CN114597360B - Composite positive electrode material with array orientation hole structure, preparation method and application thereof - Google Patents
Composite positive electrode material with array orientation hole structure, preparation method and application thereof Download PDFInfo
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- 239000002131 composite material Substances 0.000 title claims abstract description 107
- 239000007774 positive electrode material Substances 0.000 title claims abstract description 22
- 238000002360 preparation method Methods 0.000 title claims abstract description 14
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 311
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- 239000011148 porous material Substances 0.000 claims abstract description 62
- 239000007787 solid Substances 0.000 claims abstract description 54
- 239000010405 anode material Substances 0.000 claims abstract description 53
- PTFCDOFLOPIGGS-UHFFFAOYSA-N Zinc dication Chemical compound [Zn+2] PTFCDOFLOPIGGS-UHFFFAOYSA-N 0.000 claims abstract description 47
- 239000003990 capacitor Substances 0.000 claims abstract description 45
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- 244000146553 Ceiba pentandra Species 0.000 claims description 2
- 229920000742 Cotton Polymers 0.000 claims description 2
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 2
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- 239000011701 zinc Substances 0.000 description 19
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 14
- 229910052725 zinc Inorganic materials 0.000 description 14
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- 230000001737 promoting effect Effects 0.000 description 5
- HIEHAIZHJZLEPQ-UHFFFAOYSA-M sodium;naphthalene-1-sulfonate Chemical compound [Na+].C1=CC=C2C(S(=O)(=O)[O-])=CC=CC2=C1 HIEHAIZHJZLEPQ-UHFFFAOYSA-M 0.000 description 4
- 239000007784 solid electrolyte Substances 0.000 description 4
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 3
- 229910001416 lithium ion Inorganic materials 0.000 description 3
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- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 1
- 239000013543 active substance Substances 0.000 description 1
- 239000010406 cathode material Substances 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 125000004122 cyclic group Chemical group 0.000 description 1
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- 229910052708 sodium Inorganic materials 0.000 description 1
- 229910001251 solid state electrolyte alloy Inorganic materials 0.000 description 1
- 238000000527 sonication Methods 0.000 description 1
- BDHFUVZGWQCTTF-UHFFFAOYSA-M sulfonate Chemical compound [O-]S(=O)=O BDHFUVZGWQCTTF-UHFFFAOYSA-M 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 231100000331 toxic Toxicity 0.000 description 1
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Classifications
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/362—Composites
- H01M4/366—Composites as layered products
-
- 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
- H01M10/054—Accumulators with insertion or intercalation of metals other than lithium, e.g. with magnesium or aluminium
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/58—Selection of substances as active materials, active masses, active liquids of inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy; of polyanionic structures, e.g. phosphates, silicates or borates
- H01M4/583—Carbonaceous material, e.g. graphite-intercalation compounds or CFx
- H01M4/587—Carbonaceous material, e.g. graphite-intercalation compounds or CFx for inserting or intercalating light metals
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/13—Energy storage using capacitors
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- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Inorganic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Composite Materials (AREA)
- Materials Engineering (AREA)
- Manufacturing & Machinery (AREA)
- Battery Electrode And Active Subsutance (AREA)
- Carbon And Carbon Compounds (AREA)
- Electric Double-Layer Capacitors Or The Like (AREA)
Abstract
The application discloses a composite positive electrode material with an array orientation hole structure, a preparation method and application thereof. The composite positive electrode material with the array orientation hole structure comprises the following components: a conductive network skeleton having an array oriented lamellar pore structure, which is composed of at least carbon nanotubes and amorphous carbon; carbon microplates distributed on the surface of the network skeleton lamellar structure; wherein the amorphous carbon is formed by high-temperature carbonization of water-soluble polymers. The carbon microchip/carbon nanotube composite anode material with the array orientation pore structure provided by the application has an array orientation lamellar pore structure, can provide a larger effective specific surface area, can provide a rapid and effective transmission channel for electrolyte ions, can serve as an electrolyte storage buffer, and can provide enough charges and ions for electrochemical reaction on the surface of the carbon microchip, thereby improving the energy density, the multiplying power performance and the cycling stability of the solid zinc ion hybrid capacitor.
Description
Technical Field
The application relates to the technical field of electrode materials, in particular to a composite positive electrode material with an array orientation hole structure, a preparation method and application thereof.
Background
With the improvement of global economic living standard, the construction and manufacture of novel electrochemical energy systems with high power, high energy density, long service life and no pollution are favored. In the field of high energy density Lithium Ion Batteries (LIBs), much effort has been devoted to research and development. However, the practical application of lithium ion batteries is greatly hindered by the obvious disadvantages of limited lithium source, high manufacturing cost, easy flow of electrolyte, toxic electrolyte and the like.
Compared with lithium ion batteries, the zinc ion hybrid capacitor has the advantages of abundant natural resources, environmental friendliness, excellent safety, lower electrochemical potential (-0.76V vs SHE), high capacity (5850 mAh/cm) 3 ) And the like, has important research value and large-scale energy storage application prospect.
However, the main technical obstacles which are not overcome by the current zinc ion hybrid capacitor are problems of easiness in generating zinc dendrites, easiness in corroding an anode, side reactions in the electrolyte and the like. In particular, free water in the liquid electrolyte will inevitably corrode the zinc metal anode and cause continuous side reactions, thereby severely reducing the cycling stability of the zinc-ion hybrid cell. Compared with liquid electrolyte, gel or solid electrolyte can effectively inhibit side reaction of electrolyte and growth of zinc dendrite, so that the cycling stability of the zinc ion mixed capacitor is improved.
However, gel or solid state electrolytes have poor ion transport kinetics, especially in conventional porous carbon cathode materials, tortuous pore channels and limited electrochemically active sites, thereby greatly limiting the specific capacity and rate capability of solid state zinc ion hybrid capacitors.
Disclosure of Invention
The inventor of the application discovers through research that constructing a carbon-based anode material with array oriented pore channels and stable structure can effectively accelerate the transmission of solid electrolyte ions, and increase electrochemical active sites at the same time, thereby improving the electrochemical performance of a solid zinc ion battery. In addition, the electrode material has great application prospect in other solid-state battery systems in the future because of a rapid ion transmission channel and rich active sites. Therefore, the application aims to provide a composite positive electrode material with an array orientation hole structure, a preparation method and application thereof.
In order to achieve the purpose of the application, the technical scheme adopted by the application comprises the following steps:
in a first aspect, the present application provides a carbon microchip/carbon nanotube composite positive electrode material having an array oriented pore structure, comprising:
a conductive network skeleton having an array oriented lamellar pore structure, which is composed of at least carbon nanotubes and amorphous carbon;
carbon microplates distributed on the surface of the network skeleton lamellar structure;
wherein the amorphous carbon is formed by high-temperature carbonization of water-soluble polymers.
In a second aspect, the present application also provides a method for preparing the carbon microchip/carbon nanotube composite anode material, including:
preparing an aqueous dispersion liquid containing carbon nanotubes and water-soluble polymers;
dispersing carbon microplates in the aqueous dispersion liquid to form a reaction precursor liquid;
inducing water in the reaction precursor liquid to directionally crystallize by utilizing an ice template method, so that the carbon nano tube, the water-soluble polymer and the carbon microchip form a composite material precursor with an array orientation lamellar pore structure;
and carrying out high-temperature annealing treatment on the composite material precursor to carbonize the water-soluble polymer in the composite material precursor, thereby obtaining the carbon microchip/carbon nano tube composite anode material with the array orientation pore structure.
In a third aspect, the present application also provides a solid-state battery, where the positive electrode material is at least made of the carbon microchip/carbon nanotube composite positive electrode material having the array-oriented pore structure.
In some preferred embodiments, the solid state battery is a solid state zinc ion hybrid capacitor.
In some preferred embodiments, the specific capacity of the solid zinc ion hybrid capacitor is 70-140 mAh.g -1 And has excellent multiplying power performance and cycle stability, and the cycle number is 1000-10000 at 5A/g.
Based on the technical scheme, compared with the prior art, the application has the beneficial effects that:
compared with the traditional carbon microchip lamellar structure horizontally oriented stacking, the carbon microchip/carbon nanotube composite anode material with the array oriented lamellar hole structure can provide a larger effective specific surface area, can provide a rapid and effective transmission channel for gel or solid electrolyte ions, can serve as an electrolyte storage buffer, and can provide enough charges and ions for electrochemical reaction on the surface of the carbon microchip with a large specific surface area, so that the energy density, the rate capability and the cycling stability of a gel or solid ion battery using the composite anode material are improved.
The above description is only an overview of the technical solutions of the present application, and in order to enable those skilled in the art to more clearly understand the technical means of the present application, the present application may be implemented according to the content of the specification, and the following description is given of the preferred embodiments of the present application with reference to the detailed drawings.
Drawings
FIG. 1 is a diagram of a carbon microchip scanning electron microscope provided by an exemplary embodiment of the present application;
FIG. 2 is a graph of the macroscopic morphology of a carbon microchip/carbon nanotube composite anode material with an array oriented pore structure according to an exemplary embodiment of the present application;
FIG. 3 is a graph of the macroscopic morphology of a carbon microchip/carbon nanotube composite anode material with an array oriented pore structure according to an exemplary embodiment of the present application;
FIG. 4 is a scanning electron microscope topography of a longitudinal cross section of a carbon microchip/carbon nanotube composite anode material with an array oriented pore structure according to an exemplary embodiment of the present application;
FIG. 5 is a cross-plane scanning electron microscope topography of a carbon microchip/carbon nanotube composite anode material with an array oriented pore structure provided by another exemplary embodiment of the present application;
FIG. 6 is a scanning electron microscope topography of a longitudinal cross section of a carbon microchip/carbon nanotube composite anode material with an array oriented pore structure provided by another exemplary embodiment of the present application;
FIG. 7 is a scanning electron microscope topography of a longitudinal cross section of a carbon microchip/carbon nanotube composite anode material having an array oriented pore structure provided by yet another exemplary embodiment of the present application;
FIG. 8 is a scanning electron microscope topography of a longitudinal cross section of a carbon microchip/carbon nanotube composite anode material having an array oriented pore structure provided by yet another exemplary embodiment of the present application;
FIG. 9 is a scanning electron microscope topography of a longitudinal cross section of a carbon microchip/carbon nanotube composite anode material having an array oriented pore structure provided by yet another exemplary embodiment of the present application;
FIG. 10 is a cross-plane scanning electron microscope topography of a carbon microchip/carbon nanotube composite anode material with an array oriented pore structure according to still another exemplary embodiment of the present application;
FIG. 11 is a schematic diagram showing a solid zinc ion hybrid capacitor of 5, 30, 70 mV.s using carbon microchip/carbon nanotube composite positive electrode material with an array oriented pore structure in accordance with an exemplary embodiment of the present application -1 Cyclic voltammetry test plots at scan rate;
fig. 12 is a graph showing constant current charge and discharge at different current densities for a solid state zinc ion hybrid capacitor using carbon microchip/carbon nanotube composite positive electrode material with an array oriented pore structure, according to an exemplary embodiment of the present application.
Detailed Description
In view of the shortcomings in the prior art, the inventor of the present application has long studied and practiced in a large number of ways to propose the technical scheme of the present application. The technical scheme, the implementation process, the principle and the like are further explained as follows.
In the following description, numerous specific details are set forth in order to provide a thorough understanding of the present application, however, the present application may be practiced otherwise than as described herein, and therefore the scope of the present application is not limited to the specific embodiments disclosed below.
The embodiment of the application provides a carbon microchip/carbon nano tube composite anode material with an array orientation hole structure, which comprises the following components: a conductive network skeleton having an array oriented lamellar pore structure, which is composed of at least carbon nanotubes and amorphous carbon; carbon microplates distributed on the surface of the network skeleton lamellar structure; wherein the amorphous carbon is formed by high-temperature carbonization of water-soluble polymers.
The technical scheme has the beneficial effects that the carbon microchip with large specific surface area is used as a main active substance, a stable array orientation lamellar structure support and a conductive network are constructed by the carbon nano tube and the water-soluble polymer-based amorphous carbon, and the carbon microchip with large specific surface area is uniformly attached and arranged in an array orientation lamellar pore structure along the array orientation direction, so that a larger surface electrochemical active site is provided. The array oriented pore channels provide a convenient and fast channel for the transfer of electrolyte ions, especially gel or solid electrolyte ions, and can serve as an electrolyte storage buffer to provide enough charges and ions for the electrochemical reaction of the surface of the large specific surface area carbon microchip.
The positive electrode material can be used as a positive electrode material, and can be assembled with a zinc sheet negative electrode material to form a flexible solid zinc ion mixed capacitor, and the flexible solid zinc ion mixed capacitor has excellent electrochemical performance (high specific capacity, excellent multiplying power performance and cycle stability), and the specific capacity can reach 70-140 mAh.g -1 。
In some embodiments, the carbon nanotubes may include one or a combination of two or more of single-walled carbon nanotubes, double-walled carbon nanotubes, and multi-walled carbon nanotubes.
In some embodiments, the water-soluble polymer may include one or a combination of two or more of sodium carboxymethyl cellulose (CMC), polyvinyl alcohol (PVA), polyacrylic acid (PAA), polyacrylamide (PAM), sodium naphthalene sulfonate, and polylactic acid (PLA).
In some embodiments, the carbon microchip may comprise a biomass activated carbon microchip.
In some embodiments, the biomass activated carbon micro-flakes may include one or a combination of two of kapok-based carbon micro-flakes, cotton-based carbon micro-flakes, and catkin-based carbon micro-flakes.
In some embodiments, the specific surface area of the carbon micro-plate may preferably be 1000 to 3000m 2 /g。
In some embodiments, the carbon micro-plate may have a doping of one or more of nitrogen, phosphorus, and oxygen.
In some embodiments, the carbon micro-plate may preferably have an arc of 0 to 50 °, and may preferably have a size of 0.3 to 10 μm, and may preferably have a thickness of 300 to 700nm.
In some embodiments, the sheet spacing of the array oriented sheet pore structure may preferably be from 3 to 50 μm.
In some embodiments, the specific surface area of the carbon microchip/carbon nanotube composite positive electrode material may preferably be 500-2000 m 2 Preferably, the thickness per gram may be from 100 to 3000. Mu.m.
The example of the application also provides a preparation method of the carbon microchip/carbon nano tube composite anode material with the array orientation pore structure in the embodiment, which comprises the following steps:
the aqueous dispersion containing the carbon nanotubes and the water-soluble polymer is prepared by a shearing machine and a homogenizer.
Dispersing the carbon microchip in the aqueous dispersion liquid, and performing hydrothermal evaporation concentration for 2-10 hours at the temperature of 60-100 ℃ to form a reaction precursor liquid. The reaction precursor liquid with different solid contents can be prepared according to different requirements, wherein the solid content refers to the mass fraction of the carbon microchip and the carbon nano tube in the reaction precursor liquid.
And inducing water in the reaction precursor liquid to directionally crystallize by utilizing an ice template method, so that the carbon nano tube, the water-soluble polymer and the carbon microchip form a composite material precursor with an array orientation lamellar pore structure.
And carrying out high-temperature annealing treatment on the composite material precursor to carbonize the water-soluble polymer in the composite material precursor, thereby obtaining the carbon microchip/carbon nano tube composite anode material with the array orientation pore structure.
In the preparation scheme, the water-soluble polymer, the carbon nano tube and the carbon microchip with large specific surface area construct an array-oriented composite lamellar pore structure in the process of directional crystallization of the solvent by an ice template method, and the carbon microchip with large specific surface area is uniformly and stably bonded on the composite lamellar pore structure along the array orientation direction. After high-temperature annealing, the water-soluble polymer is converted into amorphous carbon, and the amorphous carbon, the carbon nano tube and the carbon micro-plate with large specific surface area are combined to construct a final stable array composite orientation plate layer pore structure and a conductive network framework.
And the carbon microchip intercalation with partial water-soluble polymer base amorphous carbon, carbon nano tube and large specific surface area plays a bridging role in the array orientation lamellar structure, and improves the structural stability of the carbon microchip/carbon nano tube composite anode material with the array orientation pore structure.
In some embodiments, the aqueous dispersion may be prepared using a shear as well as a homogenizer. Specifically, for example, a mixture of carbon nanotubes, water-soluble polymer and deionized water may be treated with a shearing sand mill at a rate of 1000-1300r/min for 1-4 hours and then homogenized with a homogenizer for 1-2 hours.
In some embodiments, the carbon nanotubes may preferably be present in the aqueous dispersion in an amount of 0.1 to 0.7wt%.
In some embodiments, the mass ratio of water-soluble polymer to carbon nanotubes in the aqueous dispersion may preferably be 2:1 to 1:4.
In some embodiments, the content of carbon nanotubes and carbon microplates in the reaction precursor solution may preferably be 5 to 40wt%.
In some embodiments, the above preparation method may further comprise: and ultrasonically dispersing the carbon microchip into the aqueous dispersion liquid by adopting a cell pulverizer.
In some embodiments, the mass ratio of carbon micro-platelets to carbon nanotubes in the reaction precursor solution may preferably be 95:5 to 1:1.
In some embodiments, the power of the cell disruptor may preferably be 400 to 900W and the sonication time may preferably be 0.25 to 4 hours.
In some embodiments, the ice template induction method may specifically include the steps of:
and injecting the reaction precursor liquid into a mould with a metal substrate, and impregnating the metal substrate with liquid nitrogen to induce water in the reaction precursor liquid to directionally crystallize to form crystals.
And freeze-drying the crystals to obtain the composite material precursor.
In some embodiments, the time of the liquid nitrogen dip is 15 to 60 minutes.
In some embodiments, the freeze-drying is at a temperature of-40 to-60 ℃ for a period of 12 to 72 hours.
And/or the high-temperature annealing treatment is carried out at 500-1000 ℃, the heating rate is 3-10 ℃/min, the time is 1-3 h, and the atmosphere is under inert gas (such as nitrogen and/or argon).
In a specific application example, the carbon microchip/carbon nanotube composite positive electrode material with the array orientation pore structure can be prepared by the following steps:
1) Firstly, preparing an aqueous dispersion liquid of the carbon nano tube by a shearing sand mill (1200 r/min2 h) and a homogenizer (2 h), wherein the aqueous dispersion liquid comprises single-wall carbon nano tubes, water-soluble polymers and a solvent (deionized water). The carbon nanotubes are single-walled carbon nanotubes, multi-walled carbon nanotubes, and mixtures thereof; the water-soluble polymer is sodium carboxymethylcellulose (CMC), polyvinyl alcohol (PVA), polyacrylic acid (PAA), polyacrylamide (PAM), sodium naphthalene sulfonate, polylactic acid (PLA) and the like. Wherein the content of the carbon nano tube is 0.1 to 0.7 weight percent, and the water-soluble polymer: the mass ratio of the carbon nano tubes is 2:1-1:4.
2) And then, ultrasonically dispersing the carbon micro-plate with a large specific area into the carbon nano tube dispersion liquid through a cell pulverizer to obtain a carbon micro-plate/carbon nano tube composite material precursor liquid (namely the reaction precursor liquid), wherein the mass ratio of the carbon micro-plate to the carbon nano tube is 95:5-1:1. The size of the carbon microchip in the precursor liquid of the carbon microchip/carbon nano tube composite material is controlled to be 0.3-10 mu m by adjusting the power (400-900W) and the ultrasonic time (0.25-4 h) of the cell grinder. The solid content of the final precursor solution is controlled to be 5-50wt% by hydrothermal evaporation (80 ℃ for 2-10 h).
3) Based on the carbon microchip/carbon nanotube composite material precursor liquid, the water solvent in the dispersion liquid is induced to directionally crystallize by an ice template method, so that the water-soluble polymer, the carbon nanotube and the carbon microchip with large specific surface area are assembled into an oriented array lamellar structure, and the carbon microchip/carbon nanotube composite material precursor with an array oriented structure is obtained; and finally, carrying out high-temperature annealing on the precursor to prepare the carbon microchip-carbon nano tube composite anode material with the array orientation structure.
The embodiment of the application also provides application of the carbon microchip/carbon nano tube composite positive electrode material with the array orientation hole structure in the field of solid-state batteries, in particular to a solid-state battery, wherein the positive electrode material is at least prepared from the carbon microchip/carbon nano tube composite positive electrode material with the array orientation hole structure.
In some embodiments, the solid state battery is preferably a solid state zinc ion hybrid capacitor.
In some embodiments, the specific capacity of the solid zinc ion hybrid capacitor is 70-140 mAh.g -1 And has excellent multiplying power performance and cycle stability, and the cycle number is 1000-10000 at 5A/g.
The technical scheme of the application is further described in detail below through a plurality of embodiments and with reference to the accompanying drawings. However, the examples are chosen to illustrate the application only and are not intended to limit the scope of the application.
Example 1
The embodiment provides a preparation method of a carbon microchip/carbon nano tube composite anode material with an array orientation pore structure, which specifically comprises the following steps:
1) Firstly, preparing an aqueous dispersion liquid of the carbon nano tube by a shearing sand mill (1200 r/min2 h) and a homogenizer (2 h), wherein the aqueous dispersion liquid comprises single-wall carbon nano tube, CMC and deionized water. Wherein the content of the carbon nano tube is 0.5 weight percent, CMC: the mass ratio of the content of the single-wall carbon tubes is 1:1.
2) Then the specific surface area is 1700m 2 Ultrasonic separation of/g carbon microchip by cell pulverizerDispersing the mixture into a carbon nano tube dispersion liquid to obtain a reaction precursor liquid of the carbon micro-plate/carbon nano tube composite material, wherein the mass ratio of the carbon micro-plate to the carbon nano tube is 9:1. The size of the carbon microchip in the precursor liquid of the carbon microchip/carbon nano tube composite material is controlled to be about 2 mu m by adjusting the power (600W) and the ultrasonic time (3 h) of the cell pulverizer. The morphology of the carbon microchip used in this step is shown in FIG. 1. The solid content of the final precursor solution was controlled by hydrothermal evaporation to 10wt%.
3) Injecting the prepared carbon microchip/carbon nanotube composite material precursor liquid into a polytetrafluoroethylene mould with metal copper as the bottom, immersing a copper substrate for 1h through liquid nitrogen so as to realize the water solvent directional crystallization in the dispersion liquid, promoting CMC, carbon nanotubes and large specific surface carbon microchip to assemble into an oriented array lamellar structure, and then obtaining the carbon microchip/carbon nanotube composite material precursor with an array oriented structure through freeze drying (the freeze drying temperature is-42 ℃ and the drying time is 24 h).
4) And finally, carrying out high-temperature annealing on the carbon microchip/carbon nanotube composite material precursor, wherein the annealing temperature is 800 ℃, the heating rate is 3 ℃/min, the annealing time is 1h, and the carbon microchip/carbon nanotube composite anode material with an array orientation pore structure is prepared under the atmosphere of argon.
The macro morphology of the carbon micro-plate/carbon nano tube composite anode material with the array orientation pore structure prepared by the steps is shown in fig. 2-3, the longitudinal cross section morphology is shown in fig. 4, the transverse plane (surface) morphology is shown in fig. 5, and as can be seen from an electron microscope picture, the composite anode material has the array orientation lamellar pore structure, micropores are arranged between lamellar layers, and a large number of carbon micro-plates are uniformly distributed on the surface of the lamellar structure.
The embodiment also provides a solid zinc ion mixed capacitor, which uses the carbon microchip/carbon nano tube composite anode material prepared by the steps as an anode material, and uses a zinc sheet as an anode, wherein the concentration of the zinc sheet is 1mol/LPVA/Zn (CF) 3 SO 3 ) 2 For gel electrolyte, solid zinc ion mixed capacitor is assembled, its specific capacity is up to 115mAh/g at 0.1A/g, and when current density is increased to 20A/g, its specific capacity can still be obtainedThe battery shows excellent rate performance by maintaining 75mAh/g, cyclic voltammetry performance test of the battery at different scanning rates is shown in figure 11, constant current charge-discharge curves at different charge-discharge current densities are shown in figure 12, and figures 11 and 12 reflect that the battery has excellent rate performance and cyclic stability.
Example 2
The embodiment provides a preparation method of a carbon microchip/carbon nano tube composite anode material with an array orientation pore structure, which specifically comprises the following steps:
1) Firstly, preparing an aqueous dispersion liquid of the carbon nano tube by a shearing sand mill (1200 r/min2 h) and a homogenizer (2 h), wherein the aqueous dispersion liquid comprises single-wall carbon nano tubes, polyvinyl alcohol PVA and deionized water. Wherein the content of the carbon nano tube is 0.2wt%, PVA: the mass ratio of the content of the single-wall carbon tubes is 1:2.
2) Then the specific surface area is 1700m 2 And (3) ultrasonically dispersing the/g carbon microchip into the carbon nanotube dispersion liquid through a cell pulverizer to obtain a reaction precursor liquid of the carbon microchip/carbon nanotube composite material, wherein the mass ratio of the carbon microchip to the carbon nanotube is 85:15. The size of the carbon microchip in the precursor liquid of the carbon microchip/carbon nano tube composite material is controlled to be about 4 mu m by adjusting the power (600W) and the ultrasonic time (2 h) of the cell pulverizer, and the solid content of the final precursor liquid is controlled to be 15wt% by hydrothermal evaporation.
3) Injecting the prepared carbon microchip/carbon nanotube composite material precursor liquid into a polytetrafluoroethylene mould with metal copper as the bottom, immersing a copper substrate for 1h through liquid nitrogen so as to realize the water solvent directional crystallization in the dispersion liquid, promoting the PVA, the carbon nanotubes and the carbon microchip with large specific surface area to assemble into an oriented array lamellar structure, and then obtaining the carbon microchip/carbon nanotube composite material precursor with an array oriented structure through freeze drying (the freeze drying temperature is-42 ℃ and the drying time is 12 h).
4) And finally, carrying out high-temperature annealing on the carbon microchip/carbon nanotube composite material precursor, wherein the annealing temperature is 700 ℃, the heating rate is 3 ℃/min, the annealing time is 1h, and the carbon microchip/carbon nanotube composite anode material with an array orientation pore structure is prepared under the atmosphere of argon.
The macro morphology of the carbon microchip/carbon nanotube composite anode material with the array orientation pore structure prepared by the steps is shown in figure 6, and as can be seen from an electron microscope picture, the composite anode material has an array orientation lamellar pore structure, micropores are arranged between lamellar layers, and a large number of carbon microchip are uniformly distributed on the surface of the lamellar structure.
The embodiment also provides a solid zinc ion mixed capacitor, which uses the carbon microchip/carbon nano tube composite anode material prepared by the steps as an anode material, and uses a zinc sheet as an anode, wherein the concentration of the zinc sheet is 1mol/LPVA/Zn (CF) 3 SO 3 ) 2 The solid zinc ion mixed capacitor is assembled as a gel electrolyte, the specific capacity of the solid zinc ion mixed capacitor is up to 110mAh/g at 0.1A/g, and when the current density is increased to 20A/g, the specific capacity of the solid zinc ion mixed capacitor can still be kept at 70mAh/g, and the solid zinc ion mixed capacitor shows excellent multiplying power performance.
Example 3
The embodiment provides a preparation method of a carbon microchip/carbon nano tube composite anode material with an array orientation pore structure, which specifically comprises the following steps:
1) Firstly, preparing an aqueous dispersion liquid of the carbon nano tube by a shearing sand mill (1200 r/min2 h) and a homogenizer (2 h), wherein the aqueous dispersion liquid comprises single-walled carbon nano tube, polyacrylamide PAM and deionized water. Wherein the content of the carbon nano tube is 0.2 weight percent, PAM: the mass ratio of the content of the single-wall carbon tubes is 1:2.
2) Then the specific surface area is 1700m 2 And (3) ultrasonically dispersing the/g carbon microchip into the carbon nanotube dispersion liquid through a cell pulverizer to obtain a reaction precursor liquid of the carbon microchip/carbon nanotube composite material, wherein the mass ratio of the carbon microchip to the carbon nanotube is 4:1. the size of the carbon microchip in the precursor liquid of the carbon microchip/carbon nano tube composite material is controlled to be about 2 mu m by adjusting the power (600W) and the ultrasonic time (4 h) of the cell pulverizer, and the solid content of the final precursor liquid is controlled to be 35wt% by hydrothermal evaporation. .
3) Injecting the prepared carbon microchip/carbon nanotube composite material precursor liquid into a polytetrafluoroethylene mould with metal copper as the bottom, immersing a copper substrate for 1h through liquid nitrogen so as to realize the water solvent directional crystallization in the dispersion liquid, promoting PAM, carbon nanotubes and large specific surface carbon microchip to assemble into an oriented array lamellar structure, and then obtaining the carbon microchip/carbon nanotube composite material precursor with an array oriented structure through freeze drying (the freeze drying temperature is-42 ℃ and the drying time is 24 h).
4) And finally, carrying out high-temperature annealing on the carbon microchip/carbon nanotube composite material precursor, wherein the annealing temperature is 900 ℃, the heating rate is 3 ℃/min, the annealing time is 1h, and the carbon microchip/carbon nanotube composite anode material with an array orientation pore structure is prepared under the atmosphere of argon.
The macro morphology of the carbon microchip/carbon nanotube composite anode material with the array orientation pore structure prepared by the steps is shown in figure 7, and as can be seen from an electron microscope picture, the composite anode material has an array orientation lamellar pore structure, micropores are arranged between lamellar layers, and a large number of carbon microchip are uniformly distributed on the surface of the lamellar structure.
The embodiment also provides a solid zinc ion mixed capacitor, which uses the carbon microchip/carbon nano tube composite anode material prepared by the steps as an anode material, and uses a zinc sheet as an anode, wherein the concentration of the zinc sheet is 1mol/LPVA/Zn (CF) 3 SO 3 ) 2 The solid zinc ion mixed capacitor is assembled as a gel electrolyte, the specific capacity of the solid zinc ion mixed capacitor is as high as 112mAh/g at 0.1A/g, and when the current density is increased to 20A/g, the specific capacity of the solid zinc ion mixed capacitor can still be kept at 71mAh/g, and the solid zinc ion mixed capacitor has excellent multiplying power performance.
Example 4
The embodiment provides a preparation method of a carbon microchip/carbon nano tube composite anode material with an array orientation pore structure, which specifically comprises the following steps:
1) Firstly, preparing an aqueous dispersion liquid of the carbon nano tube by a shearing sand mill (1200 r/min2 h) and a homogenizer (2 h), wherein the aqueous dispersion liquid comprises single-wall carbon nano tubes, polylactic acid PLA and deionized water. Wherein the content of the carbon nano tube is 0.2 weight percent, PLA: the mass ratio of the content of the single-wall carbon tubes is 1:1.
2) Then the specific surface area is 1700m 2 The/g carbon microchip is crushed by cellsMechanically and ultrasonically dispersing the carbon micro-plate and the carbon nano-tube into a carbon nano-tube dispersion liquid to obtain a reaction precursor liquid of the carbon micro-plate/carbon nano-tube composite material, wherein the mass ratio of the carbon micro-plate to the carbon nano-tube is 7:3. the size of the carbon microchip in the precursor liquid of the carbon microchip/carbon nano tube composite material is controlled to be about 4 mu m by adjusting the power (600W) and the ultrasonic time (3 h) of the cell pulverizer, and the solid content of the final precursor liquid is controlled to be 30wt% by hydrothermal evaporation. .
3) Injecting the prepared carbon microchip/carbon nanotube composite material precursor liquid into a polytetrafluoroethylene mould with metal copper as the bottom, immersing a copper substrate for 1h through liquid nitrogen so as to realize the directional crystallization of a water solvent in the dispersion liquid, promoting the assembly of PLA, carbon nanotubes and carbon microchip with large specific surface area into an oriented array lamellar structure, and then obtaining the carbon microchip/carbon nanotube composite material precursor with an array oriented structure through freeze drying (the freeze drying temperature is-42 ℃ and the drying time is 48 h).
4) And finally, carrying out high-temperature annealing on the carbon microchip/carbon nanotube composite material precursor, wherein the annealing temperature is 900 ℃, the heating rate is 5 ℃/min, the annealing time is 1h, and the carbon microchip/carbon nanotube composite anode material with an array orientation pore structure is prepared under the atmosphere of argon.
The macro morphology of the carbon microchip/carbon nanotube composite anode material with the array orientation pore structure prepared by the steps is shown in fig. 8 and 9, and as can be seen from an electron microscope picture, the composite anode material has an array orientation lamellar pore structure, micropores are formed between lamellar layers, and a large number of carbon microchip are uniformly distributed on the surface of the lamellar structure.
The embodiment also provides a solid zinc ion mixed capacitor, which uses the carbon microchip/carbon nano tube composite anode material prepared by the steps as an anode material, and uses a zinc sheet as an anode, wherein the concentration of the zinc sheet is 1mol/LPVA/Zn (CF) 3 SO 3 ) 2 The solid zinc ion mixed capacitor is assembled as a gel electrolyte, the specific capacity of the solid zinc ion mixed capacitor is as high as 111mAh/g at 0.1A/g, and the specific capacity of the solid zinc ion mixed capacitor can still keep 69mAh/g when the current density is increased to 20A/g, so that the solid zinc ion mixed capacitor has excellent multiplying power performance.
Example 5
The embodiment provides a preparation method of a carbon microchip/carbon nano tube composite anode material with an array orientation pore structure, which specifically comprises the following steps:
1) Firstly, preparing an aqueous dispersion liquid of the carbon nano tube by a shearing sand mill (1200 r/min2 h) and a homogenizer (2 h), wherein the aqueous dispersion liquid comprises single-wall carbon nano tubes, sodium naphthalene sulfonate PLA and deionized water. Wherein the content of the carbon nano tube is 0.5 weight percent, sodium sulfonate: the mass ratio of the content of the single-wall carbon tubes is 1:1.
2) Then the specific surface area is 1700m 2 And (3) ultrasonically dispersing the/g carbon microchip into the carbon nanotube dispersion liquid through a cell pulverizer to obtain a reaction precursor liquid of the carbon microchip/carbon nanotube composite material, wherein the mass ratio of the carbon microchip to the carbon nanotube is 7:3. the size of the carbon microchip in the precursor liquid of the carbon microchip/carbon nano tube composite material is controlled to be about 3 mu m by adjusting the power (600W) and the ultrasonic time (4 h) of the cell pulverizer, and the solid content of the final precursor liquid is controlled to be 40wt% by hydrothermal evaporation. .
3) Injecting the prepared carbon microchip/carbon nanotube composite material precursor liquid into a polytetrafluoroethylene mould with metal copper as the bottom, immersing a copper substrate for 1h through liquid nitrogen so as to realize the water solvent directional crystallization in the dispersion liquid, promoting the sodium naphthalene sulfonate, the carbon nanotubes and the carbon microchip with large specific surface area to assemble into an oriented array lamellar structure, and then obtaining the carbon microchip/carbon nanotube composite material precursor with an array oriented structure through freeze drying (the freeze drying temperature is-42 ℃ and the drying time is 48 h).
4) And finally, carrying out high-temperature annealing on the carbon microchip/carbon nanotube composite material precursor, wherein the annealing temperature is 800 ℃, the heating rate is 5 ℃/min, the annealing time is 1h, and the carbon microchip/carbon nanotube composite anode material with an array orientation pore structure is prepared under the atmosphere of argon.
The macro morphology of the carbon microchip/carbon nanotube composite anode material with the array orientation pore structure prepared by the steps is shown in figure 10, and as can be seen from an electron microscope picture, the composite anode material has an array orientation lamellar pore structure, micropores are arranged between lamellar layers, and a large number of carbon microchip are uniformly distributed on the surface of the lamellar structure.
The embodiment also provides a solid zinc ion mixed capacitor, which uses the carbon microchip/carbon nano tube composite anode material prepared by the steps as an anode material, and uses a zinc sheet as an anode, wherein the concentration of the zinc sheet is 1mol/LPVA/Zn (CF) 3 SO 3 ) 2 The solid zinc ion mixed capacitor is assembled for gel electrolyte, the specific capacity of the solid zinc ion mixed capacitor is as high as 105mAh/g at 0.1A/g, and when the current density is increased to 20A/g, the specific capacity of the solid zinc ion mixed capacitor can still be kept at 68mAh/g, and the solid zinc ion mixed capacitor has excellent multiplying power performance.
Based on the above embodiments, it can be clear that the carbon microchip/carbon nanotube composite anode material with the array orientation pore structure provided by the embodiment of the application has a special array orientation lamellar pore structure and carbon microchip distributed on the surface of the network skeleton lamellar structure form an active center, so that the energy density, the multiplying power performance and the cycling stability of the solid zinc ion hybrid capacitor can be obviously improved.
It should be understood that the above embodiments are merely for illustrating the technical concept and features of the present application, and are intended to enable those skilled in the art to understand the present application and implement the same according to the present application without limiting the scope of the present application. All equivalent changes or modifications made in accordance with the spirit of the present application should be construed to be included in the scope of the present application.
Claims (7)
1. The solid zinc ion mixed capacitor is characterized in that the positive electrode material of the solid zinc ion mixed capacitor is at least made of a carbon microchip/carbon nano tube composite positive electrode material with an array orientation pore structure, and the carbon microchip/carbon nano tube composite positive electrode material with the array orientation pore structure comprises the following components:
a conductive network skeleton having an array oriented lamellar pore structure composed of at least carbon nanotubes and amorphous carbon;
carbon microplates distributed on the surface of the network skeleton lamellar structure;
wherein the amorphous carbon is formed by high-temperature carbonization of water-soluble polymers, and the carbon microchip has nitrogen,Doping of any one or more than two elements of phosphorus and oxygen; the carbon microchip comprises a biomass activated carbon microchip, wherein the biomass activated carbon microchip comprises any one or more than two of a kapok-based carbon microchip, a cotton-based carbon microchip and a catkin-based carbon microchip; the specific surface area of the carbon microchip is 1000-3000 m 2 /g; the radian of the carbon microchip is 0-50 degrees, the dimension is 0.3-10 mu m, and the thickness is 300-700 nm; the lamellar spacing of the array orientation lamellar pore structure is 3-50 mu m; the specific surface area of the carbon microchip/carbon nano tube composite positive electrode material is 500-2000 m 2 /g, the thickness is 100-3000 μm;
the preparation method of the carbon microchip/carbon nano tube composite anode material with the array orientation pore structure comprises the following steps:
preparing an aqueous dispersion liquid containing carbon nanotubes and water-soluble polymers by a shearing machine and a homogenizer;
dispersing the carbon microchip in the aqueous dispersion liquid, and performing hydrothermal evaporation concentration for 2-10 hours at the temperature of 60-100 ℃ to form a reaction precursor liquid;
inducing water in the reaction precursor liquid to directionally crystallize by utilizing an ice template method, so that the carbon nano tube, the water-based polymer and the carbon microchip form a composite material precursor with an array orientation lamellar pore structure;
carrying out high-temperature annealing treatment on the composite material precursor to carbonize water-soluble polymers in the composite material precursor, so as to obtain a carbon microchip/carbon nano tube composite anode material with an array orientation pore structure;
the mass ratio of the water-soluble polymer to the carbon nano tube in the aqueous dispersion liquid is 2:1-1:4, and the mass ratio of the carbon microchip to the carbon nano tube in the reaction precursor liquid is 95:5-7:3;
the ice template method comprises the following steps:
injecting the reaction precursor liquid into a mould with a metal substrate, and impregnating the metal substrate with liquid nitrogen to induce water in the reaction precursor liquid to directionally crystallize to form crystals;
freeze-drying the crystals to obtain the composite material precursor;
wherein the time of liquid nitrogen impregnation is 15-60 min; the freeze drying temperature is-40 to-60 ℃ and the time is 12-72 h.
2. The solid state zinc ion hybrid capacitor of claim 1, wherein the carbon nanotubes comprise any one or a combination of two or more of single wall carbon nanotubes, double wall carbon nanotubes, and multi wall carbon nanotubes.
3. The solid zinc ion hybrid capacitor according to claim 1, wherein the water-soluble polymer includes any one or a combination of two or more of sodium carboxymethyl cellulose, polyvinyl alcohol, polyacrylic acid, polyacrylamide, and polylactic acid.
4. The solid state zinc ion hybrid capacitor of claim 1, wherein the carbon nanotubes are present in the aqueous dispersion in an amount of 0.1 to 0.7wt%.
5. The solid zinc ion mixed capacitor of claim 1, wherein the content of carbon nanotubes and carbon microplates in the reaction precursor solution is 5-50 wt%;
the dispersing of the carbon micro-platelets in the aqueous dispersion comprises: ultrasonically dispersing the carbon microchip into an aqueous dispersion liquid by adopting a cell pulverizer;
the power of the cell grinder is 400-900W, and the ultrasonic time is 0.25-4 h.
6. The solid zinc ion hybrid capacitor of claim 1, wherein the high temperature annealing treatment is performed at a temperature of 500-1000 ℃, a heating rate of 3-10 ℃/min, and a time of 1-3 hours.
7. The solid zinc ion hybrid capacitor of claim 1, wherein the specific capacity of the solid zinc ion hybrid capacitor is 70-140 mAh-g -1 The cycle number at a current density of 5A/g is 1000-10000 turns.
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