CN113299912A - Carbon fluoride composite positive electrode active material for lithium-carbon fluoride battery, and preparation method and application thereof - Google Patents
Carbon fluoride composite positive electrode active material for lithium-carbon fluoride battery, and preparation method and application thereof Download PDFInfo
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- TXEYQDLBPFQVAA-UHFFFAOYSA-N tetrafluoromethane Chemical compound FC(F)(F)F TXEYQDLBPFQVAA-UHFFFAOYSA-N 0.000 title claims abstract description 88
- 239000002131 composite material Substances 0.000 title claims abstract description 41
- YBDACTXVEXNYOU-UHFFFAOYSA-N C(F)(F)(F)F.[Li] Chemical compound C(F)(F)(F)F.[Li] YBDACTXVEXNYOU-UHFFFAOYSA-N 0.000 title claims abstract description 36
- 239000007774 positive electrode material Substances 0.000 title claims abstract description 33
- 238000002360 preparation method Methods 0.000 title claims abstract description 12
- 239000003273 ketjen black Substances 0.000 claims abstract description 38
- 238000000498 ball milling Methods 0.000 claims abstract description 37
- 238000003682 fluorination reaction Methods 0.000 claims abstract description 23
- 238000000034 method Methods 0.000 claims abstract description 13
- 239000007789 gas Substances 0.000 claims description 22
- 239000003153 chemical reaction reagent Substances 0.000 claims description 20
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 14
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 14
- 238000010438 heat treatment Methods 0.000 claims description 13
- 238000006243 chemical reaction Methods 0.000 claims description 10
- 239000010935 stainless steel Substances 0.000 claims description 10
- 229910001220 stainless steel Inorganic materials 0.000 claims description 10
- 229910052759 nickel Inorganic materials 0.000 claims description 7
- KRHYYFGTRYWZRS-UHFFFAOYSA-M Fluoride anion Chemical compound [F-] KRHYYFGTRYWZRS-UHFFFAOYSA-M 0.000 claims description 6
- 229910052799 carbon Inorganic materials 0.000 claims description 6
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 claims description 6
- 229910000792 Monel Inorganic materials 0.000 claims description 5
- 239000002994 raw material Substances 0.000 claims description 5
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 4
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 4
- 229910045601 alloy Inorganic materials 0.000 claims description 4
- 239000000956 alloy Substances 0.000 claims description 4
- 239000003085 diluting agent Substances 0.000 claims description 4
- 238000001035 drying Methods 0.000 claims description 3
- 229910052786 argon Inorganic materials 0.000 claims description 2
- 150000002222 fluorine compounds Chemical group 0.000 claims description 2
- 229910002804 graphite Inorganic materials 0.000 claims description 2
- 239000010439 graphite Substances 0.000 claims description 2
- 229910052734 helium Inorganic materials 0.000 claims description 2
- 239000001307 helium Substances 0.000 claims description 2
- SWQJXJOGLNCZEY-UHFFFAOYSA-N helium atom Chemical compound [He] SWQJXJOGLNCZEY-UHFFFAOYSA-N 0.000 claims description 2
- 239000000203 mixture Substances 0.000 claims description 2
- 229910052757 nitrogen Inorganic materials 0.000 claims description 2
- 230000035484 reaction time Effects 0.000 claims description 2
- 208000028659 discharge Diseases 0.000 abstract description 33
- 239000000463 material Substances 0.000 abstract description 25
- 230000000052 comparative effect Effects 0.000 description 8
- 238000011056 performance test Methods 0.000 description 7
- 238000001291 vacuum drying Methods 0.000 description 7
- 238000012360 testing method Methods 0.000 description 5
- 229910052744 lithium Inorganic materials 0.000 description 4
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 3
- BUGBHKTXTAQXES-UHFFFAOYSA-N Selenium Chemical compound [Se] BUGBHKTXTAQXES-UHFFFAOYSA-N 0.000 description 3
- 239000006183 anode active material Substances 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- 239000000843 powder Substances 0.000 description 3
- 239000010405 anode material Substances 0.000 description 2
- 239000003575 carbonaceous material Substances 0.000 description 2
- 238000009776 industrial production Methods 0.000 description 2
- 229910052711 selenium Inorganic materials 0.000 description 2
- 239000011669 selenium Substances 0.000 description 2
- 238000003860 storage Methods 0.000 description 2
- KMTRUDSVKNLOMY-UHFFFAOYSA-N Ethylene carbonate Chemical compound O=C1OCCO1 KMTRUDSVKNLOMY-UHFFFAOYSA-N 0.000 description 1
- 239000002033 PVDF binder Substances 0.000 description 1
- 241000872198 Serjania polyphylla Species 0.000 description 1
- 239000006230 acetylene black Substances 0.000 description 1
- 239000013543 active substance Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000006229 carbon black Substances 0.000 description 1
- 239000006182 cathode active material Substances 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- IEJIGPNLZYLLBP-UHFFFAOYSA-N dimethyl carbonate Chemical compound COC(=O)OC IEJIGPNLZYLLBP-UHFFFAOYSA-N 0.000 description 1
- 239000003792 electrolyte Substances 0.000 description 1
- 238000004146 energy storage Methods 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 229910021389 graphene Inorganic materials 0.000 description 1
- -1 lithium tetrafluoroborate Chemical compound 0.000 description 1
- 229910001496 lithium tetrafluoroborate Inorganic materials 0.000 description 1
- QLOAVXSYZAJECW-UHFFFAOYSA-N methane;molecular fluorine Chemical compound C.FF QLOAVXSYZAJECW-UHFFFAOYSA-N 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000002086 nanomaterial Substances 0.000 description 1
- 239000002071 nanotube Substances 0.000 description 1
- 230000010287 polarization Effects 0.000 description 1
- 229920002981 polyvinylidene fluoride Polymers 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—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
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B32/00—Carbon; Compounds thereof
- C01B32/10—Carbon fluorides, e.g. [CF]nor [C2F]n
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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
- H01M4/587—Carbonaceous material, e.g. graphite-intercalation compounds or CFx for inserting or intercalating light metals
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- 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
- H01M4/625—Carbon or graphite
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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
- H01M6/00—Primary cells; Manufacture thereof
- H01M6/14—Cells with non-aqueous electrolyte
- H01M6/16—Cells with non-aqueous electrolyte with organic electrolyte
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2006/00—Physical properties of inorganic compounds
- C01P2006/40—Electric properties
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Abstract
The invention relates to a carbon fluoride composite positive electrode active material for a lithium-carbon fluoride battery, and a preparation method and application thereof. The carbon fluoride composite positive electrode active material aims to solve the technical problems that the existing carbon fluoride composite positive electrode active material for the lithium-carbon fluoride battery is difficult to simultaneously give consideration to high specific capacity and high rate performance and improve voltage hysteresis. The material is prepared by ball milling and mixing carbon fluoride and Ketjen black, wherein the mixing mass ratio of the carbon fluoride to the Ketjen black is 1: 0.01-1: 0.1. The preparation method comprises the following steps: 1) preparing carbon fluoride by adopting a gas phase fluorination method; 2) and (3) ball-milling and mixing the carbon fluoride and the Ketjen black to obtain the uniformly mixed carbon fluoride composite material mixed with the Ketjen black. The carbon fluoride composite positive active material is applied to the carbon fluoride composite positive active material for the lithium-carbon fluoride battery, can retain higher specific capacity, improve rate capability, lead the discharge rate to reach 6C, and improve the voltage hysteresis phenomenon at the initial discharge stage.
Description
Technical Field
The invention relates to a positive electrode active material for a lithium-carbon fluoride battery, in particular to a carbon fluoride composite positive electrode active material for the lithium-carbon fluoride battery and a preparation method and application thereof.
Background
At present, the lithium-carbon fluoride battery in the lithium primary battery has the highest energy storage density which can reach more than 500Wh/kg, the annual self-discharge rate is less than 1 percent, the storage performance is excellent, and the lithium-carbon fluoride battery is the lithium battery with the best safety at present. Therefore, such high specific energy, high safety, long storage life lithium-fluorocarbon batteries are considered to be the major products of future primary batteries.
The performance of the carbon fluoride material as an active substance of the positive electrode material of the lithium-carbon fluoride battery directly determines the performance of the lithium-carbon fluoride battery. The carbon fluoride material in the current market has high specific energy, the whole discharge platform (namely the voltage change of a fully charged lithium battery during discharge) is about 2.5V, but the carbon fluoride material has poor conductivity, and obvious voltage lag occurs at the initial discharge stage, so that the rate performance of the carbon fluoride material is poor.
Although novel carbon fluoride materials such as carbon fluoride nanotubes and fluorinated nano-graphene have higher specific discharge capacity and higher discharge rate, the industrial preparation method is harsh, and more importantly, the carbon nano raw material has higher price, which is not favorable for industrial production and large-scale market popularization.
Chinese patent CN109742354A discloses a carbon fluoride composite electrode and a preparation method thereof, wherein graphite fluoride, selenium powder and ketjen black are prepared into a carbon fluoride composite material by a heat treatment method, so that the rate capability of a lithium-carbon fluoride battery is improved. However, the method introduces the metallic selenium into the battery anode material, increases the production cost, and simultaneously, the added metallic selenium and the added ketjen black have larger amounts, thereby reducing the specific capacity of the battery anode material.
Therefore, there is a need for a carbon fluoride composite positive electrode active material that can improve the rate performance of a lithium-carbon fluoride battery and improve voltage hysteresis while maintaining a high specific capacity of the lithium-carbon fluoride battery.
Disclosure of Invention
The invention aims to solve the technical problems that the existing carbon fluoride anode active material for the lithium-carbon fluoride battery is difficult to give consideration to high specific capacity and high rate performance and improve voltage hysteresis, and provides a carbon fluoride composite anode active material for the lithium-carbon fluoride battery and a preparation method and application thereof.
In order to solve the technical problems, the technical solution provided by the invention is as follows:
the invention provides a carbon fluoride composite positive active material for a lithium-carbon fluoride battery, which is characterized in that:
is prepared by ball milling and mixing carbon fluoride and Ketjen black.
Further, the mixing mass ratio of the carbon fluoride to the ketjen black is 1: 0.01-1: 0.1.
The invention also provides application of the carbon fluoride composite positive electrode active material for the lithium-carbon fluoride battery in a positive electrode material of the lithium-carbon fluoride battery.
The invention also provides a preparation method of the carbon fluoride composite positive active material for the lithium-carbon fluoride battery, which is characterized by comprising the following steps of:
1) preparing carbon fluoride by adopting a gas phase fluorination method;
2) and (3) ball-milling and mixing the carbon fluoride and the Ketjen black to obtain the uniformly mixed carbon fluoride composite material mixed with the Ketjen black.
Further, in the step 2), the mixing mass ratio of the carbon fluoride to the ketjen black is 1: 0.01-1: 0.1;
the ball milling time is 8-48 h;
the rotating speed of the ball mill is 50-400 r/min during ball milling.
Further, 1.1) placing the graphitized carbon raw material in a closed container, and introducing a fluorination reagent into the closed container;
1.2) keeping the pressure in the closed container at 100 Kpa-300 Kpa, and heating and reacting for 5 h-12 h at the temperature of 300-600 ℃;
1.3) after the reaction is finished, taking out the product and drying the product in vacuum after the temperature in the closed container is reduced to room temperature to obtain the carbon fluoride.
Further, in the step 1.1), the graphitized carbon raw material is graphite or mesoporous carbon;
the fluoridizing reagent is fluoride gas or mixed gas of fluoride and diluent gas, and the volume fraction of the fluoride in the mixed gas is more than or equal to 60 percent;
the diluent gas is one or a mixture of nitrogen, argon, helium and carbon tetrafluoride.
Further, in the step 1.2), the material of the heated part of the closed container is pure nickel or monel, and the material of the rest parts is stainless steel.
Further, in the step 1.1), the volume fraction of the fluoride is 80-100%;
in the step 1.2), the pressure in the closed container is 100 Kpa-200 Kpa, the temperature is 400-600 ℃, and the heating reaction time is 8-12 h;
in the step 2), the mixing mass ratio of the carbon fluoride to the ketjen black is 1: 0.01-1: 0.05; the ball milling time is 12-48 h; the rotating speed of the ball mill is 100-300 r/min during ball milling.
Compared with the prior art, the invention has the following beneficial effects:
1. the carbon fluoride composite positive active material for the lithium-carbon fluoride battery and the preparation method and application thereof provided by the invention have the advantages that the carbon fluoride with higher specific capacity is prepared by a gas phase fluorination method, meanwhile, the carbon fluoride and the ketjen black are mixed by a ball milling mode in combination with the ketjen black with high conductivity for advantage complementation, so that the battery rate capability of the lithium-carbon fluoride battery is improved while the higher specific capacity is kept, the discharge rate of the carbon fluoride mixed by ball milling and the ketjen black reaches 6C, and in the discharge process, the internal resistance is reduced, the polarization phenomenon is reduced, and the voltage hysteresis phenomenon of the lithium-carbon fluoride battery at the initial discharge stage is improved.
2. The carbon fluoride composite positive active material for the lithium-carbon fluoride battery, the preparation method and the application thereof provided by the invention have the advantages that the graphitized carbon material is adopted, the carbon fluoride with higher specific capacity is prepared by a gas phase fluorination method, and compared with the carbon nano material adopted in the prior art, the graphitized carbon material has low production cost and is convenient for industrial production and large-scale market popularization.
3. According to the carbon fluoride composite positive electrode active material for the lithium-carbon fluoride battery, the existing Ketjen black is adopted, the Ketjen black is carbon black prepared by a special production process, and compared with common conductive carbon black, the Ketjen black can achieve high conductivity only by extremely low addition amount.
Drawings
FIG. 1 is a graph comparing the voltage hysteresis at the initial stage of discharge at 2C discharge rate in electrochemical performance tests of examples 1, 2 and 3 according to the present invention with the comparative product;
FIG. 2 is a graph comparing the discharge curve performance at 2C discharge rate in electrochemical performance test of example 1, example 2 and example 3 of the present invention with that of the comparative product;
FIG. 3 is a graph of discharge curve performance of the product of example 1 at 0.01C, 1C, 2C, 6C discharge rates in electrochemical performance tests;
Detailed Description
The invention is further described below with reference to the figures and examples.
Example 1
1.1) placing 10.0g of pretreated graphite powder in a closed container, and introducing a fluorination reagent into the closed container, wherein the fluorination reagent is 100% NF3A gas; the material of the heated part of the closed container is pure nickel, and the material of the rest parts is stainless steel;
1.2) keeping the pressure in the closed container at 120Kpa and 500 ℃, and heating and reacting for 8 h;
1.3) after the reaction is finished, taking out a product when the temperature in the closed container is reduced to room temperature, and carrying out vacuum drying on the product at 200 ℃ for 6 hours to obtain carbon fluoride;
2) putting the carbon fluoride and the Ketjen black into a ball milling tank according to the mixing mass ratio of 1:0.02 for ball milling and mixing, wherein the ball milling time is 24 hours, and the rotating speed of the ball mill is 100 r/min, so as to obtain the uniformly mixed carbon fluoride composite material mixed with the Ketjen black.
Example 2
1.1) placing 10.0g of pretreated graphite powder in a closed container, and introducing a fluorination reagent into the closed container, wherein the fluorination reagent is 90% NF3A gas; the material of the heated part of the closed container is pure nickel, and the material of the rest parts is stainless steel;
1.2) keeping the pressure in the closed container at 140Kpa and 500 ℃, and heating and reacting for 10 h;
1.3) after the reaction is finished, taking out a product when the temperature in the closed container is reduced to room temperature, and carrying out vacuum drying on the product at 200 ℃ for 6 hours to obtain carbon fluoride;
2) putting the carbon fluoride and the Ketjen black into a ball milling tank according to the mixing mass ratio of 1:0.05 for ball milling and mixing, wherein the ball milling time is 12 hours, and the rotating speed of the ball mill is 300 r/min, so as to obtain the uniformly mixed carbon fluoride composite material mixed with the Ketjen black.
Example 3
1.1) placing 10.0g of pretreated graphite powder in a closed container, and introducing a fluorination reagent into the closed container, wherein the fluorination reagent is 80% NF3A gas; the material of the heated part of the closed container is pure nickel, and the material of the rest parts is stainless steel;
1.2) keeping the pressure in the closed container at 140Kpa and 500 ℃, and heating and reacting for 8 h;
1.3) after the reaction is finished, taking out a product when the temperature in the closed container is reduced to room temperature, and carrying out vacuum drying on the product at 200 ℃ for 6 hours to obtain carbon fluoride;
2) putting the carbon fluoride and the Ketjen black into a ball milling tank according to the mixing mass ratio of 1:0.03 for ball milling and mixing, wherein the ball milling time is 24 hours, and the rotating speed of the ball mill is 200 r/min, so as to obtain the uniformly mixed carbon fluoride composite material mixed with the Ketjen black.
Example 4
1.1) placing 10.0g of pretreated mesoporous carbon powder inIntroducing a fluorination reagent into the closed container, wherein the fluorination reagent is 100% NF3A gas; the material of the heated part of the closed container is Monel alloy, and the material of the rest parts is stainless steel;
1.2) keeping the pressure in the closed container at 140Kpa and 550 ℃, and heating and reacting for 10 h;
1.3) after the reaction is finished, taking out a product when the temperature in the closed container is reduced to room temperature, and carrying out vacuum drying on the product at 200 ℃ for 6 hours to obtain carbon fluoride;
2) putting the carbon fluoride and the Ketjen black into a ball milling tank according to the mixing mass ratio of 1:0.02 for ball milling and mixing, wherein the ball milling time is 24 hours, and the rotating speed of the ball mill is 400 r/min, so as to obtain the uniformly mixed carbon fluoride composite material mixed with the Ketjen black.
Example 5
1.1) placing 10.0g of pretreated mesoporous carbon powder in a closed container, and introducing a fluorination reagent into the closed container, wherein the fluorination reagent is 80% NF3A gas; the material of the heated part of the closed container is Monel alloy, and the material of the rest parts is stainless steel;
1.2) keeping the pressure in the closed container at 120Kpa and 500 ℃, and heating and reacting for 10 h;
1.3) after the reaction is finished, taking out a product when the temperature in the closed container is reduced to room temperature, and carrying out vacuum drying on the product at 200 ℃ for 6 hours to obtain carbon fluoride;
2) putting the carbon fluoride and the Ketjen black into a ball milling tank according to the mixing mass ratio of 1:0.05 for ball milling and mixing, wherein the ball milling time is 48 hours, and the rotating speed of the ball mill is 50 r/min, so as to obtain the uniformly mixed carbon fluoride composite material mixed with the Ketjen black.
Example 6
1.1) placing 10.0g of pretreated mesoporous carbon powder in a closed container, and introducing a fluorination reagent into the closed container, wherein the fluorination reagent is 60% NF3A gas; the material of the heated part of the closed container is Monel alloy, and the material of the rest parts is stainless steel;
1.2) keeping the pressure in the closed container at 100Kpa and 300 ℃, and heating and reacting for 5 h;
1.3) after the reaction is finished, taking out a product when the temperature in the closed container is reduced to room temperature, and carrying out vacuum drying on the product at 200 ℃ for 6 hours to obtain carbon fluoride;
2) putting the carbon fluoride and the Ketjen black into a ball milling tank according to the mixing mass ratio of 1:0.01 for ball milling and mixing, wherein the ball milling time is 8 hours, and the rotating speed of the ball mill is 100 r/min, so as to obtain the uniformly mixed carbon fluoride composite material mixed with the Ketjen black.
Example 7
1.1) placing 10.0g of pretreated graphite powder in a closed container, and introducing a fluorination reagent into the closed container, wherein the fluorination reagent is 100% NF3A gas; the material of the heated part of the closed container is pure nickel, and the material of the rest parts is stainless steel;
1.2) keeping the pressure in the closed container at 300Kpa and 600 ℃, and heating and reacting for 12 h;
1.3) after the reaction is finished, taking out a product when the temperature in the closed container is reduced to room temperature, and carrying out vacuum drying on the product at 200 ℃ for 6 hours to obtain carbon fluoride;
2) putting the carbon fluoride and the Ketjen black into a ball milling tank according to the mixing mass ratio of 1:0.1, and carrying out ball milling mixing for 48 hours at the ball milling speed of 300 r/min to obtain the uniformly mixed carbon fluoride composite material mixed with the Ketjen black.
Comparative example
1.1) placing 10.0g of pretreated graphite powder in a closed container, and introducing a fluorination reagent into the closed container, wherein the fluorination reagent is 80% NF3A gas; the material of the heated part of the closed container is pure nickel, and the material of the rest parts is stainless steel;
1.2) keeping the pressure in the closed container at 140Kpa and 500 ℃, and heating and reacting for 8 h;
1.3) after the reaction is finished, taking out the product when the temperature in the closed container is reduced to room temperature, and drying the product in vacuum at 200 ℃ for 6h to obtain the carbon fluoride.
The products of examples 1-5 and comparative example are used as positive active materials of lithium-carbon fluoride batteries to assemble button batteries, and the mass ratio of the working electrode (namely the negative electrode) in bulk phase is 8: 1: 1, a composite anode active material containing carbon fluoride, acetylene black and polyvinylidene fluoride mixed material; the counter electrode (i.e. the positive electrode) is a lithium metal sheet; the electrolyte is a 1M lithium tetrafluoroborate solution dissolved in ethylene carbonate and dimethyl carbonate (volume ratio is 1: 1);
carrying out electrochemical performance test:
1. and (3) testing the electrochemical performance with the discharge cut-off voltage of 1.5V. For example, fig. 1 is a comparison graph of initial discharge voltage hysteresis at 2C discharge rate in electrochemical performance tests of examples 1, 2, and 3 and comparative products, and test results show that the initial discharge voltage hysteresis is significantly improved after the carbon fluoride composite positive electrode active material of the present invention is used; fig. 2 is a graph comparing the discharge curve performance of the products of example 1, example 2, and example 3 with that of the comparative example under the 2C discharge rate in the electrochemical performance test, and the test result shows that the discharge performance is significantly improved after the carbon fluoride composite cathode active material of the present invention is adopted;
2. and (4) testing the electrochemical performance with the discharge multiplying power of 0.01C, 1C, 2C and 6C. For example, fig. 3 is a discharge curve performance diagram of the product of example 1 at discharge rates of 0.01C, 1C, 2C, and 6C in an electrochemical performance test, and a test result shows that after the carbon fluoride composite positive electrode active material of the present invention is adopted, the discharge rate can reach 6C, and compared with the existing carbon fluoride positive electrode active material, the discharge rate is only 1C in a normal state, and it is more reluctant to reach a higher discharge rate, and the discharge rate of the present invention is significantly improved.
Table 1 is a table of the performance of the products of examples 1-5 and comparative example as lithium-fluorocarbon cell positive active materials assembled into button cells at 2C discharge rate and 1.5V cutoff:
| sample (I) | Discharge rate | Cut-off voltage (V) | Specific capacity (mAh/g) | Specific energy (Wh/kg) |
| Example 1 | 2C | 1.5 | 737.4 | 1558.3 |
| Example 2 | 2C | 1.5 | 716.8 | 1492.1 |
| Example 3 | 2C | 1.5 | 677.5 | 1433.7 |
| Example 4 | 2C | 1.5 | 744.5 | 1573.4 |
| Example 5 | 2C | 1.5 | 710.9 | 1477.7 |
| Comparative example | 2C | 1.5 | 642.3 | 1195.8 |
Finally, it should be noted that: the above embodiments are only used for illustrating the technical solutions of the present invention, and not for limiting the same, and it is obvious for a person skilled in the art to modify the specific technical solutions described in the foregoing embodiments or to substitute part of the technical features, and these modifications or substitutions do not make the essence of the corresponding technical solutions depart from the scope of the technical solutions protected by the present invention.
Claims (9)
1. A carbon fluoride composite positive electrode active material for a lithium-carbon fluoride battery is characterized in that:
is prepared by ball milling and mixing carbon fluoride and Ketjen black.
2. The carbon fluoride composite positive electrode active material for a lithium-carbon fluoride battery according to claim 1, wherein:
the mixing mass ratio of the carbon fluoride to the ketjen black is 1: 0.01-1: 0.1.
3. Use of the carbon fluoride composite positive electrode active material for a lithium-carbon fluoride battery according to any one of claims 1 to 2 in a positive electrode material for a lithium-carbon fluoride battery.
4. A preparation method of a carbon fluoride composite positive electrode active material for a lithium-carbon fluoride battery is characterized by comprising the following steps:
1) preparing carbon fluoride by adopting a gas phase fluorination method;
2) and (3) ball-milling and mixing the carbon fluoride and the Ketjen black to obtain the uniformly mixed carbon fluoride composite material mixed with the Ketjen black.
5. The method for preparing a carbon fluoride composite positive active material for a lithium-carbon fluoride battery according to claim 4, wherein:
in the step 2), the mixing mass ratio of the carbon fluoride to the ketjen black is 1: 0.01-1: 0.1;
the ball milling time is 8-48 h;
the rotating speed of the ball mill is 50-400 r/min during ball milling.
6. The method for preparing the carbon fluoride composite positive electrode active material for the lithium-carbon fluoride battery according to claim 5, wherein the step 1) is specifically as follows:
1.1) placing the graphitized carbon raw material in a closed container, and introducing a fluorination reagent into the closed container;
1.2) keeping the pressure in the closed container at 100 Kpa-300 Kpa, and heating and reacting for 5 h-12 h at the temperature of 300-600 ℃;
1.3) after the reaction is finished, taking out the product and drying the product in vacuum after the temperature in the closed container is reduced to room temperature to obtain the carbon fluoride.
7. The method for preparing a carbon fluoride composite positive active material for a lithium-carbon fluoride battery according to claim 6, wherein:
in the step 1.1), the graphitized carbon raw material is graphite or mesoporous carbon;
the fluoridizing reagent is fluoride gas or mixed gas of fluoride and diluent gas, and the volume fraction of the fluoride in the mixed gas is more than or equal to 60 percent;
the diluent gas is one or a mixture of nitrogen, argon, helium and carbon tetrafluoride.
8. The method for preparing a carbon fluoride composite positive active material for a lithium-carbon fluoride battery according to claim 7, wherein:
in the step 1.2), the heated part of the closed container is made of pure nickel or Monel alloy, and the rest parts are made of stainless steel.
9. The method for preparing a carbon fluoride composite positive active material for a lithium-carbon fluoride battery according to claim 8, wherein:
in the step 1.1), the volume fraction of the fluoride is 80-100%;
in the step 1.2), the pressure in the closed container is 100 Kpa-200 Kpa, the temperature is 400-600 ℃, and the heating reaction time is 8-12 h;
in the step 2), the mixing mass ratio of the carbon fluoride to the ketjen black is 1: 0.01-1: 0.05; the ball milling time is 12-48 h; the rotating speed of the ball mill is 100-300 r/min during ball milling.
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