CN112176771A - 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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- CN112176771A CN112176771A CN202011023106.5A CN202011023106A CN112176771A CN 112176771 A CN112176771 A CN 112176771A CN 202011023106 A CN202011023106 A CN 202011023106A CN 112176771 A CN112176771 A CN 112176771A
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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
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- 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
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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
- 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
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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
- 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
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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
- H01M4/1395—Processes of manufacture of electrodes based on metals, Si or alloys
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/38—Selection of substances as active materials, active masses, active liquids of elements or alloys
- H01M4/381—Alkaline or alkaline earth metals elements
- H01M4/382—Lithium
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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
- H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
- H01M4/628—Inhibitors, e.g. gassing inhibitors, corrosion inhibitors
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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
- H01M4/64—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
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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
- H01M4/64—Carriers or collectors
- H01M4/66—Selection of materials
- H01M4/665—Composites
- H01M4/667—Composites in the form of layers, e.g. coatings
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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
- H01M2004/026—Electrodes composed of, or comprising, active material characterised by the polarity
- H01M2004/027—Negative electrodes
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- 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, which is characterized in that an atomic layer deposition method is adopted on the surface of a carbon nanotube to form a lithium-philic material coating layer, and then a wet papermaking process is adopted to manufacture the lithium-philic carbon nanotube paper. According to the invention, the atomic layer deposition technology is adopted to form the uniform and compact lithium-philic coating layer on the surface of the carbon nano tube, so that the nucleation barrier of lithium deposition is reduced, and lithium metal is uniformly deposited in the carbon paper, and the prepared composite lithium metal negative electrode has the effects of inhibiting the growth of lithium dendrites and modifying the components of a solid electrolyte interface film, and meanwhile, provides a space for lithium metal deposition, and obviously improves 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 is characterized in that an atomic layer deposition method is adopted on the surface of a carbon nanotube to form a lithium-philic material coating layer, and then a wet papermaking process is adopted for papermaking.
Further, the nano-cellulose is mixed and added in the wet papermaking process, and then sintering is carried out at 1200 ℃ in an inert gas environment.
For preparing a gram weight of less than 1mg/cm2The carbon nanotube paper can be conveniently peeled from the filter membrane and rolled to be less than 30 mu m in thickness, a small amount of nano cellulose can be added, and the strength of the paper is enhanced by utilizing the strong hydrogen bonds 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.
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.
Further, the surface of the composite metal lithium cathode is subjected to atomic layer deposition treatment or HF fluorination treatment to form a LiF protective layer.
The invention has the following beneficial effects:
1. according to the invention, an atomic layer deposition technology is adopted to form a uniform and compact lithium-philic coating layer on the surface of the carbon nano tube, so that the nucleation barrier of lithium deposition is reduced, and lithium metal is uniformly deposited in the carbon paper.
2. The prepared composite lithium metal negative electrode has the functions of inhibiting the growth of lithium dendrites and modifying the components of a solid electrolyte interface film, and also has the function of providing space for the deposition of lithium metal, thereby obviously improving the cycle stability and the cycle life of the lithium metal negative electrode.
3. The carbon paper prepared by adopting the carbon nanotube papermaking process is light and thin and has high porosity, and the energy density of the battery adopting the metal lithium composite cathode is greatly improved.
4. 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.
5. And a LiF coating layer is formed on the surface of the composite lithium metal negative electrode, so that a stable SEI protective layer is formed in the battery in the circulation process.
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
Placing the carbon nano tube in a reaction cavity of an atomic layer deposition instrument, vacuumizing and heating the reaction chamber to a set temperature, keeping the carbon nano tube at the set temperature for 20min, and keeping the air pressure in the reaction cavity to be lower than 0.01 atmosphere; and opening an air outlet valve, pulse scavenging air and sweeping for 30 s.
Closing the gas outlet valve, pulsing the lithium-philic material for 5s, and keeping for a period of 3 min; opening an air outlet valve, pulse scavenging air, and sweeping for 30 s; closing the gas outlet valve, vacuumizing and removing redundant reaction byproducts; repeating the steps until the coating thickness required by the carbon nano tube is reached; and taking out the carbon nano tube coated by the lithium-philic material, and papermaking by a wet papermaking process to obtain the carbon nano tube paper.
The prepared carbon nanotube paper is utilized to manufacture a composite lithium metal negative electrode: heating solid lithium to a molten state, injecting lithium in a high-temperature molten state into lithium-philic carbon nanotube paper, controlling the temperature of lithium melting and lithium filling to be 200 ℃, matching the composite lithium metal negative electrode with a nickel-cobalt-manganese ternary positive electrode material to form a lithium battery, wherein 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
Placing the carbon nano tube in a reaction cavity of an atomic layer deposition instrument, vacuumizing and heating the reaction chamber to a set temperature, keeping the carbon nano tube at the set temperature for 20min, and keeping the air pressure in the reaction cavity to be lower than 0.01 atmosphere; and opening an air outlet valve, pulse scavenging air and sweeping for 30 s.
Closing the gas outlet valve, pulsing the lithium-philic material for 5s, and keeping for a period of 3 min; opening an air outlet valve, pulse scavenging air, and sweeping for 30 s; closing the gas outlet valve, vacuumizing and removing redundant reaction byproducts; repeating the steps until the coating thickness required by the carbon nano tube is reached; and taking out the carbon nano tube coated by the lithium-philic material, mixing the carbon nano tube with the nano cellulose, using a wet papermaking process to manufacture carbon nano tube paper, sintering the carbon nano tube paper at 1200 ℃ in an argon environment, and preserving the heat for 4 hours.
The prepared carbon nanotube paper is utilized to manufacture a composite lithium metal negative electrode: heating solid lithium to a molten state, injecting lithium in a high-temperature molten state into lithium-philic carbon nanotube paper, controlling the temperature of lithium melting and lithium filling to be 200 ℃, matching the composite lithium metal negative electrode with a lithium iron phosphate positive electrode material to form a lithium battery, wherein 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
Placing the carbon nano tube in a reaction cavity of an atomic layer deposition instrument, vacuumizing and heating the reaction chamber to a set temperature, keeping the carbon nano tube at the set temperature for 20min, and keeping the air pressure in the reaction cavity to be lower than 0.01 atmosphere; and opening an air outlet valve, pulse scavenging air and sweeping for 30 s.
Closing the gas outlet valve, pulsing the lithium-philic material for 5s, and keeping for a period of 3 min; opening an air outlet valve, pulse scavenging air, and sweeping for 30 s; closing the gas outlet valve, vacuumizing and removing redundant reaction byproducts; repeating the steps until the coating thickness required by the carbon nano tube is reached; and taking out the carbon nano tube coated by the lithium-philic material, and papermaking by a wet papermaking process to obtain the carbon nano tube paper.
The prepared carbon nanotube paper is utilized to manufacture a composite lithium metal negative electrode: heating solid lithium to a molten state, injecting lithium in a high-temperature molten state into lithium-philic carbon nanotube paper, controlling the temperature of lithium melting and lithium filling to be 200 ℃, matching the composite lithium metal negative electrode with a lithium iron phosphate positive electrode material to form a lithium battery, wherein 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
Placing the carbon nano tube in a reaction cavity of an atomic layer deposition instrument, vacuumizing and heating the reaction chamber to a set temperature, keeping the carbon nano tube at the set temperature for 20min, and keeping the air pressure in the reaction cavity to be lower than 0.01 atmosphere; and opening an air outlet valve, pulse scavenging air and sweeping for 30 s.
Closing the gas outlet valve, pulsing the lithium-philic material for 5s, and keeping for a period of 3 min; opening an air outlet valve, pulse scavenging air, and sweeping for 30 s; closing the gas outlet valve, vacuumizing and removing redundant reaction byproducts; repeating the steps until the coating thickness required by the carbon nano tube is reached; and taking out the carbon nano tube coated by the lithium-philic material, mixing the carbon nano tube with the nano cellulose, using a wet papermaking process to manufacture carbon nano tube paper, sintering the carbon nano tube paper at 1200 ℃ in an argon environment, and preserving the heat for 4 hours.
The prepared carbon nanotube paper is utilized to manufacture a composite lithium metal negative electrode: heating solid lithium to a molten state, injecting the lithium in the high-temperature molten state into lithium-philic carbon nanotube paper, controlling the temperature of the molten lithium and the temperature of the injected lithium to be 200 ℃, matching the composite lithium metal negative electrode with a lithium cobaltate positive electrode material to form a lithium battery, wherein 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%.
In the embodiment, in order to better cycle the lithium metal secondary battery, the surface of the composite lithium metal negative electrode is subjected to atomic layer deposition treatment or HF fluorination treatment to form a LiF protective layer, so that a stable SEI protective layer is formed in the cycle process, and the service life of the lithium metal secondary battery is further prolonged.
The carbon nano tube papermaking process is adopted, the prepared carbon paper is light and thin and has high porosity, the prepared composite lithium metal negative electrode has the effects of inhibiting the growth of lithium dendrite and modifying components of a solid electrolyte interface film, and meanwhile, space is provided for lithium metal deposition, so that the cycle stability and the cycle life of the lithium metal negative electrode are obviously improved.
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 (7)
1. A preparation method of lithium-philic carbon nanotube paper is characterized in that a lithium-philic material coating layer is formed on the surface of a carbon nanotube by adopting an atomic layer deposition method, and then the carbon nanotube is made into paper by adopting a wet paper making process.
2. The method for preparing the lithium-philic carbon nanotube paper as set forth in claim 1, wherein: adding nano-cellulose in a wet papermaking process in a mixing manner, and then sintering at 1200 ℃ in an inert gas environment.
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.
7. The lithium metal secondary battery of claim 6, wherein: and forming a LiF protective layer on the surface of the composite metal lithium cathode through atomic layer deposition treatment or HF fluorination treatment.
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Cited By (6)
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| CN113578222A (en) * | 2021-07-12 | 2021-11-02 | 浙江大学 | Nanocomposite synthesis device based on instantaneous high-temperature Joule heating method, preparation method and application |
| CN113823795A (en) * | 2021-08-25 | 2021-12-21 | 常州大学 | Preparation method and application of composite electrode material for inhibiting growth of lithium dendrites |
| CN114171799A (en) * | 2021-11-19 | 2022-03-11 | 哈尔滨工业大学 | Method for improving wettability of lithium on surface of solid electrolyte and all-solid-state battery |
| CN114256462A (en) * | 2021-11-24 | 2022-03-29 | 郑州大学 | Preparation method of lithium battery negative electrode material |
| CN114361412A (en) * | 2021-12-16 | 2022-04-15 | 江苏大学 | Multi-walled carbon nanotube negative electrode material and preparation method and application thereof |
| CN115832217A (en) * | 2022-11-07 | 2023-03-21 | 柔电（武汉）科技有限公司 | Metal lithium composite negative electrode for secondary battery and preparation method thereof |
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