuric acid, preserving heat, calcining I and II, and obtaining the basic lead sulfate material.
The saccharide compound is at least one of glucose, sucrose, fructose, cellulose, mannose, arabitol, sorbose, maltose or starch;
alternatively, the carbohydrate is selected from glucose.
The solid-liquid ratio of the raw materials is 5:1 to 1:10; the solid-to-liquid ratio in the raw materials is selected from 5: 1. 5: 2. 5: 3. 5: 4. 1: 1. 1: 2. 1: 3. 1: 4. 1: 5. 1: 6. 1: 7. 1: 8. 1: 9. 1:10;
the saccharide compound and the PbSO 4 The mass ratio of (2) is 1:0.5 to 1:10;
optionally, the saccharide compound is mixed with the PbSO 4 The mass ratio of (2) is 1: 1-2: 1.
optionally, the saccharide compound is mixed with the PbSO 4 Is selected from the group consisting of 2:1, 1:1, 1:2, 1:3, 1:4, 1:5, 1:6, 1:8, 1:10.
The temperature of the reaction is 120-250 ℃;
optionally, the temperature of the reaction is 150-200 ℃; the upper limit of the temperature of the reaction is 200 ℃, 190 ℃,180 ℃, 170 ℃ and 160 ℃; the lower limit is 150 ℃, 160 ℃, 170 ℃,180 ℃ and 190 ℃;
the reaction time is 1-10 h;
optionally, the reaction time is 4-8 hours; the upper time limit of the reaction is 8h, 7h, 6h and 5h; the lower limit is 4h, 5h, 6h and 7h.
The carbon-coated PbSO 4 The mass ratio of the PbO to the PbO is 1: 30-1: 10;
the molar concentration of the dilute sulfuric acid is 0.5-3M;
optionally, the molar concentration of the dilute sulfuric acid is 1-2M;
the carbon-coated PbSO 4 The molar ratio of Pb in PbO to sulfate radical in the dilute sulfuric acid is 5:1 to 8:1.
the temperature of the heat preservation is 60-100 ℃; the temperature of the heat preservation is 80 ℃;
the heat preservation time is 0.5-4 h. The time of the heat preservation is 1 hour.
The temperature of the calcination I is 200-700 ℃; the temperature of the calcination I is 300 ℃, 450 ℃ and 650 ℃.
The time of calcining the material I is 1-10 h; the time of calcining I is 2 hours, 4 hours and 6 hours.
The atmosphere of the calcination I is a gas atmosphere or vacuum;
the gas atmosphere is selected from inactive gas or/and reducing gas;
the inactive gas is selected from at least one of nitrogen, argon or helium;
the reducing gas is selected from hydrogen or/and carbon monoxide;
the vacuum degree of the vacuum is 1 x 10 -3 Pa～1.5*10 -3 Pa。
The temperature of the calcination II is 300-800 ℃; the temperature of the calcination II is 300 ℃, 400 ℃, 500 ℃, 600 ℃, 700 ℃ and 800 ℃.
The time of calcining II is 1-15 h; the time of calcination II is 1 hour, 2 hours, 4 hours, 6 hours, 8 hours, 10 hours, 12 hours, 14 hours, 15 hours.
The atmosphere of calcination II comprises an oxygen-containing atmosphere comprising oxygen or air.
Specifically, the method comprises the following steps:
(1) PbSO is processed 4 The material is uniformly mixed with the aqueous solution of the saccharides, and the saccharides are polymerized on the surface of the material by high-temperature hydrothermal treatment to form the carbon-coated PbSO 4 ；
(2) Coating carbon with PbSO 4 Uniformly mixing the material with PbO material, adding a certain amount of H 2 SO 4 Stirring the solution uniformly, and preserving heat for a period of time;
(2) Subjecting the above mixture to a first stage calcination (calcination I) to prepare a carbonaceous 4BS material;
(3) The carbonaceous basic lead sulfate material was subjected to a second stage calcination (calcination II) in an oxidizing atmosphere to prepare a 4BS material.
According to another aspect of the application, there is provided a basic lead sulphate material prepared by the above-described preparation method.
According to another aspect of the present application there is provided the use of a basic lead sulphate material as described above for an electrode material for a lead acid battery.
The application has the beneficial effects that:
1. the application provides a basic lead sulfate material and a preparation method thereof. By using the preparation method, agglomeration and growth of the 4BS particles in the calcination process can be blocked by adding the saccharide compound.
2. The basic lead sulfate prepared by the method has small particles and high purity, can be used as a positive electrode additive of a lead-acid battery, and can enhance the strength of a positive electrode plate. And the preparation method of the basic lead sulfate material is simple and can be prepared in batch.
Drawings
Figure 1 is an XRD photograph of the product prepared in example 1.
Figure 2 is an XRD photograph of the product prepared in comparative example 1.
Fig. 3 is an SEM photograph of the product prepared in example 1.
Fig. 4 is an SEM photograph of the product prepared in comparative example 1.
Detailed Description
The present application will be described in further detail with reference to specific examples. It is to be understood that the following examples are illustrative only and are not to be construed as limiting the scope of the application. All techniques implemented based on the above description of the application are intended to be included within the scope of the application.
Unless otherwise indicated, the starting materials and reagents used in the following examples were either commercially available or may be prepared by known methods.
Example 1
Step 1) PbSO is processed 4 Adding glucose into 1L of aqueous solution according to the mass ratio of 10:1, uniformly stirring, putting into a hydrothermal kettle, keeping the temperature at 180 ℃ for 5 hours, cooling to room temperature and taking out at 25 ℃;
step 2) mixing the product with PbO according to the formula 1:4, adding 8mL of dilute sulfuric acid solution with the molar concentration of 1mol/L, uniformly stirring, preserving heat for 1.5 hours at 80 ℃, filtering and drying to obtain a precursor;
step 2) placing the precursor into a tube furnace, and calcining for 4 hours at 550 ℃ under the protection of nitrogen atmosphere to prepare a carbon-containing 4BS material;
and 3) calcining the carbon-containing 4BS material for 2 hours at 600 ℃ in the air atmosphere of a box furnace to prepare the 4BS material.
Figure 1 is an XRD photograph of the product prepared in example 1 and a 4BS standard card. From the figure, the prepared basic lead sulfate is well matched with basic lead sulfate marking card (PDF#23-0333), and is a high-purity basic lead sulfate product.
Fig. 3 is an SEM photograph of the product prepared in example 1. As can be seen from the figure, the prepared basic lead sulfate has a bar-shaped structure, the width is about 4um, the length is about 10um, and the particle size is smaller.
Comparative example 1
Step 1) PbO and PbSO4 are mixed according to 4:1, adding 8mL of dilute sulfuric acid solution with the molar concentration of 1mol/L, stirring uniformly, and preserving the temperature at 80 ℃ for 1.5 hours;
step 2) placing the precursor into a box-type furnace air atmosphere to calcine at 550 ℃ for 4 hours to prepare the 4BS material.
Figure 2 is an XRD photograph of the product prepared in comparative example 1. From the figure, the prepared basic lead sulfate is well matched with basic lead sulfate marking card (PDF#23-0333), and is a high-purity basic lead sulfate product.
Fig. 4 is an SEM photograph of the product prepared in comparative example 1. The rod-shaped structure can be seen from the figure, the width is about 6um, the length is about 25um, and the particle size is larger.
Example 2
Other conditions are the same as in example 1, except that in step 1), glucose and PbSO are used in step 1) 4 The mass ratio of (2) is 8:1.
Example 3
Other conditions were the same as in example 1, except that in step 2), calcination was conducted at 550℃for 2 hours under a nitrogen atmosphere.
Test example 1
The 4BS obtained in comparative example 1 or the 4BS obtained in examples 1 to 3 was added to lead-acid battery positive electrode lead paste, and then the positive electrode and the lead negative electrode were matched to prepare a lead-acid battery, and cycle life test was performed, and the test method was performed in GB22476-2008 "energy storage lead-acid storage battery". Measured data and compared with the implementation
Table 1 electrical properties of lead acid batteries
It is demonstrated that the positive electrode of the lead acid battery with the addition of basic lead sulfate exhibited a longer cycle life than comparative example 1.
While the application has been described in terms of preferred embodiments, it will be understood by those skilled in the art that various changes and modifications can be made without departing from the scope of the application, and it is intended that the application is not limited to the specific embodiments disclosed.
Claims (11)
1. A preparation method of basic lead sulfate material is characterized in that,
the method comprises the following steps:
(1) Will contain PbSO 4 Mixing the raw materials of the carbohydrate and water, and reacting to obtain the carbon-coated PbSO 4 ；
(2) Coating the carbon-coated PbSO obtained in (1) 4 Mixing with PbO and sulfuric acid, preserving heat, calcining I and II to obtain the basic lead sulfate material;
the temperature of the calcination I is 200-700 ℃;
the time of calcining the material I is 1-10 h;
the atmosphere of the calcination I is a gas atmosphere or vacuum;
the temperature of the calcination II is 300-800 ℃;
the time of calcining II is 1-15 h;
the solid-liquid ratio of the raw materials is 5: 1-1: 10;
the saccharide compound and the PbSO 4 The mass ratio of (2) is 1: 0.5-1: 10;
the temperature of the reaction is 120-250 ℃;
the reaction time is 1-10 h;
the carbon-coated PbSO 4 The mass ratio of the PbO to the PbO is 1: 30-1: 10;
the gas atmosphere is selected from inactive gas or/and reducing gas;
the inactive gas is selected from at least one of nitrogen, argon or helium;
the reducing gas is selected from hydrogen or/and carbon monoxide;
the vacuum degree of the vacuum is 1 x 10 -3 Pa~1.5*10 -3 Pa；
The atmosphere of calcination II comprises an oxygen-containing atmosphere.
2. The method according to claim 1, wherein,
the saccharide compound is at least one selected from glucose, sucrose, fructose, cellulose, mannose, arabitol, sorbose, maltose or starch.
3. The method according to claim 1, wherein,
the saccharide compound and the PbSO 4 The mass ratio of (2) is 1: 1-2: 1.
4. the method according to claim 1, wherein,
the reaction temperature is 150-200 ℃.
5. The method according to claim 1, wherein,
the reaction time is 4-8 hours.
6. The method according to claim 1, wherein,
the molar concentration of the sulfuric acid is 0.5-3M.
7. The method according to claim 1, wherein,
the molar concentration of the sulfuric acid is 1-2M.
8. The method according to claim 1, wherein,
the carbon-coated PbSO 4 The molar ratio of Pb in PbO to sulfate radical in the sulfuric acid is 5: 1-8: 1.
9. the method according to claim 1, wherein,
the temperature of the heat preservation is 60-100 ℃;
the heat preservation time is 0.5-4 h.
10. A basic lead sulphate material prepared by the preparation method of any one of claims 1 to 9.
11. The use of basic lead sulphate material as claimed in claim 10, wherein,
an electrode material for a lead acid battery.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202210791736.XA CN115286034B (en) | 2022-07-07 | 2022-07-07 | Preparation method of basic lead sulfate material, basic lead sulfate material and application |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202210791736.XA CN115286034B (en) | 2022-07-07 | 2022-07-07 | Preparation method of basic lead sulfate material, basic lead sulfate material and application |
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