CN115440966B - Copper-modified carbon fluoride/niobium oxide composite positive electrode material and preparation method thereof - Google Patents
Copper-modified carbon fluoride/niobium oxide composite positive electrode material and preparation method thereof Download PDFInfo
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- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
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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
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
- H01M4/485—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of mixed oxides or hydroxides for inserting or intercalating light metals, e.g. LiTi2O4 or LiTi2OxFy
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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
- H01M4/36—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
Abstract
The invention discloses a copper-modified carbon fluoride/niobium oxide composite positive electrode material and a preparation method thereof, which comprises the steps of firstly taking niobium ethoxide, hydrogen peroxide and fluorinated ketjen black as raw materials, taking ethanol as a solvent, and preparing the fluorinated ketjen black/alpha-Nb through sol, drying and calcining 2 O 5 The composite positive electrode material is prepared by using copper sulfate as raw material, water as solvent, adding surfactant and adopting an aqueous solvent method to prepare copper modified fluorinated ketjen black/alpha-Nb 2 O 5 And (3) compounding a positive electrode material. The niobium pentoxide composite can improve the conductivity of the material, improve the voltage hysteresis under high-rate discharge, and the copper modification can further improve the conductivity of the positive electrode material, reduce the internal resistance of the battery material, simultaneously improve the ion conductivity of the fluorinated ketjen black material, effectively improve the power performance of the lithium-carbon fluoride battery, and in addition, the copper modification can stabilize the electrode material in the discharge process, so that the electrical performance is further improved.
Description
Technical Field
The invention relates to the technical field of chemical power supplies, in particular to a copper-modified carbon fluoride/niobium oxide composite positive electrode material and a preparation method thereof.
Background
The lithium fluorocarbon battery is used as a primary battery with highest specific energy in the current practical application, and reaches 2180Wh/kg. At the same time, the structure of the graphite fluoride material ensures that the graphite fluoride material has stable physical and chemical propertiesTherefore, the battery storage property and the high temperature property are good. However, the self structure of the fluorocarbon cathode material is limited, and the electron conductivity of the fluorocarbon cathode material is low (10 -9 S/cm magnitude), a large voltage drop is generated when the battery discharges at a large current, and as the battery discharges at a large current, the ionic conductivity of the fluorocarbon material cannot meet the requirement, so that the voltage cannot meet the use requirement, and the capacity is limited.
Patent number CN201301478262.4 discloses a surface modification method of a fluorocarbon material, which adopts a physical ball milling mixing calcination mode of nano copper and fluorocarbon to improve conductivity and platform voltage of the fluorocarbon material, but only provides discharge data under 1C multiplying power, and simple physical mixing and calcination only takes copper as a conductive agent to play a role in electronic conduction.
Patent number CN201910103600.3 discloses a V 2 O 5 The carbon fluoride anode material modified by @ C improves the voltage hysteresis and the power performance of the carbon fluoride, but V2O5 in the material occupies a certain proportion, and the gram specific capacity of the material is lower, so that the specific capacity output of the material is affected.
Patent No. CN201711107845.0 discloses a ruthenium-modified fluorocarbon material, preparation and application, and RuCl is prepared by high-temperature calcination 3 The decomposition coating is coated on the surface of the carbon fluoride, so that the effects of improving a battery discharge voltage platform and reducing voltage hysteresis are achieved, but the discharge multiplying power of the battery and the discharge specific capacity under the multiplying power cannot be further improved.
Patent No. 202110722718.1 discloses an Ag 2 CrO 4 Preparation method of Ag modified carbon fluoride positive electrode material, and the function of the material is that Ag is used for preparing the carbon fluoride positive electrode material 2 CrO 4 And Ag forms a good electronic conductive network to improve conductivity, but the initial voltage of the material at the discharge stage of 2C multiplying power is reduced to below 2V, and the improvement effect is limited.
Although the power performance of the fluorocarbon cathode material is improved by means of preparation, surface modification and the like of the fluorinated graphene material in the prior art, the effect of mainly focusing on improving the electronic conductivity of the fluorinated carbon material is mainly to improve the capacity output in a small extent while improving the working voltage platform under high-rate discharge, and the effect is not obvious, particularly, the capacity output is reduced by more than 50% when the high-rate discharge is carried out at a rate of more than 3 ℃. And the ionic conductivity of the material is affected less, so that the lithium ion transmission rate in the discharge process of the fluorocarbon material cannot meet the oxidation-reduction reaction rate, the electric discharge reaction cannot be stopped, and the capacity output of the fluorocarbon material is lower.
Therefore, aiming at the ion conductivity and the electron conductivity which affect the power performance of the fluorocarbon material at present, a solution measure capable of improving the ion conductivity and the electron conductivity at the same time is needed to be provided, and the power performance of the lithium fluorocarbon battery is improved.
Disclosure of Invention
Aiming at the defects of the prior art, the invention provides a copper-modified carbon fluoride/niobium oxide composite positive electrode material and a preparation method thereof.
The method is realized by the following technical scheme:
the invention provides a preparation method of a copper-modified carbon fluoride/niobium oxide composite positive electrode material, which comprises the following steps:
(1) Adding the fluorinated ketjen black into absolute ethyl alcohol, mixing and stirring by using a magnetic stirrer, dropwise adding niobium ethoxide, fully stirring, adding hydrogen peroxide, continuously stirring, and obtaining the fluorinated ketjen black/Nb (OH) through suction filtration, absolute ethyl alcohol flushing, deionized water flushing, drying and grinding 5 The precursor is placed in a muffle furnace for calcination to obtain the fluorinated ketjen black/alpha-Nb 2 O 5 A composite positive electrode material;
(2) Dissolving copper sulfate in deionized water, dispersing with magnetic stirring, and adding fluorinated ketjen black/alpha-Nb 2 O 5 Adding the composite positive electrode material into the mixed solution for dispersion, stirring and adding the surfactant at the same time to obtain copper sulfate/fluorinated ketjen black/alpha-Nb 2 O 5 Mixing the solutions;
(3) Dissolving chemical reducing agent in deionized water, and dropwise adding the solution into the copper sulfate/fluorinated ketjen black/alpha-Nb prepared in the step (1) 2 O 5 In the mixed solution, the mixed solution is continuously stirred and is subjected to suction filtration, absolute ethyl alcohol washing and deionizationWashing with son water, and oven drying to obtain copper modified fluorinated ketjen black/alpha-Nb 2 O 5 And (3) compounding a positive electrode material.
The carbon fluoride in the copper-modified carbon fluoride/niobium oxide composite positive electrode material is ketjen black fluoride, and the niobium oxide is alpha-Nb 2 O 5 Therefore, the material is also called copper-modified fluorinated ketjen black/alpha-Nb 2 O 5 And (3) compounding a positive electrode material.
The mass concentration of the hydrogen peroxide is 20%.
The mass ratio of the fluorinated ketjen black to the niobium ethoxide to the hydrogen peroxide is 1:0.1:0.5-1:0.5:3.
The calcination temperature is 300-500 ℃.
The calcination time is 1-3 h.
The mass ratio of the copper sulfate to the fluorinated ketjen black to the deionized water is 1:100:200-10:100:200.
The magnetic stirring speed is 80 r/min-1000 r/min, preferably 300r/min.
The surfactant is any one or the combination of n-butanol and a hydrophilic nonionic surfactant OP-10; the hydrophilic nonionic surfactant OP-10 is preferable, and can be distributed on the surface of the fluorinated ketjen black material, so that the copper sulfate reaction is facilitated while the dispersion of the material is enhanced, copper particles are uniformly distributed on the surface of the fluorinated ketjen black material, and the agglomeration of the copper particles is prevented.
The mass ratio of the surfactant to the deionized water is 1:100-3:100.
The chemical reducing agent is one of potassium borohydride, sodium borohydride, hydrazine hydrate and sodium hypophosphite, the mass ratio of the chemical reducing agent to the copper sulfate is 1:1-1:10, and preferably, the chemical reducing agent is potassium borohydride, and the mass ratio of the chemical reducing agent to the copper sulfate is 1:5.
The mass ratio of the chemical reducing agent to the deionized water is 1:1-1:20, and preferably the mass ratio of the chemical reducing agent to the deionized water is 1:10.
The invention provides a copper-modified carbon fluoride/niobium oxide composite anode material prepared by the preparation method.
The invention provides a lithium fluorocarbon battery, which adopts the copper-modified carbon fluoride/niobium oxide composite anode material prepared by the invention as an anode material, wherein the anode is lithium metal, and the electrolyte system is 1mol/L LiBF6/EC:DMC:EMC.
The beneficial effects are that:
the invention discloses a copper-modified carbon fluoride/niobium oxide composite positive electrode material, which is prepared by taking niobium ethoxide, hydrogen peroxide and ketjen black as raw materials and ethanol as a solvent through sol, drying and calcining, and then taking copper sulfate as the raw material, taking water as the solvent, adding a surfactant and adopting a water solvent method. The niobium pentoxide composite can improve the conductivity of the material, improve the voltage hysteresis under high-rate discharge, and the copper modification can further improve the conductivity of the positive electrode material, reduce the internal resistance of the battery material, simultaneously improve the ion conductivity of the fluorinated ketjen black material, effectively improve the power performance of the lithium-carbon fluoride battery, and in addition, the copper modification can stabilize the electrode material in the discharge process, so that the electrical performance is further improved. Compared with the prior art, the invention has at least the following beneficial effects.
(1) The invention adopts the fluorinated ketjen black as the fluorocarbon material, is an amorphous fluorocarbon material, has better power performance and is simultaneously matched with Nb 2 O 5 Is also more compact, nb 2 O 5 Evenly distributed around the black of the fluorinated organ, and better electric performance is exerted.
(2) The invention adopts the ethanol as the raw material and ethanol as the solvent, so that the degradation rate of the ethanol niobium can be slowed down, and the product solid Nb (OH) can be obtained 5 Slowly and uniformly distributed on the surface of the fluorinated ketjen black material, and further calcined alpha-Nb 2 O 5 The hydrogen peroxide with the weight percent of 20 percent is added in the degradation process of the niobium ethoxide to have double functions, the hydrogen peroxide with the weight percent of 20 percent can provide the water for the degradation reaction of the niobium ethoxide, and simultaneously, the reaction product has gel property, which is more beneficial to Nb (OH) 5 Evenly distributed.
(3) The calcination temperature controlled by the invention is 300-450 ℃, and the alpha-Nb can be generated 2 O 5 The first discharge voltage can reach more than 2.5V, the specific capacity reaches more than 250mAh/g, the discharge capacity of the cathode material with the multiplying power of more than 10C can be effectively improved after the cathode material is compounded with the fluorinated ketjen black, the voltage hysteresis phenomenon under high-multiplying power (more than 2C) discharge is improved, the capacity output is improved (the end stage of the 7C discharge has an obvious second stage voltage platform, namely alpha-Nb) 2 O 5 A discharge platform).
(4) The invention further adopts the fast conductor copper pair fluorinated ketjen black/alpha-Nb with ionic and electronic double conductivity 2 O 5 The surface modification of the composite positive electrode material is uniformly distributed on the surface of the composite material, a conductive channel can be well constructed in the discharging process, the electronic conduction and the ionic conduction are increased, compared with unmodified fluorinated ketjen black, the multiplying power performance is obviously improved, the voltage hysteresis at the initial stage of discharging, the platform voltage and the specific discharge capacity are all improved, and constant-current discharging at a high multiplying power of 7C is realized.
(5) The hydrophilic nonionic surfactant is introduced in the surface modification process, and is distributed in the fluorinated ketjen black/alpha-Nb on one hand 2 O 5 The surface enhances the dispersion of the anode material, and is favorable for the reaction of the copper sulfate; on the other hand, the surfactant is used as a high molecular compound, the affinity group of the surfactant is coated on the surfaces of generated copper particles in the aqueous solution, the other end group of the surfactant is in the aqueous solution, so that the generated copper particles are reduced to collide with each other to prevent agglomeration, the copper particles are uniformly distributed on the surface of the fluorinated ketjen black material, if the surfactant is not used, the particles are agglomerated into larger particles after collision, the uniformity of copper modification is poor, and the electrical property of the material is further influenced.
(6) Copper-modified fluorinated ketjen black/alpha-Nb prepared by the invention 2 O 5 The gram specific capacity of the copper modified composite positive electrode material and the fluorinated ketjen black material is 771mAh/g and 808mAh/g when the composite positive electrode material is applied to a lithium fluorocarbon battery at the multiplying power of 0.1C, because of copper and alpha-Nb 2 O 5 The introduction of (3) reduces the discharge gram capacity of the active substance. But put down at 2C, 5C, 7CThe electrical property of the positive electrode material prepared by the invention is obviously improved, the discharge gram capacities are 668mAh/g, 576mAh/g and 487mAh/g respectively, compared with the untreated fluorinated ketjen black positive electrode material, the discharge gram capacities of 578mAh/g, 408mAh/g and 270mAh/g are high, the discharge specific capacity is high, and the discharge capacity is obviously reduced relative to 0.1C (copper modified fluorinated ketjen black/alpha-Nb) 2 O 5 Composite positive electrode material: 2C is reduced by 103mAh/g,5C is reduced by 195mAh/g, and 7C is reduced by 284mAh/g; fluorinated ketjen black cathode material: 230mAh/g for 2C reduction, 400mAh/g for 5C reduction and 601mAh/g for 7C reduction), the low-wave voltage at 5C is increased from 1.90V to 2.03V, the platform voltage is increased from 2.02V to 2.08V, the low-wave voltage at 7C is 1.86V, and the platform voltage is increased to 1.95V, indicating that the copper-modified fluorinated organ black/alpha-Nb 2 O 5 Both the electron conductivity and the ion conductivity of the composite positive electrode material are improved. Because the ohmic internal resistance exists to reduce the voltage when the electron conductivity is low under the high-rate discharge condition, the invention improves the electron conductivity to raise the voltage platform; however, the poor ionic conductivity can lead to the fact that the lithium ion transmission rate in the discharging process of the battery can not meet the high-rate oxidation-reduction reaction under high-rate discharging, so that the battery capacity can not be output 2 O 5 The ionic conductivity and the electronic conductivity of the composite positive electrode material are improved, so that the discharge capacity of the material at high multiplying power is obviously improved, and the power performance of the material is improved.
Drawings
FIG. 1 is a flow chart of a process for preparing a copper-modified carbon fluoride/niobium oxide composite positive electrode material;
FIG. 2 is a graph showing the discharge curves at 0.1C for a cell prepared from the copper-modified carbon fluoride/niobium oxide composite cathode material of application example 1 and a cell prepared from the pure fluorinated ketjen black material;
FIG. 3 is a graph showing the discharge curves at 2C for a battery prepared from the copper-modified carbon fluoride/niobium oxide composite cathode material of application example 2 and a battery prepared from the pure fluorinated ketjen black material;
fig. 4 is a discharge curve at 5C for a battery prepared from the copper-modified carbon fluoride/niobium oxide composite cathode material of application example 3 and a battery prepared from a pure fluorinated ketjen black material.
Fig. 5 is a graph showing the discharge curves at 7C for a battery prepared from the copper-modified carbon fluoride/niobium oxide composite cathode material of application example 3 and a battery prepared from the pure fluorinated ketjen black material.
Detailed Description
The following detailed description of the invention is provided in further detail, but the invention is not limited to these embodiments, any modifications or substitutions in the basic spirit of the present examples, which still fall within the scope of the invention as claimed.
Example 1
Copper-modified carbon fluoride/niobium oxide composite positive electrode material (also called copper-modified ketjen black/alpha-Nb) 2 O 5 Composite positive electrode material) is prepared by the following method:
(1) Weighing fluorinated ketjen black, niobium ethoxide and 20wt% of hydrogen peroxide with the mass ratio of 1:0.1:0.5, adding the fluorinated ketjen black into absolute ethyl alcohol, mixing and stirring by using a magnetic stirrer, dropwise adding the niobium ethoxide, adding 20wt% of hydrogen peroxide after fully stirring, continuously stirring for 10min, and obtaining the fluorinated ketjen black/Nb (OH) through suction filtration, absolute ethyl alcohol flushing, deionized water flushing, drying and grinding 5 Calcining the precursor in a muffle furnace at 300 ℃ to obtain fluorinated ketjen black/alpha-Nb 2 O 5 A composite positive electrode material;
(2) Weighing copper sulfate and deionized water according to the mass ratio of the copper sulfate to the fluorinated ketjen black to the deionized water of 1:100:200, dissolving the copper sulfate in a deionized water mixed solvent, and stirring and dispersing by utilizing magnetic force at the speed of 300r/min; and then the fluorinated ketjen black/alpha-Nb 2 O 5 Adding the composite positive electrode material into the mixed solution for dispersion, keeping stirring, and simultaneously adding a hydrophilic group nonionic surfactant OP-10 with the deionized water ratio of 1:100 to obtain a copper sulfate/composite positive electrode material mixed solution;
(3) Dissolving potassium borohydride with the mass ratio of 1:5 to copper sulfate in deionized water, and obtaining a potassium borohydride solution with the mass ratio of 1:10, and dropwise adding the potassium borohydride solution into the copper sulfate/composite prepared in the step (2)Continuously stirring for 3 hours in the mixed solution of the anode material, and obtaining copper modified fluorinated ketjen black/alpha-Nb by suction filtration, washing with absolute ethyl alcohol for 2 times, washing with deionized water for 3 times and drying at 80 DEG C 2 O 5 And (3) compounding a positive electrode material.
Example 2
Copper-modified carbon fluoride/niobium oxide composite positive electrode material (also called copper-modified ketjen black/alpha-Nb) 2 O 5 Composite positive electrode material) is prepared by the following method:
(1) Weighing fluorinated ketjen black, niobium ethoxide and 20wt% of hydrogen peroxide in a mass ratio of 1:0.1:3, adding the fluorinated ketjen black into absolute ethyl alcohol, mixing and stirring by using a magnetic stirrer, dropwise adding the niobium ethoxide, adding the 20wt% of hydrogen peroxide after fully stirring, continuously stirring for 10min, and obtaining the fluorinated ketjen black/Nb (OH) through suction filtration, absolute ethyl alcohol flushing, deionized water flushing, drying and grinding 5 Calcining the precursor in a muffle furnace at 400 ℃ to obtain fluorinated ketjen black/alpha-Nb 2 O 5 A composite positive electrode material;
(2) Weighing copper sulfate and deionized water according to the mass ratio of the copper sulfate to the fluorinated ketjen black to the deionized water of 5:100:200, dissolving the copper sulfate in a deionized water mixed solvent, and stirring and dispersing by utilizing magnetic force at the speed of 300r/min; and then the fluorinated ketjen black/alpha-Nb 2 O 5 Adding the composite positive electrode material into the mixed solution for dispersion, keeping stirring, and simultaneously adding a hydrophilic group nonionic surfactant OP-10 with the deionized water ratio of 1:100 to obtain a copper sulfate/composite positive electrode material mixed solution;
(3) Dissolving potassium borohydride with the mass ratio of 1:5 to copper sulfate in deionized water, and the ratio of the potassium borohydride to the deionized water is 1:10 to obtain a potassium borohydride solution, dropwise dripping the potassium borohydride solution into the copper sulfate/composite anode material mixed solution prepared in the step (2), stirring for 3 hours, and obtaining copper modified ketjen black/alpha-Nb through suction filtration, absolute ethyl alcohol flushing for 2 times, deionized water flushing for 3 times and drying at 80 ℃ 2 O 5 And (3) compounding a positive electrode material.
Example 3
Copper-modified fluorocarbon ∈ -Niobium oxide composite positive electrode material (also called copper modified fluorinated ketjen black/alpha-Nb) 2 O 5 Composite positive electrode material) is prepared by the following method:
(1) Weighing fluorinated ketjen black, niobium ethoxide and 20wt% of hydrogen peroxide in a mass ratio of 1:0.5:3, adding the fluorinated ketjen black into absolute ethyl alcohol, mixing and stirring by using a magnetic stirrer, dropwise adding the niobium ethoxide, adding the 20wt% of hydrogen peroxide after fully stirring, continuously stirring for 10min, and obtaining the fluorinated ketjen black/Nb (OH) through suction filtration, absolute ethyl alcohol flushing, deionized water flushing, drying and grinding 5 Calcining the precursor in a muffle furnace at 450 ℃ to obtain fluorinated ketjen black/alpha-Nb 2 O 5 A composite positive electrode material;
(3) Weighing copper sulfate and deionized water according to the mass ratio of the copper sulfate to the fluorinated ketjen black to the deionized water of 10:100:200, dissolving the copper sulfate in a deionized water mixed solvent, and stirring and dispersing by utilizing magnetic force at the speed of 300r/min; and then the fluorinated ketjen black/alpha-Nb 2 O 5 Adding the composite positive electrode material into the mixed solution for dispersion, keeping stirring, and simultaneously adding a hydrophilic group nonionic surfactant OP-10 with the deionized water ratio of 1:100 to obtain a copper sulfate/composite positive electrode material mixed solution;
(3) Dissolving potassium borohydride with the mass ratio of 1:5 to copper sulfate in deionized water, and the ratio of the potassium borohydride to the deionized water is 1:10 to obtain a potassium borohydride solution, dropwise dripping the potassium borohydride solution into the copper sulfate/composite anode material mixed solution prepared in the step (2), stirring for 3 hours, and obtaining copper modified ketjen black/alpha-Nb through suction filtration, absolute ethyl alcohol flushing for 2 times, deionized water flushing for 3 times and drying at 80 ℃ 2 O 5 And (3) compounding a positive electrode material.
Application example 1
The copper-modified carbon fluoride/niobium oxide composite positive electrode material prepared in the embodiment 1 is used as a positive electrode material, and the mass ratio of the positive electrode material to sodium carboxymethyl cellulose to the superconducting carbon black to the styrene-butadiene latex is 85:3:7:5 adding deionized water to prepare slurry, uniformly coating the prepared slurry on an aluminum foil current collector, drying at 70 ℃ to obtain a positive plate, and cutting and then mixing withThe lithium sheets are assembled into the button lithium carbon fluoride battery, and the electrolyte system is 1mol/LLiBF6/EC, DMC and EMC. And (3) adopting fluorinated ketjen black as a positive electrode material, and assembling another group of lithium fluorocarbon batteries by using the same formula and assembly mode. Discharging the two groups of batteries at room temperature at 0.1C, wherein the discharging curve is shown in figure 2, the gram specific capacity output of the fluorinated ketjen black material is 808mAh/g, the gram specific capacity output of the copper modified carbon fluoride/niobium oxide composite positive electrode material is 771mAh/g, the low-wave voltage is increased from 2.49V to 2.62V, the platform voltage is increased from 2.51V to 2.60V, and the copper modification and alpha-Nb are shown 2 O 5 The addition of the lithium-carbon fluoride battery can improve the conductivity of the positive electrode material, so that the internal resistance of the lithium-carbon fluoride battery is reduced, the polarization phenomenon is reduced, the voltage of a discharge platform is increased, and the output of gram specific capacity of the material under small multiplying power is reduced due to the introduction of copper.
Application example 2
The copper-modified carbon fluoride/niobium oxide composite positive electrode material prepared in the embodiment 2 is used as a positive electrode material, and the mass ratio of the positive electrode material to sodium carboxymethyl cellulose to the superconducting carbon black to the styrene-butadiene latex is 85:3:7: and 5, adding deionized water to prepare slurry, uniformly coating the prepared slurry on an aluminum foil current collector, drying at 70 ℃ to obtain a positive plate, cutting and assembling the positive plate and a lithium plate into the button type lithium fluorocarbon battery, wherein the electrolyte system is 1mol/LLiBF6/EC:DMC:EMC. And (3) adopting fluorinated ketjen black as a positive electrode material, and assembling another group of lithium fluorocarbon batteries by using the same formula and assembly mode. Discharging the two groups of batteries at room temperature at 2C, wherein the discharge curve is shown in figure 3, the gram specific capacity output of the fluorinated ketjen black material is 578mAh/g, the gram specific capacity output of the copper modified carbon fluoride/niobium oxide composite positive electrode material is 668mAh/g, the low-wave voltage is increased from 2.07V to 2.19V, the platform voltage is increased from 2.26V to 2.34V, and the alpha-Nb 2 O 5 The composite material can improve the low-wave voltage of the initial stage of discharge of the positive electrode material, the copper modification improves the conductivity of the positive electrode material, so that the internal resistance is reduced, the polarization phenomenon is reduced, the voltage of a discharge platform is improved, and the copper modification improves the ion conductivity of the fluorinated ketjen black positive electrode material, so that the lithium ion transmission rate and the oxidation under high-rate discharge in the discharge process of the battery are improvedThe reduction reaction rate is matched, so that gram capacity of the material can be well output, and discharge performance is improved under high multiplying power.
Application example 3
The copper-modified carbon fluoride/niobium oxide composite positive electrode material prepared in the embodiment 3 is used as a positive electrode material, and the mass ratio of the positive electrode material to sodium carboxymethyl cellulose to the superconducting carbon black to the styrene-butadiene latex is 85:3:7: and 5, adding deionized water to prepare slurry, uniformly coating the prepared slurry on an aluminum foil current collector, drying at 70 ℃ to obtain a positive plate, cutting and assembling the positive plate and a lithium plate into the button type lithium fluorocarbon battery, wherein the electrolyte system is 1mol/LLiBF6/EC:DMC:EMC. And (3) adopting fluorinated ketjen black as a positive electrode material, and assembling another group of lithium fluorocarbon batteries by using the same formula and assembly mode. The two groups of batteries are discharged at room temperature at 5C, the discharge curve is shown in figure 4, the gram specific capacity output of the fluorinated ketjen black material is 408mAh/g, the gram specific capacity output of the copper modified carbon fluoride/niobium oxide composite positive electrode material is 576mAh/g, the gram specific capacity output is greatly improved, the amplitude reaches 168mAh/g, the low-wave voltage of the copper modified carbon fluoride/niobium oxide composite positive electrode material is improved from 1.90V to 1.98V, and the platform voltage is increased from 2.01V to 2.09V. The discharge is carried out by 7C, the discharge curve is shown as figure 5, the gram specific capacity output of the fluorinated ketjen black material is 270mAh/g, the gram specific capacity output of the copper modified carbon fluoride/niobium oxide composite positive electrode material is 487mAh/g, the gram specific capacity output is greatly improved, the amplitude reaches 217mAh/g, and the copper modified carbon fluoride/niobium oxide composite positive electrode material has an obvious second stage voltage platform at the end stage of the discharge, namely alpha-Nb 2 O 5 The contributed capacity, low wave voltage increased from 1.61V to 1.86V and plateau voltage increased from 1.71V to 1.95V, indicated a-Nb 2 O 5 The introduction of the lithium fluorocarbon battery can improve the initial voltage hysteresis of discharge in high-rate discharge, in addition, the copper modification can further improve the conductivity of the positive electrode material, simultaneously, the internal resistance of the lithium fluorocarbon battery is reduced, the polarization phenomenon is reduced, the discharge platform voltage is improved, and the copper modification improves the ion conductivity of the positive electrode material, so that the lithium ion transmission rate in the battery discharge process and the fluorinated ketjen under high-rate dischargeThe black oxidation-reduction reaction rate is matched, so that gram capacity of the material can be well output, and discharge performance is improved under high multiplying power.
Claims (8)
1. The preparation method of the copper-modified carbon fluoride/niobium oxide composite positive electrode material is characterized by comprising the following steps of:
(1) Adding the fluorinated ketjen black into absolute ethyl alcohol, mixing and stirring by using a magnetic stirrer, dropwise adding niobium ethoxide, fully stirring, adding hydrogen peroxide, continuously stirring, filtering, washing by using absolute ethyl alcohol, washing by using deionized water, drying, grinding, and placing in a muffle furnace for calcination to obtain the fluorinated ketjen black/alpha-Nb 2 O 5 A composite positive electrode material;
(2) Dissolving copper sulfate in deionized water, dispersing with magnetic stirring, and adding fluorinated ketjen black/alpha-Nb 2 O 5 Adding the composite positive electrode material into the mixed solution for dispersion, stirring and adding the surfactant at the same time to obtain copper sulfate/fluorinated ketjen black/alpha-Nb 2 O 5 Mixing the solutions;
(3) Dissolving a chemical reducing agent in deionized water, and dropwise adding the solution into the copper sulfate/fluorinated ketjen black/alpha-Nb prepared in the step (2) 2 O 5 Continuously stirring the mixed solution, and obtaining copper modified fluorinated ketjen black/alpha-Nb through suction filtration, absolute ethyl alcohol washing, deionized water washing and drying 2 O 5 A composite positive electrode material;
the mass ratio of the fluorinated ketjen black to the niobium ethoxide to the hydrogen peroxide is 1:0.1:0.5-1:0.5:3;
the calcination temperature is 300-500 ℃ and the time is 1-3 h.
2. The method for preparing a copper-modified carbon fluoride/niobium oxide composite positive electrode material according to claim 1, wherein the mass concentration of hydrogen peroxide is 20%.
3. The method for preparing the copper-modified carbon fluoride/niobium oxide composite positive electrode material according to claim 1, wherein the mass ratio of the copper sulfate to the fluorinated ketjen black to the deionized water is 1:100:200-10:100:200.
4. The method for preparing the copper-modified carbon fluoride/niobium oxide composite positive electrode material according to claim 1, wherein the magnetic stirring speed is 80-1000 r/min.
5. The preparation method of the copper-modified carbon fluoride/niobium oxide composite positive electrode material is characterized in that the surfactant is any one or two of n-butanol and a hydrophilic nonionic surfactant OP-10, and the mass ratio of the surfactant to deionized water is 1:100-3:100.
6. The method for preparing the copper-modified carbon fluoride/niobium oxide composite positive electrode material according to claim 1, wherein the chemical reducing agent is one of potassium borohydride, sodium borohydride, hydrazine hydrate and sodium hypophosphite, and the mass ratio of the chemical reducing agent to copper sulfate is 1:1-1:10.
7. The method for preparing a copper-modified carbon fluoride/niobium oxide composite positive electrode material according to claim 1, wherein the mass ratio of the chemical reducing agent to deionized water is 1:1-1:20.
8. A copper-modified carbon fluoride/niobium oxide composite positive electrode material produced by the production method of any one of claims 1 to 7.
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| CN114975956A (en) * | 2022-06-21 | 2022-08-30 | 贵州梅岭电源有限公司 | Fluorinated graphene/fluorinated graphite composite positive electrode material and preparation method thereof |
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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 |
| CN114975956A (en) * | 2022-06-21 | 2022-08-30 | 贵州梅岭电源有限公司 | Fluorinated graphene/fluorinated graphite composite positive electrode material and preparation method thereof |
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