CN113193197A - Preparation method of lithium iron phosphate additive for cathode material of commercial lithium battery - Google Patents
Preparation method of lithium iron phosphate additive for cathode material of commercial lithium battery Download PDFInfo
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- CN113193197A CN113193197A CN202110454175.XA CN202110454175A CN113193197A CN 113193197 A CN113193197 A CN 113193197A CN 202110454175 A CN202110454175 A CN 202110454175A CN 113193197 A CN113193197 A CN 113193197A
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- 239000000654 additive Substances 0.000 title claims abstract description 48
- 230000000996 additive effect Effects 0.000 title claims abstract description 39
- GELKBWJHTRAYNV-UHFFFAOYSA-K lithium iron phosphate Chemical compound [Li+].[Fe+2].[O-]P([O-])([O-])=O GELKBWJHTRAYNV-UHFFFAOYSA-K 0.000 title claims abstract description 30
- 238000002360 preparation method Methods 0.000 title claims abstract description 15
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 title claims abstract description 9
- 229910052744 lithium Inorganic materials 0.000 title claims abstract description 9
- 239000010406 cathode material Substances 0.000 title claims description 6
- 239000000843 powder Substances 0.000 claims abstract description 64
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims abstract description 38
- 238000006243 chemical reaction Methods 0.000 claims abstract description 36
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 26
- 238000005406 washing Methods 0.000 claims abstract description 25
- 238000001914 filtration Methods 0.000 claims abstract description 19
- 238000001816 cooling Methods 0.000 claims abstract description 18
- 239000000741 silica gel Substances 0.000 claims abstract description 18
- 229910002027 silica gel Inorganic materials 0.000 claims abstract description 18
- 239000000725 suspension Substances 0.000 claims abstract description 18
- 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 abstract description 12
- 239000008103 glucose Substances 0.000 claims abstract description 12
- 238000001354 calcination Methods 0.000 claims abstract description 11
- 238000001035 drying Methods 0.000 claims abstract description 11
- 238000000227 grinding Methods 0.000 claims abstract description 10
- 238000009210 therapy by ultrasound Methods 0.000 claims abstract description 9
- 238000000967 suction filtration Methods 0.000 claims abstract description 8
- 238000010335 hydrothermal treatment Methods 0.000 claims abstract description 4
- 239000000463 material Substances 0.000 claims description 21
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 16
- 238000010438 heat treatment Methods 0.000 claims description 14
- 239000007787 solid Substances 0.000 claims description 8
- 229910052493 LiFePO4 Inorganic materials 0.000 abstract description 21
- 238000000034 method Methods 0.000 abstract description 6
- 238000004519 manufacturing process Methods 0.000 abstract description 4
- 239000010405 anode material Substances 0.000 abstract description 3
- 238000004140 cleaning Methods 0.000 abstract 1
- 229910010710 LiFePO Inorganic materials 0.000 description 19
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 9
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 8
- 229910052799 carbon Inorganic materials 0.000 description 8
- 229910001416 lithium ion Inorganic materials 0.000 description 8
- 239000004570 mortar (masonry) Substances 0.000 description 8
- 238000011056 performance test Methods 0.000 description 8
- 238000005303 weighing Methods 0.000 description 8
- 238000007605 air drying Methods 0.000 description 7
- IDGUHHHQCWSQLU-UHFFFAOYSA-N ethanol;hydrate Chemical group O.CCO IDGUHHHQCWSQLU-UHFFFAOYSA-N 0.000 description 7
- 239000000377 silicon dioxide Substances 0.000 description 6
- 239000002131 composite material Substances 0.000 description 4
- 230000001351 cycling effect Effects 0.000 description 3
- 239000002245 particle Substances 0.000 description 3
- 239000007774 positive electrode material Substances 0.000 description 3
- 235000012239 silicon dioxide Nutrition 0.000 description 3
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- 238000002441 X-ray diffraction Methods 0.000 description 2
- 229910052782 aluminium Inorganic materials 0.000 description 2
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 2
- 239000011248 coating agent Substances 0.000 description 2
- 238000000576 coating method Methods 0.000 description 2
- 239000011888 foil Substances 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 238000001291 vacuum drying Methods 0.000 description 2
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 1
- 239000002033 PVDF binder Substances 0.000 description 1
- NCZYUKGXRHBAHE-UHFFFAOYSA-K [Li+].P(=O)([O-])([O-])[O-].[Fe+2].[Li+] Chemical compound [Li+].P(=O)([O-])([O-])[O-].[Fe+2].[Li+] NCZYUKGXRHBAHE-UHFFFAOYSA-K 0.000 description 1
- 239000006230 acetylene black Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 238000001311 chemical methods and process Methods 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- 238000004146 energy storage Methods 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 239000007770 graphite material Substances 0.000 description 1
- 238000001027 hydrothermal synthesis Methods 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 238000011835 investigation Methods 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 230000003446 memory effect Effects 0.000 description 1
- 229910021645 metal ion Inorganic materials 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 238000002715 modification method Methods 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- -1 oxygen ion Chemical class 0.000 description 1
- 229920002981 polyvinylidene fluoride Polymers 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
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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
-
- 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
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/58—Selection of substances as active materials, active masses, active liquids of inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy; of polyanionic structures, e.g. phosphates, silicates or borates
- H01M4/5825—Oxygenated metallic salts or polyanionic structures, e.g. borates, phosphates, silicates, olivines
-
- 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
- H01M2004/026—Electrodes composed of, or comprising, active material characterised by the polarity
- H01M2004/028—Positive electrodes
-
- 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
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- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
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- Manufacturing & Machinery (AREA)
- Crystallography & Structural Chemistry (AREA)
- Inorganic Chemistry (AREA)
- Battery Electrode And Active Subsutance (AREA)
Abstract
The invention discloses a preparation method of a lithium iron phosphate additive for a commercial lithium battery anode material. The preparation process comprises the following steps: calcining allochroic silica gel in a muffle furnace, and then grinding the allochroic silica gel into powder A; preparing a glucose solution, placing the glucose solution in a reaction kettle, carrying out hydrothermal treatment for several hours at 160-200 ℃, naturally cooling, filtering the reaction solution, cleaning filter residues, and drying to obtain dry powder B; and adding the powder B and the powder A into a centrifuge tube together according to a certain proportion, adding secondary water for ultrasonic treatment to obtain a suspension, carrying out hydrothermal treatment on the suspension in a reaction kettle for several hours, cooling to room temperature, filtering the reaction solution, washing filter residues for several times, carrying out suction filtration, and drying a sample to obtain the additive. Doping the obtained additive into LiFePO4The lithium iron phosphate can obviously improve the first discharge capacity and show good cycle stability. The preparation method of the inventionSimple method, low cost, cleanness, no pollution and suitability for industrial mass production.
Description
Technical Field
The invention relates to a preparation method of a lithium iron phosphate additive for a commercial lithium battery anode material, belonging to the technical field of energy materials.
Background
Because of the advantages of high specific energy, small self-discharge, long cycle life, no memory effect, small environmental pollution and the like, the lithium ion battery is widely applied to the fields of electronic equipment, electric automobiles, large-scale energy storage, aerospace and the like. In the lithium ion battery, the characteristics of the positive electrode material itself are one of the key factors for controlling the capacity of the lithium ion battery, and therefore, the performance of the positive electrode material of the lithium ion battery is receiving attention. Lithium iron phosphate (LiFePO)4) The lithium ion battery cathode material has the advantages of good safety, low cost, small harm to the environment and the like, and is considered to be the most promising lithium ion battery cathode material. However, the development and application of lithium iron phosphate in the fields of power batteries and the like are severely limited by the defects of low theoretical specific capacity, low conductivity, small lithium ion diffusion coefficient and the like. Recently, many methods have been proposed to improve the performance of lithium iron phosphate. At present to LiFePO4The modification method mainly comprises the following steps: carbon coating, i.e. on LiFePO4The particles are coated with a carbon film to improve the specific capacity, rate capability and cycle life of the particles; by doping, i.e. in LiFePO4The lithium, iron and oxygen ion sites are doped with other metal ions to improve the intrinsic electronic conductivity of the material so as to promote the improvement of the performance of the material; nano-chemical processes, i.e. reduction of LiFePO4The size of the particles is used for preparing the nano lithium iron phosphate so as to improve the electrochemical performance of the nano lithium iron phosphate. Literature investigations have shown that up to now, composites containing silicon dioxide and carbon have been prepared by calcination with hydrothermal processes and used as additives to enhance LiFePO4The performance research is not reported yet.
Disclosure of Invention
The invention aims to provide a preparation method of a lithium iron phosphate additive for a commercial lithium battery cathode material. The method has the advantages of simple operation, cleanness, no pollution and low preparation cost, and is suitable for industrial mass production. After addition of a small amount of this additive, LiFePO4The discharge specific capacity, the rate capability and the cycling stability of the material are greatly improved.
The additive synthesized by the invention is a composite material containing silicon dioxide and carbon, and is added into a commercial lithium battery anode material LiFePO4In (b), the first discharge capacity can be improved.
Specifically, the preparation method comprises the following steps:
preparation of the Material
Glucose; commercially available allochroic silica gel; commercially available lithium iron phosphate
(1) Preparation of samples
Calcining a certain amount of allochroic silica gel in a muffle furnace at 650-900 ℃ for 5-10 h, and then grinding the allochroic silica gel into powder in an agate mortar, wherein the powder is marked as powder A for later use; preparing a glucose solution with the concentration of 0.1-1 mol/L, measuring 15 mL of the solution, placing the solution in a reaction kettle, heating the solution at 160-200 ℃ for 5-10 h, naturally cooling, filtering the reaction solution, washing filter residues with secondary water and absolute ethyl alcohol until the washing solution is colorless, and then placing the obtained solid sample in a forced air drying oven to dry for 6h to obtain dry powder, which is recorded as powder B;
adding the powder B and the powder A into a 10 mL centrifuge tube together according to the mass ratio of 2:3, adding a proper amount of secondary water, performing ultrasonic treatment for 40 min to obtain a suspension, transferring the suspension into a reaction kettle, performing hydrothermal treatment at 160-200 ℃ for 5-10 h, cooling to room temperature, filtering the reaction solution, washing filter residues with secondary water and absolute ethyl alcohol for several times, performing suction filtration, and drying the obtained sample for 6-10 h to obtain the additive.
The preparation process is clean, pollution-free and low in cost, and is suitable for industrial scale production, and the prepared additive can enable LiFePO to be used as LiFePO4The discharge specific capacity, the rate capability and the cycling stability of the material are greatly improved.
Experiments show that the additive is doped into LiFePO according to the mass fraction of 1-5%4The lithium iron phosphate lithium battery is assembled into a half battery, and finally electrochemical performance tests show that the addition of the additive can obviously improve the capacity of the lithium iron phosphate, and the first discharge capacity can be respectively improved when the lithium iron phosphate is charged and discharged at 0.5C, 1C, 2C and 5CThe weight is 45-50%, 40-50%, 30-35% and 25-30%.
The invention has the beneficial effects that: the invention has simple process, namely, the additive can be prepared by a simple calcination and water heating method, and the additive can ensure that LiFePO can be used4The material has obviously improved specific discharge capacity and good cycling stability during high-rate charge and discharge. Has potential application prospect in the commercial lithium ion battery manufacturing industry.
Drawings
FIG. 1 shows doped LiFePO4Materials and pure LiFePO4First charge and discharge curve of the material under 1C multiplying power.
FIG. 2 shows doped LiFePO4Materials and pure LiFePO4Graph of the rate discharge cycle of the material.
FIG. 3 shows doped LiFePO4XRD pattern of the material.
Detailed Description
The following examples serve to illustrate the invention.
Example 1
Calcining a certain amount of allochroic silica gel in a muffle furnace at 800 ℃ for 6h, and then carefully grinding the allochroic silica gel into powder in an agate mortar for later use (marked as powder A); preparing a glucose solution with the concentration of 0.5 mol/L, measuring 15 mL of the solution, placing the solution in a reaction kettle, heating the solution at 180 ℃ for 8 hours, naturally cooling, filtering the reaction solution, washing the filter residue for 5 times by using secondary water and absolute ethanol solution until the washing solution is colorless, and then placing the obtained solid sample in a forced air drying oven to dry for 6 hours to obtain dry powder (marked as powder B).
Respectively weighing 20 mg of powder B and 30 mg of powder A, adding into a 10 mL centrifuge tube together, adding a proper amount of secondary water, and performing ultrasonic treatment for 40 min to obtain a suspension. And then, transferring the suspension into a reaction kettle, heating for 6 hours at 180 ℃, cooling to room temperature, filtering the reaction solution, washing filter residues for a plurality of times by using secondary water and absolute ethyl alcohol, carrying out suction filtration, and drying the obtained sample for 7 hours to obtain the prepared additive. The additive is doped into LiFePO4 by mass fraction of 2%, a half cell is assembled, and finally electrochemical performance test is carried out.
And (3) electrochemical performance testing: accurately weighing lithium iron phosphate, polyvinylidene fluoride and acetylene black according to the mass ratio of 8:1:1, and simultaneously weighing a certain amount of additive (the amount of the additive is 2% of the mass of the lithium iron phosphate). Then, the four substances are jointly placed in an agate mortar for grinding for 20 minutes, and then a proper amount of N-methyl pyrrolidone is dripped to prepare the mixture into paste, wherein the surface of the paste has no granular feel. And then uniformly coating the paste on an aluminum foil, putting the aluminum foil into a vacuum drying oven, carrying out vacuum drying to obtain a lithium iron phosphate electrode, and then forming a half cell with a simple substance lithium sheet by the electrode according to a conventional method for carrying out electrochemical performance test.
FIG. 1 is a schematic representation of the use of LiFePO containing additives4Material (wire a) and pure LiFePO without additives4First charge-discharge curve of material (line o) at 1C rate. It can be seen that pure LiFePO4The specific discharge capacity of the material at the first time is 93 mAhg-1And LiFePO after doping 2% of additive4The first discharge specific capacity of the material reaches 138 mAhg-1The capacity is improved by nearly 48%.
FIG. 2 shows doped LiFePO4Material (wire a) and pure LiFePO4Graph of the rate discharge cycle of the material (line o). It can be seen that LiFePO was doped with 2% of the additive4The specific discharge capacity at 0.5C, 1C, 2C and 5C is higher than that of LiFePO without doping additive4Specific discharge capacity of (2). Pure LiFePO at multiplying power of 2C and 5C4The specific first discharge capacity of the material is 80 mAh g-1、51 mAh g-1And LiFePO after 2% of additive is added4The first discharge specific capacity of the material reaches 113 mAh g-1、 70 mAh g-1The capacity is increased by 41% and 37%, respectively. It can also be seen from FIG. 2 that LiFePO with additives4High discharge capacity at different rates and good cycle stability.
FIG. 3 is LiFePO containing additives4XRD pattern of (a). As can be seen from the figure, the main diffraction peak of the sample is associated with LiFePO4The standard diffraction peak of the compound is well matched, and the LiFePO after being doped with the additive is shown4Does not change. Careful observationDiffraction peaks of silica and elemental carbon were seen to appear in the diffraction peaks of the sample, indicating that the main components of the additive were silica and carbon. Research studies in the literature show that many studies have been reported on addition of silica and carbon as additives to graphite materials, but addition to the positive electrode material LiFePO4The patent method is used for preparing a composite material of silicon dioxide and carbon and adding the composite material into LiFePO4The studies have not been reported.
Example 2
Calcining a certain amount of allochroic silica gel in a muffle furnace at 850 ℃ for 6h, and then carefully grinding the allochroic silica gel into powder in an agate mortar for later use (marked as powder A); preparing a glucose solution with the concentration of 0.5 mol/L, measuring 15 mL of the solution, placing the solution in a reaction kettle, heating the solution at 170 ℃ for 8 hours, naturally cooling, filtering the reaction solution, washing the filter residue for 5 times by using secondary water and absolute ethanol solution until the washing solution is colorless, and then placing the obtained solid sample in a forced air drying oven to dry for 7 hours to obtain dry powder (marked as powder B).
Respectively weighing 30 mg of powder B and 45 mg of powder A, adding the powder B and the powder A into a 10 mL centrifuge tube together, and then adding a proper amount of secondary water for ultrasonic treatment for 40 min to obtain a suspension. And then, transferring the suspension into a reaction kettle, heating for 6 hours at 170 ℃, cooling to room temperature, filtering the reaction solution, washing filter residues for a plurality of times by using secondary water and absolute ethyl alcohol, carrying out suction filtration, and drying the obtained sample for 7 hours to obtain the prepared additive. The additive is doped into LiFePO by 3 percent of mass fraction4Assembling the half cell, and finally carrying out electrochemical performance test. The result shows that the additive can remarkably improve the capacity of the lithium iron phosphate, and the first discharge capacity can be respectively improved by 47 percent, 40 percent, 33 percent and 28 percent when the lithium iron phosphate is charged and discharged at 0.5C, 1C, 2C and 5C.
Example 3
Calcining a certain amount of allochroic silica gel in a muffle furnace at 750 ℃ for 8h, and then carefully grinding the allochroic silica gel into powder in an agate mortar for later use (marked as powder A); preparing a glucose solution with the concentration of 0.5 mol/L, measuring 15 mL of the solution, placing the solution in a reaction kettle, heating the solution at 180 ℃ for 8 hours, naturally cooling, filtering the reaction solution, washing the filter residue for 5 times by using secondary water and absolute ethanol solution until the washing solution is colorless, and then placing the obtained solid sample in a forced air drying oven to dry for 7 hours to obtain dry powder (marked as powder B).
And respectively weighing 40 mg of powder B and 60 mg of powder A, adding the powder B and the powder A into a 10 mL centrifuge tube together, and adding a proper amount of secondary water for ultrasonic treatment for 40 min to obtain a suspension. And then, transferring the suspension into a reaction kettle, heating for 6 hours at 180 ℃, cooling to room temperature, filtering the reaction solution, washing filter residues for a plurality of times by using secondary water and absolute ethyl alcohol, carrying out suction filtration, and drying the obtained sample for 7 hours to obtain the prepared additive. The additive is doped into LiFePO by the mass fraction of 1.5 percent4Assembling the half cell, and finally carrying out electrochemical performance test. The result shows that the additive can remarkably improve the capacity of the lithium iron phosphate, and the first discharge capacity can be respectively improved by 48%, 42%, 34% and 29% when the lithium iron phosphate is charged and discharged at 0.5C, 1C, 2C and 5C.
Example 4
Calcining a certain amount of allochroic silica gel in a muffle furnace at 750 ℃ for 8h, and then carefully grinding the allochroic silica gel into powder in an agate mortar for later use (marked as powder A); preparing a glucose solution with the concentration of 0.5 mol/L, measuring 15 mL of the solution, placing the solution in a reaction kettle, heating the solution at 170 ℃ for 8 hours, naturally cooling, filtering the reaction solution, washing the filter residue for 5 times by using secondary water and absolute ethanol solution until the washing solution is colorless, and then placing the obtained solid sample in a forced air drying oven to dry for 8 hours to obtain dry powder (marked as powder B).
Respectively weighing 10 mg of powder B and 15 mg of powder A, adding the powder B and the powder A into a 10 mL centrifuge tube together, and then adding a proper amount of secondary water for ultrasonic treatment for 40 min to obtain a suspension. And then, transferring the suspension into a reaction kettle, heating for 6 hours at 170 ℃, cooling to room temperature, filtering the reaction solution, washing filter residues for a plurality of times by using secondary water and absolute ethyl alcohol, carrying out suction filtration, and drying the obtained sample for 7 hours to obtain the prepared additive. The additive is doped into LiFePO by the mass fraction of 2%4Assembling the half cell, and finally carrying out electrochemical performance test. The result shows that the additive can obviously improve the capacity of the lithium iron phosphate, and when the lithium iron phosphate is charged and discharged at 0.5C, 1C, 2C and 5C,the first discharge capacity can be respectively increased by 42 percent, 40 percent, 33 percent and 28 percent.
Example 5
Calcining a certain amount of allochroic silica gel in a muffle furnace at 700 ℃ for 8.5h, and then carefully grinding into powder in an agate mortar for later use (denoted as powder A); preparing a glucose solution with the concentration of 0.8 mol/L, measuring 15 mL of the solution, placing the solution in a reaction kettle, heating the solution at 160 ℃ for 8 hours, naturally cooling, filtering the reaction solution, washing the filter residue for 5 times by using secondary water and absolute ethanol solution until the washing solution is colorless, and then placing the obtained solid sample in a forced air drying oven to dry for 7 hours to obtain dry powder (marked as powder B).
Respectively weighing 50 mg of powder B and 75 mg of powder A, adding the powder B and the powder A into a 10 mL centrifuge tube together, and then adding a proper amount of secondary water for ultrasonic treatment for 40 min to obtain a suspension. And then, transferring the suspension into a reaction kettle, heating for 6 hours at 170 ℃, cooling to room temperature, filtering the reaction solution, washing filter residues for a plurality of times by using secondary water and absolute ethyl alcohol, carrying out suction filtration, and drying the obtained sample for 7 hours to obtain the prepared additive. The additive is doped into LiFePO by the mass fraction of 2%4Assembling the half cell, and finally carrying out electrochemical performance test. The result shows that the additive can remarkably improve the capacity of the lithium iron phosphate, and the first discharge capacity can be respectively improved by 47 percent, 42 percent, 33 percent and 29 percent when the lithium iron phosphate is charged and discharged at 0.5C, 1C, 2C and 5C.
Example 6
Calcining a certain amount of allochroic silica gel in a muffle furnace at 680 ℃ for 8h, and then carefully grinding the allochroic silica gel into powder in an agate mortar for later use (marked as powder A); preparing a glucose solution with the concentration of 0.65 mol/L, measuring 15 mL of the solution, placing the solution in a reaction kettle, heating the solution at 170 ℃ for 8 hours, naturally cooling, filtering the reaction solution, washing the filter residue for 5 times by using secondary water and absolute ethanol solution until the washing solution is colorless, and then placing the obtained solid sample in a forced air drying oven to dry for 7 hours to obtain dry powder (marked as powder B).
Respectively weighing 30 mg of powder B and 45 mg of powder A, adding the powder B and the powder A into a 10 mL centrifuge tube together, and then adding a proper amount of secondary water for ultrasonic treatment for 40 min to obtain a suspension. Subsequently, the suspension is transferredHeating in a reaction kettle at 170 deg.C for 6h, cooling to room temperature, filtering the reaction solution, washing the residue with secondary water and anhydrous ethanol for several times, filtering, and drying the obtained sample for 7 h to obtain the prepared additive. The additive is doped into LiFePO by the mass fraction of 4%4Assembling the half cell, and finally carrying out electrochemical performance test. The result shows that the additive can remarkably improve the capacity of the lithium iron phosphate, and the first discharge capacity can be respectively improved by 48%, 42%, 31% and 26% when the lithium iron phosphate is charged and discharged at 0.5C, 1C, 2C and 5C.
Claims (1)
1. A preparation method of a lithium iron phosphate additive for a commercial lithium battery cathode material is characterized by comprising the following steps:
(1) preparation of the Material
Glucose; commercially available allochroic silica gel; commercially available lithium iron phosphate
(2) Preparation of samples
Calcining a certain amount of allochroic silica gel in a muffle furnace at 650-900 ℃ for 5-10 h, and then grinding into powder, and recording the powder as powder A for later use; preparing a glucose solution with the concentration of 0.1-1 mol/L, measuring 15 mL of the solution, placing the solution in a reaction kettle, heating the solution at 160-200 ℃ for 5-10 h, naturally cooling, filtering the reaction solution, washing filter residues with secondary water and absolute ethyl alcohol until the washing solution is colorless, and then placing the obtained solid sample in a drying oven to be dried for 6h to obtain dry powder which is marked as powder B;
adding the obtained powder B and the powder A into a 10 mL centrifuge tube together according to the mass ratio of 2:3, adding a proper amount of secondary water, performing ultrasonic treatment for 40 min to obtain a suspension, transferring the suspension into a reaction kettle, performing hydrothermal treatment at 160-200 ℃ for 5-10 h, cooling to room temperature, filtering the reaction solution, washing filter residues with secondary water and absolute ethyl alcohol for several times, performing suction filtration, and drying the obtained sample for 6-10 h to obtain an additive finished product.
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| CN202110454175.XA CN113193197B (en) | 2021-04-26 | 2021-04-26 | Preparation method of lithium iron phosphate additive for cathode material of commercial lithium battery |
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| CN202110454175.XA CN113193197B (en) | 2021-04-26 | 2021-04-26 | Preparation method of lithium iron phosphate additive for cathode material of commercial lithium battery |
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| CN113193197A true CN113193197A (en) | 2021-07-30 |
| CN113193197B CN113193197B (en) | 2022-03-11 |
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