CN112176772A - Preparation method of lithium-philic carbon nanotube paper and preparation method of composite metal lithium cathode - Google Patents
Preparation method of lithium-philic carbon nanotube paper and preparation method of composite metal lithium cathode Download PDFInfo
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- CN112176772A CN112176772A CN202011023113.5A CN202011023113A CN112176772A CN 112176772 A CN112176772 A CN 112176772A CN 202011023113 A CN202011023113 A CN 202011023113A CN 112176772 A CN112176772 A CN 112176772A
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- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 67
- 229910052744 lithium Inorganic materials 0.000 title claims abstract description 66
- 239000002041 carbon nanotube Substances 0.000 title claims abstract description 54
- 229910021393 carbon nanotube Inorganic materials 0.000 title claims abstract description 54
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 title claims abstract description 43
- 238000002360 preparation method Methods 0.000 title claims abstract description 13
- 239000002131 composite material Substances 0.000 title claims description 15
- 229910052751 metal Inorganic materials 0.000 title claims description 12
- 239000002184 metal Substances 0.000 title claims description 12
- 239000002086 nanomaterial Substances 0.000 claims abstract description 14
- 238000000034 method Methods 0.000 claims abstract description 11
- 239000011261 inert gas Substances 0.000 claims abstract description 8
- 239000000843 powder Substances 0.000 claims abstract description 6
- 230000008569 process Effects 0.000 claims abstract description 4
- 238000004519 manufacturing process Methods 0.000 claims abstract description 3
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 claims description 6
- 238000010438 heat treatment Methods 0.000 claims description 5
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 claims description 3
- 239000000463 material Substances 0.000 claims description 3
- 239000011787 zinc oxide Substances 0.000 claims description 3
- QPLDLSVMHZLSFG-UHFFFAOYSA-N Copper oxide Chemical compound [Cu]=O QPLDLSVMHZLSFG-UHFFFAOYSA-N 0.000 claims description 2
- 239000005751 Copper oxide Substances 0.000 claims description 2
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims description 2
- 229910000431 copper oxide Inorganic materials 0.000 claims description 2
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 claims description 2
- 229910052737 gold Inorganic materials 0.000 claims description 2
- 239000010931 gold Substances 0.000 claims description 2
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 claims description 2
- 229910052710 silicon Inorganic materials 0.000 claims description 2
- 239000010703 silicon Substances 0.000 claims description 2
- 229910052709 silver Inorganic materials 0.000 claims description 2
- 239000004332 silver Substances 0.000 claims description 2
- 239000007787 solid Substances 0.000 claims description 2
- 239000000956 alloy Substances 0.000 claims 1
- 229910045601 alloy Inorganic materials 0.000 claims 1
- 238000000151 deposition Methods 0.000 abstract description 12
- 230000008021 deposition Effects 0.000 abstract description 12
- 239000012528 membrane Substances 0.000 abstract description 8
- 229920002678 cellulose Polymers 0.000 abstract description 7
- 239000001913 cellulose Substances 0.000 abstract description 7
- 210000001787 dendrite Anatomy 0.000 abstract description 5
- 239000000126 substance Substances 0.000 abstract description 5
- 230000006911 nucleation Effects 0.000 abstract description 4
- 238000010899 nucleation Methods 0.000 abstract description 4
- 230000004888 barrier function Effects 0.000 abstract description 3
- 238000001465 metallisation Methods 0.000 abstract description 3
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 abstract description 3
- 230000002401 inhibitory effect Effects 0.000 abstract description 2
- 239000007784 solid electrolyte Substances 0.000 abstract description 2
- 239000002134 carbon nanofiber Substances 0.000 abstract 1
- 239000006185 dispersion Substances 0.000 abstract 1
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 18
- 229910052799 carbon Inorganic materials 0.000 description 12
- 239000003792 electrolyte Substances 0.000 description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 6
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 5
- 229910001416 lithium ion Inorganic materials 0.000 description 5
- 238000002156 mixing Methods 0.000 description 5
- 238000005096 rolling process Methods 0.000 description 5
- OIFBSDVPJOWBCH-UHFFFAOYSA-N Diethyl carbonate Chemical compound CCOC(=O)OCC OIFBSDVPJOWBCH-UHFFFAOYSA-N 0.000 description 4
- KMTRUDSVKNLOMY-UHFFFAOYSA-N Ethylene carbonate Chemical compound O=C1OCCO1 KMTRUDSVKNLOMY-UHFFFAOYSA-N 0.000 description 4
- -1 lithium hexafluorophosphate Chemical compound 0.000 description 4
- 230000014759 maintenance of location Effects 0.000 description 4
- 230000008018 melting Effects 0.000 description 4
- 238000002844 melting Methods 0.000 description 4
- 239000008213 purified water Substances 0.000 description 4
- 239000002002 slurry Substances 0.000 description 4
- 238000003756 stirring Methods 0.000 description 4
- 229920000049 Carbon (fiber) Polymers 0.000 description 3
- 239000010405 anode material Substances 0.000 description 3
- 239000012300 argon atmosphere Substances 0.000 description 3
- 239000004917 carbon fiber Substances 0.000 description 3
- 238000005245 sintering Methods 0.000 description 3
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- 229920001046 Nanocellulose Polymers 0.000 description 2
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 2
- 230000001351 cycling effect Effects 0.000 description 2
- 239000001257 hydrogen Substances 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- GELKBWJHTRAYNV-UHFFFAOYSA-K lithium iron phosphate Chemical compound [Li+].[Fe+2].[O-]P([O-])([O-])=O GELKBWJHTRAYNV-UHFFFAOYSA-K 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 239000005543 nano-size silicon particle Substances 0.000 description 2
- 229910021392 nanocarbon Inorganic materials 0.000 description 2
- 238000005086 pumping Methods 0.000 description 2
- 238000003828 vacuum filtration Methods 0.000 description 2
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- 239000002042 Silver nanowire Substances 0.000 description 1
- KFDQGLPGKXUTMZ-UHFFFAOYSA-N [Mn].[Co].[Ni] Chemical compound [Mn].[Co].[Ni] KFDQGLPGKXUTMZ-UHFFFAOYSA-N 0.000 description 1
- 238000005275 alloying Methods 0.000 description 1
- 238000000137 annealing Methods 0.000 description 1
- 238000013459 approach Methods 0.000 description 1
- 229910052786 argon Inorganic materials 0.000 description 1
- 238000000231 atomic layer deposition Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000010406 cathode material Substances 0.000 description 1
- 210000004027 cell Anatomy 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 238000002485 combustion reaction Methods 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000004146 energy storage Methods 0.000 description 1
- 238000004880 explosion Methods 0.000 description 1
- 239000004744 fabric Substances 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 229910021389 graphene Inorganic materials 0.000 description 1
- 239000002905 metal composite material Substances 0.000 description 1
- 239000006262 metallic foam Substances 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 238000002715 modification method Methods 0.000 description 1
- 239000002105 nanoparticle Substances 0.000 description 1
- 239000002077 nanosphere Substances 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 238000004321 preservation Methods 0.000 description 1
- 230000002035 prolonged effect Effects 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 238000007086 side reaction Methods 0.000 description 1
Classifications
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- D—TEXTILES; PAPER
- D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
- D21H—PULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
- D21H27/00—Special paper not otherwise provided for, e.g. made by multi-step processes
-
- 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
-
- D—TEXTILES; PAPER
- D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
- D21H—PULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
- D21H13/00—Pulp or paper, comprising synthetic cellulose or non-cellulose fibres or web-forming material
- D21H13/36—Inorganic fibres or flakes
- D21H13/46—Non-siliceous fibres, e.g. from metal oxides
- D21H13/50—Carbon fibres
-
- D—TEXTILES; PAPER
- D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
- D21J—FIBREBOARD; MANUFACTURE OF ARTICLES FROM CELLULOSIC FIBROUS SUSPENSIONS OR FROM PAPIER-MACHE
- D21J5/00—Manufacture of hollow articles by transferring sheets, produced from fibres suspensions or papier-mâché by suction on wire-net moulds, to couch-moulds
-
- 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
- H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
-
- 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
- H01M4/1395—Processes of manufacture of electrodes based on metals, Si or alloys
-
- 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
- H01M4/64—Carriers or collectors
- H01M4/66—Selection of materials
- H01M4/663—Selection of materials containing carbon or carbonaceous materials as conductive part, e.g. graphite, carbon fibres
-
- 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
- H01M4/64—Carriers or collectors
- H01M4/66—Selection of materials
- H01M4/665—Composites
- H01M4/666—Composites in the form of mixed materials
-
- 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
- H01M2004/027—Negative 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 provides a preparation method of lithium-philic carbon nanotube paper, and specifically, carbon nanotube powder and lithium-philic nano material powder are uniformly mixed, and a wet papermaking process is adopted to manufacture a film. In order to improve the membrane strength under low thickness, nano-cellulose can be added, then the membrane is heated in an inert gas environment to enable the lithium-philic nano-material and the carbon nano-tube to be tightly combined to prepare the membrane, and the nano-cellulose is carbonized to form the carbon nano-fiber with the lithium-philic surface. According to the lithium-philic carbon nanotube paper prepared by the method, the lithium-philic nano material is in better chemical contact with the carbon nanotube, the lithium-philic nano material in the carbon nanotube is wide in dispersion and stable in deposition; the lithium metal negative electrode prepared by the invention has the functions of inhibiting the growth of lithium dendrites and modifying the components of a solid electrolyte interface film, and also has the functions of providing space for lithium metal deposition and reducing the nucleation barrier of lithium deposition, thereby obviously improving the cycle stability and the cycle life of the lithium metal negative electrode.
Description
Technical Field
The invention belongs to the technical field of secondary batteries, and particularly relates to a preparation method of lithium-philic carbon nanotube paper and a preparation method of a composite metal lithium cathode.
Background
Since the 21 st century, mobile electronic information products have been developed rapidly, the capacity requirement of energy storage batteries is becoming severer, and the energy density of traditional lithium ion batteries approaches the upper limit and is difficult to meet the requirements of 3C products. Metallic lithium negative electrodes have gained much attention due to their ultra-high specific capacity of 3860mAh/g and lowest reduction potential of-3.04V. However, the lithium metal negative electrode has been difficult to be put into practical use so far, mainly due to the problems of dendrite growth and low coulombic efficiency during battery cycling: on one hand, the lithium ion deposition is greatly influenced by the current density, the larger the current is, the faster the lithium ion deposition is, the more the dendritic crystal growth is facilitated, the battery is internally short-circuited when the battery is pierced by the lithium ion deposition, and the danger of battery combustion and explosion exists; on the other hand, lithium metal has strong chemical activity and can continuously generate side reaction with electrolyte, thereby causing low coulombic efficiency. Many groups have proposed solutions to this problem, including alloying of metallic lithium with other metals, atomic layer deposition, electrolyte modification, etc., but these modification methods fail to solve the problems of long cycling under high current and uniform deposition of lithium ions.
Due to the unique surface chemical characteristics and the interconnected structure of the three-dimensional (3D) framework, the volume expansion of the metal lithium negative electrode can be well limited by limiting the deposition position of the metal lithium to inhibit the growth of dendrites. Therefore, a composite lithium metal anode having a 3D skeleton is considered as an effective way to solve the problems of volume change of lithium metal and lithium dendrite. In recent years, great progress is made in the design of a metal lithium 3D framework, a copper mesh, foamed nickel, carbon cloth or carbon paper is used as a three-dimensional framework, and the nucleation and uniform deposition of lithium can be adjusted by designing the 3D framework with lithium-philic sites, such as hollow carbon nanospheres, MXene, N-doped graphene and graphene with a rich edge structure. However, these three-dimensional frameworks are typically over 100um thick or have a grammage of greater than 2mg/cm 2. Therefore, even if the lithium metal composite anode is used, the energy density of the cell is not significantly increased. In addition, metal foam or carbon fiber are hard and easily pierce through the separator to cause a short circuit of the battery, which brings potential safety risk.
Disclosure of Invention
The invention aims to overcome the defects of the prior art and provides a preparation method of lithium-philic carbon nanotube paper and a preparation method of a composite metal lithium cathode.
The invention is realized by the following steps:
the invention provides a preparation method of lithium-philic carbon nanotube paper, which comprises the steps of uniformly mixing carbon nanotube powder and lithium-philic nano material powder, adopting a wet papermaking process to manufacture a film, and heating in an inert gas environment to enable the lithium-philic nano material and the carbon nanotube to be tightly combined.
The carbon paper is light, thin and high in porosity by adopting a wet papermaking process, and simultaneously, the high-temperature annealing is carried out in an inert gas environment, so that chemical bonds are formed between the lithium-philic nano material and the carbon nano tubes, and the deposition of lithium metal along the length direction of the carbon tubes and holes in the paper is facilitated. In order to prepare the carbon nanotube paper which has the gram weight of less than 1mg/cm2, can be conveniently peeled from the filter membrane and has the thickness of less than 30 mu m after rolling, a small amount of nano cellulose can be added, and the strength of the paper is enhanced by utilizing the strong hydrogen bond of the nano cellulose. Under inert gas environment, the nano-cellulose can be carbonized into conductive nano-carbon fibers with lithium-philic surfaces, so that the affinity of the carbon paper for lithium is further enhanced.
Further, the lithium-philic nanomaterial includes any material that can be alloyed with lithium, such as aluminum oxide, zinc oxide, copper oxide, silver, silicon, gold, and the like.
Further, the heating temperature of the inert gas environment is 300-1200 ℃.
The invention also provides the lithium-philic carbon nanotube paper prepared by the method.
The invention also provides a preparation method of the composite metal lithium negative electrode, which comprises the steps of heating solid lithium to a molten state, and then injecting lithium in a high-temperature molten state into the lithium-philic carbon nanotube paper.
A lithium metal secondary battery comprises the composite metal lithium negative electrode inside.
The invention has the following beneficial effects:
1. the lithium-philic carbon nanotube paper prepared by the method has better chemical contact between the lithium-philic nano material and the carbon nanotube, the lithium-philic nano material in the carbon nanotube paper is well dispersed, and the lithium deposition is stable.
2. The lithium metal negative electrode prepared by the invention has the functions of inhibiting the growth of lithium dendrites and modifying the components of a solid electrolyte interface film, and also has the functions of providing space for lithium metal deposition and reducing the nucleation barrier of lithium deposition, thereby obviously improving the cycle stability and the cycle life of the lithium metal negative electrode.
3. In order to prepare the thin carbon nanotube paper with low gram weight, a small amount of nano-cellulose can be added, and the strength of the paper is enhanced by utilizing the strong hydrogen bond of the nano-cellulose; under inert gas environment, the nano-cellulose can be carbonized into conductive nano-carbon fibers with lithium-philic surfaces, so that the affinity of the carbon paper for lithium is further enhanced.
4. Because the carbon paper prepared by the invention has light weight and thin thickness, the energy density of the battery adopting the metal lithium composite cathode can be greatly improved.
Detailed Description
The technical solutions in the embodiments of the present invention will be clearly and completely described below with reference to the embodiments of the present invention, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all of the embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
Example 1
Ultrasonically dispersing the carbon nano tube in isopropanol, wherein the volume ratio of the mass of the carbon nano tube to the isopropanol used for dispersing the carbon nano tube is 0.5mg/ml, the ultrasonic power is 300W, the time is 30min, and the dispersed carbon nano tube solution is prepared by mixing the following components in parts by mass according to the mass ratio of 4: 1 adding zinc oxide nano particles; then stirring at high speed to form uniform slurry, and removing isopropanol by vacuum filtration to form paper. The formed carbon paper was baked in a 120 ° oven to remove residual isopropyl alcohol. The gram weight of the carbon nano tube paper is 2mg/cm2. The dried self-supporting carbon nano tube paper can be conveniently stripped and transferred from the filtering membrane, the thickness of the paper is 50 microns in a rolling mode, the paper is sintered at 300 ℃ in an argon environment, and the heat preservation time is 4 hours.
The temperature of melting lithium and pouring lithium is 200 ℃, the composite lithium metal cathode is matched with a nickel-cobalt-manganese ternary cathode material to form a lithium battery, and the electrolyte comprises 1mol/L lithium hexafluorophosphate, ethylene carbonate and diethyl carbonate solution. Under the multiplying power of 0.5C, the battery can stably circulate for 130 weeks, and the capacity retention rate is 85%.
Example 2
Ultrasonically dispersing the carbon nano tube in isopropanol, wherein the volume ratio of the mass of the carbon nano tube to the isopropanol used for dispersing the carbon nano tube is 1mg/ml, the ultrasonic power is 200W, the time is 30min, and the dispersed carbon nano tube solution is prepared by mixing the following components in parts by mass according to the mass ratio of 9: 1 adding silver nanowires; then stirring at high speed to form uniform slurry, and removing isopropanol by vacuum filtration to form paper. The formed carbon paper was baked in a 120 ° oven to remove residual isopropyl alcohol. The gram weight of the carbon nano tube paper is 1.5mg/cm2. The dried self-supporting carbon nanotube paper can be conveniently peeled and transferred from the filter membrane and can reach the thickness of 40 microns in a rolling mode. Sintering at 600 ℃ in an argon atmosphere, and keeping the temperature for 4 hours.
The temperature of melting lithium and pouring lithium is 200 ℃, the composite lithium metal cathode is matched with a lithium iron phosphate anode material to form a lithium battery, and the electrolyte comprises 1mol/L lithium hexafluorophosphate, ethylene carbonate and diethyl carbonate solution. Under the multiplying power of 0.5C, the battery can stably circulate for 100 weeks, and the capacity retention rate is 90%.
Example 3
Ultrasonically dispersing the carbon nano tube in purified water, wherein the volume ratio of the mass of the carbon nano tube to the purified water for dispersing the carbon nano tube is 0.2mg/ml, the ultrasonic power is 500W, the time is 10min, and the dispersed carbon nano tube solution is prepared by mixing the following components in percentage by mass 1: 4 adding silicon nano particles; then stirring at high speed to form uniform slurry, and vacuum-pumping to remove water to obtain paper. The formed carbon paper was baked in a 120 ° oven to remove residual moisture. The gram weight of the carbon nano tube paper is 1.2mg/cm2. The dried self-supporting carbon nanotube paper can be conveniently peeled and transferred from the filter membrane and can reach the thickness of 30 microns in a rolling mode. Sintering at 900 ℃ in an argon atmosphere, and keeping the temperature for 4 hours.
The temperature of melting lithium and pouring lithium is 200 ℃, the composite lithium metal cathode is matched with a lithium iron phosphate anode material to form a lithium battery, and the electrolyte comprises 1mol/L lithium hexafluorophosphate, ethylene carbonate and diethyl carbonate solution. Under the multiplying power of 0.5C, the battery can stably circulate for 500 weeks, and the capacity retention rate is 75%.
Example 4
Ultrasonically dispersing the carbon nano tube in purified water, wherein the volume ratio of the mass of the carbon nano tube to the purified water for dispersing the carbon nano tube is 0.2mg/ml, the ultrasonic power is 500W, the time is 10min, and the dispersed carbon nano tube solution is prepared by mixing the following components in percentage by mass 1: 1: 8 adding nano-cellulose and silicon nano-particles; then stirring at high speed to form uniform slurry, and vacuum-pumping to remove water to obtain paper. The formed carbon paper was baked in a 120 ° oven to remove residual moisture. The gram weight of the carbon nano tube paper is 1mg/cm2. The dried self-supporting carbon nanotube paper can be conveniently peeled and transferred from the filter membrane and can reach the thickness of 20 microns in a rolling mode. Sintering at 1200 ℃ in an argon atmosphere, and keeping the temperature for 4 hours.
The temperature of melting lithium and pouring lithium is 200 ℃, the composite lithium metal cathode is matched with a lithium cobaltate anode material to form a lithium battery, and the electrolyte comprises 1mol/L lithium hexafluorophosphate, ethylene carbonate and diethyl carbonate solution. Under the multiplying power of 0.5C, the battery can stably circulate for 300 weeks, and the capacity retention rate is 80%.
The lithium-philic material in the lithium-philic carbon nanotube paper prepared by the method is well dispersed in the carbon nanotube, is light, thin and high in strength, and the composite lithium metal negative electrode is prepared after molten lithium is poured, so that space is provided for lithium metal deposition, a nucleation barrier of the lithium deposition is reduced, the cycle stability of the lithium metal negative electrode is obviously improved, and the cycle life of the lithium metal negative electrode is obviously prolonged.
The above description is only for the purpose of illustrating the preferred embodiments of the present invention and is not to be construed as limiting the invention, and any modifications, equivalents, improvements and the like that fall within the spirit and principle of the present invention are intended to be included therein.
Claims (6)
1. A preparation method of lithium-philic carbon nanotube paper is characterized by comprising the following steps: the carbon nano-tube powder and the lithium-philic nano-material powder are uniformly mixed, a wet papermaking process is adopted to manufacture a film, and then the film is heated in an inert gas environment to enable the lithium-philic nano-material and the carbon nano-tube to be tightly combined to prepare the lithium-philic nano-material.
2. The method for preparing the lithium-philic carbon nanotube paper as set forth in claim 1, wherein: the heating temperature of the inert gas environment is 300-1200 ℃.
3. The method for preparing the lithium-philic carbon nanotube paper as set forth in claim 1, wherein: the lithium-philic nano material comprises any material which can perform alloy reaction with lithium, such as aluminum oxide, zinc oxide, copper oxide, silver, silicon, gold and the like.
4. A lithium-philic carbon nanotube paper prepared by the method of any one of claims 1 to 3.
5. A preparation method of a composite metal lithium cathode is characterized by comprising the following steps: heating solid lithium to a molten state, and then injecting the lithium in the high-temperature molten state into the lithium-philic carbon nanotube paper as set forth in claim 4.
6. A lithium metal secondary battery, characterized by: the composite lithium metal negative electrode according to claim 5 is contained in the interior thereof.
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| CN202011023113.5A CN112176772A (en) | 2020-09-25 | 2020-09-25 | Preparation method of lithium-philic carbon nanotube paper and preparation method of composite metal lithium cathode |
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN114203963A (en) * | 2021-12-06 | 2022-03-18 | 上海大学 | Carbon material lithium metal composite negative electrode and preparation method and application thereof |
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