CN110104630B - Porous carbon composite material for battery diaphragm and preparation method and application thereof - Google Patents
Porous carbon composite material for battery diaphragm and preparation method and application thereof Download PDFInfo
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- C01B32/00—Carbon; Compounds thereof
- C01B32/05—Preparation or purification of carbon not covered by groups C01B32/15, C01B32/20, C01B32/25, C01B32/30
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- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B32/00—Carbon; Compounds thereof
- C01B32/15—Nano-sized carbon materials
- C01B32/158—Carbon nanotubes
- C01B32/16—Preparation
- C01B32/162—Preparation characterised by catalysts
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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
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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
- H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
- H01M50/40—Separators; Membranes; Diaphragms; Spacing elements inside cells
- H01M50/403—Manufacturing processes of separators, membranes or diaphragms
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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
- H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
- H01M50/40—Separators; Membranes; Diaphragms; Spacing elements inside cells
- H01M50/409—Separators, membranes or diaphragms characterised by the material
- H01M50/431—Inorganic material
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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
- H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
- H01M50/40—Separators; Membranes; Diaphragms; Spacing elements inside cells
- H01M50/409—Separators, membranes or diaphragms characterised by the material
- H01M50/449—Separators, membranes or diaphragms characterised by the material having a layered structure
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- C01—INORGANIC CHEMISTRY
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- C01B2202/00—Structure or properties of carbon nanotubes
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- 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 aims to provide a porous carbon composite material of a battery diaphragm and a preparation method and application thereof, belonging to the technical field of novel electrochemical materials. The preparation method of the porous carbon composite material designs an MOF composite material based on adenine rich in N element, Ni is added in the preparation process, Cetyl Trimethyl Ammonium Bromide (CTAB) is added as a shape and size regulator, wherein a large number of carbon nano tubes grow in the material under the catalysis of the Ni to form a sea urchin-like structure, on the basis, all substances are mutually crosslinked in the preparation process to form a three-dimensional conductive adsorption conversion network, the conductivity is improved by utilizing the autocatalysis of the Ni to generate a large number of carbon nano tubes, the cost is saved by avoiding the need of additionally adding conductive agents such as the carbon nano tubes, and the Ni is utilized3ZnC0.7The lithium polysulfide is quickly catalyzed to be converted, the generated Ni and the carbon nano tube effectively promote the transfer of electrons, and the cycle stability and the rate capability of the battery are greatly improved.
Description
Technical Field
The invention belongs to the technical field of novel electrochemical materials, and particularly relates to a porous carbon composite material for a battery diaphragm, and a preparation method and application thereof.
Background
The global shortage of fossil fuels generates the explosion demand of efficient economic energy, the situation of shortage of primary fossil energy such as petroleum and coal mines is more severe, the trend of severe environment is not optimistic, and the global urgent demand is for the development of green new energy capable of replacing the fossil energy. The chemical power source is an energy storage device for mutual conversion of chemical electric energy and electric energy, and becomes one of the research directions of new energy subjects. Lithium ion batteryPonds are a new green chemical energy source that has developed rapidly over the last decades. In recent decades of research, lithium ion batteries have almost reached their theoretical specific capacity, but still cannot meet the requirements of high specific capacity and high specific energy, and in the search for the next generation of high energy density and economic green rechargeable battery systems, lithium sulfur batteries are widely researched by people with their high theoretical energy density (2600 Wh/Kg) and high theoretical specific capacity (1675 mAh/g), and the ultrahigh specific capacity has undoubtedly led much research and attention. The lithium-sulfur battery not only has the above-mentioned excellent theoretical energy density and specific capacity, but also has rich and economical sulfur storage as a positive electrode material, and these advantages make the lithium-sulfur battery one of the secondary battery systems with the most development prospects at present. Rechargeable lithium sulfur batteries have attracted a great deal of scientific research due to their superior energy density. However, the lithium-sulfur electrochemical reaction involves multiple electron redox reactions, and the morphological precipitates that ultimately form solid lithium sulfide during the complex phase transition of the process largely determine the performance, insulation and insoluble charge and discharge products (S and Li) of the battery2S) results in slow redox kinetics and low sulfur utilization. Based on this, researchers have devised the development of various materials for solving the problems of lithium sulfur batteries. For example, as a sulfur-carrying positive electrode material, such as porous carbon, the design and development of materials, the optimization of the electrolyte formulation, the design of functional separator coatings, and the like. The modification of the positive electrode of the lithium-sulfur battery makes certain progress under the continuous efforts of researchers, and various positive electrode plates with better electrochemical properties are designed. However, under the action of the concentration gradient and the electric field between the positive and negative electrodes, polysulfide ions are inevitably dissolved and diffused, which results in the loss of active materials. The separator plays important roles of conducting ions and isolating electrons as an important component of the lithium-sulfur battery. The lithium polysulphides produced in the reaction have to pass through the separator before they can be shuttled to the negative electrode, which means that separator modification is also an effective way of inhibiting shuttling of lithium polysulphides. The diaphragm is coated with a diaphragm functional coating to inhibit shuttle of polysulfide ions, and the diaphragm is simple in preparation process, stable in structure, light in coating weight and small in influence on overall energy density of the battery, so that the diaphragm is relatively low in energy densityAn efficient method.
In the reported studies on the coating of the lithium-sulfur battery separator, the carbon material can physically adsorb lithium polysulfide generated in the reaction by virtue of the loose porous structure of the carbon material, so that the shuttle effect is relieved. Some studies of metal oxide-doped membrane modification have found that certain metal oxides have some chemisorption on lithium polysulfides. The chemical adsorption can more effectively inhibit the shuttling of lithium polysulfide, so that the battery shows excellent cycling stability and rate performance. However, lithium polysulfide adsorbed in the oxide is difficult to fully utilize due to poor conductivity of the metal oxide, so that the capacity of the battery suffers from partial loss. However, the carbon material has a weak interaction with lithium polysulfide, and the adsorption of lithium polysulfide is usually physical adsorption, so that the inhibition effect of the carbon material on the shuttle effect is poor. In order to simultaneously utilize the good conductivity of the carbon material and the strong chemical adsorption effect of the metal oxide on lithium polysulfide, the preparation of the metal oxide and the conductive carbon material into a compound for application on the functional diaphragm coating is an excellent strategy of comprehensive consideration.
In recent years, Metal Organic Frameworks (MOFs) and carbon materials using MOFs as precursors have been extensively studied as novel sulfur carriers and functional film coating materials in lithium batteries. The MOFs are crystal materials composed of metal ion/cluster nodes in infinite arrangement and organic link bodies, have large specific surface area and adjustable size and pore diameter, and are paid much attention to by people. The composite material of the metal compound and the porous carbon can be simply prepared by taking MOFs as a precursor.
Disclosure of Invention
Aiming at the problems, the invention provides a porous carbon composite material rich in nitrogen and nickel and based on MOF synthesis, and a preparation method and application thereof, aiming at solving the problems of shuttle effect, poor conductivity or poor chemical stability of a coating of a battery diaphragm in the prior art.
The invention aims to provide a porous carbon composite material for a battery diaphragm, which comprises N, Ni and Ni3ZnC0.7Of porous carbon composite material which is rich in NNi and Ni3ZnC0.7。
The invention also provides a preparation method of the porous carbon composite material for the battery diaphragm, which comprises the following steps:
1) mixing and dissolving zinc acetate, nickel acetate and Cetyl Trimethyl Ammonium Bromide (CTAB) to fully dissolve reaction raw materials to obtain a solution A;
2) dissolving adenine and 4, 4-biphenyldicarboxylic acid respectively, and mixing with the solution A after dissolving to fully dissolve organic ligands adenine and 4, 4-biphenyldicarboxylic acid to obtain a solution B;
3) mixing and stirring the solution B, the carbon nanotube solution, methanol and deionized water, fully mixing and reacting the reaction raw materials with the carbon nanotubes, and centrifuging after the reaction is finished to obtain gray powder;
4) washing the grey powder, drying to obtain a Ni-MOF compound, and calcining to obtain a porous carbon composite material named as Ni-MOF-800-8H; removing unreacted impurities by washing; carbonizing the mixture in an inert atmosphere to obtain a nickel and nitrogen doped porous carbon material;
further, the solvents used for the dissolution described in step 1) and step 2) include N, N-Dimethylformamide (DMF);
the carbon nanotube solution in the step 3) is a solution which is pre-dispersed and activated in N, N-Dimethylformamide (DMF), and the carbon nanotubes are pre-dispersed so that nanoparticles can grow on the carbon nanotubes more uniformly;
the solvent used for the washing in step 4) includes N, N-Dimethylformamide (DMF) and methanol;
in the step 4), the calcination is high-temperature calcination in a nitrogen atmosphere, the calcination condition lasts for 8 hours at 800 ℃, and Ni is subjected to autocatalysis to generate the carbon nano tube by utilizing a long-time high-temperature inert gas atmosphere; the carbon material is catalyzed by the simple substance nickel obtained by reduction under the inert atmosphere to generate the carbon nano tube, thereby improving the conductivity of the material.
The invention also provides the application of the porous carbon composite material for the battery diaphragm, which is applied to the coating material of the battery diaphragm;
the preparation method of the coating material of the battery separator comprises the following steps: mixing Ni-MOF-800-8H prepared by the preparation method of the porous carbon composite material, a conductive agent, a binder and an n-propanol solution to prepare slurry, coating the slurry on a battery diaphragm, and then drying and slicing to obtain a coating diaphragm; the prepared carbon composite material is coated on the diaphragm and the battery is assembled, so that the improvement condition of the coating material on the electrochemical performance of the battery is tested;
in the preparation method of the coating material of the battery diaphragm, the conductive agent comprises conductive carbon black, and the binder comprises LA 132; the carbon black functions to improve conductivity, and the binder functions to adhere the material to the separator.
The invention has the following beneficial effects:
the preparation method of the porous carbon composite material designs an MOF composite material based on adenine rich in N element, Ni is added in the preparation process, Cetyl Trimethyl Ammonium Bromide (CTAB) is added as a shape and size regulator, wherein a large number of carbon nano tubes grow in the material under the catalysis of the Ni to form a sea urchin-like structure, on the basis, all substances are mutually crosslinked in the preparation process to form a three-dimensional conductive adsorption conversion network, the conductivity is improved by utilizing the autocatalysis of the Ni to generate a large number of carbon nano tubes, the cost is saved by avoiding the need of additionally adding conductive agents such as the carbon nano tubes, and the Ni is utilized3ZnC0.7The lithium polysulfide is quickly catalyzed to be converted, the generated Ni and the carbon nano tube effectively promote the transfer of electrons, and the cycle stability and the rate capability of the battery are greatly improved;
most of the current-stage diaphragm coatings are applied to lithium-sulfur batteries, lithium polysulfide migration cannot be effectively and quickly blocked under high current density and high sulfur loading capacity, the discharge specific capacity of the batteries is quickly attenuated, and stable long circulation under the high sulfur loading capacity and the high current density cannot be supported.
Drawings
FIG. 1 is a scanning electron micrograph of Ni-MOF;
FIG. 2 is a scanning electron micrograph of Ni-MOF-800-8H;
FIG. 3 is a cross-sectional view of a Ni-MOF-800-8H coated membrane;
FIG. 4 is a schematic diagram of the electrochemical cycle of a Ni-MOF-800-8H coated membrane.
Detailed Description
The present invention is described in further detail in the following description of specific embodiments and the accompanying drawings, it is to be understood that these embodiments are merely illustrative of the present invention and are not intended to limit the scope of the invention, which is defined by the appended claims, and modifications thereof by those skilled in the art after reading this disclosure that are equivalent to the above described embodiments.
All the raw materials and reagents of the invention are conventional market raw materials and reagents unless otherwise specified.
Example 1
A preparation method of a porous carbon composite material for a battery separator comprises the following steps:
1) dissolving zinc acetate, nickel acetate and hexadecyl trimethyl ammonium bromide in DMF at a molar ratio of 9:1:1, and ultrasonically dissolving to obtain a solution A;
2) dissolving adenine and 4, 4-diphenyl dicarboxylic acid in DMF with the molar ratio of 1:1 respectively in the same volume, and ultrasonically dissolving to obtain a solution, and mixing the solution with the solution A to obtain a solution B;
3) mixing and stirring the solution B, activated carbon nanotube solution dispersed in DMF, methanol and deionized water in a volume ratio of 5:4:1, and centrifuging after the reaction is finished to obtain gray powder;
4) washing the gray powder with DMF and MeOH in sequence, drying in an oven to obtain Ni-MOF, calcining the MOF in a tubular furnace under a nitrogen atmosphere, wherein the calcining condition is 800 ℃ for 8H, the heating rate is 5 ℃/min, and the calcined product is named as Ni-MOF-800-8H;
the Ni-MOF-800-8H, Super-P, LA132 binder prepared in example 1 was taken as follows: 2: 2, dispersing and mixing the mixture into slurry by using an n-propanol solution, coating the slurry on a PP (Celgard-2400) diaphragm, drying the membrane for 24 hours in a vacuum drying box at the temperature of 60 ℃, and cutting the membrane into a wafer with the diameter of 19mm by using a slicing machine to obtain the Ni-MOF-800-8H coating diaphragm.
Example 2
A preparation method of a porous carbon composite material for a battery separator comprises the following steps:
1) dissolving zinc acetate, nickel acetate and hexadecyl trimethyl ammonium bromide in DMF at a molar ratio of 8:1:1, and ultrasonically dissolving to obtain a solution A;
2) dissolving adenine and 4, 4-diphenyl dicarboxylic acid in DMF with the molar ratio of 1:1 respectively in the same volume, and ultrasonically dissolving to obtain a solution, and mixing the solution with the solution A to obtain a solution B;
3) mixing and stirring the solution B, activated carbon nanotube solution dispersed in DMF, methanol and deionized water in a volume ratio of 5:4:1, and centrifuging after the reaction is finished to obtain gray powder;
4) washing the gray powder with DMF and MeOH in sequence, drying in an oven to obtain Ni-MOF, calcining the MOF in a tubular furnace under a nitrogen atmosphere, wherein the calcining condition is 800 ℃ for 8H, the heating rate is 5 ℃/min, and the calcined product is named as Ni-MOF-800-8H;
the Ni-MOF-800-8H, Super-P, LA132 binder prepared in example 1 was taken as follows: 2: 2, dispersing and mixing the mixture into slurry by using an n-propanol solution, coating the slurry on a PP (Celgard-2400) diaphragm, drying the membrane for 24 hours in a vacuum drying box at the temperature of 60 ℃, and cutting the membrane into a wafer with the diameter of 19mm by using a slicing machine to obtain the Ni-MOF-800-8H coating diaphragm.
Example 3
A preparation method of a porous carbon composite material for a battery separator comprises the following steps:
1) dissolving zinc acetate, nickel acetate and hexadecyl trimethyl ammonium bromide in DMF at a molar ratio of 7:1:1, and ultrasonically dissolving to obtain a solution A;
2) dissolving adenine and 4, 4-diphenyl dicarboxylic acid in DMF with the molar ratio of 1:1 respectively in the same volume, and ultrasonically dissolving to obtain a solution, and mixing the solution with the solution A to obtain a solution B;
3) mixing and stirring the solution B, activated carbon nanotube solution dispersed in DMF, methanol and deionized water in a volume ratio of 5:4:1, and centrifuging after the reaction is finished to obtain gray powder;
4) washing the gray powder with DMF and MeOH in sequence, drying in an oven to obtain Ni-MOF, calcining the MOF in a tubular furnace under a nitrogen atmosphere, wherein the calcining condition is 800 ℃ for 8H, the heating rate is 5 ℃/min, and the calcined product is named as Ni-MOF-800-8H;
the Ni-MOF-800-8H, Super-P, LA132 binder from example 3 was taken as 6: 2: 2, dispersing and mixing the mixture into slurry by using an n-propanol solution, coating the slurry on a PP (Celgard-2400) diaphragm, drying the membrane for 24 hours in a vacuum drying box at the temperature of 60 ℃, and cutting the membrane into a wafer with the diameter of 19mm by using a slicing machine to obtain the Ni-MOF-800-8H coating diaphragm.
The scanning electron microscope picture of the Ni-MOF prepared in the embodiment of the invention is shown in figure 1, and the scanning electron microscope picture of the Ni-MOF-800-8H prepared in the embodiment of the invention is shown in figure 2, so that a three-dimensional conductive adsorption conversion network structure is formed; the cross section of the prepared Ni-MOF-800-8H coating membrane is shown in figure 3, and the thickness is only about 4 mu m.
Comparative experiment: s (sulfur substances) and Ketjen black (conductive carbon black) react in a reaction kettle at 155 ℃ for 24 hours according to the ratio of 1:4 to prepare a C/S composite, the C/S composite and a Super-P, LA132 binder are dispersed in an n-propanol solution according to the ratio of 8:1:1 to prepare slurry, the slurry is coated on an aluminum foil, and the aluminum foil is dried in a vacuum drying oven at 60 ℃ for 24 hours. Cutting into electrode discs with diameter of 12mm by a slicer, and preparing into electrode discs with sulfur loading of 2 mg/cm by scrapers with different thicknesses2、6 mg/cm2The pole piece of (2). In a glove box, the prepared pole piece is used as a positive electrode, a lithium piece is used as a negative electrode, a PP (Celgard-2400) diaphragm or a PP (Celgard-2400) diaphragm coated with materials and 1.0M LiTFSI DOL/DME (v: v, 1:1) is used as an electrolyte to assemble a CR-2302 button cell, wherein a coating layer faces to a C/S positive electrode.
Electric appliance for useCell test System for testing the electrochemical Performance of the cells, as shown in FIG. 4, the coated separator material of the present invention was at 2 mg/cm2The specific discharge capacity of 400 mAh/g can be still maintained by circulating 1200 circles with 5C super-high current density under the surface sulfur loading capacity, the stable discharge performance can be seen, the equivalent specific discharge capacity can be still maintained by circulating 1200 circles, the coulombic efficiency is stabilized at about 100%, and the overcharge phenomenon does not occur.
Claims (7)
1. A preparation method of a porous carbon composite material for a battery diaphragm is characterized by comprising the following steps:
1) mixing and dissolving zinc acetate, nickel acetate and hexadecyl trimethyl ammonium bromide to obtain a solution A;
2) dissolving adenine and 4, 4-biphenyldicarboxylic acid respectively, and mixing with the solution A after dissolving to obtain a solution B;
3) mixing and stirring the solution B, the carbon nanotube solution, methanol and deionized water, and centrifuging after the reaction is finished to obtain gray powder;
4) washing the grey powder, drying to obtain a Ni-MOF compound, and calcining to obtain a porous carbon composite material named as Ni-MOF-800-8H;
the composition of the porous carbon composite material comprises N, Ni and Ni3ZnC0.7The structure is a three-dimensional conductive adsorption conversion network structure;
the carbon nanotube solution in the step 3) is a solution which is dispersed and activated in N, N-dimethylformamide in advance.
2. The method for preparing a porous carbon composite material for a battery separator according to claim 1, wherein the solvent used for dissolution in step 1) and step 2) includes N, N-dimethylformamide.
3. The method for preparing a porous carbon composite material for a battery separator according to claim 2, wherein the solvent used for the washing in step 4) includes N, N-dimethylformamide and methanol.
4. A porous carbon composite material for a battery diaphragm, which is characterized by being prepared by the preparation method of any one of claims 1-3, and comprising N, Ni and Ni3ZnC0.7。
5. Use of the porous carbon composite according to claim 4 as a coating material for battery separators.
6. The use of a porous carbon composite according to claim 5, characterized in that the preparation method of the coating material of the battery separator comprises the following steps: mixing the porous carbon composite material of claim 4 with a conductive agent, a binder and an n-propanol solution to prepare slurry, coating the slurry on a battery diaphragm, and then drying and slicing the battery diaphragm to obtain the coating diaphragm.
7. The use of a porous carbon composite as claimed in claim 5, wherein the coating material for a battery separator is prepared by a method in which the conductive agent comprises conductive carbon black and the binder comprises LA 132.
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| CN111001428B (en) * | 2019-12-24 | 2021-05-14 | 山西大学 | Metal-free carbon-based electrocatalyst, preparation method and application |
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| CN113972437A (en) * | 2021-10-22 | 2022-01-25 | 陕西科技大学 | Battery diaphragm modified by zinc-nickel alloy/carbon nanotube composite material and preparation method thereof |
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| CN114956039A (en) * | 2022-06-09 | 2022-08-30 | 西安理工大学 | Hollow sea urchin-shaped double-metal MOFs (metal-organic frameworks) derived carbon material as well as preparation method and application thereof |
| CN114976484B (en) * | 2022-07-11 | 2023-04-11 | 大连理工大学 | Loaded with Ni 2 P-Co Schottky junction active site echinoid carbon material electrocatalyst, preparation method and application thereof |
| CN115513468B (en) * | 2022-11-22 | 2023-02-28 | 河北北方学院 | Preparation method of CNTs/OMC ordered microporous carbon nanospheres and application method of CNTs/OMC ordered microporous carbon nanospheres in lithium-sulfur battery |
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| CN104710965A (en) * | 2015-04-02 | 2015-06-17 | 北京科技大学 | Method for preparing multilevel porous carbon base composite phase change material |
| CN106531476B (en) * | 2016-12-29 | 2018-10-02 | 湖北文理学院 | A kind of preparation method of metal oxide/carbon composite |
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