CN109873137B - V-shaped groove2O5Preparation method of @ C modified carbon fluoride cathode material - Google Patents
V-shaped groove2O5Preparation method of @ C modified carbon fluoride cathode material Download PDFInfo
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Abstract
The invention discloses a V2O5The preparation method of the @ C modified fluorocarbon cathode material comprises the following steps: (1) reacting NH4VO3Adding into deionized water, and stirring to obtain mixed solution 1; (2) adding carbon fluoride into a mixed solution of absolute ethyl alcohol and ultrapure water, and uniformly stirring to obtain a mixed solution 2; (3) uniformly mixing the mixed solution 1 and the mixed solution 2, and performing high-energy ball milling to form mixed slurry; (4) drying and sieving the mixed slurry to obtain mixed powder; (5) calcining the mixed powder in an air atmosphere furnace, taking out, cooling, grinding, and sieving with a 100-200 mesh sieve to obtain V2O5A @ C modified fluorocarbon positive electrode material. Application V2O5The @ C modified fluorocarbon anode material can effectively solve the problem of voltage hysteresis at the initial discharge stage of the fluorocarbon battery, greatly improve the rate capability and platform voltage of the lithium fluorocarbon battery and reduce the temperature rise of the lithium fluorocarbon battery in the discharge process, and is simple in preparation method and low in cost.
Description
Technical Field
The invention belongs to the technical field of lithium battery materials, and particularly relates to a V2O5A preparation method of a @ C modified fluorocarbon cathode material.
Background
A primary lithium battery (primary lithium battery), which is a high-energy chemical primary battery and is commonly called a lithium battery. The lithium metal is used as a negative electrode, solid salt or salt dissolved in an organic solvent is used as an electrolyte, and metal oxide or other solid and liquid oxidants are used as positive active substances. 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 application 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 application CN104577124B discloses a preparation method of 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 the productDrying the 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, it is important to develop a carbon fluoride material which can significantly improve the voltage hysteresis of carbon fluoride and greatly improve the high rate performance and low temperature performance.
Disclosure of Invention
The invention provides a V for solving the technical problems2O5A preparation method of a @ C modified fluorocarbon cathode material. V made herein2O5The @ C modified fluorocarbon anode material can effectively solve the problem of voltage hysteresis at the initial discharge stage of the fluorocarbon battery, greatly improve the rate capability and platform voltage of the lithium fluorocarbon battery and reduce the temperature rise of the lithium fluorocarbon battery in the discharge process, and is simple in preparation method and low in cost.
In order to achieve the above purpose, the invention adopts the following technical scheme:
v-shaped groove2O5The preparation method of the @ C modified fluorocarbon cathode material comprises the following steps:
(1) proportionally mixing NH4VO3Adding the mixture into deionized water, and uniformly stirring for 0.6-1.5 h to obtain a mixed solution 1;
(2) adding carbon fluoride into a mixed solution of absolute ethyl alcohol and ultrapure water according to a ratio, and uniformly stirring for 0.6-1.5 h to obtain a mixed solution 2;
(3) uniformly mixing the mixed solution 1 and the mixed solution 2 to obtain a mixed solution, and then feeding the mixed solution into a high-energy ball mill for high-energy ball milling to form mixed slurry;
(4) drying and sieving the mixed slurry obtained in the step (3) to obtain mixed powder;
(5) putting the mixed powder in the step (4) into an air atmosphere furnace for calcination, taking out the calcined powderCooling and grinding the mixture powder, and sieving the mixture powder with a 100-200-mesh sieve to obtain the V2O5A @ C modified fluorocarbon positive electrode material.
Further, in step (1), the NH4VO3And deionized water in a mass ratio of 1 to (3-5).
In step (2), the mass ratio of the carbon fluoride, the absolute ethyl alcohol and the ultrapure water is 1 (1-1.5) to 1-1.5.
Further, in the steps (1) and (2), the fluorocarbon is reacted with NH4VO3The mass ratio of (1) to (0.1 to 0.9).
Further, in step (3), the method of high energy ball milling is as follows: firstly carrying out ball milling for 0.5-2 min, then stopping running, cooling the high-energy ball mill for more than 10min, and then carrying out high-energy ball milling, and repeating the high-energy ball milling for 1-2 h in total.
Further, in the step (3), the rotating speed of the high-energy ball mill is more than 3000 r/min.
Further, in the step (3), the high-energy ball mill is a high-energy ball milling cup.
Further, in the step (3), before the mixed liquid is sent to a high-energy ball mill for high-energy ball milling, zirconia balls are added, and the mass ratio of the mixed liquid to the zirconia balls is 1: 2.8-3.3.
Further, in the step (4), the drying temperature is 70-90 ℃, and the drying time is 8-12 hours; the screening is a screen of 100-200 meshes.
Further, in the step (5), the calcining temperature is 300-400 ℃, and the time is 8-10 h.
Due to the adoption of the technical scheme, the invention has the following beneficial effects:
(1) this application employs V2O5Modification of carbon fluoride material with @ C, and reacting NH with solvent4VO3And carbon fluoride are respectively dispersed uniformly, then are uniformly mixed by a high-energy ball milling mode, and NH is calcined at high temperature in air atmosphere4VO3Reaction on the surface of carbon fluoride to form V2O5Simultaneously, the carbon fluoride is partially decomposed to generate conductive carbon which is uniformly coated on the surface of the carbon fluoride material, and finally V is prepared2O5@ C modified fluorocarbon positive electrode material due to V2O5The material has a higher working voltage platform and V2O5The conductive carbon has good conductivity, can make up the problem of voltage lag at the initial discharge stage of the carbon fluoride material, effectively improves the large-current discharge capacity of the carbon fluoride material, greatly improves the rate capability of the lithium-carbon fluoride battery and reduces the temperature rise of the lithium-carbon fluoride battery in the discharge process.
(2) This application adopts the mode of high energy ball-milling to carry out the ball-milling under the effect of solvent, can be well with NH4VO3Mixing with carbon fluoride material, calcining at high temperature to obtain V2O5The @ C is uniformly coated on the surface of the carbon fluoride material, 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 V2O5The @ C modified carbon fluoride cathode material is different from common manganese dioxide and silver metavanadate modified carbon fluoride cathode materials in 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 carbon fluoride cathode material is coated with a small amount of V on the surface of the carbon fluoride material2O5@ C, increase the electric conductivity of carbon fluoride material, 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) V prepared by the method2O5The @ C modified carbon fluoride cathode material is applied to a lithium carbon fluoride battery, the voltage hysteresis of the battery can be effectively improved, the temperature rise of the battery in the discharging process is reduced, the low-wave voltage under the condition of 0.2C multiplying power is increased from 1.98V to 2.23V, the platform voltage is increased from 2.39V to 2.45V, and the temperature rise is reduced from 22 ℃ to 21 ℃;the low-wave voltage under the condition of 1.0C multiplying power is increased to 2.02V from 1.68V, the platform voltage is increased to 2.43V from 2.35V, and the temperature rise is reduced to 31.1 ℃ from 36 ℃; the low-wave voltage under the condition of 2.0C multiplying power is improved to 1.81V from 1.13V, the platform voltage is improved to 2.35V from 2.2V, the temperature rise is reduced to 45.6 ℃ from 55 ℃, and particularly, the effect under the condition of large multiplying power is more obvious. The discharge performance of the carbon fluoride material is greatly improved.
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 V obtained in example 1 of the present application2O5An XRD comparison spectrogram of the @ C modified carbon fluoride cathode material and a pure carbon fluoride material;
FIG. 2 is a discharge comparison curve of 0.2C rate at 25 ℃ of a battery prepared from a V2O5@ C modified fluorocarbon positive electrode material and a battery prepared from pure fluorocarbon in application example 1;
FIG. 3 shows V in example 1 of application of the present application2O5The temperature rise contrast curve of 0.2C rate discharge of a battery prepared from the @ C modified carbon fluoride cathode material and a battery prepared from pure carbon fluoride at 25 ℃;
FIG. 4 shows V in example 2 of application of the present application2O5The discharging contrast curve of 1C multiplying power of a battery prepared from the @ C modified carbon fluoride cathode material and a battery prepared from pure carbon fluoride at 25 ℃;
FIG. 5 shows V in example 2 of application of the present application2O5The temperature rise contrast curve of 1C multiplying power discharge of a battery prepared from the @ C modified carbon fluoride cathode material and a battery prepared from pure carbon fluoride at 25 ℃;
FIG. 6 shows V in example 3 of application of the present application2O5The discharging contrast curve of 2C multiplying power of a battery prepared from the carbon fluoride anode material modified by @ C and the battery prepared from pure carbon fluoride at 25 ℃;
FIG. 7 shows V in example 3 of application of the present application2O5The temperature rise contrast curve of 2C multiplying power discharge of a battery prepared from the @ C modified carbon fluoride cathode material and a battery prepared from pure carbon fluoride at 25 ℃.
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
V-shaped groove2O5The preparation method of the @ C modified fluorocarbon cathode material comprises the following steps:
(1) proportionally mixing NH4VO3Adding the mixture into deionized water, and stirring the mixture uniformly for 0.6h to obtain a mixed solution 1; the NH4VO3And deionized water at a mass ratio of 1: 3;
(2) adding carbon fluoride into a mixed solution of absolute ethyl alcohol and ultrapure water according to a proportion, and uniformly stirring for 0.6h to obtain a mixed solution 2; the mass ratio of the carbon fluoride to the absolute ethyl alcohol to the ultrapure water is 1:1: 1;
(3) uniformly mixing the mixed solution 1 and the mixed solution 2 to obtain a mixed solution, and then feeding the mixed solution into a high-energy ball mill for high-energy ball milling to form mixed slurry; the method for high-energy ball milling comprises the following steps: firstly, ball milling is carried out for 0.5min, then the operation is stopped, the high-energy ball mill is cooled for more than 10min, then the high-energy ball milling is carried out, the high-energy ball milling is carried out repeatedly, and the total operation time is 1 h; the rotating speed of the high-energy ball mill is more than 3000 r/min; the high-energy ball mill is a high-energy ball milling cup; adding zirconia balls before feeding the mixed solution into a high-energy ball mill for high-energy ball milling, wherein the mass ratio of the mixed solution to the zirconia balls is 1: 2.8;
(4) drying and sieving the mixed slurry obtained in the step (3) to obtain mixed powder; the drying temperature is 70 ℃, and the drying time is 8 hours; the screening is a 100-mesh screen;
(5) placing the mixed powder of the step (4) in an air atmosphereCalcining in a furnace, taking out calcined mixture powder, cooling, grinding, and sieving with a 100-mesh sieve to obtain the V2O5A @ C modified fluorocarbon positive electrode material; the calcining temperature is 300 ℃ and the calcining time is 8 h.
Further, in the steps (1) and (2), the fluorocarbon is reacted with NH4VO3The mass ratio of (a) to (b) is 1: 0.1.
Example 2
V-shaped groove2O5The preparation method of the @ C modified fluorocarbon cathode material comprises the following steps:
(1) proportionally mixing NH4VO3Adding the mixture into deionized water, and stirring uniformly for 1.5h to obtain a mixed solution 1; the NH4VO3And deionized water at a mass ratio of 1: 5;
(2) adding carbon fluoride into a mixed solution of absolute ethyl alcohol and ultrapure water according to a proportion, and uniformly stirring for 1.5 hours to obtain a mixed solution 2; the mass ratio of the carbon fluoride to the absolute ethyl alcohol to the ultrapure water is 1:1.5: 1.5;
(3) uniformly mixing the mixed solution 1 and the mixed solution 2 to obtain a mixed solution, and then feeding the mixed solution into a high-energy ball mill for high-energy ball milling to form mixed slurry; the method for high-energy ball milling comprises the following steps: firstly, ball milling is carried out for 2min, then the operation is stopped, the high-energy ball mill is cooled for more than 10min, then the high-energy ball milling is carried out, the high-energy ball milling is carried out repeatedly, and the total operation time is 2 h; the rotating speed of the high-energy ball mill is more than 3000 r/min; the high-energy ball mill is a high-energy ball milling cup; adding zirconia balls before feeding the mixed solution into a high-energy ball mill for high-energy ball milling, wherein the mass ratio of the mixed solution to the zirconia balls is 1: 3.3;
(4) drying and sieving the mixed slurry obtained in the step (3) to obtain mixed powder; the drying temperature is 90 ℃, and the drying time is 12 hours; the sieving is a 200-mesh sieve;
(5) putting the mixed powder obtained in the step (4) into an air atmosphere furnace for calcining, taking out the calcined mixed powder, cooling, grinding, and sieving with a 100-200-mesh sieve to obtain the V2O5A @ C modified fluorocarbon positive electrode material;the calcining temperature is 400 ℃ and the calcining time is 10 hours.
Further, in the steps (1) and (2), the fluorocarbon is reacted with NH4VO3The mass ratio of (a) to (b) is 1: 0.9.
Example 3
V-shaped groove2O5The preparation method of the @ C modified fluorocarbon cathode material comprises the following steps:
(1) proportionally mixing NH4VO3Adding the mixture into deionized water, and stirring uniformly for 0.8h to obtain a mixed solution 1; the NH4VO3And deionized water at a mass ratio of 1: 3.5;
(2) adding carbon fluoride into a mixed solution of absolute ethyl alcohol and ultrapure water according to a proportion, and uniformly stirring for 0.8h to obtain a mixed solution 2; the mass ratio of the carbon fluoride to the absolute ethyl alcohol to the ultrapure water is 1:1.1: 1.1;
(3) uniformly mixing the mixed solution 1 and the mixed solution 2 to obtain a mixed solution, and then feeding the mixed solution into a high-energy ball mill for high-energy ball milling to form mixed slurry; the method for high-energy ball milling comprises the following steps: firstly, ball milling is carried out for 0.8min, then the operation is stopped, the high-energy ball mill is cooled for more than 10min, then the high-energy ball milling is carried out, the high-energy ball milling is carried out repeatedly, and the total operation time is 1.2 h; the rotating speed of the high-energy ball mill is more than 3000 r/min; the high-energy ball mill is a high-energy ball milling cup; before the mixed solution is sent into a high-energy ball mill for high-energy ball milling, adding zirconia balls, wherein the mass ratio of the mixed solution to the zirconia balls is 1: 2.9;
(4) drying and sieving the mixed slurry obtained in the step (3) to obtain mixed powder; the drying temperature is 75 ℃, and the drying time is 9 hours; the sieving is a 120-mesh sieve;
(5) putting the mixed powder in the step (4) into an air atmosphere furnace for calcining, taking out the calcined mixed powder, cooling, grinding, and sieving with a 120-mesh sieve to obtain the V2O5A @ C modified fluorocarbon positive electrode material; the calcining temperature is 320 ℃ and the calcining time is 8.5 h.
Further, in the steps (1) and (2), the fluorocarbon is reacted with NH4VO3The mass ratio of (a) to (b) is 1: 0.2.
Example 4
V-shaped groove2O5The preparation method of the @ C modified fluorocarbon cathode material comprises the following steps:
(1) proportionally mixing NH4VO3Adding the mixture into deionized water, and stirring uniformly for 1.3h to obtain a mixed solution 1; the NH4VO3And deionized water at a mass ratio of 1: 4.5;
(2) adding carbon fluoride into a mixed solution of absolute ethyl alcohol and ultrapure water according to a proportion, and uniformly stirring for 1.3 hours to obtain a mixed solution 2; the mass ratio of the carbon fluoride to the absolute ethyl alcohol to the ultrapure water is 1:1.4: 1.4;
(3) uniformly mixing the mixed solution 1 and the mixed solution 2 to obtain a mixed solution, and then feeding the mixed solution into a high-energy ball mill for high-energy ball milling to form mixed slurry; the method for high-energy ball milling comprises the following steps: firstly, ball milling is carried out for 1.8min, then the operation is stopped, the high-energy ball mill is cooled for more than 10min, then the high-energy ball milling is carried out, the high-energy ball milling is carried out repeatedly, and the total operation time is 1.8 h; the rotating speed of the high-energy ball mill is more than 3000 r/min; the high-energy ball mill is a high-energy ball milling cup; adding zirconia balls before feeding the mixed solution into a high-energy ball mill for high-energy ball milling, wherein the mass ratio of the mixed solution to the zirconia balls is 1: 3.2;
(4) drying and sieving the mixed slurry obtained in the step (3) to obtain mixed powder; the drying temperature is 85 ℃, and the drying time is 8-12 h; the screening is performed by a screen of 100-200 meshes;
(5) putting the mixed powder in the step (4) into an air atmosphere furnace for calcining, taking out the calcined mixed powder, cooling, grinding, and sieving with a 180-mesh sieve to obtain the V2O5A @ C modified fluorocarbon positive electrode material; the calcining temperature is 390 ℃, and the calcining time is 9.5 h.
Further, in the steps (1) and (2), the fluorocarbon is reacted with NH4VO3The mass ratio of (a) to (b) is 1: 0.8.
Example 5
V-shaped groove2O5@ C modified fluorineThe preparation method of the carbon-modified cathode material comprises the following steps:
(1) proportionally mixing NH4VO3Adding the mixture into deionized water, and stirring uniformly for 1.1h to obtain a mixed solution 1; the NH4VO3And deionized water at a mass ratio of 1: 4;
(2) adding carbon fluoride into a mixed solution of absolute ethyl alcohol and ultrapure water according to a proportion, and uniformly stirring for 1.1h to obtain a mixed solution 2; the mass ratio of the carbon fluoride to the absolute ethyl alcohol to the ultrapure water is 1:1.3: 1.3;
(3) uniformly mixing the mixed solution 1 and the mixed solution 2 to obtain a mixed solution, and then feeding the mixed solution into a high-energy ball mill for high-energy ball milling to form mixed slurry; the method for high-energy ball milling comprises the following steps: firstly, ball milling is carried out for 1.2min, then the operation is stopped, the high-energy ball mill is cooled for more than 10min, then the high-energy ball milling is carried out, the high-energy ball milling is carried out repeatedly, and the total operation time is 1.5 h; the rotating speed of the high-energy ball mill is more than 3000 r/min; the high-energy ball mill is a high-energy ball milling cup; adding zirconia balls before feeding the mixed solution into a high-energy ball mill for high-energy ball milling, wherein the mass ratio of the mixed solution to the zirconia balls is 1: 3;
(4) drying and sieving the mixed slurry obtained in the step (3) to obtain mixed powder; the drying temperature is 80 ℃, and the drying time is 10 hours; the screening is a 150-mesh screen;
(5) putting the mixed powder in the step (4) into an air atmosphere furnace for calcining, taking out the calcined mixed powder, cooling, grinding, and sieving with a 150-mesh sieve to obtain the V2O5A @ C modified fluorocarbon positive electrode material; the calcining temperature is 350 ℃ and the calcining time is 9 h.
Further, in the steps (1) and (2), the fluorocarbon is reacted with NH4VO3The mass ratio of (a) to (b) is 1: 0.5.
Application example 1
V made in example 12O5The @ C modified fluorocarbon positive electrode material is used as a positive electrode material, SP and CNTS are conductive agents, CMC and SBR are binding agents, and the mass ratio of the positive electrode material to the conductive agent to the binding agent is 80:10:10And uniformly mixing to prepare anode slurry, coating the anode slurry on an aluminum foil, drying at the temperature of 100 ℃, taking metal lithium as a negative electrode, and assembling a group of lithium batteries in a 1% drying room. And then, adopting pure carbon fluoride as a positive electrode material, SP and CNTS as conductive agents, and CMC and SBR as binders, and assembling another group of lithium batteries by adopting the method. Simultaneously carrying out discharge tests on the two groups of lithium batteries under the conditions of normal temperature and 0.2C multiplying power shown in figure 2, and testing the temperature rise in the discharge process, wherein the temperature rise curve is shown in figure 3; it is evident from fig. 2 that the low-wave voltage at the initial stage of discharge of the battery made of pure fluorocarbon is 1.98V, the voltage hysteresis is relatively obvious, and the plateau voltage is 2.39V. Instead, V from example 1 was used2O5The battery made of the @ C modified fluorocarbon anode material has the low-wave voltage of 2.23V at the initial discharge stage, the voltage hysteresis phenomenon is obviously improved, the platform voltage is 2.45V, and V is reflected2O5Higher working voltage and V of material2O5And the conductive carbon material has good conductivity; it is evident from fig. 3 that the maximum temperature during discharge of the cell made of pure carbon fluoride was 22 ℃; and V in example 1 was used2O5The battery made of the @ C modified fluorocarbon anode material has the highest temperature of 21 ℃ in the discharging process, and the temperature rise is reduced, so that V is further embodied2O5And good conductivity of the conductive carbon material; due to V2O5The material itself has a specific gram capacity of 280mAh/g, and V2O5The material and the conductive carbon both have good conductivity, and on the premise of sacrificing a small amount of the capacity of the carbon fluoride material, the voltage lag of the carbon fluoride material is greatly improved, the temperature rise in the discharge process is reduced, and the performance of the carbon fluoride material is greatly improved.
Application example 2
V made using example 22O5The method comprises the following steps of taking the @ C modified carbon fluoride positive electrode material as a positive electrode material, taking SP and CNTS as conductive agents, taking CMC and SBR as binders, uniformly mixing the materials according to the mass ratio of 80:10:10 to prepare positive electrode slurry, coating the positive electrode slurry on an aluminum foil, drying the positive electrode slurry at the temperature of 100 ℃, taking metal lithium as a negative electrode, feeding the positive electrode slurry into a 1% drying roomAnd assembling a group of lithium batteries. And then, adopting pure carbon fluoride as a positive electrode material, SP and CNTS as conductive agents, and CMC and SBR as binders, and assembling another group of lithium batteries by adopting the method. The two groups of lithium batteries are subjected to discharge tests at normal temperature and under the condition of 1.0C multiplying power shown in figure 4 at the same time, and the temperature rise in the discharge process is tested, wherein the temperature rise curve is shown in figure 5; it is evident from fig. 4 that the low-wave voltage at the initial stage of discharge of the cell made of pure fluorocarbon is 1.68V, the voltage hysteresis is relatively obvious, and the plateau voltage is 2.35V. While V in example 2 was used2O5The battery made of the @ C modified fluorocarbon anode material has the low-wave voltage of 2.02V at the initial discharge stage, the voltage hysteresis phenomenon is obviously improved, the plateau voltage is 2.43V, and V is reflected2O5Higher working voltage and V of material2O5And the conductive carbon material has good conductivity; it is evident from fig. 5 that the maximum temperature during discharge of the cell made of pure carbon fluoride was 36 ℃; and V in example 2 was used2O5The maximum temperature of the battery made of the @ C modified fluorocarbon anode material is 31.1 ℃ in the discharging process, the temperature rise is obviously reduced, and V is further embodied2O5And good conductivity of the conductive carbon material; due to V2O5The material itself has a specific gram capacity of 280mAh/g, and V2O5The material and the conductive carbon both have good conductivity, and on the premise of sacrificing a small amount of the capacity of the carbon fluoride material, the voltage lag of the carbon fluoride material is greatly improved, the temperature rise in the discharge process is reduced, and the performance of the carbon fluoride material is greatly improved.
Application example 3
V made in example 32O5The @ C modified fluorocarbon anode material is used as an anode material, SP and CNTS are conductive agents, CMC and SBR are binders, and the anode material is characterized in that: conductive agent: and uniformly mixing the binders in a mass ratio of 80:10:10 to prepare anode slurry, coating the anode slurry on an aluminum foil, drying at 100 ℃, taking metal lithium as a negative electrode, and assembling a group of lithium batteries in a 1% drying room. Pure carbon fluoride is adopted as a positive electrode material, SP and CNTS are adopted as conductive agents, CMC and SBR are adopted as bindersAnd assembling another group of lithium batteries by adopting the method. The two groups of lithium batteries are subjected to discharge tests at normal temperature and 2.0C multiplying power shown in fig. 6 at the same time, and the temperature rise in the discharge process is tested, wherein the temperature rise curve is shown in fig. 7; it is evident from fig. 6 that the low-wave voltage at the initial stage of discharge of the battery made of pure fluorocarbon is 1.13V, the voltage hysteresis is relatively obvious, and the plateau voltage is 2.2V. While V in example 3 was used2O5The battery made of the @ C modified fluorocarbon anode material has the low-wave voltage of 1.81V at the initial discharge stage, the plateau voltage of 2.35V and the voltage hysteresis phenomenon which is obviously improved, and shows that V is2O5Higher working voltage and V of material2O5And the conductive carbon material has good conductivity; it is evident from fig. 7 that the maximum temperature during discharge of the cell made of pure carbon fluoride is 55 ℃; and V in example 3 was used2O5The maximum temperature of the battery made of the @ C modified fluorocarbon anode material is 45.6 ℃ in the discharging process, the temperature rise is obviously reduced, and V is further embodied2O5And good conductivity of the conductive carbon material; due to V2O5The material itself has a specific gram capacity of 280mAh/g, and V2O5The material and the conductive carbon both have good conductivity, and on the premise of sacrificing a small amount of the capacity of the carbon fluoride material, the voltage lag of the carbon fluoride material is greatly improved, the temperature rise in the discharge process is reduced, and the performance of the carbon fluoride material is greatly improved.
In conclusion, the present application employs V2O5Modification of carbon fluoride material with @ C, and reacting NH with solvent4VO3And carbon fluoride are respectively dispersed uniformly, then are uniformly mixed by a high-energy ball milling mode, and NH is calcined at high temperature in air atmosphere4VO3Reaction on the surface of carbon fluoride to form V2O5Simultaneously, the carbon fluoride is partially decomposed to generate conductive carbon which is uniformly coated on the surface of the carbon fluoride material, and finally V is prepared2O5@ C modified fluorocarbon positive electrode material due to V2O5The material has a higher working voltage platform and V2O5And is electrically conductiveThe carbon has good conductivity, can make up for the problem of voltage hysteresis at the initial discharge stage of the carbon fluoride material, effectively improves the large-current discharge capacity of the carbon fluoride material, greatly improves the rate capability of the lithium fluorocarbon battery and reduces the temperature rise of the lithium fluorocarbon battery in the discharge process. V prepared by the method2O5The @ C modified carbon fluoride cathode material is applied to a lithium carbon fluoride battery, the voltage hysteresis of the battery can be effectively improved, the temperature rise of the battery in the discharging process is reduced, the low-wave voltage under the condition of 0.2C multiplying power is increased from 1.98V to 2.23V, the platform voltage is increased from 2.39V to 2.45V, and the temperature rise is reduced from 22 ℃ to 21 ℃; the low-wave voltage under the condition of 1.0C multiplying power is increased to 2.02V from 1.68V, the platform voltage is increased to 2.43V from 2.35V, and the temperature rise is reduced to 31.1 ℃ from 36 ℃; the low-wave voltage under the condition of 2.0C multiplying power is improved to 1.81V from 1.13V, the platform voltage is improved to 2.35V from 2.2V, the temperature rise is reduced to 45.6 ℃ from 55 ℃, and particularly, the effect under the condition of large multiplying power is more obvious. The discharge 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 (7)
1. V-shaped groove2O5A preparation method of the @ C modified fluorocarbon cathode material is characterized by comprising the following steps of:
(1) proportionally mixing NH4VO3Adding the mixture into deionized water, and uniformly stirring for 0.6-1.5 h to obtain a mixed solution 1;
(2) adding carbon fluoride into a mixed solution of absolute ethyl alcohol and ultrapure water according to a ratio, and uniformly stirring for 0.6-1.5 h to obtain a mixed solution 2;
(3) uniformly mixing the mixed solution 1 and the mixed solution 2 to obtain a mixed solution, and then feeding the mixed solution into a high-energy ball mill for high-energy ball milling to form mixed slurry;
(4) drying and sieving the mixed slurry obtained in the step (3) to obtain mixed powder;
(5) putting the mixed powder obtained in the step (4) into an air atmosphere furnace for calcining, taking out the calcined mixed powder, cooling, grinding, and sieving with a 100-200-mesh sieve to obtain the V2O5A @ C modified fluorocarbon positive electrode material;
in step (3), the method of high-energy ball milling is as follows: firstly, ball milling is carried out for 0.5-2 min, then the operation is stopped, the high-energy ball mill is cooled for more than 10min, then the high-energy ball milling is carried out, the high-energy ball milling is carried out repeatedly, and the total operation time is 1-2 h;
adding zirconia balls before the mixed solution is sent into a high-energy ball mill for high-energy ball milling in the step (3), wherein the mass ratio of the mixed solution to the zirconia balls is 1: 2.8-3.3;
in the step (5), the calcining temperature is 300-400 ℃, and the time is 8-10 h.
2. A V according to claim 12O5A preparation method of a @ C modified fluorocarbon cathode material is characterized by comprising the following steps: in step (1), the NH4VO3And deionized water in a mass ratio of 1 to (3-5).
3. A V according to claim 12O5A preparation method of a @ C modified fluorocarbon cathode material is characterized by comprising the following steps: in the step (2), the mass ratio of the carbon fluoride, the absolute ethyl alcohol and the ultrapure water is 1 (1-1.5) to 1-1.5.
4. A V according to claim 12O5A preparation method of a @ C modified fluorocarbon cathode material is characterized by comprising the following steps: in steps (1) and (2), the fluorocarbon is reacted with NH4VO3The mass ratio of (1) to (0.1 to 0.9).
5. A V according to claim 12O5A preparation method of a @ C modified fluorocarbon cathode material is characterized by comprising the following steps: in the step (3), the rotating speed of the high-energy ball mill is more than 3000 r/min.
6. A V according to claim 12O5A preparation method of a @ C modified fluorocarbon cathode material is characterized by comprising the following steps: in step (3), the high-energy ball mill is a high-energy ball milling cup.
7. A V according to claim 12O5A preparation method of a @ C modified fluorocarbon cathode material is characterized by comprising the following steps: in the step (4), the drying temperature is 70-90 ℃, and the drying time is 8-12 h; and sieving the materials by a sieve of 100-200 meshes.
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