CN114628670B - Application of nitrogen doped-carbon coated carbon fluoride in lithium/carbon fluoride battery - Google Patents

Application of nitrogen doped-carbon coated carbon fluoride in lithium/carbon fluoride battery Download PDF

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CN114628670B
CN114628670B CN202011460344.2A CN202011460344A CN114628670B CN 114628670 B CN114628670 B CN 114628670B CN 202011460344 A CN202011460344 A CN 202011460344A CN 114628670 B CN114628670 B CN 114628670B
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刘翠连
李先锋
张洪章
张华民
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Dalian Institute of Chemical Physics of CAS
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    • H01M2004/028—Positive electrodes

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Abstract

The invention provides an application of nitrogen-doped carbon-coated carbon fluoride in a lithium/carbon fluoride battery. According to the invention, an aqueous solution of tris (hydroxymethyl) aminomethane is used as a buffer solution, a polydopamine fluorocarbon composite material is obtained through self-polymerization reaction of dopamine hydrochloride, and finally the composite material is calcined in an inert atmosphere to obtain the nitrogen-doped carbon-coated fluorocarbon electrode material. The preparation process is simple, the carbon coating layer is N-doped carbon (N atoms are amino groups derived from dopamine) and uniform, the conductivity of the fluorocarbon material is improved, and the rate performance of the battery is further improved.

Description

Application of nitrogen doped-carbon coated carbon fluoride in lithium/carbon fluoride battery
Technical Field
The invention relates to the technical field of electrode material preparation, in particular to application of a nitrogen-doped carbon-coated fluorocarbon electrode material in a lithium/fluorocarbon battery.
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. As same asThe theoretical specific energy value of the Li/CFx cell is highest (2180 Wh/kg) compared to other primary cells, 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.
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 battery is severely self-discharged, so that the discharge capacity and the discharge voltage platform are reduced, the voltage hysteresis is more obvious, and the voltage hysteresis is further increased along with the increase of the external temperature and the increase of the storage time. In addition, li/CF is caused by poor conductivity of the fluorocarbon material itself x The battery has small discharge power, serious polarization and low voltage platform. For this reason, researchers have tried various methods of modifying fluorocarbon materials. Yong Pan et al (see comparative document) prepared carbon coated fluorocarbon materials by carbonization of polyurea to improve battery voltage plateau and rate discharge performance. The voltage platform of the prepared lithium fluorocarbon battery is improved, and the multiplying power performance is improved. However, the preparation process related to the method needs to use a surfactant and a catalyst, and is complex and unsuitable for large-scale application; the coating layer on the surface of the fluorocarbon is uneven; the carbon-coated fluorocarbon material prepared by the method is still unsatisfactory in high-rate discharge (such as 2C) capability when being used for a lithium/fluorocarbon battery, and still needs to be improved.
According to the invention, an aqueous solution of tris (hydroxymethyl) aminomethane is used as a buffer solution, a polydopamine fluorocarbon composite material is obtained through self-polymerization reaction of dopamine hydrochloride, and finally the composite material is calcined in an inert atmosphere to obtain the nitrogen-doped carbon-coated fluorocarbon electrode material. The preparation process is simple, the carbon coating layer is N-doped carbon (N atoms are amino groups derived from dopamine) and uniform, the conductivity of the fluorocarbon material is improved, the rate performance of the battery is further improved, in addition, the self-discharge phenomenon of the fluorocarbon battery is reduced due to the existence of the uniform nitrogen-doped carbon coating layer on the surface of the fluorocarbon, and the high-temperature shelving performance of the fluorocarbon battery is further improved.
Disclosure of Invention
The invention aims to improve the electronic conductivity of a fluorocarbon material, the actual specific discharge capacity of the fluorocarbon material and the discharge rate of a fluorocarbon battery; the self-discharge phenomenon of the fluorocarbon battery is reduced, and the high Wen Gezhi stability of the fluorocarbon battery is further improved (along with the increase of the storage temperature and the extension of the storage time, the CFx cathode in the fluorocarbon battery can continuously perform self-discharge reaction with the metal lithium cathode, and the active substances of the battery are continuously consumed, so that the discharge specific capacity of the Li/CFx battery can be gradually reduced, and the discharge platform is also gradually lowered).
The invention aims to improve the discharge power of a fluorocarbon battery, and a layer of high-conductivity nitrogen doped-carbon layer is coated on the surface of the fluorocarbon by improving the conductivity of a fluorinated material; in addition, the invention aims to improve the high Wen Gezhi stability of the fluorocarbon battery, and the method is mainly used for uniformly coating a compact carbon protective layer on the surface of the fluorocarbon by a method of isolating the fluorocarbon active material, so that the self-discharge reaction of the fluorocarbon material in the high-temperature shelving process is reduced.
The technical scheme of the invention is as follows:
the invention provides an application of a nitrogen-doped carbon-coated carbon fluoride material, wherein the nitrogen-doped carbon-coated carbon fluoride material is used as a positive electrode active material to be applied to a lithium/carbon fluoride battery, and the nitrogen-doped carbon-coated carbon fluoride refers to coating a nitrogen-doped carbon layer on the surface of the carbon fluoride. The lithium/carbon fluoride battery takes metal lithium as a negative electrode.
Preferably, the nitrogen-doped carbon layer has a thickness of 20-40nm.
Preferably, the carbon fluoride is one or more than two of KB fluoride, graphite fluoride, carbon nano-tube, carbon nano-fiber fluoride, graphene fluoride and mesoporous carbon fluoride material, and the molar ratio of the carbon fluoride to the carbon fluoride is 0.5-95, preferably 0.7-0.85.
Preferably, the nitrogen-doped carbon-coated fluorocarbon is prepared as follows:
1) Dissolving tris (hydroxymethyl) aminomethane in water to obtain a solution A;
2) The pH value of the solution A is regulated to 8-10 by concentrated hydrochloric acid (the concentration is 36% -38%), so as to obtain solution B;
3) Adding a fluorocarbon material into the solution B, and stirring until the fluorocarbon material is fully dispersed to obtain a solution C;
4) Dissolving dopamine hydrochloride in water to obtain a solution D, dropwise adding the solution C, carrying out self-polymerization reaction under the stirring condition, centrifuging and drying a reaction product after the reaction is finished to obtain the polydopamine nano film coated carbon fluoride;
5) Calcining the polydopamine nano film coated carbon fluoride obtained in the step 4) for 1-5h under the inert environment at 800-900 ℃ to obtain the nitrogen-doped carbon coated carbon fluoride material.
Preferably, the mass fraction of the dopamine hydrochloride in the solution D is (0.5-10) wt%, and the mass ratio of the dopamine hydrochloride to the fluorocarbon is (1-5): (10-50).
Preferably, the inert environment refers to an atmosphere environment in one or more of argon, nitrogen or helium;
preferably, in the step 1), the mass percentage of the trihydroxymethyl aminomethane in the aqueous solution is 0.05-5%; in the step 2), the concentration of hydrochloric acid is 36% -38%; in the step 4), the stirring time is 20-48h.
Advantageous effects
1. The carbon coating layer on the surface of the fluorocarbon is N-doped carbon (the N atoms are the amino groups derived from dopamine) and is uniform and compact, so that the conductivity of the fluorocarbon material is obviously improved, and the discharge power (rate capability) of the battery is improved.
2. According to the invention, the nitrogen-doped carbon coating layer (about 20-40 nm) uniformly exists on the surface of the carbon fluoride, so that the self-discharge phenomenon of the carbon fluoride battery is reduced, and the high-temperature shelving performance of the carbon fluoride battery is further improved.
3. The preparation process is simple, and the large-scale production and application are easy to realize.
Drawings
FIG. 1 is a graph showing the rate performance of a fluorinated carbon battery having a fluorinated KB (comparative example 2) as a positive electrode without carbon coating treatment;
fig. 2 is a graph of the rate performance of a fluorinated carbon battery having a nitrogen doped-carbon coated fluorinated KB (example 1) as the positive electrode.
Detailed Description
Comparative example 1. Prior Art
Adding 0.05g of alkylphenol ethoxylates and 0.05g of polyvinyl alcohol as a surfactant into 100mL of distilled water, stirring uniformly by a glass rod, adding 2g of graphite fluoride, and stirring uniformly; 1g of isophorone diisocyanate is added into the solution, the solution is stirred for 15min (1500 r/min), then the solution is placed into a constant-temperature water bath at 45 ℃ and stirred at 400rpm, 0.05g of dibutyltin dilaurate catalyst is added simultaneously, after reaction for 8h, polyurea coated graphite fluoride is obtained after filtration, washing and drying for 12h, and finally the polyurea coated graphite fluoride is subjected to high-temperature treatment (under argon atmosphere, at 350 ℃ for 3 h) to obtain the carbon coated fluorinated KB material. The prepared carbon-coated fluorinated KB positive electrode material and Super P, sodium carboxymethylcellulose (CMC) are prepared into positive electrode slurry according to the mass ratio of 8:1:1, distilled water is used as a homogenate solvent, the positive electrode slurry is coated on an aluminum foil current collector, the positive electrode is prepared after drying, the lithium metal is used as a negative electrode, a lithium/fluorocarbon battery is assembled by taking cellgard2400 as a diaphragm, and the discharge performance of the lithium/fluorocarbon battery is evaluated according to different discharge multiplying powers (0.1C-5C, and theoretical capacity is calculated according to 600 mAh/g).
The prepared carbon-coated fluorinated KB material is taken as an anode active material, lithium metal is taken as a cathode, and the button cell is assembled and tested for charge and discharge performance and high-temperature (60 ℃ for 30 days) shelf stability.
Comparative example 2.
The method comprises the steps of taking uncoated fluorinated KB as an anode active substance, taking metallic lithium as a cathode, assembling a battery, preparing anode slurry by taking uncoated fluorinated KB anode material, super P and sodium carboxymethylcellulose (CMC) according to a mass ratio of 8:1:1, using distilled water as a homogenate solvent, coating the anode slurry on an aluminum foil current collector, drying to obtain an anode, taking metallic lithium as the cathode, taking cellgard2400 as a diaphragm, assembling a lithium/carbon fluoride battery, and evaluating the discharge performance and the high-temperature (60 ℃ for 30 days) shelving stability performance of the battery according to different discharge multiplying powers (0.1C-5C and theoretical capacity are calculated according to 600 mAh/g).
Example 1.
1. 0.12g of tris (hydroxymethyl) aminomethane was weighed and added to a beaker containing 100mL of distilled water;
2. the pH value of the solution in the step 1 is adjusted to 8.5 by concentrated hydrochloric acid (the mass concentration is 37 percent);
3. adding 1g of fluorinated KB material (fluorinated carbon, molar ratio of fluorocarbon is 0.8) to the solution in the step 2 while stirring until the material is fully dispersed;
4. weighing 0.16g of dopamine hydrochloride, dissolving the dopamine hydrochloride in 10mL of water, dropwise adding the solution into the mixed solution in the step 3 after the dopamine hydrochloride is fully dissolved, stirring the solution for 24 hours (fully self-polymerizing), centrifuging the solution, and drying the solution to obtain the polydopamine nano-film coated carbon fluoride;
5. calcining the polydopamine nano film coated carbon fluoride obtained in the step 4 for 2 hours at 850 ℃ in a nitrogen environment to obtain the nitrogen doped-carbon coated fluorinated KB material, wherein the thickness of the coating layer is 25nm. The prepared nitrogen doped-carbon coated fluorinated KB positive electrode material and Super P, sodium carboxymethylcellulose (CMC) are prepared into positive electrode slurry according to the mass ratio of 8:1:1, distilled water is used as a homogenate solvent, the positive electrode slurry is coated on an aluminum foil current collector, the positive electrode is prepared after drying, a lithium metal is used as a negative electrode, a cellgard2400 is used as a diaphragm to assemble a lithium/carbon fluoride battery, and the discharge performance and the high-temperature (0.1C, 60 ℃ for 30 days) shelving stability performance of the lithium/carbon fluoride battery are evaluated according to different discharge rates (0.1C-5C, theoretical capacity is calculated according to 600 mAh/g).
Example 2.
1. 0.08g of tris (hydroxymethyl) aminomethane was weighed and added to a beaker containing 100mL of distilled water;
2. adjusting the pH value of the solution in the step 1 to 8.5 by using concentrated hydrochloric acid;
3. adding 1g of graphite fluoride material (molar ratio of fluorocarbon is 0.85) to the solution 2 while stirring until the graphite fluoride material is fully dispersed;
4. weighing 0.16g of dopamine hydrochloride, dissolving the dopamine hydrochloride in 10mL of water, dropwise adding the solution into the mixed solution 3 after the dopamine hydrochloride is fully dissolved, stirring the solution for 24 hours (fully self-polymerizing), centrifuging the solution, and drying the solution to obtain the polydopamine nano-film coated carbon fluoride;
5. calcining the polydopamine nano film coated carbon fluoride obtained in the step 4 for 2 hours under the inert environment at 850 ℃ to obtain the nitrogen doped-carbon coated graphite fluoride material, wherein the thickness of the coating layer is 30nm. The prepared nitrogen doped-carbon coated graphite fluoride anode material and Super P, sodium carboxymethylcellulose (CMC) are prepared into anode slurry according to the mass ratio of 8:1:1, distilled water is used as a homogenate solvent, the anode slurry is coated on an aluminum foil current collector, the anode is prepared after drying, a lithium metal is used as a negative electrode, a cellgard2400 is used as a diaphragm to assemble a lithium/carbon fluoride battery, and the discharge performance and the high-temperature (0.1C, 60 ℃ for 30 days) shelving stability performance of the lithium/carbon fluoride battery are evaluated according to different discharge rates (0.1C-5C, theoretical capacity is calculated according to 600 mAh/g).
Example 3.
1. 0.12g of tris (hydroxymethyl) aminomethane was weighed and added to a beaker containing 100mL of distilled water;
2. adjusting the pH value of the solution in the step 1 to 8.5 by using concentrated hydrochloric acid;
3. adding 1g of graphite fluoride material (0.7 molar ratio of fluorocarbon) to the solution 2 while stirring until the material is fully dispersed;
4. weighing 0.12g of dopamine hydrochloride, dissolving the dopamine hydrochloride in 10mL of water, dropwise adding the solution into the mixed solution 3 after the solution is fully dissolved, stirring the solution for 24 hours (fully self-polymerizing), centrifuging the solution, and drying the solution to obtain the polydopamine nano-film coated carbon fluoride;
6. calcining the polydopamine nano film coated carbon fluoride obtained in the step 4 for 2 hours under the inert environment at 850 ℃ to obtain the nitrogen doped-carbon coated graphite fluoride material, wherein the thickness of the coating layer is 20nm. The prepared nitrogen doped-carbon coated graphite fluoride anode material and Super P, sodium carboxymethylcellulose (CMC) are prepared into anode slurry according to the mass ratio of 8:1:1, distilled water is used as a homogenate solvent, the anode slurry is coated on an aluminum foil current collector, the anode is prepared after drying, a lithium metal is used as a negative electrode, a cellgard2400 is used as a diaphragm to assemble a lithium/carbon fluoride battery, and the discharge performance and the high-temperature (0.1C, 60 ℃ for 30 days) shelving stability performance of the lithium/carbon fluoride battery are evaluated according to different discharge rates (0.1C-5C, theoretical capacity is calculated according to 600 mAh/g).
Example 4.
1. 0.12g of tris (hydroxymethyl) aminomethane was weighed and added to a beaker containing 100mL of distilled water;
2. adjusting the pH value of the solution in the step 1 to 8.5 by using concentrated hydrochloric acid;
3. 0.5g of fluorinated KB material (molar ratio of fluorocarbon of 0.95) was added to the solution in 2 while stirring until well dispersed;
4. weighing 0.16g of dopamine hydrochloride, dissolving the dopamine hydrochloride in 10mL of water, dropwise adding the solution into the mixed solution 3 after the dopamine hydrochloride is fully dissolved, stirring the solution for 24 hours (fully self-polymerizing), centrifuging the solution, and drying the solution to obtain the polydopamine nano-film coated carbon fluoride;
5. calcining the polydopamine nano film coated fluorocarbon obtained in the step 4 for 2 hours under the inert environment at 850 ℃ to obtain the nitrogen doped-carbon coated fluorinated KB material, wherein the thickness of the coating layer is 40nm. The prepared nitrogen doped-carbon coated graphite fluoride anode material and Super P, sodium carboxymethylcellulose (CMC) are prepared into anode slurry according to the mass ratio of 8:1:1, distilled water is used as a homogenate solvent, the anode slurry is coated on an aluminum foil current collector, the anode is prepared after drying, a lithium metal is used as a negative electrode, a cellgard2400 is used as a diaphragm to assemble a lithium/carbon fluoride battery, and the discharge performance and the high-temperature (0.1C, 60 ℃ for 30 days) shelving stability performance of the lithium/carbon fluoride battery are evaluated according to different discharge rates (0.1C-5C, theoretical capacity is calculated according to 600 mAh/g).
Example 5.
1. 0.12g of tris (hydroxymethyl) aminomethane was weighed and added to a beaker containing 100mL of distilled water;
2. adjusting the pH value of the solution in the step 1 to 8.5 by using concentrated hydrochloric acid;
3. 3g of fluorinated KB material (molar ratio of fluorocarbon 0.6) was added to the solution in 2 while stirring until well dispersed;
4. weighing 0.16g of dopamine hydrochloride, dissolving the dopamine hydrochloride in 10mL of water, dropwise adding the solution into the mixed solution 3 after the dopamine hydrochloride is fully dissolved, stirring the solution for 24 hours (fully self-polymerizing), centrifuging the solution, and drying the solution to obtain the polydopamine nano-film coated carbon fluoride;
5. calcining the polydopamine nano film coated fluorocarbon obtained in the step 4 for 2 hours under the inert environment at 850 ℃ to obtain the nitrogen doped-carbon coated fluorinated KB material, wherein the thickness of the coating layer is 20nm. The prepared nitrogen doped-carbon coated graphite fluoride anode material and Super P, sodium carboxymethylcellulose (CMC) are prepared into anode slurry according to the mass ratio of 8:1:1, distilled water is used as a homogenate solvent, the anode slurry is coated on an aluminum foil current collector, the anode is prepared after drying, a lithium metal is used as a negative electrode, a cellgard2400 is used as a diaphragm to assemble a lithium/carbon fluoride battery, and the discharge performance and the high-temperature (0.1C, 60 ℃ for 30 days) shelving stability performance of the lithium/carbon fluoride battery are evaluated according to different discharge rates (0.1C-5C, theoretical capacity is calculated according to 600 mAh/g).
TABLE 1
Table 2 high temperature shelf life properties of fluorocarbon cells having the fluorocarbon materials of the respective examples and comparative examples as positive electrodes
Table 1 is the rate performance (discharge specific volume value at each rate) of the fluorocarbon battery having the fluorocarbon material as the positive electrode in each of the examples and comparative examples;
table 2 is the high temperature rest performance (discharge specific volume values before and after rest at 60 ℃ at 0.1C discharge magnification) of the fluorocarbon battery using the fluorocarbon materials in each of the examples and comparative examples as the positive electrode.
As can be seen by comparing fig. 1 and fig. 2: the rate performance of the carbon fluoride battery using the nitrogen-doped-carbon-coated fluorinated KB of example 1 as a positive electrode was significantly better than that of the carbon fluoride battery using the non-carbon-coated fluorinated KB of comparative example 2 as a positive electrode; compared with the fluorinated KB without carbon coating treatment in the comparative example 2, the discharge plateau and discharge capacity of the nitrogen-doped carbon-coated fluorinated KB in the example 1 are obviously improved under the same multiplying power, and in addition, the fluorinated KB still has the specific capacity of 638mAh/g under the high multiplying power of 5C, which indicates that the intrinsic conductivity of the fluorinated KB is obviously improved after being coated with carbon, and particularly, the carbon coating layer prepared by the invention is nitrogen-doped, thereby being more beneficial to improving the conductivity of the fluorinated carbon and further improving the multiplying power performance (as shown in fig. 2 and table 2);
as can be seen from table 2: compared with the carbon-coated fluorocarbon (comparative example 1) and the fluorocarbon KB which is not subjected to carbon coating treatment (comparative example 2) in the prior art, the fluorocarbon battery taking the nitrogen-doped carbon-coated fluorocarbon KB prepared by the invention as the positive electrode has better high Wen Gezhi stability (still has higher discharge specific capacity after being placed for 30 days at the temperature of 60 ℃ under the multiplying power of 0.1C), and has better discharge capacity retention rate compared with the battery before being placed), because the coating layer of the nitrogen-doped carbon-coated fluorocarbon KB prepared by the invention is more uniform and compact, the reaction of the active material fluorocarbon is avoided, namely the self-discharge of the fluorocarbon battery in the high-temperature placing process is reduced, and thus the discharge specific capacity of the fluorocarbon battery after being placed is still higher.

Claims (8)

1. The application of the nitrogen-doped carbon-coated fluorocarbon material is characterized in that the nitrogen-doped carbon-coated fluorocarbon material is used as a positive electrode active material in a lithium/fluorocarbon battery, and the nitrogen-doped carbon-coated fluorocarbon refers to coating a nitrogen-doped carbon layer on the surface of the fluorocarbon.
2. Use according to claim 1, characterized in that the thickness of the nitrogen-doped carbon layer is 20-40nm.
3. The use according to claim 1, wherein the fluorinated carbon is one or more of fluorinated KB, graphite fluoride, fluorinated carbon nanotubes, fluorinated carbon nanofibers, graphene fluoride, and fluorinated mesoporous carbon material, and the molar ratio of the fluorinated carbon in the fluorinated carbon is 0.5-95.
4. Use according to claim 3, wherein the molar ratio of fluorocarbon in the fluorocarbon is between 0.7 and 0.85.
5. Use according to claim 1, wherein the nitrogen-doped-carbon coated fluorocarbon is prepared by:
1) Dissolving trihydroxymethyl aminomethane in water to obtain a solution A;
2) Adjusting the pH value of the solution A to 8-10 by hydrochloric acid to obtain a solution B;
3) Adding a fluorocarbon material into the solution B, and stirring until the fluorocarbon material is dispersed to obtain a solution C;
4) Dissolving dopamine hydrochloride in water to obtain a solution D, dropwise adding the solution C, carrying out self-polymerization reaction under the stirring condition, centrifuging and drying a reaction product after the reaction is finished to obtain the polydopamine nano film coated carbon fluoride;
5) Calcining the polydopamine nano film coated carbon fluoride obtained in the step 4) for 1-5h under the inert environment at 800-900 ℃ to obtain the nitrogen-doped carbon coated carbon fluoride material.
6. The use according to claim 5, wherein the mass fraction of dopamine hydrochloride in the solution D is between 0.5 and 10% by weight, the mass ratio of dopamine hydrochloride to fluorocarbon being (1-5): (10-50).
7. The use according to claim 5, wherein the inert atmosphere is an atmosphere of one or more of argon, nitrogen or helium.
8. The use according to claim 5, characterized in that in step 1) the mass percentage of the tris-hydroxymethyl-aminomethane in the aqueous solution is between 0.05 and 5%; in the step 2), the concentration of hydrochloric acid is 36% -38%; in the step 4), the stirring time is 20-48h.
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