CN112952089B - Preparation method and application of modified fluorinated carbon material - Google Patents

Preparation method and application of modified fluorinated carbon material Download PDF

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CN112952089B
CN112952089B CN201911260366.1A CN201911260366A CN112952089B CN 112952089 B CN112952089 B CN 112952089B CN 201911260366 A CN201911260366 A CN 201911260366A CN 112952089 B CN112952089 B CN 112952089B
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carbon fluoride
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CN112952089A (en
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刘翠连
张洪章
李先锋
张华民
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Dalian Institute of Chemical Physics of CAS
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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
    • 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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Abstract

The application discloses a preparation method of a modified carbon fluoride material, which comprises the steps of reacting carbon fluoride and lithium nitride in an organic solvent for a certain time, and removing the solvent to obtain the modified carbon fluoride material. Compared with the material before modification, the fluorine content on the surface of the material is reduced, the self-discharge behavior of the lithium/carbon fluoride battery can be avoided to a certain extent, the self-discharge is effectively reduced, and the high Wen Gezhi stability of the lithium/carbon fluoride battery can be effectively improved, so that the material has important significance for practical application.

Description

Preparation method and application of modified fluorinated carbon material
Technical Field
The application relates to a modification method of a positive electrode material for a lithium/carbon fluoride battery, and belongs 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 has become an urgent need for national economic development. The development of lithium primary batteries using lithium as the negative electrode has received great attention because of the characteristics of light weight and negative electrode potential of lithium metal. The lithium primary battery mainly comprises lithium-manganese dioxide (Li/MnO) 2 ) Lithium-sulfur dioxide (Li/SO) 2 ) Lithium-thionyl chloride (Li/SOCl) 2 ) And lithium-carbon fluoride (Li/CF) x ) And battery systems. Li/CF compared to other primary cells x The theoretical specific energy value of the battery is highest (2180 Wh/kg), while Li/CF x The 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 cardiac pacemakers, missile ignition systems, radio transmitters, underwater electronic detectors and the like, and particularly has great application potential when used as a communication power supply for military remote investigation and carried by soldiers.
The discharge mechanism of the Li/CFx cell is as follows:
anode reaction: xLi+xS→xLi + ·S+xe
Cathode reaction: CF (compact flash) x +xLi + ·S+xe→C(Li + ·S-F - )x
Total reaction: xLi+xS+CF x →C(Li + ·S-F - )x→C+xLiF+xS
Wherein S in the reaction formula represents solvent molecules coordinated and aggregated with lithium ions in the electrolyte.
In addition, li/CF x The discharging process of the battery can also be realized by a CF x The "core-shell" model consisting of the core and the layer of the discharge product (lif+c) is roughly described: as the discharge process proceeds continuously, CF x The radius of the inner core is also continuously decreasing, and the thickness of the discharge product layer composed of LiF grains and amorphous carbon is continuously increasing.
Li/CF as the primary chemical source with highest theoretical specific energy x Batteries inevitably require storage and shelving during actual use, particularly in the field of aeronautics and military applications. Li/CF during storage, especially at elevated temperature x The capacity of the battery may be attenuated to various degrees and may be further increased as the outside temperature increases. Thus, li/CF is being extensively explored x Storage performance of battery under high temperature condition, for high performance Li/CF x The design and development of the battery have important significance. The research finds that: li/CF x After the battery is stored at high temperature, CF x A self-discharge product layer is formed on the surface of the cathode, and CF x The charge transfer resistance of the cathode increases with the self-discharge, leading to Li/CF x The discharge capacity and voltage plateau of the discharge of the battery decrease and the voltage hysteresis becomes more pronounced. However, no improvement in Li/CF has been found to date x The high temperature storage performance and self-discharge behavior of the battery are reported in the literature.
Disclosure of Invention
The invention aims to modify a fluorinated carbon material, and the fluorine content of the surface of the modified fluorinated carbon is effectively reduced. The modified carbon fluoride material is used for lithium/carbon fluoride (Li/CF) x ) A battery capable of effectively reducing Li/CF x Self-discharge behavior during high temperature storage. The basic technical scheme provided by the invention is as follows: dispersing carbon fluoride material in organic solvent, adding lithium nitride powder of certain quality, stirring for a certain time, and removing solvent to obtainTo the modified carbon fluoride material, lithium nitride acts as a "defluorinating agent" which can react with fluorine on the surface of the carbon fluoride material to produce lithium fluoride. .
As one aspect of the present application, there is provided a method for producing a modified carbon fluoride material, 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) and 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 (c) 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) at least includes:
(a1) Adding the carbon fluoride powder into an organic solvent to obtain carbon fluoride dispersion liquid;
(a2) Adding lithium nitride powder into the carbon fluoride dispersion liquid in the step (a 1), and stirring for reaction.
Optionally, in step (a 1), the mass fraction of the carbon fluoride in the dispersion is 5% to 20% by weight.
Optionally, the upper limit of the mass fraction of the carbon fluoride in the dispersion is selected from 6wt%, 8wt%, 10wt%, 12wt%, 14wt%, 15wt%, 16wt%, 18wt% or 20wt%; the upper limit is selected from 5wt%, 6wt%, 8wt%, 10wt%, 12wt%, 14wt%, 15wt%, 16wt% or 18wt%.
Optionally, in step (a 2), the mass fraction of lithium nitride to the total mass of solids (sum of carbon fluoride and lithium nitride mass) is 1% -10% by weight.
Optionally, the upper limit of the mass fraction of lithium nitride to the total mass of solids (sum of carbon fluoride and lithium nitride mass) is selected from 2wt%, 3wt%, 4wt%, 5wt%, 6wt%, 7wt%, 8wt%, 9wt% or 10wt%; the lower limit is selected from 1wt%, 2wt%, 3wt%, 4wt%, 5wt%, 6wt%, 7wt%, 8wt% or 9wt%.
Optionally, in step (a 2), the stirring reaction conditions are: the stirring time is 5-20h, and the stirring speed is 300-800r/min.
Optionally, in step (a 2), the stirring reaction conditions are: the stirring time is 10-20h, and the stirring speed is 500-700r/min.
Optionally, in step (a 2), the stirring reaction conditions are: the stirring time was 15h and the stirring speed was 600r/min.
Optionally, step (b) is: and (c) standing the mixed solution in the step (a) for 10-72h, 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 30-80 ℃, and drying to obtain the modified carbon fluoride material.
Optionally, step (b) is: and (c) standing the mixed solution 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 (c) standing the mixed solution 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 a certain volume of organic solvent, and stirring the mixture to fully disperse the carbon fluoride powder and form carbon fluoride dispersion liquid, wherein the carbon fluoride powder accounts for 5-20wt% of the dispersion liquid;
(2) Weighing a certain mass of lithium nitride powder, adding the lithium nitride powder into the step (1), and stirring at the stirring speed of 300-800r/min for 5-20 h;
(3) And (3) standing the mixed solution in the step (2) for 10-72h, taking out the supernatant after the solid product is settled to the bottom of the container, and placing the supernatant on a heating table for removing a small amount of residual 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 'pull net shape' protective film on the surface.
As a further aspect of the present application, there is provided a positive electrode material characterized in that the positive electrode material contains a modified carbon fluoride material produced according to any one of the above methods.
As a further aspect of the present application, there is provided a lithium/carbon fluoride primary battery characterized in that the primary battery contains the above-described carbon fluoride cathode material.
The beneficial effects that this application can produce include:
compared with the material before modification, the fluorine content of the surface of the modified carbon fluoride material is reduced, the probability of self-discharge behavior of the battery during high-temperature storage is effectively reduced, and the high Wen Gezhi stability of the lithium/carbon fluoride battery can be effectively improved, so that the modified carbon fluoride material has important significance for practical application.
Detailed Description
The present application is described in detail below with reference to examples, but the present application is not limited to these examples.
Unless otherwise indicated, the starting materials and materials in the examples of this application were purchased commercially.
The carbon fluoride powder used in the present application was purchased from xifluoro technologies limited in Xiamen.
The lithium nitride powder used in the present application was purchased from carbofuran technologies.
The analytical method in the examples of the present application is as follows:
the specific capacity analysis was performed using a blue cell test system (Land CT 2001A) under the following conditions: constant current discharge, discharge multiplying power of 0.1C, discharge cut-off voltage of 1V.
According to one embodiment of the present application, the modified carbon fluoride material is obtained by reacting carbon fluoride and lithium nitride in an organic solvent for a certain period of time and removing the solvent.
The specific embodiment 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 (c) 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, specific embodiments of the present application include the steps of:
(1) Adding the carbon fluoride powder into an organic solvent to obtain 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 after the reaction in the step (2), taking out the 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.
The relevant content of the preparation method is explained as follows:
in the step (1), the organic solvent is a low boiling point solvent and is at least one selected from dimethyl carbonate (DMC), N-Dimethylformamide (DMF), ethylene glycol dimethyl ether (DME), 1, 3-Dioxolane (DOL) and Tetrahydrofuran (THF); the mass fraction of the fluorinated carbon in the dispersion liquid is 5-20wt%;
in the step (2), the stirring time is 5-20h, and the stirring speed is 300-800r/min; the mass fraction of the lithium nitride accounting for the total mass of the solid (the sum of the mass of the carbon fluoride and the mass of the lithium nitride) is 1-10wt%;
in the step (3), standing 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 a small amount of residual solvent, wherein the temperature of the heating table is 30-80 ℃; the powder obtained after drying is the modified carbon fluoride material.
The technical scheme of the invention is not limited to the specific embodiments listed below, but also includes any combination of the specific embodiments.
Comparative example lithium fluoride untreated
Example 1
(1) 1.584g of the carbon fluoride powder is weighed and added into 6.336mL of DMF solvent, and the mixture is stirred to be fully dispersed to form carbon fluoride dispersion liquid; fluorinated carbon accounts for 20%;
(2) Weighing 0.016g of lithium nitride powder, adding into the step (1), stirring for 15 hours at the stirring speed of 600r/min; lithium nitride accounts for 1% of the total mass of solids (sum of carbon fluoride and lithium nitride mass);
(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 for removing a small amount of residual solvent, wherein the temperature of the heating table is 60 ℃. The powder obtained after drying is mainly modified carbon fluoride material and is marked as sample No. 1.
Example 2
(1) 1.568g of the carbon fluoride powder is weighed and added into 14.2mL of DMF solvent, and the mixture is stirred to be fully dispersed to form carbon fluoride dispersion liquid; fluorinated carbon accounts for 10%;
(2) Weighing 0.032g of lithium nitride powder, adding the lithium nitride powder into the step (1), and stirring for 15 hours at a stirring speed of 600r/min; lithium nitride accounts for 2% of the total mass of solids (sum of carbon fluoride and lithium nitride mass);
(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 for removing a small amount of residual solvent, wherein the temperature of the heating table is 60 ℃. The powder obtained after drying is mainly modified carbon fluoride material and is marked as sample No. 2.
Example 3
(1) 1.536g of the carbon fluoride powder is weighed and added into 11.3mL of DMF solvent, and the mixture is stirred to be fully dispersed to form carbon fluoride dispersion liquid; the fluorinated carbon accounts for 12%;
(2) Weighing 0.064g of lithium nitride powder, adding the lithium nitride powder into the step (1), and stirring for 15 hours at a stirring speed of 600r/min; lithium nitride accounts for 4% of the total mass of solids (sum of carbon fluoride and lithium nitride mass);
(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 for removing a small amount of residual solvent, wherein the temperature of the heating table is 60 ℃. The powder obtained after drying is mainly a modified carbon fluoride material with a 'pull net' protective film on the surface, and is marked as sample No. 3.
Example 4
(1) 1.44g of the carbon fluoride powder is weighed and added into 27.4mL of DMF solvent, and the mixture is stirred to be fully dispersed to form carbon fluoride dispersion liquid; fluorinated carbon accounts for 5%;
(2) Weighing 0.16g of lithium nitride powder, adding the lithium nitride powder into the step (1), and stirring for 15 hours at a stirring speed of 600r/min; lithium nitride accounts for 10% of the total mass of solids (sum of carbon fluoride and lithium nitride mass);
(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 for removing a small amount of residual solvent, wherein the temperature of the heating table is 60 ℃. The powder obtained after drying is mainly modified carbon fluoride material and is marked as sample No. 4.
Examples 5 to 6
The procedure is as in example 1, except that the corresponding material types and conditions are changed, as specified in Table 1. For ease of comparative analysis, the operating conditions of examples 1-4 are also shown in the table.
TABLE 1
Figure BDA0002311445680000071
Example 7
The modified carbon fluoride material obtained in the above example is used as an active material, and the following active materials are used: conductive agent (Super P): preparing a fluorinated carbon anode by using a binder (polyvinylidene fluoride) =8:1:1 ratio (total mass is 1.6 g), assembling a lithium/fluorinated carbon battery by using metallic lithium as a counter electrode, placing the battery in a constant temperature box at 60 ℃ for different times, and testing the discharge specific capacity of the battery at 0.1C multiplying power; and under the same conditions, compared with a lithium/carbon fluoride battery using unmodified carbon fluoride as an active material.
Table 2 specific capacity comparison (specific capacity unit: mAh/g) at 0.1C discharge rate for different times stored at 60℃
Figure BDA0002311445680000081
/>
Analysis of experimental results:
1) The self-discharge behavior of the lithium/carbon fluoride battery in the comparative example is increased along with the increase of the storage time, and a self-discharge product layer is formed on the surface of the carbon fluoride cathode, so that the charge transfer resistance of the carbon fluoride cathode is increased along with the increase 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 the capacity retention rate is only 7% compared with that of the battery which is not stored;
2) The improved carbon fluoride materials used in examples 1-6 as cathode active materials effectively inhibited the self-discharge behavior of lithium/carbon fluoride batteries, and still had a higher specific discharge capacity even after 30 days of storage at 60 ℃. When lithium nitride accounts for 4-8% 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 smaller self-discharge when used for a lithium/carbon fluoride battery, and still has higher discharge capacity after being stored for 30 days at 60 ℃. When lithium nitride is 5% of the total mass of the solid (sum of carbon fluoride and lithium nitride mass), the resulting modified carbon fluoride material exhibits minimal self-discharge when used in a lithium/carbon fluoride battery, and has a capacity up to 750mAh/g after storage for 30 days, as does the enlarged capacity after storage for 10 days at 60 ℃.
3) The beneficial effects of the invention can be seen from the experimental results (examples 1-6), and the modified carbon fluoride material prepared by the invention has the advantages that the probability of self-discharge behavior of the battery during high-temperature storage is effectively reduced due to the reduction of the surface fluorine content, namely, the capacity decay (caused by self-discharge) of the lithium/carbon fluoride battery during storage at 60 ℃ is effectively inhibited through pretreatment of the carbon fluoride material, so that the high-temperature storage stability of the lithium/carbon fluoride is improved.
In summary, lithium/carbon fluoride batteries employing modified carbon fluoride as an active material have excellent high-temperature storage stability, which is of great importance for their practical use.
The foregoing description is only a few examples of the present application and is not intended to limit the present application in any way, and although the present application is disclosed in the preferred examples, it is not intended to limit the present application, and any person skilled in the art may make some changes or modifications to the disclosed technology without departing from the scope of the technical solution of the present application, and the technical solution is equivalent to the equivalent embodiments.

Claims (4)

1. A lithium/carbon fluoride primary battery is characterized in that,
the primary battery contains a positive electrode material;
the positive electrode material contains a modified carbon fluoride material;
the preparation method of the modified carbon fluoride material at least comprises the following steps:
(a) Obtaining a mixed solution of carbon fluoride and lithium nitride in an organic solvent, and reacting;
(b) Standing the mixed solution after the reaction in the step (a), taking out supernatant when the solid product is settled to the bottom of a container, removing the solvent in the rest mixture, and drying to obtain the modified carbon fluoride material;
said step (a) comprises at least:
(a1) Adding the carbon fluoride powder into an organic solvent to obtain carbon fluoride dispersion liquid;
(a2) Adding lithium nitride powder into the carbon fluoride dispersion liquid in the step (a 1), and stirring for reaction;
in the step (a 1), the mass fraction of the carbon fluoride in the dispersion liquid is 5-20wt%;
in the step (a 2), the mass fraction of the lithium nitride in the total mass of the solid is 1-10wt%;
the stirring reaction conditions are as follows: the stirring time is 5-20h, and the stirring speed is 300-800r/min.
2. The lithium/carbon fluoride primary battery of claim 1, wherein the organic solvent is a low boiling point solvent.
3. The lithium/carbon fluoride primary battery of claim 2, wherein the low boiling point solvent is selected from at least one of dimethyl carbonate, N-dimethylformamide, ethylene glycol dimethyl ether, 1, 3-dioxolane, tetrahydrofuran.
4. The lithium/carbon fluoride primary battery of claim 1, wherein step (b) is: and (c) standing the mixed solution in the step (a) for 10-72h, 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 30-80 ℃, and drying to obtain the modified carbon fluoride material.
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