CN115467159B - In-situ etching nitrogen-doped modified carbon cloth and preparation method and application thereof - Google Patents

In-situ etching nitrogen-doped modified carbon cloth and preparation method and application thereof Download PDF

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CN115467159B
CN115467159B CN202211084240.5A CN202211084240A CN115467159B CN 115467159 B CN115467159 B CN 115467159B CN 202211084240 A CN202211084240 A CN 202211084240A CN 115467159 B CN115467159 B CN 115467159B
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carbon cloth
nitrogen
modified carbon
situ
drying
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CN115467159A (en
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卢文
成方
杨晓萍
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Kunming Yunda New Energy Co ltd
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    • D06L1/00—Dry-cleaning or washing fibres, filaments, threads, yarns, fabrics, feathers or made-up fibrous goods
    • D06L1/02—Dry-cleaning or washing fibres, filaments, threads, yarns, fabrics, feathers or made-up fibrous goods using organic solvents
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    • D06L1/00—Dry-cleaning or washing fibres, filaments, threads, yarns, fabrics, feathers or made-up fibrous goods
    • D06L1/12—Dry-cleaning or washing fibres, filaments, threads, yarns, fabrics, feathers or made-up fibrous goods using aqueous solvents
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    • D06M11/58—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising with nitrogen or compounds thereof, e.g. with nitrides
    • D06M11/64—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising with nitrogen or compounds thereof, e.g. with nitrides with nitrogen oxides; with oxyacids of nitrogen or their salts
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    • D06M13/322—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment with compounds containing nitrogen
    • D06M13/35—Heterocyclic compounds
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    • D06M13/402—Amides imides, sulfamic acids
    • D06M13/432—Urea, thiourea or derivatives thereof, e.g. biurets; Urea-inclusion compounds; Dicyanamides; Carbodiimides; Guanidines, e.g. dicyandiamides
    • 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
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    • D06M2101/40—Fibres of carbon
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    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/10—Energy storage using batteries

Abstract

The invention relates to in-situ etching nitrogen-doped modified carbon cloth and a preparation method and application thereof, and belongs to the technical field of new materials. The preparation method comprises the steps of carbon cloth pretreatment, carbon cloth acid treatment, in-situ etching nitrogen doping, cleaning and drying. According to the invention, in-situ etching and nitrogen doping are carried out on the surface of the carbon fiber by a one-step hydrothermal synthesis method, and simultaneously, the etching pore-forming and nitrogen element doping modification on the surface of the carbon fiber are realized. The modified carbon cloth is used as the negative electrode of a metal battery system, can obviously improve the electrochemical performance of the battery, can improve the coulomb efficiency, the cycle life, the safety and the like, and is easy to popularize and apply.

Description

In-situ etching nitrogen-doped modified carbon cloth and preparation method and application thereof
Technical Field
The invention belongs to the technical field of new materials, and particularly relates to in-situ etching nitrogen-doped modified carbon cloth, and a preparation method and application thereof.
Background
In recent years, with the rapid development of economy and society, the requirements of the fields of portable electronic equipment, electric automobiles, large-scale energy storage and the like on the performance (such as endurance time, service life, safety and the like) of energy storage devices are higher and higher. While traditional metal ion batteries (e.g., lithium ion batteries, sodium ion batteries, etc.) are limited by the lower theoretical capacity of the graphite negative electrode (372 mAh g -1 ) Making it increasingly difficult to meet market demand for high performance energy storage devices. A metal battery (such as lithium, sodium, potassium, magnesium, zinc and aluminum metal battery) system represented by a lithium metal battery adopts a metal negative electrode with ultra-high theoretical capacity (such as lithium and sodium metal negative electrodes with theoretical capacities of 3860 and 1166mAh g respectively) -1 ) And the graphite cathode is replaced, so that the energy density of the metal battery system can be remarkably improved, and the demand of the market on high energy density is met. However, the lithium and sodium metal cathodes are too active in chemical nature and have low surface energy and high diffusion barrier, so that irregular metal dendrites are easily formed in the cycling process, side reactions with the electrolyte are further aggravated, and volume expansion of the electrodes and polarization of the battery are increased. On one hand, the generated metal dendrite is easy to fall off to form dead lithium, dead sodium and the like, so that the coulomb efficiency of the battery is reduced and the capacity is fastAnd (5) fast decay. On the other hand, the formed metal dendrites may pierce through the separator to cause internal short circuit of the battery, and even fire or explosion safety accidents occur. These problems severely limit the practical application of metal battery systems.
In order to solve the problems of the metal battery, the most commonly used technical means at present mainly comprise methods of optimizing and modifying electrolyte, designing an artificial solid electrolyte interface film (SEI), using solid electrolyte and the like, but the methods cannot avoid the use of an active metal cathode, and still have great potential safety hazards. Therefore, a metal-free negative electrode design is required for a metal battery system to avoid the use of active metals (such as lithium, sodium, potassium metals, etc.), thereby reducing the difficulty of the battery preparation process, lowering the cost and improving the safety of the metal battery. The non-negative metal battery constructed by using the copper foil current collector to replace the active metal negative electrode is the earliest proposed strategy, but the copper foil has low specific surface area and poor lithium-philicity, so that the electrochemical performance of the metal battery based on the copper foil current collector is poor. The modified 3D current collector (such as 3D foam copper (nickel) and the like) has large specific surface area, can effectively reduce the local current density on the surface of an electrode, inhibit the growth of metal dendrites, and the 3D space structure is also beneficial to relieving the volume change in the circulation process, but the density of the metal current collector material is greatly unfavorable for improving the energy density. For example, chinese patent application No. 201610259475.1 discloses a "metal lithium secondary battery, a negative electrode thereof and a porous copper current collector", which mainly uses a three-dimensional porous copper current collector as a substrate, and metal lithium is adsorbed on the surface and inside of a cavity, so that the specific surface area of the electrode can be increased, and the effective current density on the surface of the electrode can be reduced, thereby inhibiting the generation of lithium dendrites, but the performance still needs to be further improved. In addition, this method is costly and disadvantageous in terms of energy density due to the relatively high price and high density of copper.
Compared with a 3D metal current collector, the 3D carbon material has good conductivity, light weight and good structural stability, but has insufficient lithium affinity, and is modified by adopting methods such as vapor deposition, in-situ growth, nitrogen/phosphorus doping and the like. By constructing the high-conductivity lithium-philic carbon carrier with the 3D structure, the volume expansion of the metal battery in the circulation process can be effectively regulated, the growth of metal dendrites can be inhibited, and the overall electrochemical performance of the metal battery can be improved. For example, niu et al prepared Li-C composite cathodes for high energy lithium metal batteries using ammonia treated functional 3D mesoporous carbon fibers. The strong interaction between the functional defects and the metallic lithium facilitates uniform deposition of lithium and preferential nucleation of lithium in the pores or defects, significantly improving the coulombic efficiency and cycling stability of lithium metal batteries (nat. Nanotechnol.,2019, 14, 594-601). The method of growing nitrogen doped lithium-philic Co-MOF nano-sheets on the surface of commercial Carbon Cloth (CC) is proposed by Zhou et al, which effectively improves the lithium philicity and specific surface area of the CC and inhibits the growth of lithium dendrites in the circulation process (adv. Function. Mater 2020, 30, 1909159). The research results provide a thought for inhibiting the growth of metal dendrites and improving the performance of metal batteries, but the preparation methods have complex processes and are difficult to realize large-scale production and application.
Therefore, the 3D porous carbon anode carrier with low cost, high conductivity, high specific surface area, good structural stability and good lithium-philic characteristic is prepared by developing a preparation method with simple process and easy operation, so that the growth of metal dendrites is inhibited, the coulomb efficiency, the cycle life and the safety of the metal battery are improved, and the preparation method has very important significance for accelerating the practical application of the metal battery.
Disclosure of Invention
The invention aims to solve the defects of the prior art, and provides in-situ etching nitrogen-doped modified carbon cloth which is good in stability, light in weight, high in specific surface area and excellent in lithium-philic characteristic, and a preparation method and application thereof.
In order to achieve the above purpose, the technical scheme adopted by the invention is as follows:
the invention provides a method for carrying out in-situ etching and nitrogen doping on the surface of a carbon fiber by a one-step hydrothermal synthesis method, and simultaneously realizing etching pore-forming and nitrogen element doping modification on the surface of the carbon fiber. Specifically, the invention provides a method for simultaneously adding an etchant and a dopant into a reaction medium in a hydrothermal reaction process, and simultaneously carrying out in-situ etching and nitrogen doping on the surface of a carbon fiber by the etchant and the dopant under a high-temperature and high-pressure environment, wherein evenly-distributed etching grooves or concave holes and nitrogen elements are introduced into the surface of the carbon fiber, so that the specific surface area and the lithium-philicity of the carbon fiber are improved, the local current density of the surface of an electrode is reduced, the growth of metal dendrites is inhibited, and the comprehensive improvement of the coulomb efficiency, the cycle life and the safety is realized.
The invention also provides a method for using the in-situ etched nitrogen-doped modified carbon cloth as a negative electrode of a metal battery (including lithium, sodium, potassium, magnesium, zinc, aluminum metal batteries and the like) to remarkably improve the electrochemical performance (improve coulombic efficiency, cycle life, safety and the like).
Specifically:
the preparation method of the in-situ etching nitrogen-doped modified carbon cloth comprises the following steps:
step (1), pretreating carbon cloth: cleaning the carbon cloth in a room temperature environment to remove stains on the surface of the carbon cloth, and then drying;
step (2), carbon cloth acid treatment: soaking the carbon cloth pretreated in the step (1) in concentrated acid at the temperature of 30-80 ℃, standing for 30-300 min, washing and drying;
step (3), in-situ etching nitrogen doping: adding the carbon cloth subjected to the acid treatment in the step (2) into a reaction medium containing an etching agent and a doping agent, standing for 3-12 h at room temperature, and performing hydrothermal reaction at 80-200 ℃;
the using amount of the etchant is 0.1 to 10mol L -1 ；
The dosage of the doping agent is 0.1 to 10mol L -1 ；
Step (4), cleaning and drying: and (3) washing the carbon cloth subjected to the hydrothermal reaction in the step (3) to be neutral by water, and drying to obtain the in-situ etching nitrogen-doped modified carbon cloth.
Further, preferably, in the step (1), during cleaning, the carbon cloth is ultrasonically cleaned by adopting acetone, ethanol and deionized water respectively, wherein the cleaning time is 10-120 min each time; the drying temperature is 60 ℃ and the drying time is 12 hours.
Further, preferably, in step (2), the concentrated acid is concentrated sulfuric acid: the volume ratio of the concentrated nitric acid is 1:1 to 10: 1; the washing is to adopt deionized water to wash to neutrality; the drying temperature is 60 ℃ and the drying time is 12 hours.
Further, it is preferable that in the step (3), the hydrothermal reaction is performed in a hydrothermal reaction kettle; the hydrothermal reaction time is 6-48 h.
Further, preferably, in the step (3), the etchant is at least one of potassium hydroxide, sodium hydroxide, hydrogen peroxide, potassium permanganate, hydrofluoric acid, hydrochloric acid, nitric acid, and perchloric acid;
the doping agent is at least one of urea, ammonia water, ammonium fluoborate, ammonium phosphate, ammonium hydrogen phosphate, ammonium dihydrogen phosphate and melamine;
the reaction medium is at least one of deionized water, acetonitrile, ethylene glycol, N-dimethylacetamide, N-dimethylformamide, dichloromethane, chloroform and ethanol.
Wherein the acidic substance and the basic substance cannot be used as an etchant and/or a dopant at the same time, and the highly oxidizing substance and the basic substance cannot be used as an etchant and/or a dopant at the same time.
Further, preferably, in the step (4), deionized water is used for washing in the water washing process; the drying temperature is 60 ℃ and the drying time is 12 hours.
The invention also provides the in-situ etching nitrogen-doped modified carbon cloth prepared by the preparation method of the in-situ etching nitrogen-doped modified carbon cloth.
The invention also provides an in-situ etching nitrogen-doped modified carbon cloth, which comprises a three-dimensional continuous base carbon cloth woven by carbon fibers; etching grooves or concave holes uniformly distributed on the surface of the carbon fiber, and uniformly distributed doping nitrogen elements; the specific surface area of the modified carbon cloth is 5-100 m 2 g -1 The method comprises the steps of carrying out a first treatment on the surface of the The diameter of the carbon fiber is 3-10 mu m; and the aperture of the etched groove or concave hole is 0.1-5 mu m; the content of the doped nitrogen element is 1-10at%.
The invention further provides a metal battery, which contains the in-situ etched nitrogen-doped modified carbon cloth.
Further, it is preferable that the metal battery includes a case, a positive electrode, a negative electrode, and a separator mounted in the case; the diaphragm is arranged between the anode and the cathode; electrolyte is filled in the gaps between the positive electrode and the diaphragm and between the negative electrode and the diaphragm; the negative electrode adopts the in-situ etching nitrogen-doped modified carbon cloth as claimed in claims 1-8.
The carbon cloth adopted by the invention is commercial carbon cloth.
In order to solve the problems (such as low coulomb efficiency, large volume expansion, short cycle life, poor safety and the like) existing in the metal battery and overcome the defects of low energy density, complex preparation process, difficult mass production and the like caused by the adoption of a metal current collector anode with high density in the prior art, the invention provides an in-situ etching nitrogen-doped modified carbon cloth with small mass, good stability, high specific surface area and good lithium-philicity, and provides a preparation method for preparing the modified carbon cloth, which has the advantages of simple technological process, easily available raw materials and easy mass production.
Compared with the prior art, the invention has the following advantages:
1. the in-situ etching nitrogen-doped modified carbon cloth has the advantages of low cost, light weight, good conductivity, flexibility and structural stability, higher specific surface area, good lithium-philic property and the like.
2. The preparation method of the in-situ etching nitrogen-doped modified carbon cloth is completed in one step by a hydrothermal synthesis method, has good etching and doping effects, simple technological process, easily obtained raw materials, no additional post-treatment process and easy mass production.
3. When the in-situ etched nitrogen-doped modified carbon cloth is used as a negative electrode of a metal battery (including lithium, sodium, potassium, magnesium, zinc, aluminum metal batteries and the like), the local current density on the surface of the electrode can be effectively reduced, the bonding energy between a carbon cloth matrix and metal is enhanced, the uniform deposition of the metals such as lithium, sodium, potassium and the like on the surface of carbon cloth fiber is guided, the growth of metal dendrites such as lithium, sodium, potassium and the like is inhibited, the volume expansion in the circulation process is regulated and controlled, and the comprehensive improvement of electrochemical performance (coulomb efficiency, cycle life, safety and the like) is realized.
4. (1) the KNCC-Li half cell prepared by the invention is at 2mAh cm -2 Surface area of (2) and 2mA cm -2 Can realize stable circulation for 400 times, and the average coulomb efficiency reaches more than 99.8%; (2) KNCC anode prepared by the invention and high load (14 mg cm) -2 ) The capacity retention rate of the LFP positive electrode matching of the lithium ion battery is as high as 85.9% after 500 times of circulation under the current of 1C; (3) the KNCC replaces the metal lithium sheet as the negative electrode, so that the use of active metal lithium can be avoided, the difficulty of a battery manufacturing process can be reduced, the cost is reduced, and the safety of the battery can be improved.
Drawings
Fig. 1 is SEM images of comparative example 1, comparative example 2, comparative example 3 and example 1; wherein, (a) is comparative example 1, (b) is comparative example 2, (c) is comparative example 3, and (d) is example 1;
FIG. 2 is an XPS elemental analysis chart of comparative example 2, comparative example 3, example 1;
fig. 3 is a Raman test chart of comparative example 2, comparative example 3, example 1;
FIG. 4 is a BET test chart of comparative example 2, comparative example 3, example 1;
fig. 5 is a graph of capacity versus voltage for the Li-half batteries of comparative example 1, comparative example 2, comparative example 3, example 1 at different discharge capacities;
FIG. 6 is a graph showing that the Li-half batteries of comparative examples 1, 2, 3 and 1 had a current density of 2mA cm -2 Is a cyclic curve of (2); wherein (a) the discharge capacity is 1mAh cm -2 (b) discharge capacity of 2mAh cm -2 ；
FIG. 7 is a graph showing that the Li-half batteries of comparative examples 1, 2, 3 and 1 had a current density of 2mA cm -2 Discharge capacity of 2mAh cm -2 An EIS test curve after different cycle times is performed; wherein (a) is in OCP state and (b) is 50 cycles(c) is 100 cycles and (d) is 200 cycles;
FIG. 8 is a graph showing that the Li-half batteries of comparative examples 1, 2, 3 and 1 had a current density of 2mA cm -2 Discharge capacity of 2mAh cm -2 SEM images of different cathodes after 200 cycles down; wherein, (a) is comparative example 1, (b) is comparative example 2, (c) is comparative example 3, and (d) is example 1;
Fig. 9 is a cycle test curve of LFP-full cells of comparative example 4, comparative example 5, comparative example 6, example 4 at 1C current;
fig. 10 is an SEM image of different cathodes after the LFP-full cell of comparative example 4, comparative example 5, comparative example 6, example 4 was cycled 500 times at 1C current; wherein, (a) is comparative example 4, (b) is comparative example 5 (c) is comparative example 6, and (d) is example 4.
Detailed Description
The present invention will be described in further detail with reference to examples.
It will be appreciated by those skilled in the art that the following examples are illustrative of the present invention and should not be construed as limiting the scope of the invention. The specific techniques or conditions are not identified in the examples and are performed according to techniques or conditions described in the literature in this field or according to the product specifications. The materials or equipment used are conventional products available from commercial sources, not identified to the manufacturer.
According to the invention, the in-situ etching nitrogen-doped modified carbon cloth is prepared by adding an etchant and a doping agent into a reaction medium simultaneously in a hydrothermal reaction process by a one-step hydrothermal synthesis method. The in-situ etching nitrogen-doped modified carbon cloth comprises a three-dimensional continuous substrate carbon cloth woven by carbon fibers, etching grooves or concave holes uniformly distributed on the surfaces of the carbon fibers and uniformly distributed nitrogen-doped elements. The specific surface area of the modified carbon cloth is 5-100 m 2 g -1 The method comprises the steps of carrying out a first treatment on the surface of the The diameter of the carbon fiber is 3-10 mu m; the aperture of the etched groove or concave hole is 0.1-5 mu m; the content of the doped nitrogen element is 1-10at%.
The invention discloses a preparation method of in-situ etching nitrogen-doped modified carbon cloth, which comprises the following steps:
1. pretreatment of carbon cloth: respectively ultrasonically cleaning commercial carbon cloth in an environment of room temperature for 10-120 min through acetone, ethanol and deionized water to remove stains on the surface of the carbon cloth, and then drying at 60 ℃ for 12h;
2. acid treatment of carbon cloth: soaking the pretreated carbon cloth in concentrated sulfuric acid at the temperature of 30-80 ℃: the volume ratio of the concentrated nitric acid is 1:1 to 10:1, standing for 30-300 min, washing with deionized water to neutrality, and drying at 60 ℃ for 12h to enhance the hydrophilicity of the carbon cloth;
3. and (3) in-situ etching nitrogen doping: adding the carbon cloth subjected to acid treatment into a reaction medium containing an etching agent and a doping agent, standing for 3-12 hours at room temperature, transferring into a hydrothermal reaction kettle, controlling the temperature to be 80-200 ℃ and the reaction time to be 6-48 hours, so that the carbon cloth subjected to acid treatment fully reacts in the hydrothermal reaction kettle;
the etchant is potassium hydroxide (KOH), sodium hydroxide (NaOH), hydrogen peroxide (H) 2 O 2 ) Potassium permanganate (KMnO) 4 ) Hydrofluoric acid (HF), hydrochloric acid (HCl), nitric acid (HNO) 3 ) Perchloric acid (HClO) 4 ) At least one of (a) and (b); the using amount of the etchant is 0.1 to 10mol L -1 ；
The doping agent is Urea (Urea), ammonia water (NH) 3 H 2 O), ammonium fluoroborate (NH) 4 BF 4 ) Ammonium phosphate ((NH) 4 ) 3 PO 4 ) Ammonium hydrogen phosphate ((NH) 4 ) 2 HPO 4 ) Monoammonium phosphate (NH) 4 H 2 PO 4 ) At least one of Melamine (Melamine); the dosage of the doping agent is 0.1 to 10mol L -1 ；
The reaction medium is deionized water (H) 2 O), acetonitrile (Acetonitrile), ethylene glycol (Ethylene glycol), N-Dimethylacetamide (DMA), N-Dimethylformamide (DMF), dichloromethane (CH) 2 Cl 2 ) Chloroform (CHCl) 3 ) At least one of Ethanol (Ethanol).
4. And (5) cleaning and drying: washing the carbon cloth subjected to the hydrothermal reaction to be neutral by deionized water, and then carrying out vacuum drying at 60 ℃ for 12 hours to obtain a final product in-situ etching nitrogen-doped modified carbon cloth.
The in-situ etched nitrogen-doped modified carbon cloth is used as a negative electrode of the metal battery to prepare the metal battery and improve the electrochemical performance of the metal battery.
The metal battery comprises at least one of lithium, sodium, potassium, magnesium, zinc and aluminum metal batteries; the metal battery has a structure including a positive electrode, a negative electrode, a separator interposed between the positive electrode and the negative electrode, an electrolyte filled in the gaps of the positive electrode, the negative electrode, and the separator, and a case. The preparation method comprises the following specific steps:
1) Preparing a corresponding positive electrode according to the requirements of different metal battery systems on electrode plates;
2) The in-situ etched nitrogen-doped modified carbon cloth prepared by the preparation method is used as a negative electrode;
3) And under the inert gas atmosphere condition of controlling oxygen to be less than 1ppm and moisture to be less than 1ppm, packaging the anode, the cathode, the diaphragm and the electrolyte into a shell to obtain the metal battery.
The positive electrode is any one of corresponding positive electrodes of metal batteries (lithium, sodium, potassium, magnesium, zinc, aluminum metal batteries and the like). For example, lithium iron phosphate (LFP) positive electrodes for lithium metal batteries.
The negative electrode is the in-situ etched nitrogen-doped modified carbon cloth prepared by the method.
The membrane is at least one of a polypropylene porous membrane, a polyethylene porous membrane, a polypropylene/polyethylene composite porous membrane (namely a polypropylene and polyethylene composite porous membrane), a cellulose acetate porous membrane, a glass fiber porous membrane, ceramic, nylon and asbestos paper.
The electrolyte is any one of corresponding electrolytes of metal batteries (lithium, sodium, potassium, magnesium, zinc, aluminum metal batteries and the like). For example, 1mol L -1 Lithium bis (trifluoromethanesulfonyl) imide (LiTFSI) electrolyte (1, 3 dioxolane/1, 2-dimethoxyethane (DOL/DME) in a volume ratio of 1:1) +2wt.% lithium nitrate (LiNO) 3 ））。
The packaging mode of the metal battery is any one of button type, cylinder type, square type and special-shaped.
The packaging shell of the metal battery is any one of a steel shell, a plastic shell, an aluminum shell and an aluminum-plastic film.
The invention is further illustrated in the following figures and examples, which are not intended to be limiting in any way, and any alterations or modifications based on the teachings of the invention are within the scope of the invention.
Comparative example 1: current commercial copper foil (Cu) current collector negative electrode and physicochemical property thereof
1. The current commercial Cu current collector is taken as a negative electrode, and a Scanning Electron Microscope (SEM) is used for testing the surface morphology. In controlling oxygen<1ppm and moisture<Cu negative electrode, polypropylene/polyethylene composite porous film, lithium (Li) plate and 1mol L under inert gas atmosphere condition of 1ppm -1 Lithium bis (trifluoromethanesulfonyl) imide (LiTFSI) electrolyte (1, 3 dioxolane/1, 2-dimethoxyethane (DOL/DME) in a volume ratio of 1:1) +2wt.% lithium nitrate (LiNO) 3 ) Packaging into LIR2025 button Cu// Li half-cell. Electrochemical testing of the assembled half cell (voltage range of-0.5-1.0V; current density of 1.0-2.0 mA cm) -2 The method comprises the steps of carrying out a first treatment on the surface of the The discharge capacity is 1.0-2.0 mAh cm -2 The method comprises the steps of carrying out a first treatment on the surface of the The Electrochemical Impedance (EIS) frequency range is 10 mHz-100 kHz and the amplitude is 10 mV. And carrying out SEM morphology characterization on the Cu negative electrode after charge and discharge circulation.
2. Analysis of results: because the Cu negative electrode surface is smooth and flat (as in fig. 1 a), has a small specific surface area and poor lithium-philicity, the assembled Cu// Li half cell exhibits a large initial nucleation overpotential of 78.28mV (as in fig. 5 inset i) at the time of first discharge (Li deposition), resulting in non-uniform Li deposition and easy generation of lithium dendrites. At 2mA cm -2 Under the current density, the discharge capacity of the Cu// Li half-cell is 1mAh cm respectively -2 And 2mAh cm -2 All showed very poor cycling stability, low coulombic efficiency and rapid decay as cycling proceeds (see fig. 6). Due to the generation of large amounts of lithium dendrites and accumulation of "spent lithium" during cycling (as in FIG. 8 a), a Cu// Li half-cell resultsThe EIS impedance increases rapidly as the cycle proceeds (see fig. 7). The above reasons together result in extremely poor electrochemical performance of Cu// Li half cells with commercial Cu current collectors as negative electrodes.
Comparative example 2: current commercial Carbon Cloth (CC) negative electrode and physicochemical property thereof
1. The current commercial CC is respectively ultrasonically cleaned by acetone, ethanol and deionized water for 20min, then dried for 12h at 60 ℃, and then concentrated sulfuric acid is used for: the volume ratio of the concentrated nitric acid is 3:1 is acid treated at 50 ℃ for 240min, then washed to neutrality with deionized water and dried in vacuum at 60 ℃ for 12h to be used as a negative electrode, which is subjected to SEM morphology characterization, specific surface area (BET) test, X-ray spectroscopy (XPS) test and Raman (Raman) test. In controlling oxygen <1ppm and moisture<Under the inert gas atmosphere condition of 1ppm, CC negative electrode, polypropylene/polyethylene composite porous film, li sheet and 1mol L -1 LiTFSI electrolyte (solvent is DOL/DME+2wt.% LiNO in a volume ratio of 1:1) 3 ) And packaging into a LIR2025 button type CC// Li half battery. Electrochemical testing was performed on assembled half cells under the same conditions. And carrying out SEM morphology characterization on the CC cathode after charge and discharge circulation.
2. Analysis of results: unlike the low specific surface area of commercial Cu anodes, commercial CCs are three-dimensional continuous structure fabrics woven from large amounts of carbon fibers with relatively higher specific surface areas (-10.48 m) 2 g -1 ) (as in figure 4). The carbon fiber surface of the CC after acid treatment was smoother, with shallower streaks (fig. 1 b) distributed, and XPS detected only a very small N element distribution (0.29 at.%) (fig. 2), derived from nitric acid introduced during acid treatment. Raman test I D /I G A value of 1.09 indicates a high degree of surface order and few defects (see FIG. 3). Thanks to the higher specific surface area of CC than Cu, the local current density at the electrode surface is reduced, so that the initial nucleation overpotential of the CC// Li half-cell at the time of first discharge (Li deposition) is reduced to 5.94mV (fig. 5, inset ii), the generation of lithium dendrites can be reduced to some extent, thus exhibiting lower EIS resistance (fig. 7), higher coulombic efficiency and better cycling stability (fig. 6). But due to insufficient specific surface area of CC And the surface lacks a lithium-philic functional group, so that the uniform deposition of Li can not be continuously and effectively guided in a long-cycle process, and the CC// Li half-cell has a discharge capacity of 1mAh cm -2 And 2mAh cm -2 Only about 500 and 190 stable cycles, respectively, can be maintained, after which the cell is shorted due to the massive cumulative growth of lithium dendrites (fig. 8 b), with the EIS impedance increasing as the cycle proceeds (fig. 7).
Comparative example 3: nitrogen-doped modified carbon cloth (NCC) negative electrode and physicochemical property thereof
1. The current commercial CC is respectively ultrasonically cleaned by acetone, ethanol and deionized water for 20min, then dried for 12h at 60 ℃, and then concentrated sulfuric acid is used for: the volume ratio of the concentrated nitric acid is 3:1 is acid treated at 50 ℃ for 240min, then washed with deionized water to neutrality and dried at 60 ℃ for 12h. Adding acid-treated CC to a solution containing 4mol L -1 In the Urea aqueous solution, standing for 12h at room temperature, transferring into a reaction kettle, carrying out hydrothermal reaction for 24h at 180 ℃, naturally cooling to room temperature, washing to neutrality by deionized water, drying (vacuum drying at 60 ℃ for 12 h), preparing the nitrogen-doped modified carbon cloth (NCC) negative electrode, and carrying out SEM, BET, XPS, raman test. In controlling oxygen <1ppm and moisture<NCC negative electrode, polypropylene/polyethylene composite porous film, li sheet and 1mol L under inert gas atmosphere condition of 1ppm -1 LiTFSI electrolyte (solvent is DOL/DME+2wt.% LiNO in a volume ratio of 1:1) 3 ) And packaging into a LIR2025 button NCC// Li half battery. Electrochemical testing was performed on assembled half cells under the same conditions. SEM morphology characterization is carried out on the NCC cathode after charge and discharge circulation.
2. Analysis of results: compared with CC, the N-doped NCC anode has similar surface morphology features to CC, no obvious change (as shown in figure 1 c), and basically equivalent specific surface area (-10.81 m) 2 g -1 ) (as in fig. 4), but XPS detected a significantly increased N content (5.61 at.%) (as in fig. 2), and I D /I G The value increased to 1.15 (as in fig. 3), indicating that doping with N element can increase the surface defect level of the fiber. Based on CC, the fiber surface contains N functional groups to effectively enhance the lithium-philicity of NCC negative electrodeThe initial nucleation overpotential (3.26 mV) (see fig. 5) was reduced in one step and the growth of lithium dendrites was further suppressed, thereby improving the electrochemical performance of the NCC// Li half cell, allowing it to exhibit lower EIS impedance and impedance increase (see fig. 7), and more stable coulombic efficiency. At a discharge capacity of 1mAh cm -2 And 2mAh cm -2 The number of settling cycles was increased to about 800 and 280 times, respectively (see fig. 6). Thereafter, 200 cycles (2 mAh cm) -2 ) After NCC negative electrode fiber surface had little lithium dendrite formation (as in fig. 8 c), resulting in performance decay.
Example 1: in-situ etching nitrogen-doped modified carbon cloth (KNCC) negative electrode and physicochemical property thereof
1. The current commercial CC is respectively ultrasonically cleaned by acetone, ethanol and deionized water for 20min, then dried for 12h at 60 ℃, and then concentrated sulfuric acid is used for: the volume ratio of the concentrated nitric acid is 3:1 is acid treated at 50 ℃ for 240min, then washed with deionized water to neutrality and dried at 60 ℃ for 12h. Adding acid-treated CC to a solution containing 1mol L -1 KOH and 4mol L -1 And (3) standing in an aqueous solution of Urea at room temperature for 12h, transferring into a reaction kettle, carrying out hydrothermal reaction at 180 ℃ for 24h, naturally cooling to room temperature, washing to neutrality by deionized water, drying (vacuum drying at 60 ℃ for 12 h), preparing the in-situ etched nitrogen-doped modified carbon cloth (KNCC) cathode, and carrying out SEM, BET, XPS and Raman tests. In controlling oxygen<1ppm and moisture<KNCC cathode, polypropylene/polyethylene composite porous film, li sheet and 1mol L under inert gas atmosphere condition of 1ppm -1 LiTFSI electrolyte (solvent is DOL/DME+2wt.% LiNO in a volume ratio of 1:1) 3 ) And packaging the mixture into the LIR2025 button type KNCC// Li half battery. Electrochemical testing was performed on assembled half cells under the same conditions. And carrying out SEM morphology characterization on the KNCC cathode after charge and discharge circulation.
2. Analysis of results: compared with NCC, the N-doped KNCC anode has a large number of deep grooves/holes (shown in figure 1 d) formed by etching on the fiber surface, and can effectively increase the specific surface area (18.71 m 2 g -1 ) (as in FIG. 4), and further improvesDegree of surface defects of fiber (I) D /I G The value increased to 1.20). And the fiber surface is also uniformly doped with a higher content of N element (5.32 at.%) (fig. 2). The increase of the specific surface area and the introduction of the active defect sites of the surface of the fiber with lithium further reduce the local current density and the initial nucleation overpotential (1.21 mV) of the surface of the electrode (as shown in figure 5), obviously enhance the lithium affinity of the electrode, guide the uniform deposition of lithium along the two-dimensional direction of the surface of the fiber and inhibit the formation and growth of lithium dendrites, so that the KNCC// Li half cell shows the lowest EIS impedance and impedance increase (as shown in figure 7), the highest coulombic efficiency and the best cycle stability. At a discharge capacity of 1mAh cm -2 And 2mAh cm -2 The number of stable cycles at this time reaches 1000 and 400 times (as in FIG. 6), respectively, and 200 cycles (2 mAh cm) -2 ) The surface of the KNCC anode fiber after the preparation is free from lithium dendrite formation (as shown in figure 8 d).
Example 2: in-situ etching nitrogen-doped modified carbon cloth (KMNCC) cathode and physicochemical properties thereof
The current commercial CC is respectively ultrasonically cleaned by acetone, ethanol and deionized water for 10min, then dried for 12h at 60 ℃, and then concentrated sulfuric acid is used for: the volume ratio of the concentrated nitric acid is 10:1 is acid treated at 80 ℃ for 30min, then washed with deionized water to neutrality and dried at 60 ℃ for 12h. Adding acid-treated CC to a solution containing 0.1mol L -1 KMnO 4 And 10mol L -1 In the Urea aqueous solution, standing for 8 hours at room temperature, transferring into a reaction kettle, carrying out hydrothermal reaction for 48 hours at 80 ℃, naturally cooling to room temperature, washing to neutrality by deionized water, drying (vacuum drying for 12 hours at 60 ℃) to prepare an in-situ etched nitrogen-doped modified carbon cloth (KMNCC) cathode, and carrying out SEM, BET, XPS and Raman tests on the cathode. In controlling oxygen<1ppm and moisture<Under the inert gas atmosphere condition of 1ppm, KMNCC anode, polypropylene/polyethylene composite porous film, li sheet and 1mol L -1 LiTFSI electrolyte (1:1 (volume ratio of solvent) DOL/DME+2wt.% LiNO 3 ) And packaging into a LIR2025 button KMNCC// Li half battery. Electrochemical testing was performed on assembled half cells under the same conditions. SEM morphology characterization is carried out on the KMNCC cathode after charge and discharge cycles.
Example 3: in-situ etching nitrogen-doped modified carbon cloth (HCNCC) negative electrode and physicochemical property thereof
The current commercial CC is respectively ultrasonically cleaned by acetone, ethanol and deionized water for 120min, then dried for 12h at 60 ℃, and then concentrated sulfuric acid is used for: the volume ratio of the concentrated nitric acid is 1:1 is acid treated at 30 ℃ for 300min, then washed with deionized water to neutrality and dried at 60 ℃ for 12h. Adding acid-treated CC to a solution containing 10mol L -1 HClO 4 And 0.1mol L -1 In an aqueous solution of Melamine, standing for 3 hours at room temperature, transferring into a reaction kettle, carrying out hydrothermal reaction for 6 hours at 200 ℃, naturally cooling to room temperature, washing to neutrality by deionized water, drying (vacuum drying at 60 ℃ for 12 hours), preparing an in-situ etched nitrogen-doped modified carbon cloth (HCNCC) cathode, and carrying out SEM, BET, XPS and Raman tests. In controlling oxygen<1ppm and moisture<HCNCC negative electrode, polypropylene/polyethylene composite porous film, li sheet and 1mol L under inert gas atmosphere condition of 1ppm -1 LiTFSI electrolyte (1:1 (volume ratio of solvent) DOL/DME+2wt.% LiNO 3 ) And packaging into LIR2025 button type HCNCC// Li half battery. Electrochemical testing was performed on assembled half cells under the same conditions. And carrying out SEM morphology characterization on the HCNCC cathode after charge and discharge circulation.
Comparative example 4: cu// LFP metal battery based on commercial copper foil (Cu) current collector cathode
1. In controlling oxygen<1ppm and moisture<Under the inert gas atmosphere condition of 1ppm, the Cu negative electrode, the polypropylene/polyethylene composite porous film and LiFePO 4 (LFP) positive electrode sheet (composition mass ratio, LFP: SP: CNT: KS6: pvdf=91:3:1:1:4) and 1mol L -1 LiTFSI electrolyte (solvent is DOL/DME+2wt.% LiNO in a volume ratio of 1:1) 3 ) And packaging into the LIR2025 button Cu// LFP metal battery. Electrochemical testing of assembled cells (voltage range 2.0-4.0V, 1C current defined as 170mA g) -1 The method comprises the steps of carrying out a first treatment on the surface of the The EIS frequency ranges from 10mHz to 100kHz and the amplitude is 10 mV). And carrying out SEM morphology characterization on the Cu negative electrode after charge and discharge circulation.
2. Analysis of results: because the Cu negative electrode surface is smooth and flat (as shown in figure 1 a), the specific surface areaSmall and poorly lithium-philic, and cannot guide Li uniform deposition and efficient exfoliation, so the assembled Cu// LFP metal cell exhibits the lowest specific discharge capacity (77.38 mAh g when first activated at 0.1C -1 ) And coulombic efficiency (47.02%) (as in fig. 9). The specific discharge capacity decays rapidly with a large fluctuation in coulomb efficiency when cycled at 1C current density, and decays to 0 after 100 cycles. The generation of large amounts of lithium dendrites and the accumulation of "dead lithium" during cycling (see fig. 10 a) are the main causes of very poor electrochemical performance of Cu// LFP metal cells.
Comparative example 5: commercial Carbon Cloth (CC) negative electrode-based CC// LFP metal battery
1. In controlling oxygen<1ppm and moisture<Under the inert gas atmosphere condition of 1ppm, the CC negative electrode, the polypropylene/polyethylene composite porous film and LiFePO 4 (LFP) positive electrode sheet (composition mass ratio, LFP: SP: CNT: KS6: pvdf=91:3:1:1:4) and 1mol L -1 LiTFSI electrolyte (solvent is DOL/DME+2wt.% LiNO in a volume ratio of 1:1) 3 ) And packaging into the LIR2025 button type CC// LFP metal battery. And (3) carrying out electrochemical test on the assembled battery under the same condition, and carrying out SEM morphology characterization on the CC cathode after charge and discharge circulation.
2. Analysis of results: unlike commercial Cu cathodes, commercial CCs have a relatively high specific surface area (-10.48 m) 2 g -1 ) (as in FIG. 4), can reduce the local current density at the electrode surface to a certain extent, reduce the initial nucleation overpotential (as in FIG. 5, inset ii), and reduce the generation of lithium dendrites, so that the CC// LFP metal battery shows higher specific discharge capacity (130.87 mAh g) when activated for the first time at 0.1C -1 ) And coulombic efficiency (78.96%), as well as better cycle stability at 1C cycles (see fig. 9). However, due to the insufficient specific surface area of CC and lack of lithium-philic functional groups on the surface, li is not continuously and effectively guided to deposit uniformly and peel off efficiently, so that the discharge capacity of the CC// LFP metal battery starts to decay rapidly after 220 cycles, and with fluctuation of coulombic efficiency, lithium dendrites and "dead lithium" are generated on the surface of the CC fiber after 500 cycles, and by-products of massive decomposition of the electrolyte are generated (as shown in fig. 10 b).
Comparative example 6: NCC// LFP metal battery based on nitrogen doped modified carbon cloth (NCC) negative electrode
1. In controlling oxygen<1ppm and moisture<Under the inert gas atmosphere condition of 1ppm, NCC negative electrode, polypropylene/polyethylene composite porous film and LiFePO 4 (LFP) positive electrode sheet (composition mass ratio, LFP: SP: CNT: KS6: pvdf=91:3:1:1:4) and 1mol L -1 LiTFSI electrolyte (solvent is DOL/DME+2wt.% LiNO in a volume ratio of 1:1) 3 ) And packaging into LIR2025 button NCC// LFP metal battery. Electrochemical tests are carried out on the assembled battery under the same conditions, and SEM morphology characterization is carried out on the NCC cathode after charge and discharge cycles.
2. Analysis of results: compared with CC, the introduction of N-containing functional groups on the surface of NCC negative electrode fiber effectively enhances the lithium-philicity of NCC negative electrode, further reduces the initial nucleation overpotential (3.26 mV) (as shown in figure 5) and can inhibit the formation and growth rate of lithium dendrite, thereby improving the electrochemical performance of NCC// LFP metal battery. The specific discharge capacity and the coulombic efficiency of the catalyst are respectively improved to 135.67mAh g when the catalyst is activated for the first time at 0.1C -1 81.05% and a specific discharge capacity and a capacity retention of 100.71mAh g after 500 cycles, respectively -1 And 79.96% (see fig. 9). However, due to the insufficient specific surface area of NCC, a small amount of electrolyte decomposition products and lithium dendrites formed on the surface of NCC negative electrode fiber after 500 cycles (see fig. 10 c).
Example 4: KNCC// LFP metal battery based on in-situ etching nitrogen doped modified carbon cloth (KNCC) negative electrode
1. In controlling oxygen<1ppm and moisture<Under the inert gas atmosphere condition of 1ppm, the KNCC anode, the polypropylene/polyethylene composite porous film and the LiFePO are subjected to the reaction 4 (LFP) positive electrode sheet (composition mass ratio, LFP: SP: CNT: KS6: pvdf=91:3:1:1:4) and 1mol L -1 LiTFSI electrolyte (solvent is DOL/DME+2wt.% LiNO in a volume ratio of 1:1) 3 ) And packaging the lithium ion battery into the LIR2025 button type KNCC// LFP metal battery. And (3) carrying out electrochemical test on the assembled battery under the same condition, and carrying out SEM morphology characterization on the KNCC cathode after charge and discharge circulation.
2. Analysis of results: compared with NCC, the method is N doped after in-situ etchingThe KNCC anode has a large number of deep grooves/holes (as shown in figure 1 d) formed by etching on the fiber surface, and can effectively increase the specific surface area (18.71 m 2 g -1 ) (as in FIG. 4) and further increase the degree of surface defects (I) D /I G The value increased to 1.20). And the fiber surface is also uniformly doped with a higher content of N element (5.32 at.%) (fig. 2). The increase of the specific surface area and the introduction of the lithium-philic active defect sites on the surface of the fiber further reduce the local current density and the initial nucleation overpotential (1.21 mV) (as shown in figure 5) on the surface of the electrode and obviously enhance the lithium-philic property of the electrode, guide the uniform deposition of lithium along the two-dimensional direction of the surface of the fiber and obviously inhibit the formation and growth of lithium dendrites, so that the KNCC// LFP metal battery shows the optimal electrochemical performance. The specific discharge capacity and the coulombic efficiency of the catalyst are respectively improved to 135.72mAh g when the catalyst is activated for the first time at 0.1C -1 81.29% and a specific discharge capacity and a capacity retention rate after 500 cycles of 108.22mAh g, respectively -1 And 85.90% (as in fig. 9), and the surface of the KNCC negative electrode fiber after 500 cycles was free of any electrolyte decomposition products and lithium dendrite formation (as in fig. 10 d).
Example 5: in-situ etching nitrogen-doped modified carbon cloth (KMNCC) anode-based KMNCC// LFP metal battery
In controlling oxygen<1ppm and moisture<Under the inert gas atmosphere condition of 1ppm, KMNCC cathode, polypropylene/polyethylene composite porous film and LiFePO 4 (LFP) positive electrode sheet (composition mass ratio, LFP: SP: CNT: KS6: pvdf=91:3:1:1:4) and 1mol L -1 LiTFSI electrolyte (solvent is DOL/DME+2wt.% LiNO in a volume ratio of 1:1) 3 ) And packaging into the LIR2025 button KMNCC// LFP metal battery. Electrochemical tests are carried out on the assembled battery under the same conditions, and SEM morphology characterization is carried out on the KMNCC cathode after charge and discharge cycles.
Example 6
The preparation method of the in-situ etching nitrogen-doped modified carbon cloth comprises the following steps:
step (1), pretreating carbon cloth: cleaning the carbon cloth in a room temperature environment to remove stains on the surface of the carbon cloth, and then drying;
step (2), carbon cloth acid treatment: soaking the carbon cloth pretreated in the step (1) in concentrated acid at 50 ℃, standing for 100min, washing and drying;
step (3), in-situ etching nitrogen doping: adding the carbon cloth subjected to the acid treatment in the step (2) into a reaction medium containing an etchant and a doping agent, standing for 7 hours at room temperature, and performing hydrothermal reaction at 100 ℃;
the using amount of the etchant is 0.5mol L -1 ；
The dosage of the dopant is 2mol L -1 ；
Step (4), cleaning and drying: and (3) washing the carbon cloth subjected to the hydrothermal reaction in the step (3) to be neutral by water, and drying to obtain the in-situ etching nitrogen-doped modified carbon cloth.
In the step (1), during cleaning, respectively ultrasonically cleaning the carbon cloth by adopting acetone, ethanol and deionized water, wherein the cleaning time is 50min each time; the drying temperature is 60 ℃ and the drying time is 12 hours.
In the step (2), the concentrated acid is concentrated sulfuric acid: the volume ratio of the concentrated nitric acid is 6: 1; the washing is to adopt deionized water to wash to neutrality; the drying temperature is 60 ℃ and the drying time is 12 hours.
In the step (3), the hydrothermal reaction is carried out in a hydrothermal reaction kettle; the hydrothermal reaction time was 13h.
In the step (3), the etchant is hydrogen peroxide, hydrofluoric acid and hydrochloric acid (the molar ratio is 1:1:1);
the doping agent is melamine;
the reaction medium is acetonitrile.
In the step (4), deionized water is adopted for washing during water washing; the drying temperature is 60 ℃ and the drying time is 12 hours.
Example 7
The preparation method of the in-situ etching nitrogen-doped modified carbon cloth comprises the following steps:
step (1), pretreating carbon cloth: cleaning the carbon cloth in a room temperature environment to remove stains on the surface of the carbon cloth, and then drying;
step (2), carbon cloth acid treatment: soaking the carbon cloth pretreated in the step (1) in concentrated acid at 60 ℃, standing for 200min, washing and drying;
Step (3), in-situ etching nitrogen doping: adding the carbon cloth subjected to the acid treatment in the step (2) into a reaction medium containing an etchant and a doping agent, standing at room temperature for 7 hours, and performing hydrothermal reaction at 150 ℃;
the using amount of the etchant is 2mol L -1 ；
The dosage of the dopant is 3mol L -1 ；
Step (4), cleaning and drying: and (3) washing the carbon cloth subjected to the hydrothermal reaction in the step (3) to be neutral by water, and drying to obtain the in-situ etching nitrogen-doped modified carbon cloth.
In the step (1), during cleaning, respectively ultrasonically cleaning the carbon cloth by adopting acetone, ethanol and deionized water, wherein the cleaning time is 60 minutes each time; the drying temperature is 60 ℃ and the drying time is 12 hours.
In the step (2), the concentrated acid is concentrated sulfuric acid: the volume ratio of the concentrated nitric acid is 5: 1; the washing is to adopt deionized water to wash to neutrality; the drying temperature is 60 ℃ and the drying time is 12 hours.
In the step (3), the hydrothermal reaction is carried out in a hydrothermal reaction kettle; the hydrothermal reaction time was 24h.
In the step (3), the etchant is nitric acid and perchloric acid (the molar ratio is 1:1);
the doping agent is melamine;
the reaction medium is water, glycol and N, N-dimethylacetamide (volume ratio is 1:1:1).
In the step (4), deionized water is adopted for washing during water washing; the drying temperature is 60 ℃ and the drying time is 12 hours.
Example 8
The preparation method of the in-situ etching nitrogen-doped modified carbon cloth comprises the following steps:
step (1), pretreating carbon cloth: cleaning the carbon cloth in a room temperature environment to remove stains on the surface of the carbon cloth, and then drying;
step (2), carbon cloth acid treatment: soaking the carbon cloth pretreated in the step (1) in concentrated acid at 70 ℃, standing for 180min, washing and drying;
step (3), in-situ etching nitrogen doping: adding the carbon cloth subjected to the acid treatment in the step (2) into a reaction medium containing an etchant and a doping agent, standing at room temperature for 7 hours, and performing hydrothermal reaction at 90 ℃;
the etching agent is used in an amount of 7mol L -1 ；
The dosage of the dopant is 5mol L -1 ；
Step (4), cleaning and drying: and (3) washing the carbon cloth subjected to the hydrothermal reaction in the step (3) to be neutral by water, and drying to obtain the in-situ etching nitrogen-doped modified carbon cloth.
In the step (1), during cleaning, respectively ultrasonically cleaning the carbon cloth by adopting acetone, ethanol and deionized water, wherein the cleaning time is 90 minutes each time; the drying temperature is 60 ℃ and the drying time is 12 hours.
In the step (2), the concentrated acid is concentrated sulfuric acid: the volume ratio of the concentrated nitric acid is 8: 1; the washing is to adopt deionized water to wash to neutrality; the drying temperature is 60 ℃ and the drying time is 12 hours.
In the step (3), the hydrothermal reaction is carried out in a hydrothermal reaction kettle; the hydrothermal reaction time was 24h.
In the step (3), the etchant is potassium hydroxide and sodium hydroxide (the molar ratio is 1:1);
the doping agent is ammonia water, ammonium fluoborate and ammonium phosphate (the molar ratio is 1:1);
the reaction medium is dichloromethane, chloroform and ethanol (the molar ratio is 1:1); .
In the step (4), deionized water is adopted for washing during water washing; the drying temperature is 60 ℃ and the drying time is 12 hours.
Example 9
The preparation method of the in-situ etching nitrogen-doped modified carbon cloth comprises the following steps:
step (1), pretreating carbon cloth: cleaning the carbon cloth in a room temperature environment to remove stains on the surface of the carbon cloth, and then drying;
step (2), carbon cloth acid treatment: soaking the carbon cloth pretreated in the step (1) in concentrated acid at 30 ℃, standing for 300min, washing and drying;
step (3), in-situ etching nitrogen doping: adding the carbon cloth subjected to the acid treatment in the step (2) into a reaction medium containing an etchant and a doping agent, standing for 5 hours at room temperature, and performing hydrothermal reaction at 100 ℃;
The using amount of the etchant is 9mol L -1 ；
The dosage of the dopant is 3mol L -1 ；
Step (4), cleaning and drying: and (3) washing the carbon cloth subjected to the hydrothermal reaction in the step (3) to be neutral by water, and drying to obtain the in-situ etching nitrogen-doped modified carbon cloth.
In the step (1), during cleaning, respectively ultrasonically cleaning the carbon cloth by adopting acetone, ethanol and deionized water, wherein the cleaning time is 80 minutes each time; the drying temperature is 60 ℃ and the drying time is 12 hours.
In the step (2), the concentrated acid is concentrated sulfuric acid: the volume ratio of the concentrated nitric acid is 7: 1; the washing is to adopt deionized water to wash to neutrality; the drying temperature is 60 ℃ and the drying time is 12 hours.
In the step (3), the hydrothermal reaction is carried out in a hydrothermal reaction kettle; the hydrothermal reaction time was 15h.
In the step (3), the etchant is sodium hydroxide;
the doping agent is ammonium hydrogen phosphate and ammonium dihydrogen phosphate (the mol ratio is 1:1);
the reaction medium is deionized water, N-dimethylformamide, methylene dichloride and ethanol (the molar ratio is 1:1:1:1).
In the step (4), deionized water is adopted for washing during water washing; the drying temperature is 60 ℃ and the drying time is 12 hours.
Example 10
An in-situ etching nitrogen-doped modified carbon cloth comprises a three-dimensional continuous base carbon cloth woven by carbon fibers; etching grooves or concave holes uniformly distributed on the surface of the carbon fiber, and uniformly distributed doping nitrogen elements; the specific surface area of the modified carbon cloth is 5-30 m 2 g -1 The method comprises the steps of carrying out a first treatment on the surface of the The diameter of the carbon fiber is 3-5 mu m; the aperture of the etched groove or concave hole is 0.1-2 mu m; the content of the doped nitrogen element is 1at.%.
Example 11
An in-situ etching nitrogen-doped modified carbon cloth comprises a three-dimensional continuous base carbon cloth woven by carbon fibers; etching grooves or concave holes uniformly distributed on the surface of the carbon fiber, and uniformly distributed doping nitrogen elements; the specific surface area of the modified carbon cloth is 60-100 m 2 g -1 The method comprises the steps of carrying out a first treatment on the surface of the The diameter of the carbon fiber is 8-10 mu m; the aperture of the etched groove or concave hole is 4-5 mu m; the content of the doped nitrogen element is 10at.%.
Example 12
An in-situ etching nitrogen-doped modified carbon cloth comprises a three-dimensional continuous base carbon cloth woven by carbon fibers; etching grooves or concave holes uniformly distributed on the surface of the carbon fiber, and uniformly distributed doping nitrogen elements; the specific surface area of the modified carbon cloth is 40-60 m 2 g -1 The method comprises the steps of carrying out a first treatment on the surface of the The diameter of the carbon fiber is 5-7 mu m; the aperture of the etched groove or concave hole is 2-3 mu m; the content of the doped nitrogen element is 8at.%.
The foregoing has shown and described the basic principles, principal features and advantages of the invention. It will be understood by those skilled in the art that the present invention is not limited to the embodiments described above, and that the above embodiments and descriptions are merely illustrative of the principles of the present invention, and various changes and modifications may be made without departing from the spirit and scope of the invention, which is defined in the appended claims. The scope of the invention is defined by the appended claims and equivalents thereof.

Claims (10)

1. The preparation method of the in-situ etching nitrogen-doped modified carbon cloth is characterized by comprising the following steps of:
step (1), pretreating carbon cloth: cleaning the carbon cloth in a room temperature environment to remove stains on the surface of the carbon cloth, and then drying;
step (2), carbon cloth acid treatment: soaking the carbon cloth pretreated in the step (1) in concentrated acid at the temperature of 30-80 ℃, standing for 30-300 min, washing and drying;
step (3), in-situ etching nitrogen doping: adding the carbon cloth subjected to the acid treatment in the step (2) into a reaction medium containing an etching agent and a doping agent, standing for 3-12 h at room temperature, and performing hydrothermal reaction at 80-200 ℃;
The using amount of the etchant is 0.1 to 10mol L -1 ；
The dosage of the doping agent is 0.1 to 10mol L -1 ；
Step (4), cleaning and drying: and (3) washing the carbon cloth subjected to the hydrothermal reaction in the step (3) to be neutral by water, and drying to obtain the in-situ etching nitrogen-doped modified carbon cloth.
2. The method for preparing the in-situ etching nitrogen-doped modified carbon cloth according to claim 1, wherein in the step (1), during cleaning, the carbon cloth is respectively ultrasonically cleaned by adopting acetone, ethanol and deionized water, and the cleaning time is 10-120 min each time; the drying temperature is 60 ℃ and the drying time is 12 hours.
3. The method for preparing the in-situ etched nitrogen-doped modified carbon cloth according to claim 1, wherein in the step (2), the concentrated acid is concentrated sulfuric acid: the volume ratio of the concentrated nitric acid is 1:1 to 10: 1; the washing is to adopt deionized water to wash to neutrality; the drying temperature is 60 ℃ and the drying time is 12 hours.
4. The method for preparing the in-situ etching nitrogen-doped modified carbon cloth according to claim 1, wherein in the step (3), the hydrothermal reaction is performed in a hydrothermal reaction kettle; the hydrothermal reaction time is 6-48 h.
5. The method for preparing the in-situ etching nitrogen-doped modified carbon cloth according to claim 1, wherein in the step (3), the etchant is at least one of potassium hydroxide, sodium hydroxide, hydrogen peroxide, potassium permanganate, hydrofluoric acid, hydrochloric acid, nitric acid and perchloric acid;
The doping agent is at least one of urea, ammonia water, ammonium fluoborate, ammonium phosphate, ammonium hydrogen phosphate, ammonium dihydrogen phosphate and melamine;
the reaction medium is at least one of deionized water, acetonitrile, ethylene glycol, N-dimethylacetamide, N-dimethylformamide, dichloromethane, chloroform and ethanol.
6. The method for preparing the in-situ etching nitrogen-doped modified carbon cloth according to claim 1, wherein in the step (4), deionized water is used for washing during water washing; the drying temperature is 60 ℃ and the drying time is 12 hours.
7. The in-situ etched nitrogen-doped modified carbon cloth prepared by the method for preparing the in-situ etched nitrogen-doped modified carbon cloth according to any one of claims 1-6.
8. The in-situ etched nitrogen-doped modified carbon cloth of claim 7, wherein: comprises three-dimensional continuous base carbon cloth woven by carbon fiber; etching grooves or concave holes uniformly distributed on the surface of the carbon fiber, and uniformly distributed doping nitrogen elements; the specific surface area of the modified carbon cloth is 5-100 m 2 g -1 The method comprises the steps of carrying out a first treatment on the surface of the The diameter of the carbon fiber is 3-10 mu m; the aperture of the etched groove or concave hole is 0.1-5 mu m; the content of the doped nitrogen element is 1-10at%.
9. A metal battery comprising the in-situ etched nitrogen-doped modified carbon cloth of claim 7.
10. The metal battery of claim 9, comprising a housing, a positive electrode, a negative electrode, and a separator mounted within the housing; the diaphragm is arranged between the anode and the cathode; electrolyte is filled in the gaps between the positive electrode and the diaphragm and between the negative electrode and the diaphragm; the negative electrode adopts the in-situ etching nitrogen-doped modified carbon cloth as claimed in any one of claims 7-8.
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Publication number Priority date Publication date Assignee Title
CN116031418A (en) * 2023-02-20 2023-04-28 中海储能科技(北京)有限公司 Method for modifying defects of carbon cloth electrode of iron-chromium flow battery
CN116613324A (en) * 2023-07-14 2023-08-18 福建巨电新能源股份有限公司 Secondary lithium battery without negative electrode structure

Citations (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN107190366A (en) * 2017-06-30 2017-09-22 天津工业大学 The preparation method of ultracapacitor N doping porous carbon fiber
CN107359320A (en) * 2017-06-07 2017-11-17 同济大学 A kind of N doping porous carbon/MoS2Anode material of lithium-ion battery and preparation method
CN109638339A (en) * 2018-12-21 2019-04-16 广东维都利新能源有限公司 A kind of battery and preparation method thereof of positive and negative anodes difference diaphragm bag making
CN109755594A (en) * 2018-12-17 2019-05-14 中国科学院广州能源研究所 A kind of porous carbon cloth of nitrating and its application as bioelectrochemical system anode
CN110255697A (en) * 2019-06-26 2019-09-20 合肥工业大学 A kind of preparation of N doping carbon materials anode and its application in catalytic wet air oxidation
CN111223682A (en) * 2020-03-19 2020-06-02 桂林理工大学 Electrode composite material of flexible supercapacitor and preparation method thereof
CN114164658A (en) * 2021-12-08 2022-03-11 盐城工学院 Preparation method and application of nitrogen-doped carbon fabric material with high nitrogen content
CN114583174A (en) * 2022-03-21 2022-06-03 蜂巢能源科技股份有限公司 Sodium ion battery and preparation method thereof

Family Cites Families (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20210351401A1 (en) * 2018-09-06 2021-11-11 Virginia Tech Intellectual Properties, Inc. Porous carbon fiber electrodes, methods of making thereof, and uses thereof
CN112151762B (en) * 2019-06-26 2022-06-10 重庆大学 Lithium-sulfur battery positive electrode material and preparation method thereof, lithium-sulfur battery positive electrode and preparation method thereof, and lithium-sulfur battery

Patent Citations (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN107359320A (en) * 2017-06-07 2017-11-17 同济大学 A kind of N doping porous carbon/MoS2Anode material of lithium-ion battery and preparation method
CN107190366A (en) * 2017-06-30 2017-09-22 天津工业大学 The preparation method of ultracapacitor N doping porous carbon fiber
CN109755594A (en) * 2018-12-17 2019-05-14 中国科学院广州能源研究所 A kind of porous carbon cloth of nitrating and its application as bioelectrochemical system anode
CN109638339A (en) * 2018-12-21 2019-04-16 广东维都利新能源有限公司 A kind of battery and preparation method thereof of positive and negative anodes difference diaphragm bag making
CN110255697A (en) * 2019-06-26 2019-09-20 合肥工业大学 A kind of preparation of N doping carbon materials anode and its application in catalytic wet air oxidation
CN111223682A (en) * 2020-03-19 2020-06-02 桂林理工大学 Electrode composite material of flexible supercapacitor and preparation method thereof
CN114164658A (en) * 2021-12-08 2022-03-11 盐城工学院 Preparation method and application of nitrogen-doped carbon fabric material with high nitrogen content
CN114583174A (en) * 2022-03-21 2022-06-03 蜂巢能源科技股份有限公司 Sodium ion battery and preparation method thereof

Non-Patent Citations (5)

* Cited by examiner, † Cited by third party
Title
Azide-assisted hydrothermal synthesis of N-doped mesoporous carboncloth for high-performance symmetric supercapacitor employing LiClO4 as electrolyte;Qian Zhang et al.;《Composites: Part A》;第58–65页 *
In-situ cobalt-nickel alloy catalyzed nitrogen-doped carbon nanotube arrays as superior freestanding air electrodes for flexible zinc-air and aluminum-air batteries;Wen-Wen Tiana et al.;《Applied CatalysisB:Environmental》;第1-13页 *
Nitrogen-DopedCarbon for Sodium-Ion Battery Anode by Self-Etching and Graphitization of Bimetallic MOF-Based Composite;Yuming Chen et al.;《Chem 3》;第152–163页 *
基于碳布柔性超级电容器负极材料的设计与制备;周帅;《中国优秀硕士学位论文全文数据库 工程科技I辑》;第B020-325页 *
氮掺杂多孔碳布制备及超级电容器性能研究;陈婷婷等;《棉纺织技术》;第第50卷卷(第第6期期);第8-13页 *

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