CN113363495A - Ag2CrO4Preparation method of @ Ag modified carbon fluoride cathode material - Google Patents

Ag2CrO4Preparation method of @ Ag modified carbon fluoride cathode material Download PDF

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CN113363495A
CN113363495A CN202110722718.1A CN202110722718A CN113363495A CN 113363495 A CN113363495 A CN 113363495A CN 202110722718 A CN202110722718 A CN 202110722718A CN 113363495 A CN113363495 A CN 113363495A
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carbon fluoride
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mixed
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CN113363495B (en
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张红梅
肖鹏
王京亮
姚德明
甘潦
王庆杰
石斌
王毅
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Chongqing University
Guizhou Meiling Power Supply Co Ltd
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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
    • H01M4/628—Inhibitors, e.g. gassing inhibitors, corrosion inhibitors
    • 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
    • H01M4/583—Carbonaceous material, e.g. graphite-intercalation compounds or CFx
    • H01M4/5835—Comprising fluorine or fluoride salts
    • 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
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
    • H01M4/624—Electric conductive fillers
    • H01M4/626—Metals
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M6/00—Primary cells; Manufacture thereof
    • H01M6/14—Cells with non-aqueous electrolyte
    • 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
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    • 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 the technical field of modification of carbon fluoride anode materials, in particular to Ag2CrO4The preparation method of the @ Ag modified fluorocarbon cathode material comprises the following steps: (1) preparing a potassium chromate solution; (2) preparing a carbon fluoride dispersion liquid; (3) preparing a mixed solution: uniformly stirring the potassium chromate solution and the carbon fluoride dispersion liquid to prepare a mixed solution; (4) preparing a silver nitrate solution; (5) preparing mixed slurry: slowly adding a silver nitrate solution into the mixed solution, continuing to react after the addition is finished to prepare a mixed reaction solution, and carrying out high-energy ball milling to prepare a mixed slurry; (6) drying and sieving the mixed slurry to obtain mixed powder; (7) and (3) calcining: calcining the mixed powder to obtain the catalyst; the invention effectively solves the problem of voltage lag at the initial discharge stage of the carbon fluoride battery, improves the rate capability,The platform voltage reduces the temperature rise of the lithium fluorocarbon battery in the discharging process, and the preparation method is simple and low in cost.

Description

Ag2CrO4Preparation method of @ Ag modified carbon fluoride cathode material
Technical Field
The invention relates to the technical field of modification of carbon fluoride anode materials, in particular to Ag2CrO4A preparation method of a @ Ag modified fluorocarbon cathode material.
Background
A primary lithium battery (primary lithium battery), which is a high-energy chemical primary battery, commonly called a lithium battery, uses metal lithium as a negative electrode, solid salts or salts dissolved in an organic solvent as an electrolyte, and metal oxides or other solid and liquid oxidants as positive active materials. The developed systems at present mainly include lithium-manganese dioxide batteries, lithium-thionyl chloride batteries, lithium-sulfur dioxide batteries and the like. In recent years, lithium-fluorocarbon batteries have attracted attention because of their higher energy density. However, the carbon fluoride is a compound formed by the reaction of carbon in various forms and fluorine gas, so that the carbon fluoride material has poor conductivity, and the problems of serious voltage delay in the initial discharge stage of the material, poor large-current discharge capacity, heat generation and the like are caused, so that the lithium-carbon fluoride battery generates large electrochemical polarization in the initial discharge stage, the large-rate discharge performance of the battery is seriously influenced, and the engineering application range of the lithium-carbon fluoride battery is hindered.
Patent CN104577107A discloses a surface modification method of carbon fluoride material, comprising the steps of: mixing nano copper and carbon fluoride, adding a solvent, and performing ball milling to form mixed slurry; drying the mixed slurry to form a mixture; sieving the mixture to obtain mixture powder; sieving the mixture to obtain mixture powder; placing the mixture powder into an atmosphere furnace for calcining; and taking out the calcined mixture powder, cooling to room temperature, and sieving to obtain the carbon fluoride material modified by the nano-copper. According to the method, after the carbon fluoride and the nano-copper with good conductivity are mixed, and the nano-copper is calcined at high temperature in an inert atmosphere, the nano-copper reacts on the surface of the carbon fluoride, so that the voltage hysteresis phenomenon of the carbon fluoride is obviously improved, and the high rate performance and the low temperature performance are improved. Although the patent application improves the voltage hysteresis of the carbon fluoride, the 0.1C multiplying power of the prepared battery only improves the initial discharge voltage of the carbon fluoride material from 2.35V to 2.49V, and the plateau voltage from 2.49V to 2.52V, so the improvement effect is not obvious.
Patent CN104577124B discloses a method for preparing a mixed positive electrode material for a lithium battery, which comprises the following steps: doping of Ag in carbon fluoride materials2V4O11The doping process comprises: adding carbon fluoride and Ag2V4O11Placing the mixed slurry and a solvent in a ball mill for ball milling to form mixed slurry, drying the mixed slurry, and cooling to obtain a dry mixture; and screening the dried mixture to obtain the mixed cathode material for the lithium battery. Although the voltage hysteresis of the carbon fluoride battery is improved, the initial discharge voltage of the prepared battery is only increased from 1.7V to 2.0V at the normal temperature and the 1.0C multiplying power of the carbon fluoride battery, and is only increased from 1.81V to 2.06V at the temperature of minus 10 ℃ and the 0.1C multiplying power of the battery, so that the improvement effect is not obvious.
Therefore, there is a need for a fluorocarbon positive electrode material that can be modified to improve the voltage hysteresis of the fluorocarbon positive electrode material, so as to greatly improve the high-rate performance and the low-temperature performance.
Disclosure of Invention
Aiming at the defects of the prior art, the invention provides Ag2CrO4A preparation method of a @ Ag modified fluorocarbon cathode material.
The method is realized by the following technical scheme:
ag2CrO4The preparation method of the @ Ag modified fluorocarbon cathode material comprises the following steps:
(1) preparing a potassium chromate solution: will K2CrO4Dispersing in deionized water, and stirring for 0.6-1.5 h to be uniform to prepare a potassium chromate solution;
(2) preparing a carbon fluoride dispersion liquid: uniformly mixing absolute ethyl alcohol and ultrapure water, adding carbon fluoride, slowly adding polyvinylpyrrolidone, and stirring for 1-2 hours until the mixture is uniform to prepare a carbon fluoride dispersion liquid;
(3) preparing a mixed solution: stirring the potassium chromate solution and the carbon fluoride dispersion liquid for 0.6-1.5 hours until the potassium chromate solution and the carbon fluoride dispersion liquid are uniform to prepare a mixed solution;
(4) preparing a silver nitrate solution: dispersing silver nitrate in deionized water, and stirring for 0.6-1.5 h to be uniform to prepare a silver nitrate solution;
(5) preparing mixed slurry: slowly adding a silver nitrate solution into the mixed solution according to a proportion, continuing to react for 3-8h after the addition is finished to prepare a mixed reaction solution, and carrying out high-energy ball milling on the mixed reaction solution by using a high-energy ball mill to prepare mixed slurry;
(6) preparing mixed powder: drying and sieving the mixed slurry to obtain mixed powder;
(7) and (3) calcining: calcining the mixed powder in a nitrogen atmosphere furnace, cooling, grinding, washing with ultrapure water for multiple times, drying, and sieving with a 100-200-mesh sieve to obtain the Ag2CrO4A @ Ag modified fluorocarbon positive electrode material.
Further, in the step (1), the mass concentration of the potassium chromate solution is 16.6-25%.
Further, in the step (2), the mass ratio of the carbon fluoride, the absolute ethyl alcohol, the ultrapure water and the polyvinylpyrrolidone in the carbon fluoride dispersion liquid is carbon fluoride: anhydrous ethanol: ultrapure water: polyvinylpyrrolidone 1 (1-1.5) and (1-1.5): (1-1.5).
Further, in the step (4), the mass concentration of the silver nitrate solution is 16.6-25%.
Further, in the step (5), the proportion is carbon fluoride and K2CrO4With AgNO3The mass ratio of (A) to (B) is carbon fluoride: k2CrO4：AgNO3＝1:(0.1～0.9):(0.3～0.9)。
Further, in the step (5), the high-energy ball milling is performed for 0.5-2 min, and then the machine is stopped for cooling for more than 10min, and the operation is repeated in this way, and the total operation time is 1-2 h.
Further, in the step (5), the rotating speed of the high-energy ball mill is more than 5000 r/min.
Further, in the step (5), the high-energy ball mill is a high-energy ball milling cup.
Further, in the step (5), zirconia balls are added to the mixed reaction liquid according to the mass ratio of the mixed reaction liquid to the zirconia balls being 1: 2.8-3.3 before the mixed reaction liquid enters the high-energy ball mill.
Further, in the step (6), the drying is carried out at the temperature of 70-90 ℃ for 8-12 h.
Further, in the step (6), the sieving is a sieve of 100-200 meshes.
Further, in the step (7), the calcining is carried out at the temperature of 440-500 ℃ for 8-10 h.
Has the advantages that:
(1) this application uses Ag2CrO4Modifying carbon fluoride material with @ Ag, and reacting K with solvent2CrO4、AgNO3And carbon fluoride are uniformly dispersed to ensure that K is2CrO4With AgNO3Reacting on the surface of carbon fluoride to generate Ag2CrO4Then further evenly mixed by a high-energy ball milling mode, and simultaneously excessive AgNO is added after high-temperature calcination in a nitrogen atmosphere3Decomposing to generate Ag, uniformly coating the Ag on the surface of the carbon fluoride material to finally prepare the Ag2CrO4@ Ag modified fluorocarbon positive electrode material due to Ag2CrO4The material has a higher working voltage platform and Ag2CrO4And Ag has good conductivity, so that the problem of voltage hysteresis at the initial discharge stage of the carbon fluoride material can be solved, the large-current discharge capacity of the carbon fluoride material is effectively improved, the rate performance of the lithium fluorocarbon battery is greatly improved, and the temperature rise of the lithium fluorocarbon battery in the discharge process is reduced.
The method is to make Ag source AgNO3Dissolving in solvent, coating uniformly on the surface of carbon fluoride material in the subsequent treatment process, and calciningThe reaction is carried out, firstly, the coating effect is more uniform, and secondly, in the calcining process, the CF2 inactive groups on the surface of the carbon fluoride material are partially decomposed, so that the amount of the inactive groups on the surface of the carbon fluoride material is reduced, and the conductivity of the carbon fluoride material is increased. If the finished product Ag is used2CrO4More Ag is adopted when the Ag and the carbon fluoride are compounded by the adhesive2CrO4And Ag materials, to form a good conductive network, so that the amount of carbon fluoride is reduced, and the specific energy of the battery is reduced, which is not favorable for cost control.
(2) The invention adopts a high-energy ball milling mode to perform ball milling under the action of the solvent, and can further well mill Ag2CrO4、AgNO3Mixing with carbon fluoride material, calcining at high temperature to obtain Ag2CrO4The surface of the carbon fluoride material is uniformly coated with the @ Ag, so that the problem of voltage hysteresis of the carbon fluoride anode material in the initial discharge stage and the problem of large heat generation under the condition of large-current discharge are further solved.
(3) The zirconia balls are added in the high-energy ball milling process, so that the uniformity of the mixed material is further improved.
(4) The invention adopts Ag2CrO4The difference between the @ Ag modified carbon fluoride anode material and common manganese dioxide and silver metavanadate modified carbon fluoride anode materials is that the mode of improving the conductivity of the carbon fluoride electrode modified by the manganese dioxide and the silver metavanadate is equivalent to the synergistic reaction of a composite electrode, and the invention coats a small amount of Ag on the surface of the carbon fluoride material2CrO4@ Ag, increase carbon fluoride material's electric conductivity, the voltage lag improvement effect of carbon fluoride material voltage lag is more obvious, can also improve the voltage platform simultaneously, reduces the temperature rise in the discharge process.
(5) Ag prepared by the method of the invention2CrO4The @ Ag modified carbon fluoride cathode material is applied to a lithium carbon fluoride battery, can effectively improve voltage hysteresis of the battery, reduces temperature rise in the discharging process of the battery, improves low-wave voltage under the condition of 2.0C multiplying power from 1.83V to 2.30V, improves platform voltage from 2.60V to 2.77V, and reduces temperature rise from 60.9 ℃ to 44.The effect is more obvious at 1 ℃, especially under a large multiplying power. The discharge performance of the carbon fluoride material is greatly improved.
(6) The preparation method of the invention has the advantages of easy control of control parameters and low cost.
Drawings
In order to illustrate the embodiments of the present invention or the technical solutions in the prior art more clearly, the drawings needed in the description of the embodiments or the prior art will be briefly introduced below, it is obvious that the drawings in the following description are only some examples of the present invention, and for a person skilled in the art, without inventive step, other drawings can be obtained according to these drawings:
FIG. 1 shows Ag prepared in example 12CrO4The discharging contrast curve of 0.2C multiplying power at 25 ℃ of a battery made of the @ Ag modified carbon fluoride cathode material and a battery made of pure carbon fluoride;
FIG. 2 shows Ag prepared in example 12CrO4Temperature rise contrast curves of 0.2C rate discharge at 25 ℃ of batteries made of the @ Ag modified carbon fluoride cathode material and batteries made of pure carbon fluoride;
FIG. 3 shows Ag prepared in example 22CrO4The discharging contrast curve of 1C multiplying power at 25 ℃ of a battery made of the @ Ag modified carbon fluoride cathode material and a battery made of pure carbon fluoride;
FIG. 4 shows Ag prepared in example 22CrO4Temperature rise contrast curves of 1C rate discharge at 25 ℃ of batteries made of the @ Ag modified carbon fluoride cathode material and batteries made of pure carbon fluoride;
FIG. 5 shows Ag prepared in example 32CrO4The discharging contrast curve of 2C multiplying power at 25 ℃ of a battery made of the @ Ag modified carbon fluoride cathode material and a battery made of pure carbon fluoride;
FIG. 6 shows Ag prepared in example 32CrO4Temperature rise contrast curves of 2C rate discharge at 25 ℃ of batteries made of the @ Ag modified carbon fluoride cathode material and batteries made of pure carbon fluoride.
Detailed Description
The following is a detailed description of the embodiments of the present invention, but the present invention is not limited to these embodiments, and any modifications or substitutions in the basic spirit of the embodiments are included in the scope of the present invention as claimed in the claims.
Example 1
Ag2CrO4The preparation method of the @ Ag modified fluorocarbon cathode material comprises the following steps:
(1) preparing a potassium chromate solution: will K2CrO4Dispersing in deionized water, and stirring for 0.6h to be uniform to prepare a potassium chromate solution with mass concentration of 16.6%;
(2) preparing a carbon fluoride dispersion liquid: according to the weight ratio of carbon fluoride: anhydrous ethanol: ultrapure water: uniformly mixing absolute ethyl alcohol and ultrapure water according to a mass ratio of 1:1:1:1, adding carbon fluoride, slowly adding polyvinylpyrrolidone, and stirring for 1h until the mixture is uniform to obtain a carbon fluoride dispersion liquid;
(3) preparing a mixed solution: stirring the potassium chromate solution and the carbon fluoride dispersion liquid for 0.6h to be uniform to prepare a mixed solution;
(4) preparing a silver nitrate solution: dispersing silver nitrate in deionized water, and stirring for 0.6h to be uniform to prepare a silver nitrate solution with the mass concentration of 16.6%;
(5) preparing mixed slurry: according to the weight ratio of carbon fluoride: k2CrO4：AgNO3Slowly adding a silver nitrate solution into the mixed solution according to the mass ratio of 1:0.1:0.3, continuously reacting for 3 hours after the addition is finished to obtain a mixed reaction solution, and performing high-energy ball milling on the mixed reaction solution for 1 hour by adopting a high-energy ball mill at the rotating speed of 5000r/min to obtain mixed slurry;
(6) preparing mixed powder: drying the mixed slurry at 70 ℃ for 8h, and sieving with a 200-mesh sieve to obtain mixed powder;
(7) and (3) calcining: calcining the mixed powder in a nitrogen atmosphere furnace at 440 ℃ for 10h, cooling, grinding, washing with ultrapure water for multiple times, drying, and sieving with a 200-mesh sieve to obtain the Ag2CrO4A @ Ag modified fluorocarbon positive electrode material.
Example 2
Ag2CrO4The preparation method of the @ Ag modified fluorocarbon cathode material comprises the following steps:
(1) preparing a potassium chromate solution: will K2CrO4Dispersing in deionized water, and stirring for 0.7h to be uniform to prepare a potassium chromate solution with the mass concentration of 25%;
(2) preparing a carbon fluoride dispersion liquid: according to the weight ratio of carbon fluoride: anhydrous ethanol: ultrapure water: polyvinylpyrrolidone ═ 1:1.5:1.5, firstly, uniformly mixing absolute ethyl alcohol and ultrapure water, adding carbon fluoride, simultaneously slowly adding polyvinylpyrrolidone, and stirring for 1.1h until uniform to prepare a carbon fluoride dispersion liquid;
(3) preparing a mixed solution: stirring the potassium chromate solution and the carbon fluoride dispersion liquid for 0.7h to be uniform to prepare a mixed solution;
(4) preparing a silver nitrate solution: dispersing silver nitrate in deionized water, and stirring for 0.7h to be uniform to prepare a silver nitrate solution with the mass concentration of 25%;
(5) preparing mixed slurry: according to the weight ratio of carbon fluoride: k2CrO4：AgNO3Slowly adding a silver nitrate solution into the mixed solution according to the mass ratio of 1:0.2:0.4, continuously reacting for 8 hours after the addition is finished to prepare a mixed reaction solution, and performing high-energy ball milling on the mixed reaction solution for 2 hours by adopting a high-energy ball milling cup under the condition that the rotating speed is 8000r/min, wherein the mass ratio of the mixed reaction solution to zirconia balls is 1:3 to prepare mixed slurry;
(6) preparing mixed powder: drying the mixed slurry at 90 ℃ for 12h, and sieving by a 100-mesh sieve to obtain mixed powder;
(7) and (3) calcining: calcining the mixed powder in a nitrogen atmosphere furnace at 500 ℃ for 8h, cooling, grinding, washing with ultrapure water for multiple times, drying, and sieving with a 200-mesh sieve to obtain the Ag2CrO4A @ Ag modified fluorocarbon positive electrode material;
in the step (5), the high-energy ball milling is carried out for 2min, then the machine is stopped for cooling for 10min, and the operation is repeated in such a way, wherein the total running time is 2 h.
Example 3
Ag2CrO4The preparation method of the @ Ag modified fluorocarbon cathode material comprises the following steps:
(1) preparing a potassium chromate solution: will K2CrO4Dispersing in deionized water, and stirring for 0.8h to be uniform to prepare a potassium chromate solution with the mass concentration of 20%;
(2) preparing a carbon fluoride dispersion liquid: according to the weight ratio of carbon fluoride: anhydrous ethanol: ultrapure water: polyvinylpyrrolidone ═ 1:1.1: 1.2: 1, firstly, uniformly mixing absolute ethyl alcohol and ultrapure water, adding carbon fluoride, slowly adding polyvinylpyrrolidone, and stirring for 1.2 hours until the mixture is uniform to prepare a carbon fluoride dispersion liquid;
(3) preparing a mixed solution: stirring the potassium chromate solution and the carbon fluoride dispersion liquid for 0.8h to be uniform to prepare a mixed solution;
(4) preparing a silver nitrate solution: dispersing silver nitrate in deionized water, and stirring for 0.8h to be uniform to prepare a silver nitrate solution with the mass concentration of 16.6-25%;
(5) preparing mixed slurry: according to the weight ratio of carbon fluoride: k2CrO4：AgNO3Slowly adding a silver nitrate solution into the mixed solution according to the mass ratio of 1:0.3:0.5, continuing to react for 3 hours after the addition is finished to prepare a mixed reaction solution, and performing high-energy ball milling on the mixed reaction solution for 1.5 hours by adopting a high-energy ball milling cup under the condition that the rotating speed is 10000r/min, wherein the mass ratio of the mixed reaction solution to zirconia balls is 1:3.3 to prepare mixed slurry;
(6) preparing mixed powder: drying the mixed slurry at 80 ℃ for 10h, and sieving by a 120-mesh sieve to obtain mixed powder;
(7) and (3) calcining: calcining the mixed powder in a nitrogen atmosphere furnace at 475 ℃ for 9h, cooling, grinding, washing with ultrapure water for multiple times, drying, and sieving with a 120-mesh sieve to obtain the Ag2CrO4A @ Ag modified fluorocarbon positive electrode material;
in the step (5), the high-energy ball milling is performed for 1min, then the machine is stopped for cooling for 15min, and the operation is repeated in such a way, and the total running time is 1.5 h.
Application example 1
Ag prepared in example 12CrO4The method comprises the following steps of (a) taking Ag modified fluorocarbon anode material as an anode material, SP and CNTS as conductive agents, CMC and SBR as binders, uniformly mixing the anode material, the conductive agents and the binders in a mass ratio of 80:10:10 to prepare anode slurry, coating the anode slurry on an aluminum foil, drying the anode slurry at 100 ℃, taking metal lithium as a negative electrode, and assembling a group of lithium batteries in a 1% drying room;
meanwhile, pure carbon fluoride is used as a positive electrode material, SP and CNTS are used as conductive agents, CMC and SBR are used as binders, and the method is adopted for assembling another group of lithium batteries;
carrying out discharge test on the two groups of lithium batteries at normal temperature and 0.2C multiplying power, and testing the temperature rise in the discharge process;
FIG. 1 shows Ag prepared in example 12CrO4The discharging contrast curve of 0.2C multiplying power at 25 ℃ of a battery made of the @ Ag modified carbon fluoride cathode material and a battery made of pure carbon fluoride;
FIG. 2 shows Ag prepared in example 12CrO4Temperature rise contrast curves of 0.2C rate discharge at 25 ℃ of batteries made of the @ Ag modified carbon fluoride cathode material and batteries made of pure carbon fluoride;
as is apparent from FIG. 1, the low-wave voltage at the initial stage of discharge of the battery made of pure fluorocarbon was 2.32V, the voltage hysteresis was relatively significant, and the plateau voltage was 2.75V, while the Ag prepared in example 1 was used2CrO4The battery made of the @ Ag modified fluorocarbon anode material has the low-wave voltage of 2.52V at the initial discharge stage, the voltage hysteresis phenomenon is obviously improved, the platform voltage is 2.87V, and the Ag is reflected2CrO4@ Ag modified fluorocarbon positive electrode material higher working voltage and Ag2CrO4The @ Ag modified carbon fluoride cathode material has good conductivity;
it is evident from fig. 2 that the maximum temperature during discharge of the cell made of pure carbon fluoride was 24.2 ℃; and Ag in example 1 was used2CrO4The battery made of the @ Ag modified fluorocarbon anode material has the highest temperature of 20.9 ℃ in the discharging process and the temperature rise is reducedFurther embodies Ag2CrO4The carbon fluoride cathode material modified by @ Ag has good conductivity; due to Ag2CrO4The material itself has a specific gram capacity of 380mAh/g, and Ag2CrO4And the Ag material has good conductivity, the voltage lag of the carbon fluoride material is greatly improved on the premise of sacrificing a small amount of the capacity of the carbon fluoride material, the temperature rise in the discharging process is reduced, and the performance of the carbon fluoride material is greatly improved.
Application example 2
Ag prepared in example 22CrO4The method comprises the following steps of (a) taking Ag modified fluorocarbon anode material as an anode material, SP and CNTS as conductive agents, CMC and SBR as binders, uniformly mixing the anode material, the conductive agents and the binders in a mass ratio of 80:10:10 to prepare anode slurry, coating the anode slurry on an aluminum foil, drying the anode slurry at 100 ℃, taking metal lithium as a negative electrode, and assembling a group of lithium batteries in a 1% drying room;
meanwhile, pure carbon fluoride is used as a positive electrode material, SP and CNTS are used as conductive agents, CMC and SBR are used as binders, and the method is adopted for assembling another group of lithium batteries;
carrying out discharge test on the two groups of lithium batteries at normal temperature and under the condition of 1C multiplying power, and testing the temperature rise in the discharge process;
FIG. 3 shows Ag prepared in example 22CrO4The discharging contrast curve of 1C multiplying power at 25 ℃ of a battery made of the @ Ag modified carbon fluoride cathode material and a battery made of pure carbon fluoride;
FIG. 4 shows Ag prepared in example 22CrO4Temperature rise contrast curves of 1C rate discharge at 25 ℃ of batteries made of the @ Ag modified carbon fluoride cathode material and batteries made of pure carbon fluoride;
it is obvious from fig. 3 that the low-wave voltage at the initial stage of discharge of the battery made of pure carbon fluoride is 2.06V, the voltage hysteresis is obvious, and the platform voltage is 2.71V; instead, Ag obtained in example 2 was used2CrO4The battery made of the @ Ag modified fluorocarbon anode material has the low-wave voltage of 2.45V at the initial discharge stage, the voltage hysteresis phenomenon is obviously improved, and the plateau voltage is generatedPressing 2.84V to show Ag2CrO4@ Ag modified fluorocarbon positive electrode material higher working voltage and Ag2CrO4The @ Ag modified carbon fluoride cathode material has good conductivity;
it is evident from fig. 4 that the maximum temperature during discharge of the cell made of pure carbon fluoride was 31.5 ℃; and Ag in example 2 was used2CrO4The battery made of the @ Ag modified carbon fluoride cathode material has the highest temperature of 25.9 ℃ in the discharging process, and the temperature rise is reduced, so that Ag is further embodied2CrO4The carbon fluoride cathode material modified by @ Ag has good conductivity; due to Ag2CrO4The material itself has a specific gram capacity of 380mAh/g, and Ag2CrO4And the Ag material has good conductivity, the voltage lag of the carbon fluoride material is greatly improved on the premise of sacrificing a small amount of the capacity of the carbon fluoride material, the temperature rise in the discharging process is reduced, and the performance of the carbon fluoride material is greatly improved.
Application example 3
Ag prepared in example 32CrO4The method comprises the following steps of (a) taking Ag modified fluorocarbon anode material as an anode material, SP and CNTS as conductive agents, CMC and SBR as binders, uniformly mixing the anode material, the conductive agents and the binders in a mass ratio of 80:10:10 to prepare anode slurry, coating the anode slurry on an aluminum foil, drying the anode slurry at 100 ℃, taking metal lithium as a negative electrode, and assembling a group of lithium batteries in a 1% drying room;
meanwhile, pure carbon fluoride is used as a positive electrode material, SP and CNTS are used as conductive agents, CMC and SBR are used as binders, and the method is adopted for assembling another group of lithium batteries;
carrying out discharge test on the two groups of lithium batteries at normal temperature and 2C multiplying power, and testing the temperature rise in the discharge process;
FIG. 5 shows Ag prepared in example 32CrO4The discharging contrast curve of 2C multiplying power at 25 ℃ of a battery made of the @ Ag modified carbon fluoride cathode material and a battery made of pure carbon fluoride;
FIG. 6 shows Ag prepared in example 32CrO4'@' Ag repairThe temperature rise contrast curve of 2C multiplying power discharge at 25 ℃ of the battery made of decorated fluorocarbon anode material and the battery made of pure fluorocarbon;
it is obvious from fig. 5 that the low-wave voltage at the initial stage of discharge of the battery made of pure carbon fluoride is 1.83V, the voltage hysteresis is obvious, and the platform voltage is 2.60V; and Ag obtained in example 3 was used2CrO4The battery made of the @ Ag modified fluorocarbon anode material has the low-wave voltage of 2.30V at the initial discharge stage, the voltage hysteresis phenomenon is obviously improved, the platform voltage is 2.77V, and the Ag is reflected2CrO4@ Ag modified fluorocarbon positive electrode material higher working voltage and Ag2CrO4The @ Ag modified carbon fluoride cathode material has good conductivity;
it is evident from fig. 6 that the maximum temperature during discharge of the cell made of pure carbon fluoride was 60.9 ℃; and Ag in example 3 was used2CrO4The battery made of the @ Ag modified carbon fluoride cathode material has the highest temperature of 44.1 ℃ in the discharging process, and the temperature rise is reduced, so that Ag is further embodied2CrO4The carbon fluoride cathode material modified by @ Ag has good conductivity; due to Ag2CrO4The material itself has a specific gram capacity of 380mAh/g, and Ag2CrO4And the Ag material has good conductivity, the voltage lag of the carbon fluoride material is greatly improved on the premise of sacrificing a small amount of the capacity of the carbon fluoride material, the temperature rise in the discharging process is reduced, and the performance of the carbon fluoride material is greatly improved.
It will be evident to those skilled in the art that the invention is not limited to the details of the foregoing illustrative embodiments, and that the present invention may be embodied in other specific forms without departing from the spirit or essential attributes thereof. The present embodiments are therefore to be considered in all respects as illustrative and not restrictive, the scope of the invention being indicated by the appended claims rather than by the foregoing description, and all changes which come within the meaning and range of equivalency of the claims are therefore intended to be embraced therein.

Claims (10)

1. Ag2CrO4The preparation method of the @ Ag modified carbon fluoride cathode material is characterized by comprising the following steps of:
(1) preparing a potassium chromate solution: will K2CrO4Dispersing in deionized water, and stirring for 0.6-1.5 h to be uniform to prepare a potassium chromate solution;
(2) preparing a carbon fluoride dispersion liquid: uniformly mixing absolute ethyl alcohol and ultrapure water, adding carbon fluoride, slowly adding polyvinylpyrrolidone, and stirring for 1-2 hours until the mixture is uniform to prepare a carbon fluoride dispersion liquid;
(3) preparing a mixed solution: stirring the potassium chromate solution and the carbon fluoride dispersion liquid for 0.6-1.5 hours until the potassium chromate solution and the carbon fluoride dispersion liquid are uniform to prepare a mixed solution;
(4) preparing a silver nitrate solution: dispersing silver nitrate in deionized water, and stirring for 0.6-1.5 h to be uniform to prepare a silver nitrate solution;
(5) preparing mixed slurry: slowly adding a silver nitrate solution into the mixed solution according to a proportion, continuing to react for 3-8h after the addition is finished to prepare a mixed reaction solution, and carrying out high-energy ball milling on the mixed reaction solution by using a high-energy ball mill to prepare mixed slurry;
(6) preparing mixed powder: drying and sieving the mixed slurry to obtain mixed powder;
(7) and (3) calcining: calcining the mixed powder in a nitrogen atmosphere furnace, cooling, grinding, washing with ultrapure water for multiple times, drying, and sieving with a 100-200-mesh sieve to obtain the Ag2CrO4A @ Ag modified fluorocarbon positive electrode material.
2. Ag according to claim 12CrO4The preparation method of the @ Ag modified carbon fluoride cathode material is characterized in that in the step (1), the mass concentration of the potassium chromate solution is 16.6-25%.
3. Ag according to claim 12CrO4A method for producing a @ Ag-modified fluorocarbon positive electrode material, characterized in that in step (2), fluorocarbon, absolute ethyl alcohol, and super-fine are contained in the fluorocarbon dispersion liquidThe mass ratio of the pure water to the polyvinylpyrrolidone is 1 (1-1.5) to 1-1.5): (1-1.5).
4. Ag according to claim 12CrO4The preparation method of the @ Ag modified carbon fluoride cathode material is characterized in that in the step (4), the mass concentration of the silver nitrate solution is 16.6-25%.
5. Ag according to claim 12CrO4The preparation method of the @ Ag modified fluorocarbon cathode material is characterized in that in the step (5), the fluorocarbon and the K are used according to the proportion2CrO4With AgNO3The mass ratio of (1) (0.1-0.9) to (0.3-0.9).
6. Ag according to claim 12CrO4The preparation method of the @ Ag modified carbon fluoride cathode material is characterized in that in the step (5), the high-energy ball milling is carried out for 0.5-2 min, then the machine is stopped and cooled for more than 10min, the operation is repeated, and the total operation time is 1-2 h.
7. Ag according to claim 12CrO4The preparation method of the @ Ag modified carbon fluoride cathode material is characterized in that in the step (5), the zirconia balls are added into the mixed reaction liquid according to the mass ratio of the mixed reaction liquid to the zirconia balls being 1: 2.8-3.3 before the mixed reaction liquid enters the high-energy ball mill.
8. Ag according to claim 12CrO4The preparation method of the @ Ag modified fluorocarbon cathode material is characterized in that in the step (6), the drying is carried out at the temperature of 70-90 ℃ for 8-12 h.
9. Ag according to claim 12CrO4The method for preparing the @ Ag modified fluorocarbon cathode material is characterized in that in the step (6), the sieving is a sieve which passes through a 100-200 mesh sieve.
10. Ag according to claim 12CrO4The preparation method of the @ Ag modified fluorocarbon cathode material is characterized in that in the step (7), the calcination is carried out at the temperature of 440-500 ℃ for 8-10 h.
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AU2003251798A1 (en) * 2003-01-15 2005-10-07 Quallion Llc Battery
US20110059355A1 (en) * 2009-09-10 2011-03-10 Battelle Memorial Institute High-energy metal air batteries
CN105765008A (en) * 2013-11-13 2016-07-13 R.R.当纳利父子公司 Battery
CN109309206A (en) * 2017-07-26 2019-02-05 中能中科（天津）新能源科技有限公司 Disposable lithium-battery, serondary lithium battery and preparation method thereof
CN109659515A (en) * 2018-11-23 2019-04-19 贵州梅岭电源有限公司 A kind of preparation method of the fluorination carbon electrode material of Ag C modification
CN111244391A (en) * 2020-03-02 2020-06-05 清华大学 Preparation of organic polymer-inorganic particle composite film for protecting lithium metal surface

Patent Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS52136328A (en) * 1976-05-10 1977-11-15 Japan Storage Battery Co Ltd Nonnaqueous electrolyte battery
AU2003251798A1 (en) * 2003-01-15 2005-10-07 Quallion Llc Battery
US20110059355A1 (en) * 2009-09-10 2011-03-10 Battelle Memorial Institute High-energy metal air batteries
CN105765008A (en) * 2013-11-13 2016-07-13 R.R.当纳利父子公司 Battery
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CN109659515A (en) * 2018-11-23 2019-04-19 贵州梅岭电源有限公司 A kind of preparation method of the fluorination carbon electrode material of Ag C modification
CN111244391A (en) * 2020-03-02 2020-06-05 清华大学 Preparation of organic polymer-inorganic particle composite film for protecting lithium metal surface

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