CN114188509B - Preparation method of lithium sulfide electrode based on carbon nano tube packaging means - Google Patents
Preparation method of lithium sulfide electrode based on carbon nano tube packaging means Download PDFInfo
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- CN114188509B CN114188509B CN202111455107.1A CN202111455107A CN114188509B CN 114188509 B CN114188509 B CN 114188509B CN 202111455107 A CN202111455107 A CN 202111455107A CN 114188509 B CN114188509 B CN 114188509B
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- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 90
- 229910021393 carbon nanotube Inorganic materials 0.000 title claims abstract description 81
- 239000002041 carbon nanotube Substances 0.000 title claims abstract description 81
- GLNWILHOFOBOFD-UHFFFAOYSA-N lithium sulfide Chemical compound [Li+].[Li+].[S-2] GLNWILHOFOBOFD-UHFFFAOYSA-N 0.000 title claims abstract description 58
- 238000002360 preparation method Methods 0.000 title claims abstract description 9
- 238000004806 packaging method and process Methods 0.000 title claims abstract description 8
- 229910052744 lithium Inorganic materials 0.000 claims abstract description 65
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims abstract description 59
- 238000010438 heat treatment Methods 0.000 claims abstract description 53
- 229910052751 metal Inorganic materials 0.000 claims abstract description 53
- 239000002184 metal Substances 0.000 claims abstract description 53
- 239000000463 material Substances 0.000 claims abstract description 49
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims abstract description 42
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims abstract description 38
- 229910052786 argon Inorganic materials 0.000 claims abstract description 19
- 239000012300 argon atmosphere Substances 0.000 claims abstract description 18
- 238000001816 cooling Methods 0.000 claims abstract description 15
- 239000010453 quartz Substances 0.000 claims abstract description 11
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims abstract description 11
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 9
- 239000007772 electrode material Substances 0.000 claims abstract description 9
- 238000000926 separation method Methods 0.000 claims abstract description 9
- 238000002791 soaking Methods 0.000 claims abstract description 9
- 238000000034 method Methods 0.000 claims description 14
- 229910052799 carbon Inorganic materials 0.000 claims description 9
- 238000001035 drying Methods 0.000 claims description 8
- 238000005538 encapsulation Methods 0.000 claims description 3
- 239000007789 gas Substances 0.000 claims description 2
- 238000004519 manufacturing process Methods 0.000 claims 3
- 229920001021 polysulfide Polymers 0.000 description 5
- 239000005077 polysulfide Substances 0.000 description 5
- 150000008117 polysulfides Polymers 0.000 description 5
- 238000012360 testing method Methods 0.000 description 4
- 230000009286 beneficial effect Effects 0.000 description 3
- 239000003575 carbonaceous material Substances 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 238000012986 modification Methods 0.000 description 3
- 230000004048 modification Effects 0.000 description 3
- 239000002245 particle Substances 0.000 description 3
- JDZCKJOXGCMJGS-UHFFFAOYSA-N [Li].[S] Chemical compound [Li].[S] JDZCKJOXGCMJGS-UHFFFAOYSA-N 0.000 description 2
- 230000006978 adaptation Effects 0.000 description 2
- 238000009792 diffusion process Methods 0.000 description 2
- 239000003792 electrolyte Substances 0.000 description 2
- 229910018091 Li 2 S Inorganic materials 0.000 description 1
- 239000011149 active material Substances 0.000 description 1
- 239000013543 active substance Substances 0.000 description 1
- 239000010405 anode material Substances 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- 230000008025 crystallization Effects 0.000 description 1
- 230000001351 cycling effect Effects 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 238000007599 discharging Methods 0.000 description 1
- 238000013467 fragmentation Methods 0.000 description 1
- 238000006062 fragmentation reaction Methods 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 229910003473 lithium bis(trifluoromethanesulfonyl)imide Inorganic materials 0.000 description 1
- QSZMZKBZAYQGRS-UHFFFAOYSA-N lithium;bis(trifluoromethylsulfonyl)azanide Chemical compound [Li+].FC(F)(F)S(=O)(=O)[N-]S(=O)(=O)C(F)(F)F QSZMZKBZAYQGRS-UHFFFAOYSA-N 0.000 description 1
- 238000010297 mechanical methods and process Methods 0.000 description 1
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 238000007709 nanocrystallization Methods 0.000 description 1
- 239000005486 organic electrolyte Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 239000007774 positive electrode material Substances 0.000 description 1
Classifications
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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
- H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
- H01M4/139—Processes of manufacture
- H01M4/1397—Processes of manufacture of electrodes based on inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y30/00—Nanotechnology for materials or surface science, e.g. nanocomposites
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y40/00—Manufacture or treatment of nanostructures
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/052—Li-accumulators
-
- 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
- H01M4/624—Electric conductive fillers
- H01M4/625—Carbon or graphite
-
- 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
- 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
Abstract
The invention discloses a preparation method of a lithium sulfide electrode based on a carbon nano tube packaging means, which comprises the following steps: s1, heating a certain amount of metal lithium and carbon nano tubes in a tube furnace, wherein the mass ratio of the metal lithium to the carbon nano tubes is 1:1 to 10:1; s2, under the condition that argon is introduced into the tube furnace at the flow rate of 10 ml/min, the heating temperature is increased from 180 ℃ to 300 ℃, and the temperature is naturally reduced; s3, respectively placing a certain amount of elemental sulfur and the metal lithium/carbon nano tube mixed material obtained in the S2 into a quartz tube of a tube furnace under the protection of argon atmosphere, wherein the mass ratio of the elemental sulfur to the metal lithium/carbon nano tube mixed material is 2:1-20:1; s4, introducing argon into the tube furnace, and enabling air flow to flow from elemental sulfur to the direction of the metal lithium/carbon nano tube mixed material; s5, starting the tube furnace to heat to 200 ℃; s6, raising the temperature of the tube furnace from 200 ℃ to 400 ℃ and naturally cooling; and S7, soaking the material obtained in the step S6 in alcohol for 1 hour in an argon atmosphere, and performing centrifugal separation to obtain the carbon nanotube packaged lithium sulfide electrode material.
Description
Technical Field
The invention belongs to the technical field of material preparation, and particularly relates to a preparation method of a lithium sulfide electrode based on a carbon nano tube packaging means.
Background
The current commercial chargeable and dischargeable battery anode material is close to the theoretical capacity, and can not meet the requirements of the current society. Lithium sulfide is considered to be an ideal choice for the positive electrode material of the next-generation charge-discharge battery because of its theoretical specific capacity as high as 1165 mAh/g.
However, to realize commercialization of lithium sulfide electrodes, problems including poor electron and ion conductivity of lithium sulfide, which have large volume changes during charge and discharge, are faced, in which lithium polysulfide (Li 2 S x 4.ltoreq.x.ltoreq.8) is a major cause of decreasing the battery coulombic efficiency and resulting in a decrease in the cycle life of the lithium sulfur battery. In recent years, researchers have made many studies on how to improve the electrochemical performance of lithium sulfide electrodes. In order to prevent the diffusion of lithium polysulfide in organic electrolyte, one of the most effective methods is to mix lithium sulfide with carbon materials, such as carbon nanotubes, mesoporous carbon, carbon spheres, and the like, which are compounded with lithium sulfide, but the shuttle effect is not effectively solved. Because lithium sulfide has high mechanical strength, nanocrystallization is difficult to realize by a mechanical method. In addition, the mechanical mixing of lithium sulfide and carbon materials is difficult to realize effective coating of lithium sulfide, and most of lithium sulfide is still distributed on the surface of the carbon materials. This results in low utilization of active materials, low coulombic efficiency of lithium sulfur batteries, and poor cycling stability. Accordingly, there is a need for a more efficient method of preparing lithium sulfide electrodes.
Disclosure of Invention
In view of the above technical problems, the present invention provides a method for preparing a lithium sulfide electrode based on a carbon nanotube encapsulation means, comprising the following steps:
step S1, heating a certain amount of metal lithium and carbon nano tubes in a tube furnace for 5 hours at 180 ℃ and a vacuum degree of the tube furnace of 1 multiplied by 10 -4 The mass ratio of the lithium metal to the carbon nano tube is 1:1 to 10:1;
step S2, under the condition that argon is introduced into the tube furnace at a flow rate of 10 milliliters per minute, heating temperature is increased from 180 ℃ to 300 ℃, heating rate is 10 ℃ per minute, heating is continued for 10 minutes at 300 ℃, and natural cooling is performed;
step S3, respectively placing a certain amount of elemental sulfur and the metal lithium/carbon nano tube mixed material obtained in the step S2 into a quartz tube of a tube furnace under the protection of argon atmosphere, wherein the mass ratio of the elemental sulfur to the metal lithium/carbon nano tube mixed material is 2:1-20:1, and the elemental sulfur is positioned in a heating center, and the metal lithium/carbon nano tube mixed material obtained in the step S2 is positioned at a position of 10 cm on one side of the elemental sulfur;
step S4, introducing argon into the tube furnace, and enabling air flow to flow from elemental sulfur to the direction of the metal lithium/carbon nano tube mixed material, wherein the air flow rate is 5-20 ml/min;
step S5, starting a tube furnace to heat to 200 ℃, wherein the heating rate is 2 ℃ per minute, and the heating time lasts 0.5 to 2 hours at 200 ℃;
step S6, the temperature of the tube furnace is increased from 200 ℃ to 400 ℃, the temperature increasing rate is 10 ℃ per minute, and the tube furnace is naturally cooled after the temperature is continuously increased to 400 ℃ for 10 minutes;
and S7, soaking the material obtained in the step S6 in alcohol for 1 hour in an argon atmosphere, performing centrifugal separation, and drying at 100 ℃ for 12 hours to obtain the carbon nanotube-encapsulated lithium sulfide electrode material.
Preferably, in step S1, the metal lithium and the carbon nano tube with the mass ratio of 8:1 are heated in a tube furnace for 5 hours, the heating temperature is 180 ℃, and the vacuum degree of the tube furnace is 1 multiplied by 10 -4 Handkerchief;
preferably, in step S3, the elemental sulfur and the metal lithium/carbon nanotube mixed material obtained in S2 are respectively placed in a quartz tube of a tube furnace, and the mass ratio of the elemental sulfur to the metal lithium/carbon nanotube mixed material obtained in S2 is 20:1;
preferably, in step S4, the gas flow rate is 10 ml/min;
preferably, in step S5, the tube furnace is started to heat to 200 degrees celsius at a heating rate of 2 degrees celsius/minute, 200 degrees celsius for 2 hours;
the preparation of the lithium sulfide electrode by adopting the technical scheme of the invention can encapsulate nano lithium sulfide particles in the carbon nano tube, is beneficial to improving the electronic conductivity of the lithium sulfide electrode, can buffer the volume expansion of the lithium sulfide electrode in the charge and discharge process, can inhibit the shuttle effect of lithium polysulfide, and effectively improves the electrochemical performance of the lithium sulfide electrode.
Compared with the prior art, the invention has the following beneficial effects:
(1) The method provided by the invention has simple process and is easy to realize.
(2) The lithium sulfide is encapsulated in the carbon nano tube, the crystallization scale is limited, and the electronic conductivity of the lithium sulfide electrode is effectively improved;
(3) The lithium sulfide is encapsulated in the carbon nano tube, and the carbon nano tube is tightly contacted with the lithium sulfide particles, so that the electronic conductivity of the lithium sulfide electrode is effectively improved;
(4) The lithium sulfide is encapsulated in the carbon nano tube, and the carbon nano tube effectively inhibits the volume expansion of the lithium sulfide electrode in the charging and discharging process, so that the fragmentation of the lithium sulfide electrode is avoided;
(5) The lithium sulfide is encapsulated in the carbon nano tube, and the carbon nano tube can effectively inhibit the diffusion of the polysulfide lithium generated in the charge and discharge process into the electrolyte, so that the coulomb efficiency of the lithium sulfide electrode is improved;
(6) The invention can effectively improve the content of active substances in the lithium sulfide electrode.
Drawings
FIG. 1 is a flow chart of the steps for preparing a lithium sulfide electrode according to the present invention;
fig. 2 is a cycle performance curve of the lithium sulfide electrode prepared in example 1 of the present invention.
The invention will be further illustrated by the following specific examples in conjunction with the above-described figures.
Detailed Description
In order to better illustrate the flow and aspects of the present invention, the following invention is further described with reference to the drawings and examples. The specific embodiments described herein are merely illustrative of the invention and are not intended to limit the invention.
Referring to fig. 1, a flow chart of a preparation method of a lithium sulfide electrode based on a carbon nanotube packaging means is shown, which comprises the following steps:
s1, heating a certain amount of metal lithium and carbon nano tubes in a tube furnace for 5 hours at 180 ℃ and 1X 10 vacuum degree -4 The mass ratio of the lithium metal to the carbon nano tube is 1:1 to 10:1;
s2, under the condition that argon is introduced into the tube furnace at a flow rate of 10 milliliters per minute, heating temperature is increased from 180 ℃ to 300 ℃, heating rate is 10 ℃ per minute, heating is continued for 10 minutes at 300 ℃, and natural cooling is performed;
s3, respectively placing a certain amount of elemental sulfur and the metal lithium/carbon nano tube mixed material obtained in the step S2 into a quartz tube of a tube furnace under the protection of argon atmosphere, wherein the mass ratio of the elemental sulfur to the metal lithium/carbon nano tube mixed material is 2:1-20:1, and the elemental sulfur is positioned in a heating center, and the metal lithium/carbon nano tube mixed material obtained in the step S2 is positioned at a position of 10 cm on one side of the elemental sulfur;
s4, introducing argon into the tube furnace, and enabling air flow to flow from elemental sulfur to the direction of the metal lithium/carbon nano tube mixed material, wherein the air flow rate is 5-20 ml/min;
s5, starting the tube furnace to heat to 200 ℃, wherein the heating rate is 2 ℃ per minute, and the heating time lasts 0.5 to 2 hours at 200 ℃;
s6, raising the temperature of the tube furnace from 200 ℃ to 400 ℃, raising the temperature to 10 ℃ per minute, and naturally cooling after the temperature of the tube furnace is kept at 400 ℃ for 10 minutes;
and S7, soaking the material obtained in the step S6 in alcohol for 1 hour in argon atmosphere, performing centrifugal separation, and drying at 100 ℃ for 12 hours to obtain the carbon nanotube-encapsulated lithium sulfide electrode material.
The preparation of the lithium sulfide electrode by adopting the technical scheme of the invention can encapsulate nano lithium sulfide particles in the carbon nano tube, is beneficial to improving the electronic conductivity of the lithium sulfide electrode, can buffer the volume expansion of the lithium sulfide electrode in the charge and discharge process, can inhibit the shuttle effect of lithium polysulfide, and effectively improves the electrochemical performance of the lithium sulfide electrode.
Example 1
S1, heating a certain amount of metal lithium and carbon nano tubes in a tube furnace for 5 hours at 180 ℃ and 1X 10 vacuum degree -4 The mass ratio of the lithium metal to the carbon nano tube is 8:1;
s2, under the condition that argon is introduced into the tube furnace at a flow rate of 10 milliliters per minute, heating temperature is increased from 180 ℃ to 300 ℃, heating rate is 10 ℃ per minute, heating is continued for 10 minutes at 300 ℃, and natural cooling is performed;
s3, respectively placing a certain amount of elemental sulfur and the metal lithium/carbon nano tube mixed material obtained in the step S2 into a quartz tube of a tube furnace under the protection of argon atmosphere, wherein the mass ratio of the elemental sulfur to the metal lithium/carbon nano tube mixed material is 20:1, and the metal lithium/carbon nano tube mixed material obtained in the step S2 is positioned at the position of 10 cm on one side of the elemental sulfur;
s4, introducing argon into the tube furnace, and enabling air flow to flow from elemental sulfur to the metal lithium/carbon nano tube mixed material, wherein the air flow rate is 10 ml/min;
s5, starting the tube furnace to heat to 200 ℃, wherein the heating rate is 2 ℃ per minute, and the heating time lasts for 2 hours at 200 ℃;
s6, raising the temperature of the tube furnace from 200 ℃ to 400 ℃, raising the temperature to 10 ℃ per minute, and naturally cooling after the temperature of the tube furnace is kept at 400 ℃ for 10 minutes;
and S7, soaking the material obtained in the step S6 in alcohol for 1 hour in argon atmosphere, performing centrifugal separation, and drying at 100 ℃ for 12 hours to obtain the carbon nanotube-encapsulated lithium sulfide electrode material.
Instantiation 2
S1, heating a certain amount of metal lithium and carbon nano tubes in a tube furnace for 5 hours at 180 ℃ and 1X 10 vacuum degree -4 The mass ratio of the metal lithium to the carbon nano tube is 1:1;
s2, under the condition that argon is introduced into the tube furnace at a flow rate of 10 milliliters per minute, heating temperature is increased from 180 ℃ to 300 ℃, heating rate is 10 ℃ per minute, heating is continued for 10 minutes at 300 ℃, and natural cooling is performed;
s3, respectively placing a certain amount of elemental sulfur and the metal lithium/carbon nano tube mixed material obtained in the step S2 into a quartz tube of a tube furnace under the protection of argon atmosphere, wherein the mass ratio of the elemental sulfur to the metal lithium/carbon nano tube mixed material is 2:1, and the metal lithium/carbon nano tube mixed material obtained in the step S2 is positioned at the position of 10 cm on one side of the elemental sulfur;
s4, introducing argon into the tube furnace, and enabling air flow to flow from elemental sulfur to the direction of the metal lithium/carbon nano tube mixed material, wherein the air flow rate is 5 ml/min;
s5, starting the tube furnace to heat to 200 ℃, wherein the heating rate is 2 ℃ per minute, and the heating time lasts 0.5 hour at 200 ℃;
s6, raising the temperature of the tube furnace from 200 ℃ to 400 ℃, raising the temperature to 10 ℃ per minute, and naturally cooling after the temperature of the tube furnace is kept at 400 ℃ for 10 minutes;
and S7, soaking the material obtained in the step S6 in alcohol for 1 hour in argon atmosphere, performing centrifugal separation, and drying at 100 ℃ for 12 hours to obtain the carbon nanotube-encapsulated lithium sulfide electrode material.
Instantiation 3
S1, heating a certain amount of metal lithium and carbon nano tubes in a tube furnace for 5 hours at 180 ℃ and 1X 10 vacuum degree -4 The mass ratio of the lithium metal to the carbon nano tube is 10:1;
s2, under the condition that argon is introduced into the tube furnace at a flow rate of 10 milliliters per minute, heating temperature is increased from 180 ℃ to 300 ℃, heating rate is 10 ℃ per minute, heating is continued for 10 minutes at 300 ℃, and natural cooling is performed;
s3, respectively placing a certain amount of elemental sulfur and the metal lithium/carbon nano tube mixed material obtained in the step S2 into a quartz tube of a tube furnace under the protection of argon atmosphere, wherein the mass ratio of the elemental sulfur to the metal lithium/carbon nano tube mixed material is 20:1, and the metal lithium/carbon nano tube mixed material obtained in the step S2 is positioned at the position of 10 cm on one side of the elemental sulfur;
s4, introducing argon into the tube furnace, and enabling air flow to flow from elemental sulfur to the direction of the metal lithium/carbon nano tube mixed material, wherein the air flow rate is 20 ml/min;
s5, starting the tube furnace to heat to 200 ℃, wherein the heating rate is 2 ℃ per minute, and the heating time lasts for 2 hours at 200 ℃;
s6, raising the temperature of the tube furnace from 200 ℃ to 400 ℃, raising the temperature to 10 ℃ per minute, and naturally cooling after the temperature of the tube furnace is kept at 400 ℃ for 10 minutes;
and S7, soaking the material obtained in the step S6 in alcohol for 1 hour in argon atmosphere, performing centrifugal separation, and drying at 100 ℃ for 12 hours to obtain the carbon nanotube-encapsulated lithium sulfide electrode material.
Instantiation 4
S1, heating a certain amount of metal lithium and carbon nano tubes in a tube furnace for 5 hours at 180 ℃ and 1X 10 vacuum degree -4 The mass ratio of the lithium metal to the carbon nano tube is 6:1;
s2, under the condition that argon is introduced into the tube furnace at a flow rate of 10 milliliters per minute, heating temperature is increased from 180 ℃ to 300 ℃, heating rate is 10 ℃ per minute, heating is continued for 10 minutes at 300 ℃, and natural cooling is performed;
s3, respectively placing a certain amount of elemental sulfur and the metal lithium/carbon nano tube mixed material obtained in the step S2 into a quartz tube of a tube furnace under the protection of argon atmosphere, wherein the mass ratio of the elemental sulfur to the metal lithium/carbon nano tube mixed material is 10:1, and the metal lithium/carbon nano tube mixed material obtained in the step S2 is positioned at the position of 10 cm on one side of the elemental sulfur;
s4, introducing argon into the tube furnace, and enabling air flow to flow from elemental sulfur to the direction of the metal lithium/carbon nano tube mixed material, wherein the air flow rate is 20 ml/min;
s5, starting the tube furnace to heat to 200 ℃, wherein the heating rate is 2 ℃ per minute, and the heating time lasts for 1 hour at 200 ℃;
s6, raising the temperature of the tube furnace from 200 ℃ to 400 ℃, raising the temperature to 10 ℃ per minute, and naturally cooling after the temperature of the tube furnace is kept at 400 ℃ for 10 minutes;
and S7, soaking the material obtained in the step S6 in alcohol for 1 hour in argon atmosphere, performing centrifugal separation, and drying at 100 ℃ for 12 hours to obtain the carbon nanotube-encapsulated lithium sulfide electrode material.
Instantiation 5
S1, heating a certain amount of metal lithium and carbon nano tubes in a tube furnace for 5 hours at 180 ℃ and 1X 10 vacuum degree -4 The mass ratio of the metal lithium to the carbon nano tube is 5:1;
s2, under the condition that argon is introduced into the tube furnace at a flow rate of 10 milliliters per minute, heating temperature is increased from 180 ℃ to 300 ℃, heating rate is 10 ℃ per minute, heating is continued for 10 minutes at 300 ℃, and natural cooling is performed;
s3, respectively placing a certain amount of elemental sulfur and the metal lithium/carbon nano tube mixed material obtained in the step S2 into a quartz tube of a tube furnace under the protection of argon atmosphere, wherein the mass ratio of the elemental sulfur to the metal lithium/carbon nano tube mixed material is 15:1, and the metal lithium/carbon nano tube mixed material obtained in the step S2 is positioned at the position of 10 cm on one side of the elemental sulfur;
s4, introducing argon into the tube furnace, and enabling air flow to flow from elemental sulfur to the direction of the metal lithium/carbon nano tube mixed material, wherein the air flow rate is 5 ml/min;
s5, starting the tube furnace to heat to 200 ℃, wherein the heating rate is 2 ℃ per minute, and the heating time lasts for 1 hour at 200 ℃;
s6, raising the temperature of the tube furnace from 200 ℃ to 400 ℃, raising the temperature to 10 ℃ per minute, and naturally cooling after the temperature of the tube furnace is kept at 400 ℃ for 10 minutes;
and S7, soaking the material obtained in the step S6 in alcohol for 1 hour in argon atmosphere, performing centrifugal separation, and drying at 100 ℃ for 12 hours to obtain the carbon nanotube-encapsulated lithium sulfide electrode material.
Further, the above method was subjected to performance testing. The specific test process is as follows: the electrochemical performance of the lithium sulfide electrode is tested by adopting a half battery, a negative electrode is a lithium sheet, celgard2325 is taken as a diaphragm, an electrolyte is 1M LiTFSI DOL/DME solution, and the battery is assembled by using a LIR2032 coin-type battery shell in a glove box full of argon protection under the humidity and oxygen concentration of less than 1 ppm. In the charge-discharge test system, the charge-discharge test voltage is 1.6-2.8V.
FIG. 1 is a flow chart of the steps for preparing a lithium sulfide electrode according to the present invention; fig. 2 is a cycle performance curve of the lithium sulfide electrode prepared in example 1 of the present invention. It can be seen therefrom that it has an initial capacity of 893mAh/g and exhibits excellent cycle performance.
From the above analysis, it can be seen that the lithium sulfide electrode prepared by the method has an initial capacity of 893mAh/g and exhibits excellent cycle performance.
The above description of the embodiments is only for aiding in the understanding of the method of the present invention and its core ideas. It should be noted that it will be apparent to those skilled in the art that various modifications and adaptations of the invention can be made without departing from the principles of the invention and these modifications and adaptations are intended to be within the scope of the invention as defined in the following claims.
The previous description of the disclosed embodiments is provided to enable any person skilled in the art to make or use the present invention. Various modifications to these embodiments will be readily apparent to those skilled in the art, and the generic principles defined herein may be applied to other embodiments without departing from the spirit or scope of the invention. Thus, the present invention is not intended to be limited to the embodiments shown herein but is to be accorded the widest scope consistent with the principles and novel features disclosed herein.
Claims (5)
1. The preparation method of the lithium sulfide electrode based on the carbon nano tube encapsulation means is characterized by comprising the following steps of:
step S1, heating a certain amount of metal lithium and carbon nano tubes in a tube furnace for 5 hours at 180 ℃ and a vacuum degree of the tube furnace of 1 multiplied by 10 -4 The mass ratio of the lithium metal to the carbon nano tube is 1:1 to 10:1;
step S2, under the condition that argon is introduced into the tube furnace at a flow rate of 10 milliliters per minute, heating temperature is increased from 180 ℃ to 300 ℃, heating rate is 10 ℃ per minute, heating is continued for 10 minutes at 300 ℃, and natural cooling is performed;
step S3, respectively placing a certain amount of elemental sulfur and the metal lithium/carbon nano tube mixed material obtained in the step S2 into a quartz tube of a tube furnace under the protection of argon atmosphere, wherein the mass ratio of the elemental sulfur to the metal lithium/carbon nano tube mixed material is 2:1-20:1, and the elemental sulfur is positioned in a heating center, and the metal lithium/carbon nano tube mixed material obtained in the step S2 is positioned at a position of 10 cm on one side of the elemental sulfur;
step S4, introducing argon into the tube furnace, and enabling air flow to flow from elemental sulfur to the direction of the metal lithium/carbon nano tube mixed material, wherein the air flow rate is 5-20 ml/min;
step S5, starting a tube furnace to heat to 200 ℃, wherein the heating rate is 2 ℃ per minute, and the heating time lasts 0.5 to 2 hours at 200 ℃;
step S6, the temperature of the tube furnace is increased from 200 ℃ to 400 ℃, the temperature increasing rate is 10 ℃ per minute, and the tube furnace is naturally cooled after the temperature is continuously increased to 400 ℃ for 10 minutes;
and S7, soaking the material obtained in the step S6 in alcohol for 1 hour in an argon atmosphere, performing centrifugal separation, and drying at 100 ℃ for 12 hours to obtain the carbon nanotube-encapsulated lithium sulfide electrode material.
2. The method for producing a lithium sulfide electrode by a carbon nanotube packaging means according to claim 1, wherein in step S1, the metal lithium and the carbon nanotubes in a mass ratio of 8:1 are heated in a tube furnace at 180 degrees centigrade for 5 hours, and the vacuum degree in the tube furnace is 1 x 10 -4 Handkerchief.
3. The method for preparing a lithium sulfide electrode based on a carbon nanotube packaging means according to claim 1, wherein in step S3, elemental sulfur and the metal lithium/carbon nanotube mixed material obtained in S2 are placed in a quartz tube of a tube furnace, respectively, and the mass ratio of elemental sulfur to the metal lithium/carbon nanotube mixed material obtained in S2 is 20:1.
4. The method for producing a lithium sulfide electrode based on a carbon nanotube encapsulation means according to claim 1, wherein in step S4, the gas flow rate is 10 ml/min.
5. The method for producing a lithium sulfide electrode based on a carbon nanotube packaging means according to claim 1, wherein in step S5, the tube furnace is started to heat to 200 degrees celsius at a heating rate of 2 degrees celsius/minute for 2 hours at 200 degrees celsius.
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