CN110745806B - Method for preparing multi-stage porous carbon material by using bacteria as template to grow MOF and application of multi-stage porous carbon material in energy storage device - Google Patents

Method for preparing multi-stage porous carbon material by using bacteria as template to grow MOF and application of multi-stage porous carbon material in energy storage device Download PDF

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CN110745806B
CN110745806B CN201911039216.8A CN201911039216A CN110745806B CN 110745806 B CN110745806 B CN 110745806B CN 201911039216 A CN201911039216 A CN 201911039216A CN 110745806 B CN110745806 B CN 110745806B
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邓昭
赵晓辉
胡加鹏
袁协涛
王崇龙
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Abstract

The invention discloses a method for growing MOF materials on the surfaces of bacteria and converting the MOF materials into multi-stage porous carbon materials by taking the bacteria as templates, which comprises the following steps: (1) dispersing bacterial powder in a precursor solution, sequentially adding an organic ligand and soluble metal salt, uniformly mixing, sealing and standing for 12-24 hours; (2) and centrifuging and cleaning the solution after standing, and drying, carbonizing and grinding the obtained precipitate to obtain the multistage porous carbon material. The invention also discloses the multistage porous carbon material prepared by the method and a lithium-sulfur battery and a zinc-air battery prepared by the multistage porous carbon material. According to the preparation method of the multi-stage porous carbon material, bacteria are used as biological templates and partial carbon sources, and the multi-stage porous carbon material is constructed by combining the bacterial structure with the MOF material with multiple pore channels, so that the method is extremely simple and effective.

Description

Method for preparing multi-stage porous carbon material by using bacteria as template to grow MOF and application of multi-stage porous carbon material in energy storage device
Technical Field
The invention relates to the technical field of porous carbon materials, in particular to a multistage porous carbon material prepared by using bacteria as templates to grow MOF (metal organic framework) and application thereof in an energy storage device.
Background
The lithium-sulfur battery is formed by combining an elemental sulfur cathode and a metallic lithium anodeThe theoretical specific mass capacity of the novel battery which is combined with the electrodes is 1675 mAh.g-1The energy density is as high as 2500 Wh/kg-1Is a traditional lithium ion battery (500 Wh.kg)-1) 5 times of the total weight of the powder. The cathode sulfur material is abundant in the earth, simple substances and compounds of the cathode sulfur material are widely present in various minerals, and the cathode sulfur material has the advantages of wide sources, low cost, environmental friendliness and the like, and is urgently needed by rapidly-developed electric vehicles and large-scale intelligent power grids. Although lithium sulfur batteries show very promising performance, practical application of lithium sulfur batteries is still hampered by scientific and technical problems, such as sulfur and its products (Li)2S2/Li2S), the insulating property, the volume expansion effect, the shuttle effect and the like.
The basic structure of the zinc-air battery consists of a zinc electrode, an alkaline electrolyte and a porous air electrode containing an active material. During the discharge, the zinc oxidizes, releasing electrons that reach the air electrode through an external circuit. At the same time, atmospheric oxygen molecules diffuse into the air electrode and, through ORR reduction, hydroxide ions are formed at the three-phase boundary of oxygen (gas), electrolyte (liquid), active species (solid). Compared with closed systems such as lithium batteries, zinc-air batteries have a unique semi-open system, utilize oxygen in ambient air to minimize the mass and volume required for air electrodes, and increase energy density, which has attracted much attention in recent years. Theoretical energy density of zinc-air battery (1218 Wh kg)-1) About 3 times of lithium ion battery and low manufacturing cost. Therefore, zinc air batteries are considered to be a promising alternative to lithium ion batteries in future energy applications.
At present, carbon materials are indispensable components of electrochemical energy storage devices (such as lithium batteries and lithium-sulfur batteries), and particularly, carbon nanomaterials are considered as the main body of the lithium-sulfur battery most suitable for containing sulfur to form a composite cathode. Through reasonable combination of sulfur and the nano carbon material, the conductivity of the whole electrode is enhanced, and the advantages of high-quality load of active sulfur, inhibition of shuttle effect of intermediate polysulfide to a certain extent and the like are realized. The common carbon material has low density and small specific surface area, and does not have abundant multistage pore channel structure and high pore volume to deal with volume expansion effect. In addition, conventional non-polar carbon materials repel polar polysulfides, neither physically coating the sulfur and polysulfides, nor chemisorbed anchoring the polysulfides, and do not completely hinder the shuttling effect.
For zinc-air cells, the catalyst is a critical component of the air electrode, which determines the structure, performance and cost of the zinc-air cell, and therefore the primary task of the air electrode is an efficient, robust, inexpensive catalyst. At present, the noble metal platinum and the metal oxide IrO2And RuO2Are widely used as baseline catalysts for ORR and OER, respectively. Although Pt and IrO2、RuO2Has good activity, but the scarcity, the high price and the insufficient stability of the noble metal catalyst seriously restrict the wide application of the noble metal catalyst in zinc-air batteries. Furthermore, a single noble metal catalyst cannot act as a dual function electrocatalyst for ORR and OER simultaneously. Therefore, the development of an inexpensive, durable, and highly active bifunctional oxygen catalyst is critical to its practical application in zinc-air batteries.
Disclosure of Invention
The invention aims to solve the technical problem of providing a method for growing MOF materials on the surfaces of bacteria and converting the MOF materials into multi-stage porous carbon materials by taking the bacteria as templates, wherein the method is extremely simple and effective, and the multi-stage porous carbon materials are constructed by taking the bacteria as biological templates and partial carbon sources and utilizing the cell structures of the bacteria and the MOF materials with multiple pore passages.
In order to solve the technical problem, the invention provides a method for growing an MOF material on the surface of bacteria and converting the MOF material into a multi-stage porous carbon material by taking the bacteria as a template, which comprises the following steps:
(1) dispersing bacterial powder in methanol, adding dimethyl imidazole, soluble zinc salt and/or soluble cobalt salt, uniformly mixing, sealing and standing for 12-24 hours;
(2) and centrifuging and cleaning the solution after standing, and drying, carbonizing and grinding the obtained precipitate to obtain the multistage porous carbon material.
The bacteria have wide sources, and can change waste into valuable and benefitThe method comprises the steps of uniformly growing Zn and Co bimetal MOF precursors on the surfaces of bacteria serving as templates, and then carbonizing the precursors at high temperature. Under the high temperature condition, Zn metal is reduced into a simple substance to volatilize, auxiliary pore forming is carried out on the surface of the material, and a microporous-mesoporous-macroporous hierarchical pore carbon structure is formed by the Zn metal, the MOF micropores and the macropores in the bacteria. The remaining Co metal can react with rich P and N elements contained in the phospholipid bilayer on the surface of the bacteria to generate polar Co2P，Co-NxAnd (5) structure. In addition, partial P and N elements enter the three-dimensional porous carbon in a doped form, so that the conductivity of the whole material is improved, and the material is formed into a capsule shape and loaded with polar Co2P and Co-NxThe multistage porous carbon material of (3).
In the invention, Zn is used for separating Co on one hand, so that Co is not agglomerated and can be better generated with P to form Co2P; on the other hand, Zn is evaporated in the carbonization process, and the pore channels are opened, so that the specific surface area of the product multi-stage pore channel carbon material is increased.
Further, in the step (1), the mass content of the bacteria in the bacteria powder is 5-10%.
Further, in the step (1), the concentration of the bacterial powder dispersed in the methanol is 0.98-2 ml/g.
Further, in step (1), the bacteria include, but are not limited to, escherichia coli and staphylococcus.
Further, in the step (1), the soluble zinc salt is zinc nitrate, and the soluble cobalt salt is cobalt nitrate.
Further, in the step (1), the zinc nitrate and the cobalt nitrate are added in the form of solid of crystalline hydrate; further, the mass ratio of the nitrate to the dimethyl imidazole is 0.5-1: 1; further, the mass ratio of the zinc nitrate to the cobalt nitrate is 1-9: 1-9, for example, the mass ratio of the zinc nitrate to the cobalt nitrate can be 9:1, 5:1, 3:1, 1:1, 1:3, 1:5, 1:9, preferably 3:1, and the obtained product has a large specific surface area, and at the same time, Co has a large specific surface area2P is also distributed more uniformly and the active material is fully exposed.
Further, in the step (2), the drying conditions are as follows: the drying temperature is 45-60 ℃, and the drying time is 6-12 h.
Further, in the step (2), the carbonization conditions are as follows: heating to 700-1000 ℃ at a speed of 1-10 ℃/min, and carbonizing for 2-7 hours.
The invention also provides the multistage porous carbon material prepared by the preparation method.
Further, Co in the multistage porous carbon material2The content of P is 0-10 wt%.
The invention also provides a lithium-sulfur battery, and the cathode of the lithium-sulfur battery is prepared from the capsule-shaped multistage porous carbon material.
The invention also provides a zinc-air battery, and an air electrode of the zinc-air battery takes the capsule-shaped multistage porous carbon material as a catalyst.
The invention has the beneficial effects that:
1. the invention takes bacteria as a biological template and part of carbon sources, and utilizes the combination of a bacterial cell structure and a porous MOF material to construct a multi-stage porous carbon material, the bacteria have wide sources, are easy to obtain, are convenient for industrial fermentation, and can be produced and synthesized in a large scale; and the composite material has the advantages of simple synthesis process, no pollution and environmental protection.
2. Due to the characteristics of rich pore channels and high specific surface area, the multistage porous carbon material realizes high load on sulfur simple substance and can deal with the problem of volume expansion, polar Co2The existence of materials such as P and the like can anchor lithium polysulfide strongly in a chemical adsorption mode, the movement of sulfur and lithium polysulfide is physically blocked by the core-shell structure, the shuttle effect can be fully inhibited by physical and chemical double insurance, and the cycle life of the lithium-sulfur battery is effectively prolonged. The multistage porous activated carbon material shows good cycle performance when being applied as a sulfur storage matrix material.
The N and P doped porous carbon has higher conductivity and is more beneficial to the transmission of current carriers; co supported on the surface2The P material can be converted into hydroxide of Co in alkaline electrolyte more quickly than Co nano particles, and has comparable RuO2OER performance of (2), while Co-NxIt has also been shown to have excellent ORR performance with a half-wave potential of up to 0.85V, which is slightly better than 0.84V for commercial Pt/C. The material has excellent bifunctional (OER and ORR) catalytic performance, is an excellent, cheap and efficient electrode material, and has great potential in zinc-air battery air electrode application.
Drawings
FIG. 1 is a XRD characterization of activated carbon materials prepared in examples 1-4;
FIG. 2 is an SEM image of the carbon material prepared in example 1;
FIG. 3 is an SEM image of the carbon material prepared in example 2;
FIG. 4 is an SEM image of the carbon material prepared in example 3;
FIG. 5 is an SEM image of the carbon material prepared in example 4;
FIG. 6 cycle test plots of a simulated lithium sulfur battery in example 5;
fig. 7 is a side view of a long cycle of the lithium sulfur cell of example 5 under 1C conditions.
FIG. 8 is a LSV plot of OER and ORR in example 6.
FIG. 9 shows the zinc-air cell of example 6 at 10mA cm-2Charge and discharge curves at current density.
FIG. 10 shows the flexible zinc-air cell of example 6 at 5mA cm-2Charge and discharge curves at current density.
FIG. 11 is an SEM image of a carbon material prepared from Staphylococcus in example 7.
Detailed Description
The present invention is further described below in conjunction with the following figures and specific examples so that those skilled in the art may better understand the present invention and practice it, but the examples are not intended to limit the present invention.
Example 1
Uniformly dispersing 0.2g of escherichia coli bacterial powder into bacterial suspension by using 200mL of methanol, then sequentially adding 2.4g of dimethylimidazole and 1.2g of zinc nitrate, uniformly stirring, performing ultrasonic treatment for 30min, and standing at a sealed room temperature to grow ZIF-8 (an MOF material). Centrifuging after 24h, washing with methanol for multiple times to obtain white precipitate, vacuum drying in a 60-degree oven for 12h, taking out, grinding, weighing, and carbonizing at 900 ℃ at a heating rate of 5 ℃/min under the protection of nitrogen or argon for 5 h. And grinding after carbonization and cooling to obtain the capsule-shaped multi-stage pore canal active multifunctional carbon material.
The micro-morphology of the multifunctional carbon material obtained in example 1 is shown in FIG. 2.
Example 2
Uniformly dispersing 0.2g of escherichia coli bacterial powder into bacterial suspension by 200mL of methanol, then sequentially adding 2.4g of dimethylimidazole, 0.9g of zinc nitrate and 0.3g of cobalt nitrate, uniformly stirring, performing ultrasonic treatment for 30min, sealing, and standing at room temperature to grow ZIF. Centrifuging after 24h, washing with methanol for multiple times to obtain light blue precipitate, vacuum drying in a 60-degree oven for 12h, taking out, grinding, weighing, and carbonizing at 900 ℃ at a heating rate of 5 ℃/min under the protection of nitrogen or argon for 5 h. And grinding after carbonization and cooling to obtain the capsule-shaped multi-stage pore canal active multifunctional carbon material.
The micro-morphology of the multifunctional carbon material obtained in example 2 is shown in FIG. 3.
Example 3
Uniformly dispersing 0.2g of escherichia coli bacterial powder into bacterial suspension by 200mL of methanol, then sequentially adding 2.4g of dimethylimidazole, 0.6g of zinc nitrate and 0.6g of cobalt nitrate, uniformly stirring, performing ultrasonic treatment for 30min, sealing, and standing at room temperature to grow ZIF. Centrifuging after 24h, washing with methanol for multiple times to obtain blue precipitate, vacuum drying in a 60-degree oven for 12h, taking out, grinding, weighing, and carbonizing at 900 ℃ at a heating rate of 5 ℃/min under the protection of nitrogen or argon for 5 h. And grinding after carbonization and cooling to obtain the capsule-shaped multi-stage pore canal active multifunctional carbon material.
As the Co content increased, the product contained more Co nanoparticles product enriched on the surface, SEM image is shown in figure 4.
Example 4
Uniformly dispersing 0.2g of escherichia coli bacterial powder into bacterial suspension by using 200mL of methanol, then sequentially adding 2.4g of dimethylimidazole and 1.2g of cobalt nitrate, uniformly stirring, performing ultrasonic treatment for 30min, sealing, and standing at room temperature to grow ZIF-67. Centrifuging after 24h, washing with methanol for multiple times to obtain a bluish purple precipitate, vacuum drying in a 60-DEG C oven for 12h, taking out, grinding, weighing, carbonizing at 900 ℃ at a heating rate of 5 ℃/min under the protection of nitrogen or argon, and carbonizing for 5 h. And grinding after carbonization and cooling to obtain the capsule-shaped multi-stage pore canal active multifunctional carbon material.
As the Co content increased, the product contained more Co nanoparticles product enriched on the surface, SEM image is shown in fig. 5.
Example 5
Weighing multistage porous carbon-based materials, conductive carbon black (super-P) and polyvinylidene fluoride respectively according to a mass ratio of 70:20:10, grinding uniformly to prepare an electrode, taking a metal lithium sheet as a positive electrode, and taking electrolyte as 0.1MLiNO3the/DME/DOL is prepared by using a solvent, and the polypropylene microporous film is a diaphragm to assemble the simulated lithium-sulfur battery. The simulated lithium sulfur cell was subjected to cycling tests on the novice cell test instrument at a voltage interval of 1.8-2.6V at a current density of 0.5C, and the results are shown in fig. 6.
As can be seen from fig. 6, Zn: Co battery performance was best at 3:1, with the highest specific capacity and stability, while the specific capacity gradually decreased with increasing Co content. In addition, the pure Zn carbonized multi-stage porous carbon material does not contain Co2The presence of P, the specific capacity and the cycling performance are all the lowest.
As can be seen from FIG. 7, the discharge capacity of the lithium-sulfur battery with Zn: Co of 3:1 of the invention after 500 cycles of 1C is close to 700mAh g-1And is very stable.
Example 6
With 6M KOH +0.2M ZnCl2The metal zinc sheet is a metal electrode, and the gas diffusion layer loaded with the catalyst is an air electrode to form the simulated zinc-air battery. Wherein the multi-stage porous carbon-based material and acetylene black (mass ratio of 4:1) are dispersed in ethanol and 5% Nafion solution to form mixed slurry, the concentration of the catalyst is 10mg/ml, and then the mixed slurry is dripped on carbon paper to ensure that the mass load is 1mg/cm2. As a comparison, the slurry active materials for standard cells consisted of pure Pt/C and RuO2Mixed according to the mass ratio of 1: 1. The prepared zinc-air battery is at 10mA/cm2The charge and discharge test was cycled on a blue test rig at current density.
As can be seen in FIG. 8, the OER performance approaches RuO2At 10mA cm-2The overpotential at the current density of (a) is 320 mV; the half-wave potential is higher than 0.84V of Pt/C and reaches 0.85V.
As can be seen from FIG. 9, the zinc-air cell of the present invention has excellent long cycle performance at 10mA cm-2The power is continuously stabilized for more than 140h under the current density, and the Pt/C-RuO of the noble metal2Only 22 h.
FIG. 10 shows that the flexible zinc-air battery is stably charged and discharged for 35h and is also superior to Pt/C-RuO2。
The above results show that the multistage porous carbon material of the present invention exhibits high catalytic activity (OER performance comparable to RuO performance) as a catalyst2320mV over-potential, ORR performance exceeds Pt/C by 0.85V). The metal air electrode with the bifunctional catalytic performance is applied to a zinc-air battery and a flexible zinc-air battery to show good cycle performance (the open-circuit voltage of the zinc-air battery is 1.4V for 140h, and the open-circuit voltage of the flexible zinc-air battery is kept at 1.31V at 30 degrees, 90 degrees and 180 degrees, and the flexible zinc-air battery is cyclically charged and discharged for at least 30 h).
Example 7
Uniformly dispersing 0.2g of staphylococcus powder into bacterial suspension by 200mL of methanol, then sequentially adding 2.4g of dimethylimidazole, 0.9g of zinc nitrate and 0.3g of cobalt nitrate, uniformly stirring, carrying out ultrasonic treatment for 30min, sealing, and standing at room temperature to grow ZIF. Centrifuging after 24h, washing with methanol for multiple times to obtain light blue precipitate, vacuum drying in a 60-degree oven for 12h, taking out, grinding, weighing, and carbonizing at 900 ℃ at a heating rate of 5 ℃/min under the protection of nitrogen or argon for 5 h. And grinding after carbonization and cooling to obtain the multi-stage porous active multifunctional carbon material.
The micro-morphology of the multifunctional carbon material obtained in example 7 is shown in FIG. 11.
The above-mentioned embodiments are merely preferred embodiments for fully illustrating the present invention, and the scope of the present invention is not limited thereto. The equivalent substitution or change made by the technical personnel in the technical field on the basis of the invention is all within the protection scope of the invention. The protection scope of the invention is subject to the claims.

Claims (7)

1. A method for growing MOF materials on the surface of bacteria and converting the MOF materials into multi-stage porous carbon materials by taking the bacteria as templates is characterized by comprising the following steps:
(1) dispersing bacterial powder in methanol, adding dimethyl imidazole, zinc nitrate and cobalt nitrate, uniformly mixing, sealing and standing for 12-24 h; the bacteria are escherichia coli or staphylococcus; the zinc nitrate and the cobalt nitrate are added in a solid form of crystalline hydrate, the mass ratio of the metal salt to the dimethyl imidazole is 0.5-1: 1, and the mass ratio of the zinc nitrate to the cobalt nitrate is 1-9: 1-9;
(2) and centrifuging and cleaning the solution after standing, and drying, carbonizing and grinding the obtained precipitate to obtain the multistage porous carbon material.
2. The method according to claim 1, wherein in the step (1), the mass content of the bacterial cells in the bacterial powder is 5-10%.
3. The method of claim 1, wherein in step (2), the carbonization conditions are: heating to 700-1000 ℃ at a speed of 1-10 ℃/min, and carbonizing for 2-7 hours.
4. A multi-stage porous carbon material prepared by the method according to any one of claims 1 to 3.
5. The multi-stage porous carbon material according to claim 4, wherein Co in the multi-stage porous carbon material2The content of P is 0-10 wt%.
6. A lithium-sulfur battery, characterized in that a negative electrode of the lithium-sulfur battery is prepared from the multi-stage porous carbon material according to claim 4 or 5.
7. A zinc-air battery, characterized in that an air electrode of the zinc-air battery uses the multi-stage porous carbon material according to claim 4 or 5 as a catalyst.
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