CN112952089A - Preparation method and application of modified carbon fluoride material - Google Patents
Preparation method and application of modified carbon fluoride material Download PDFInfo
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- CN112952089A CN112952089A CN201911260366.1A CN201911260366A CN112952089A CN 112952089 A CN112952089 A CN 112952089A CN 201911260366 A CN201911260366 A CN 201911260366A CN 112952089 A CN112952089 A CN 112952089A
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- TXEYQDLBPFQVAA-UHFFFAOYSA-N tetrafluoromethane Chemical class FC(F)(F)F TXEYQDLBPFQVAA-UHFFFAOYSA-N 0.000 title claims abstract description 93
- 239000000463 material Substances 0.000 title claims abstract description 42
- 238000002360 preparation method Methods 0.000 title claims description 5
- IDBFBDSKYCUNPW-UHFFFAOYSA-N lithium nitride Chemical compound [Li]N([Li])[Li] IDBFBDSKYCUNPW-UHFFFAOYSA-N 0.000 claims abstract description 42
- 239000002904 solvent Substances 0.000 claims abstract description 29
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims abstract description 21
- 229910052744 lithium Inorganic materials 0.000 claims abstract description 21
- 239000003960 organic solvent Substances 0.000 claims abstract description 15
- 238000000034 method Methods 0.000 claims abstract description 13
- QLOAVXSYZAJECW-UHFFFAOYSA-N methane;molecular fluorine Chemical compound C.FF QLOAVXSYZAJECW-UHFFFAOYSA-N 0.000 claims abstract description 6
- 239000000843 powder Substances 0.000 claims description 40
- 238000003756 stirring Methods 0.000 claims description 30
- 239000006228 supernatant Substances 0.000 claims description 20
- 239000000203 mixture Substances 0.000 claims description 18
- 239000006185 dispersion Substances 0.000 claims description 16
- 239000007788 liquid Substances 0.000 claims description 16
- 239000011259 mixed solution Substances 0.000 claims description 16
- 238000006243 chemical reaction Methods 0.000 claims description 14
- 238000001035 drying Methods 0.000 claims description 14
- 239000012265 solid product Substances 0.000 claims description 14
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 10
- 239000007787 solid Substances 0.000 claims description 10
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 9
- XTHFKEDIFFGKHM-UHFFFAOYSA-N Dimethoxyethane Chemical compound COCCOC XTHFKEDIFFGKHM-UHFFFAOYSA-N 0.000 claims description 6
- 238000009835 boiling Methods 0.000 claims description 5
- 239000007774 positive electrode material Substances 0.000 claims description 5
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 5
- WNXJIVFYUVYPPR-UHFFFAOYSA-N 1,3-dioxolane Chemical compound C1COCO1 WNXJIVFYUVYPPR-UHFFFAOYSA-N 0.000 claims description 3
- IEJIGPNLZYLLBP-UHFFFAOYSA-N dimethyl carbonate Chemical compound COC(=O)OC IEJIGPNLZYLLBP-UHFFFAOYSA-N 0.000 claims description 3
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 abstract description 10
- KRHYYFGTRYWZRS-UHFFFAOYSA-M Fluoride anion Chemical compound [F-] KRHYYFGTRYWZRS-UHFFFAOYSA-M 0.000 abstract description 10
- 229910052799 carbon Inorganic materials 0.000 abstract description 10
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 abstract description 8
- 229910052731 fluorine Inorganic materials 0.000 abstract description 8
- 239000011737 fluorine Substances 0.000 abstract description 8
- 230000009467 reduction Effects 0.000 abstract description 3
- 238000012986 modification Methods 0.000 abstract description 2
- 230000004048 modification Effects 0.000 abstract description 2
- 238000010438 heat treatment Methods 0.000 description 12
- 238000005303 weighing Methods 0.000 description 10
- NBVXSUQYWXRMNV-UHFFFAOYSA-N fluoromethane Chemical compound FC NBVXSUQYWXRMNV-UHFFFAOYSA-N 0.000 description 9
- PQXKHYXIUOZZFA-UHFFFAOYSA-M lithium fluoride Chemical compound [Li+].[F-] PQXKHYXIUOZZFA-UHFFFAOYSA-M 0.000 description 8
- LCGLNKUTAGEVQW-UHFFFAOYSA-N Dimethyl ether Chemical compound COC LCGLNKUTAGEVQW-UHFFFAOYSA-N 0.000 description 4
- 238000011161 development Methods 0.000 description 4
- 239000000047 product Substances 0.000 description 4
- 239000013543 active substance Substances 0.000 description 3
- 229910001416 lithium ion Inorganic materials 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- XKTYXVDYIKIYJP-UHFFFAOYSA-N 3h-dioxole Chemical compound C1OOC=C1 XKTYXVDYIKIYJP-UHFFFAOYSA-N 0.000 description 2
- 238000004458 analytical method Methods 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 230000008569 process Effects 0.000 description 2
- 230000001681 protective effect Effects 0.000 description 2
- 238000012546 transfer Methods 0.000 description 2
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 1
- 239000002033 PVDF binder Substances 0.000 description 1
- SOZVEOGRIFZGRO-UHFFFAOYSA-N [Li].ClS(Cl)=O Chemical compound [Li].ClS(Cl)=O SOZVEOGRIFZGRO-UHFFFAOYSA-N 0.000 description 1
- GJCNZQUZWSHFHP-UHFFFAOYSA-N [Li].O=S=O Chemical compound [Li].O=S=O GJCNZQUZWSHFHP-UHFFFAOYSA-N 0.000 description 1
- FBDMJGHBCPNRGF-UHFFFAOYSA-M [OH-].[Li+].[O-2].[Mn+2] Chemical compound [OH-].[Li+].[O-2].[Mn+2] FBDMJGHBCPNRGF-UHFFFAOYSA-M 0.000 description 1
- 239000011149 active material Substances 0.000 description 1
- 230000004075 alteration Effects 0.000 description 1
- 229910003481 amorphous carbon Inorganic materials 0.000 description 1
- 230000003321 amplification Effects 0.000 description 1
- 239000011230 binding agent Substances 0.000 description 1
- DUEPRVBVGDRKAG-UHFFFAOYSA-N carbofuran Chemical compound CNC(=O)OC1=CC=CC2=C1OC(C)(C)C2 DUEPRVBVGDRKAG-UHFFFAOYSA-N 0.000 description 1
- 230000000747 cardiac effect Effects 0.000 description 1
- 239000006182 cathode active material Substances 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 238000004891 communication Methods 0.000 description 1
- 238000010835 comparative analysis Methods 0.000 description 1
- 239000006258 conductive agent Substances 0.000 description 1
- 239000011258 core-shell material Substances 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 238000007599 discharging Methods 0.000 description 1
- 238000012983 electrochemical energy storage Methods 0.000 description 1
- 239000003792 electrolyte Substances 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000005562 fading Methods 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 230000014759 maintenance of location Effects 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 238000010295 mobile communication Methods 0.000 description 1
- 238000002715 modification method Methods 0.000 description 1
- 238000003199 nucleic acid amplification method Methods 0.000 description 1
- 229920002981 polyvinylidene fluoride Polymers 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
Classifications
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/58—Selection of substances as active materials, active masses, active liquids of inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy; of polyanionic structures, e.g. phosphates, silicates or borates
- H01M4/583—Carbonaceous material, e.g. graphite-intercalation compounds or CFx
- H01M4/5835—Comprising fluorine or fluoride salts
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
- H01M4/628—Inhibitors, e.g. gassing inhibitors, corrosion inhibitors
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M6/00—Primary cells; Manufacture thereof
- H01M6/14—Cells with non-aqueous electrolyte
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M2004/026—Electrodes composed of, or comprising, active material characterised by the polarity
- H01M2004/028—Positive electrodes
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
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- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Manufacturing & Machinery (AREA)
- Inorganic Chemistry (AREA)
- Battery Electrode And Active Subsutance (AREA)
Abstract
本申请公开了一种改性氟化炭材料的制备方法，将氟化炭和氮化锂在有机溶剂中反应一定时间，去除溶剂后得到所述改性氟化炭材料。与改性前的相比，该材料表面的氟含量减少，表面氟含量的降低能够在一定程度上避免锂/氟化炭电池的自放电行为，其自放电得到有效降低，可以有效提高锂/氟化炭电池的高温搁置稳定性，这对其实际应用具有重要意义。The present application discloses a method for preparing a modified carbon fluoride material. The carbon fluoride and lithium nitride are reacted in an organic solvent for a certain period of time, and the modified carbon fluoride material is obtained after removing the solvent. Compared with the one before modification, the fluorine content on the surface of the material is reduced, and the reduction of the surface fluorine content can avoid the self-discharge behavior of lithium/carbon fluoride batteries to a certain extent, and the self-discharge is effectively reduced, which can effectively improve the lithium/carbon fluoride battery. The high-temperature shelf stability of fluorinated carbon batteries is of great significance for their practical applications.
Description
Technical Field
The application relates to a modification method of a positive electrode material for a lithium/carbon fluoride battery, belonging to the technical field of electrochemical energy storage.
Background
With the technical progress in the fields of mobile communication, aerospace, transportation, military equipment and the like, the development of various high-specific-energy power batteries is an urgent need for national economic development. Because the metallic lithium has the characteristics of light weight and negative electrode potential, the development of the lithium primary battery taking the lithium as the negative electrodeHave received great attention. The primary lithium battery consists essentially of lithium-manganese dioxide (Li/MnO)2) Lithium-sulfur dioxide (Li/SO)2) Lithium thionyl chloride (Li/SOCl)2) And lithium-fluorinated carbon (Li/CF)x) And the like. Li/CF compared to other galvanic cellsxThe theoretical specific energy value of the battery is the highest (2180Wh/kg), and Li/CFxThe battery also has the advantages of high safety, stable discharge voltage, environmental friendliness and the like, and is particularly suitable for being used as a power supply of instrument equipment used in an unmanned or closed environment. Such as a cardiac pacemaker, a missile ignition system, a radio transmitter, an underwater electronic detector and the like, and particularly has great application potential as a military remote detection and communication power supply carried by soldiers.
The discharge mechanism of the Li/CFx cell is as follows:
and (3) anode reaction: xLi + xS → xLi+·S+xe
And (3) cathode reaction: CF (compact flash)x+xLi+·S+xe→C(Li+·S-F-)x
And (3) total reaction: xLi + xS + CFx→C(Li+·S-F-)x→C+xLiF+xS
Wherein S in the reaction formula represents solvent molecules which are coordinated and aggregated with lithium ions in the electrolyte.
Furthermore, Li/CFxThe discharging process of the battery can also be carried out by using a CFxThe "core-shell" model of the core and the layer of discharge products (LiF + C) is roughly described: with the continuous progress of the discharge process, CFxThe radius of the inner core is also continuously decreased, and the thickness of the discharge product layer composed of LiF grains and amorphous carbon is continuously increased.
As the primary chemical power source with the highest theoretical specific energy, Li/CFxThe batteries inevitably need to be stored and shelved during practical use, particularly in aeronautical and military applications. Li/CF during storage, especially at elevated temperaturesxThe capacity of the battery is degraded to various degrees and is further increased as the external temperature increases. Therefore, the deep search for Li/CFxStorage property of battery under high temperature conditionCan, for high performance Li/CFxThe design and development of batteries are of great significance. The research finds that: Li/CFxAfter the battery is stored at high temperature, CFxA self-discharge product layer is formed on the cathode surface, and CFxThe charge transfer resistance of the cathode will increase with the self-discharge, resulting in Li/CFxThe discharge capacity of the battery and the voltage plateau of the discharge are reduced, and the voltage hysteresis phenomenon is more obvious. However, no improvement in Li/CF has been found so farxLiterature reports of high temperature storage performance and self-discharge behavior of batteries.
Disclosure of Invention
The invention aims to modify the carbon fluoride material, and the fluorine content on the surface of the modified carbon fluoride is effectively reduced. Application of modified carbon fluoride material to lithium/carbon fluoride (Li/CF)x) Battery capable of effectively reducing Li/CFxSelf-discharge behavior during high temperature storage. The basic technical scheme provided by the invention is as follows: dispersing the carbon fluoride material in an organic solvent, adding lithium nitride powder with a certain mass, stirring simultaneously, removing the solvent after a certain time to obtain the modified carbon fluoride material, wherein the lithium nitride is used as a fluorine removing agent and can react with fluorine on the surface of the carbon fluoride material to generate the lithium fluoride. .
The present application provides, as one aspect thereof, a method for preparing a modified carbon fluoride material, which is characterized in that carbon fluoride and lithium nitride are reacted in an organic solvent, and the solvent is removed to obtain the modified carbon fluoride material.
Optionally, the organic solvent is a low boiling point solvent.
Optionally, the low boiling point solvent is selected from at least one of dimethyl carbonate (DMC), N-Dimethylformamide (DMF), ethylene glycol dimethyl ether (DME), 1, 3-Dioxolane (DOL), Tetrahydrofuran (THF).
Optionally, at least the following steps are included:
(a) obtaining a mixed solution of carbon fluoride and lithium nitride in an organic solvent, and reacting for a certain time;
(b) and (b) standing the mixed solution after the reaction in the step (a), taking out supernatant after the solid product is settled to the bottom of the container, removing the solvent in the rest mixture, and drying to obtain the modified carbon fluoride material.
Optionally, the step (a) comprises at least:
(a1) adding carbon fluoride powder into an organic solvent to obtain a carbon fluoride dispersion liquid;
(a2) adding lithium nitride powder to the carbon fluoride dispersion liquid in (a1), and stirring for reaction.
Optionally, in the step (a1), the mass fraction of the carbon fluoride in the dispersion is 5-20 wt%.
Optionally, the upper limit of the mass fraction of the fluorinated carbon in the dispersion is selected from 6 wt%, 8 wt%, 10 wt%, 12 wt%, 14 wt%, 15 wt%, 16 wt%, 18 wt%, or 20 wt%; the upper limit is selected from 5 wt%, 6 wt%, 8 wt%, 10 wt%, 12 wt%, 14 wt%, 15 wt%, 16 wt% or 18 wt%.
Optionally, in the step (a2), the mass fraction of lithium nitride based on the total mass of the solid (the sum of the mass of carbon fluoride and the mass of lithium nitride) is 1-10 wt%.
Optionally, the upper limit of the mass fraction of lithium nitride to the total mass of solids (sum of the mass of carbon fluoride and lithium nitride) is selected from 2 wt%, 3 wt%, 4 wt%, 5 wt%, 6 wt%, 7 wt%, 8 wt%, 9 wt% or 10 wt%; the lower limit is selected from 1 wt%, 2 wt%, 3 wt%, 4 wt%, 5 wt%, 6 wt%, 7 wt%, 8 wt% or 9 wt%.
Alternatively, in step (a2), the reaction conditions are stirred: the stirring time is 5-20h, and the stirring speed is 800 r/min.
Alternatively, in step (a2), the reaction conditions are stirred: the stirring time is 10-20h, and the stirring speed is 500-700 r/min.
Alternatively, in step (a2), the reaction conditions are stirred: the stirring time is 15h, and the stirring speed is 600 r/min.
Optionally, step (b) is: and (b) standing the mixed solution obtained in the step (a) for 10-72h, taking out supernatant liquid after the solid product is settled to the bottom of the container, removing the solvent in the rest mixture at the temperature of 30-80 ℃, and drying to obtain the modified carbon fluoride material.
Optionally, step (b) is: and (c) standing the mixed solution obtained in the step (a) for 12-36h, taking out supernatant after the solid product is settled to the bottom of the container, removing the solvent in the rest mixture at the temperature of 50-70 ℃, and drying to obtain the modified carbon fluoride material.
Optionally, step (b) is: and (b) standing the mixed solution obtained in the step (a) for 24 hours, taking out supernatant after the solid product is settled to the bottom of the container, removing the solvent in the rest mixture at the temperature of 60 ℃, and drying to obtain the modified carbon fluoride material.
The preparation method of the modified carbon fluoride material specifically comprises the following steps:
(1) weighing a certain amount of carbon fluoride powder, adding the carbon fluoride powder into an organic solvent with a certain volume, and stirring to fully disperse the carbon fluoride powder and form a carbon fluoride dispersion liquid, wherein the carbon fluoride powder accounts for 5-20 wt% of the dispersion liquid;
(2) weighing a certain mass of lithium nitride powder, adding the lithium nitride powder into the mixture obtained in the step (1), and stirring the mixture for 5 to 20 hours at a stirring speed of 800 r/min;
(3) and (3) standing the mixed solution in the step (2) for 10-72h, taking out supernatant after the solid product is settled to the bottom of the container, and placing the supernatant on a heating table to remove the residual small amount of solvent, wherein the temperature of the heating table is 30-80 ℃. The powder obtained after drying is mainly a modified carbon fluoride material with a 'stretched net' protective film on the surface.
In another aspect of the present invention, there is provided a positive electrode material comprising the modified carbon fluoride material prepared by any one of the methods described above.
In another aspect of the present invention, there is provided a lithium/fluorinated carbon primary battery comprising the fluorinated carbon positive electrode material described above.
The beneficial effects that this application can produce include:
compared with the modified carbon fluoride material before modification, the fluorine content of the surface of the modified carbon fluoride material is reduced, the reduction of the fluorine content of the surface effectively reduces the probability of self-discharge behavior of the battery during high-temperature storage, can effectively improve the high-temperature shelf stability of the lithium/carbon fluoride battery, and has important significance for practical application thereof.
Detailed Description
The present application will be described in detail with reference to examples, but the present application is not limited to these examples.
The raw materials and materials in the examples of the present application were all purchased from commercial sources unless otherwise specified.
The powdered carbon fluoride used in the present application was purchased from Kochif technologies, Inc. in Xiamen.
The lithium nitride powder used in this application was purchased from carbofuran technologies.
The analysis method in the examples of the present application is as follows:
the specific capacity analysis is obtained by adopting a blue battery test system (LAND CT2001A), and the test conditions are as follows: constant current discharge with a discharge rate of 0.1C and a discharge cut-off voltage of 1V.
According to one embodiment of the application, the modified carbon fluoride material is obtained by reacting carbon fluoride and lithium nitride in an organic solvent for a certain time and removing the solvent.
The specific implementation mode of the application comprises the following steps:
(a) obtaining a mixed solution of carbon fluoride and lithium nitride in an organic solvent, and reacting for a certain time;
(b) and (b) standing the mixed solution after the reaction in the step (a), taking out supernatant after the solid product is settled to the bottom of the container, removing the solvent in the rest mixture, and drying to obtain the modified carbon fluoride material.
Further, embodiments of the present application include the steps of:
(1) adding carbon fluoride powder into an organic solvent to obtain a carbon fluoride dispersion liquid;
(2) adding lithium nitride powder into the carbon fluoride dispersion liquid in the step (1), and stirring for reaction;
(3) and (3) standing the mixed solution reacted in the step (2), taking out supernatant liquid after the solid product is settled to the bottom of the container, removing the solvent in the rest mixture, and drying to obtain the modified carbon fluoride material.
The relevant content of the above preparation method is explained as follows:
in the step (1), the organic solvent is a low-boiling point solvent and is selected from at least one of dimethyl carbonate (DMC), N-Dimethylformamide (DMF), ethylene glycol dimethyl ether (DME), 1, 3-Dioxolane (DOL) and Tetrahydrofuran (THF); the mass fraction of the carbon fluoride in the dispersion liquid is 5-20 wt%;
in the step (2), the stirring time is 5-20h, and the stirring speed is 800 r/min; the mass fraction of lithium nitride in the total solid mass (the sum of the mass of carbon fluoride and the mass of lithium nitride) is 1-10 wt%;
in the step (3), after standing for 10-72 hours, taking out supernatant after the solid product is settled to the bottom of the container, and placing the supernatant on a heating table to remove the residual small amount of solvent, wherein the temperature of the heating table is 30-80 ℃; the powder obtained after drying is the modified carbon fluoride material.
The technical solution of the present invention is not limited to the specific embodiments listed below, and includes any combination of the specific embodiments.
Comparative example lithium fluoride was untreated
Example 1
(1) Weighing 1.584g of carbon fluoride powder, adding the carbon fluoride powder into 6.336mL of DMF solvent, and stirring to fully disperse the carbon fluoride powder to form a carbon fluoride dispersion liquid; 20% of carbon fluoride;
(2) weighing 0.016g of lithium nitride powder, adding the lithium nitride powder into the mixture obtained in the step (1), and stirring the mixture for 15 hours at a stirring speed of 600 r/min; lithium nitride accounts for 1 percent of the total mass of the solid (the sum of the mass of carbon fluoride and the mass of lithium nitride);
(3) and (3) standing the mixed solution in the step (2) for 24 hours, taking out supernatant after the solid product is settled to the bottom of the container, and placing the supernatant on a heating table to remove the residual small amount of solvent, wherein the temperature of the heating table is 60 ℃. The powder obtained after drying is mainly a modified carbon fluoride material and is marked as sample No. 1.
Example 2
(1) Weighing 1.568g of carbon fluoride powder, adding the carbon fluoride powder into 14.2mL of DMF solvent, and stirring to fully disperse the carbon fluoride powder to form carbon fluoride dispersion liquid; 10% of carbon fluoride;
(2) weighing 0.032g of lithium nitride powder, adding the lithium nitride powder into the mixture obtained in the step (1), and stirring the mixture for 15 hours at a stirring speed of 600 r/min; lithium nitride accounts for 2 percent of the total mass of the solid (the sum of the mass of carbon fluoride and the mass of lithium nitride);
(3) and (3) standing the mixed solution in the step (2) for 24 hours, taking out supernatant after the solid product is settled to the bottom of the container, and placing the supernatant on a heating table to remove the residual small amount of solvent, wherein the temperature of the heating table is 60 ℃. The powder obtained after drying is mainly a modified carbon fluoride material and is marked as sample No. 2.
Example 3
(1) Weighing 1.536g of carbon fluoride powder, adding the carbon fluoride powder into 11.3mL of DMF solvent, and stirring to fully disperse the carbon fluoride powder to form carbon fluoride dispersion liquid; the carbon fluoride accounts for 12 percent;
(2) weighing 0.064g of lithium nitride powder, adding the lithium nitride powder into the mixture obtained in the step (1), and stirring the mixture for 15 hours at a stirring speed of 600 r/min; lithium nitride accounts for 4% of the total mass of the solid (the sum of the mass of carbon fluoride and the mass of lithium nitride);
(3) and (3) standing the mixed solution in the step (2) for 24 hours, taking out supernatant after the solid product is settled to the bottom of the container, and placing the supernatant on a heating table to remove the residual small amount of solvent, wherein the temperature of the heating table is 60 ℃. The powder obtained after drying is mainly a modified carbon fluoride material with a 'stretched mesh' protective film on the surface, and is marked as sample # 3.
Example 4
(1) Weighing 1.44g of carbon fluoride powder, adding the carbon fluoride powder into 27.4mL of DMF solvent, and stirring to fully disperse the carbon fluoride powder to form a carbon fluoride dispersion liquid; 5% of carbon fluoride;
(2) weighing 0.16g of lithium nitride powder, adding the lithium nitride powder into the mixture obtained in the step (1), and stirring the mixture for 15 hours at a stirring speed of 600 r/min; lithium nitride accounts for 10% of the total mass of the solid (the sum of the mass of carbon fluoride and the mass of lithium nitride);
(3) and (3) standing the mixed solution in the step (2) for 24 hours, taking out supernatant after the solid product is settled to the bottom of the container, and placing the supernatant on a heating table to remove the residual small amount of solvent, wherein the temperature of the heating table is 60 ℃. The powder obtained after drying is mainly a modified carbon fluoride material and is marked as sample No. 4.
Examples 5 to 6
The operation is the same as example 1, except that the corresponding material types and conditions are changed, as shown in Table 1. For comparative analysis, the operating conditions of examples 1-4 are also shown in the table.
TABLE 1
Example 7
The modified carbon fluoride material obtained in the above embodiment is used for active substances, and the ratio of the active substance: conductive agent (Super P): preparing a carbon fluoride positive electrode by using a binder (polyvinylidene fluoride) in a ratio of 8:1:1 (total mass is 1.6g), assembling a lithium/carbon fluoride battery by using metal lithium as a counter electrode, storing the battery in a constant temperature box at 60 ℃ for different time, and testing the discharge specific capacity of the battery at 0.1C rate; and comparing the discharge specific capacity with that of a lithium/carbon fluoride battery which adopts unmodified carbon fluoride as an active substance under the same condition.
TABLE 260 ℃ storage of specific capacity comparison at 0.1C discharge Rate at different times (specific capacity unit: mAh/g)
And (3) analyzing an experimental result:
1) in the comparative example, the self-discharge behavior of the lithium/fluorocarbon battery is aggravated along with the increase of the storage time, and a self-discharge product layer is formed on the surface of the fluorocarbon cathode, so that the charge transfer resistance of the fluorocarbon cathode is continuously increased along with the aggravation of self-discharge, and finally, the discharge capacity of the battery is only 57mAh/g after the battery is stored for 30 days at 60 ℃, and compared with the battery which is not stored, the capacity retention rate is only 7%;
2) in examples 1-6, the improved fluorocarbon material was used as a cathode active material, and the self-discharge behavior of the lithium/fluorocarbon battery was effectively suppressed, and the battery still had a high specific discharge capacity even after 30 days of storage at 60 ℃. When the lithium nitride accounts for 4-8% of the total solid mass (the sum of the mass of the carbon fluoride and the mass of the lithium nitride), the obtained modified carbon fluoride material has small self-discharge when being used for a lithium/carbon fluoride battery, and still has high discharge capacity after being stored for 30 days at 60 ℃. When the lithium nitride accounts for 5 percent of the total mass of the solid (the sum of the mass of the carbon fluoride and the mass of the lithium nitride), the obtained modified carbon fluoride material has the minimum self-discharge when being used for a lithium/carbon fluoride battery, the amplification capacity after 10 days of storage at 60 ℃ is the same as that before the storage, and the capacity after 30 days of storage is up to 750 mAh/g.
3) The experimental results (examples 1-6) show that the modified fluorocarbon material prepared by the invention has the beneficial effects that the reduction of the surface fluorine content effectively reduces the probability of self-discharge behavior during high-temperature storage of the battery, namely, the pretreatment of the fluorocarbon material effectively inhibits the capacity fading (caused by self-discharge) of the lithium/fluorocarbon battery during storage at 60 ℃, thereby improving the high-temperature storage stability of the lithium/fluorocarbon battery.
In conclusion, the lithium/carbon fluoride battery using the modified carbon fluoride as the active material has excellent high-temperature storage stability, which is of great significance for practical application thereof.
Although the present application has been described with reference to a few embodiments, it should be understood that various changes, substitutions and alterations can be made herein without departing from the spirit and scope of the application as defined by the appended claims.
Claims (10)
1. The preparation method of the modified carbon fluoride material is characterized by comprising the steps of reacting carbon fluoride and lithium nitride in an organic solvent, and removing the solvent to obtain the modified carbon fluoride material.
2. The method of claim 1, wherein the organic solvent is a low boiling point solvent.
3. The method according to claim 2, wherein the low boiling point solvent is at least one selected from the group consisting of dimethyl carbonate, N-dimethylformamide, ethylene glycol dimethyl ether, 1, 3-dioxolane, and tetrahydrofuran.
4. Method according to claim 1, characterized in that it comprises at least the following steps:
(a) obtaining a mixed solution of carbon fluoride and lithium nitride in an organic solvent, and reacting;
(b) and (b) standing the mixed solution after the reaction in the step (a), taking out supernatant after the solid product is settled to the bottom of the container, removing the solvent in the rest mixture, and drying to obtain the modified carbon fluoride material.
5. The method of claim 4, wherein step (a) comprises at least:
(a1) adding carbon fluoride powder into an organic solvent to obtain a carbon fluoride dispersion liquid;
(a2) adding lithium nitride powder to the carbon fluoride dispersion liquid in (a1), and stirring for reaction.
6. The method of claim 5, wherein in step (a1), the mass fraction of the fluorinated carbon in the dispersion is 5-20 wt%;
in the step (a2), the mass fraction of lithium nitride in the total mass of the solid is 1-10 wt%.
7. The method of claim 5, wherein in step (a2), the stirring reaction conditions are: the stirring time is 5-20h, and the stirring speed is 800 r/min.
8. The method of claim 4, wherein step (b) is: and (b) standing the mixed solution obtained in the step (a) for 10-72h, taking out supernatant liquid after the solid product is settled to the bottom of the container, removing the solvent in the rest mixture at the temperature of 30-80 ℃, and drying to obtain the modified carbon fluoride material.
9. A positive electrode material comprising the modified carbon fluoride material produced by the method according to any one of claims 1 to 8.
10. A lithium/fluorinated carbon primary battery comprising the positive electrode material according to claim 9.
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Cited By (3)
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| CN114400305A (en) * | 2021-12-14 | 2022-04-26 | 中国电子科技集团公司第十八研究所 | Thermal battery high-voltage spherical carbon fluoride anode material and preparation method thereof |
| CN114628631A (en) * | 2022-03-07 | 2022-06-14 | 湘潭大学 | Preparation method of high-capacity alkali metal-carbon fluoride secondary battery |
| WO2024245458A1 (en) * | 2023-11-09 | 2024-12-05 | 惠州亿纬锂能股份有限公司 | Carbon fluoride modification method, modified carbon fluoride and lithium/carbon fluoride battery |
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| CN114400305A (en) * | 2021-12-14 | 2022-04-26 | 中国电子科技集团公司第十八研究所 | Thermal battery high-voltage spherical carbon fluoride anode material and preparation method thereof |
| CN114628631A (en) * | 2022-03-07 | 2022-06-14 | 湘潭大学 | Preparation method of high-capacity alkali metal-carbon fluoride secondary battery |
| CN114628631B (en) * | 2022-03-07 | 2023-09-19 | 湘潭大学 | A kind of preparation method of high-capacity alkali metal-fluorocarbon secondary battery |
| WO2024245458A1 (en) * | 2023-11-09 | 2024-12-05 | 惠州亿纬锂能股份有限公司 | Carbon fluoride modification method, modified carbon fluoride and lithium/carbon fluoride battery |
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