CN114388786B - Method for preparing carbon skeleton from wood hypha symbiotic material and application of sulfur-carrying energy storage - Google Patents

Method for preparing carbon skeleton from wood hypha symbiotic material and application of sulfur-carrying energy storage Download PDF

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CN114388786B
CN114388786B CN202111569872.6A CN202111569872A CN114388786B CN 114388786 B CN114388786 B CN 114388786B CN 202111569872 A CN202111569872 A CN 202111569872A CN 114388786 B CN114388786 B CN 114388786B
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wood
hypha
symbiotic
sulfur
carbon skeleton
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CN114388786A (en
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燕映霖
杨媛媛
刘璞方
景玮
赵颖娟
邹一鸣
杨蓉
钟黎声
许云华
樊潮江
张行盛
宋牧泽
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Xian University of Technology
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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/64—Carriers or collectors
    • H01M4/66—Selection of materials
    • H01M4/663—Selection of materials containing carbon or carbonaceous materials as conductive part, e.g. graphite, carbon fibres
    • 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
    • H01M4/581—Chalcogenides or intercalation compounds thereof
    • H01M4/5815—Sulfides
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/64—Carriers or collectors
    • H01M4/66—Selection of materials
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/10—Energy storage using batteries

Abstract

The invention discloses a method for preparing a carbon skeleton by using a wood hypha symbiotic material and application of sulfur-carrying energy storage, which comprises the following steps: inoculating strains by using wood loaded with nutrient solution as a matrix, culturing for a period of time, cleaning, freeze-drying and hot-pressing the wood matrix after hyphae grow fully, and then putting the wood matrix in a nitrogen atmosphere furnace for carbonization to obtain a carbon skeleton derived from the wood hyphae symbiotic material; and further, a high-concentration lithium octasulfide solution is adsorbed by rotary drop coating to serve as a self-supporting positive plate of the lithium-sulfur battery, and the self-supporting positive plate, a lithium foil negative electrode, a polypropylene diaphragm and a special electrolyte are assembled to form the soft package lithium-sulfur battery. The method utilizes hypha filling to reconstruct a wood directional ordered pore structure, has low cost and simple preparation, and can effectively improve the sulfur-carrying density and improve the electrochemical dynamic performance, thereby obtaining the soft package lithium-sulfur battery with high energy density and power density.

Description

Method for preparing carbon skeleton from wood hypha symbiotic material and application of sulfur-carrying energy storage
Technical Field
The invention relates to the technical field of preparation and application of novel energy storage electrode materials, in particular to a method for preparing a carbon skeleton by using a wood hypha symbiotic material and application of sulfur-carrying energy storage.
Background
With the development of human civilization and the advancement of technological innovation, energy crisis and environmental pollution become two major problems facing the world at present. Due to the fact that renewable energy sources such as solar energy, wind energy, tidal energy, geothermal energy and the like are unstable and discontinuous, people look to development and utilization of key technologies of an electrochemical energy storage system with economy and high efficiency. Through the development of the last decade, the energy density of the lithium ion battery tends to the theoretical limit, the actually assembled battery energy density is less than 260Wh/kg, the higher requirements of emerging industries such as modern society electric vehicles, smart grids and the like on electrochemical energy storage systems cannot be met, and the development of novel efficient battery energy storage systems is urgent.
The lithium-sulfur battery has ultrahigh theoretical specific capacity (1675 mAh/g) and theoretical energy density (2600 Wh/L), is rich in elemental sulfur storage, is environment-friendly, and has natural advantages in cost and energy density. However, lithium sulfur batteries have been slow to develop due to the insulating and volume strain of the active material, "shuttling" of the intermediate product, and the safety hazards of lithium metal. For many years, scholars at home and abroad have adopted active substance (S) 8 Or Li 2 S) and a conductive material are compounded to improve the electron conduction capability in the positive electrode of the lithium-sulfur battery, and the commonly used conductive material comprises a carbon material, a polymer material, a metal compound and the like. The carbon material has the advantages of low density, excellent electric and heat conducting performance, stable physical and chemical properties, convenient structural regulation and the like, and is widely accepted.
However, the energy density of the lithium-sulfur battery is still lower than that of the conventional lithium ion battery due to the limited sulfur content in the positive electrode. In the report of the conventional coated electrode, the amount of sulfur supported in the positive electrode is mostly less than 3mg/cm 2 This is contrary to the original intention of high energy density lithium sulfur batteries. In addition, the conventional sulfur positive electrode is prepared by coating a slurry containing a sulfur host material and a binder on an aluminum foil with a doctor blade. Simply increasing the electrode thickness causes the sulfur body to fall off the current collector (i.e., aluminum foil) and reduces the transport kinetics of lithium ions and electrons, reduces the sulfur utilization and specific capacity of the lithium sulfur battery, and causes problems of high polarization voltage, poor cycle performance, and low capacity. To advance the surface capacity of lithium-sulfur batteriesAbove the level of lithium ion batteries, it is particularly important to increase the surface loading and content of sulfur. At the same time, the "shuttling effect" of the intermediate polysulfide from the electrochemical reaction leads to a lower coulombic efficiency and a rapid capacity decay, and is limited by the weak electrochemical kinetics and the poor rate capability. The above comprehensive reasons severely limit the energy storage capacity, cycle life and charging speed of lithium-sulfur batteries, and thus commercial application is difficult to realize.
As a green carbon source, the biomass material usually has a hierarchical pore structure and rich organic macromolecules (sugars, proteins and the like), and generally contains a plurality of non-carbon elements, so that heteroatom doping can be synchronously realized in the carbonization process, and the application performance of the biomass material is improved. The application of the biomass carbon material precursor to the preparation of the novel environment-friendly sustainable energy storage device is a research hotspot at present, among a plurality of precursor materials, the wood material is cheap and easy to obtain, has wide sources and easy to process, can be conveniently prepared into a self-supporting electrode, has a layered porous structure (such as a vertical channel and a plurality of micro/nano pores) inside, can rapidly transfer electrons and charges, and is favored by a plurality of researchers. However, when the wood-based carbon material is used in the lithium sulfur battery, the active material sulfur is easily lost though being stored in a large amount due to the oversized vertical channels, and the binding capacity to the active material sulfur is low, resulting in poor energy storage performance, and further research and improvement of microstructure thereof are needed. On the other hand, fungal hyphae produced by biosynthetic techniques are filamentous materials rich in proteins, amino acids, polysaccharides and vitamins. A large amount of fungus hypha can form a spatial network structure in the growth and propagation process, and the hypha has a hollow fiber structure, so the hypha-based carbon aerogel has an ultra-large specific surface area and good trafficability, in addition, nutrient substances of the fungus hypha are synthesized in the growth process, and the biosynthesis process is simple, cheap and environment-friendly, and is very suitable for mass production.
Disclosure of Invention
Aiming at the defects of the prior art, the invention aims to provide a preparation method of a wood hypha symbiotic biomass derived carbon skeleton. Firstly, wood is a natural material which is rich in cellulose and has a hierarchical structure and pore channels which are vertically arranged, the natural material is prepared into a main structure of a carbon skeleton, and a layered porous structure (such as a vertical channel and a plurality of micro/nano pores) is arranged inside the natural material, so that electrons and charges can be rapidly transferred, the transmission and infiltration of electrode liquid are accelerated, the ion diffusion rate is improved, and the electrochemical reaction is promoted to rapidly proceed. Secondly, hypha grows in wood pores to play a role in modifying wood pore space, and the ultrahigh specific surface area is provided by utilizing the rich one-dimensional fiber pipeline structure in the hypha-based carbon film, so that ultrahigh-density sulfur carrying on the inner side and the outer side is realized, and the capacity of the positive electrode is increased; in addition, the hypha three-dimensional network structure provides a complete conductive network, and the rich pore structure is favorable for the diffusion and transmission of ions, increases the reactive sites, increases the power of electrochemical reaction, and improves the electrochemical kinetics performance; finally, the high-density loading of lithium octasulfide in the carbon skeleton derived from symbiosis of wood hyphae is realized by a rotary dripping coating method, and the uniform distribution of active substances is realized.
In order to achieve the purpose, the invention provides the following technical scheme: a preparation method of a wood hypha symbiotic biomass derived carbon skeleton comprises the following steps of providing a wood derived directional ordered pore array with low deflection, filling hypha derived carbon fibers in pores, and using the pore array as a sulfur-carrying self-supporting anode in a soft package lithium-sulfur battery:
a method for preparing a carbon skeleton by using a wood hypha symbiotic material comprises the following steps:
step (1): cutting wood into strips, keeping the height direction as the growth direction of the wood, cutting the wood into slices with the thickness of 2mm vertical to the height direction, soaking the wood slices in deionized water, preserving the temperature at 70 ℃ until the wood slices sink, soaking the wood slices in a diluted potato dextrose water culture solution, heating and boiling, and sterilizing;
step (2): selecting fungus strains capable of growing fibrous hyphae, and obtaining a biomass symbiotic material for growing hyphae fibers in wood pores based on a microbial culture technology, wherein the method specifically comprises the following steps: inoculating the activated fungus strain into the potato dextrose water culture solution containing the wood chips in the step (1), shaking for a period of time at a constant temperature of 25-30 ℃, then transferring to a constant temperature incubator for standing culture for a period of time, and collecting a wood hypha symbiotic precursor;
and (3): repeatedly washing the wood hypha symbiotic precursor obtained in the step (2) with deionized water, then soaking the wood hypha symbiotic precursor into 0.1-1 mol/L NaOH solution for 2 hours in water bath at the temperature of 70-80 ℃, controlling the vacuum degree by using a suction filtration method, washing the wood hypha symbiotic precursor with the deionized water until the pH value is about =7.0, then placing the wood hypha symbiotic precursor into liquid nitrogen for quick freezing at the temperature of-50 ℃, and freeze-drying the wood hypha symbiotic precursor for 48 hours to obtain a wood hypha symbiotic material;
and (4): placing the wood hypha symbiotic material obtained in the step (3) on a hot press, heating at a constant speed, pre-carbonizing at a low temperature for a period of time, then pressing a pre-carbonized sheet between two layers of graphite plates, heating to 800-1100 ℃ at a speed of 5 ℃/min in a nitrogen atmosphere furnace, and preserving heat for 3 hours to obtain a carbon skeleton derived from the wood hypha symbiotic material;
the application of the sulfur-carrying energy storage for preparing the carbon skeleton by using the wood hypha symbiotic material is as follows:
sending the wood hypha symbiotic biomass derived carbon skeleton into a dry chamber or a glove box, fixing on a rotating table, and dropwise adding Li while rotating 2 S 8 The DOL/DME mixed solution is dripped, and the derived carbon skeleton sulfur-carrying self-supporting anode of the wood hypha symbiotic material is obtained after standing;
and respectively welding lugs on a sulfur-carrying self-supporting positive electrode of the derived carbon skeleton made of the wood hypha symbiotic material and a lithium foil negative electrode, separating by using a polypropylene diaphragm, stacking in a laminated manner, dropwise adding a lithium sulfur special electrolyte between layers, respectively welding a positive lug cluster and a negative lug cluster, and sealing by using an aluminum plastic shell to obtain the soft-packaged lithium sulfur battery adopting the sulfur-carrying self-supporting positive electrode of the derived carbon skeleton made of the wood hypha symbiotic material.
Preferably, the wood in step (1) includes, but is not limited to, linden americana, aspen alba and balsa wood, and the fungal species capable of growing filamentous hyphae in step (1) include, but is not limited to, penicillium chrysogenum, rhizopus stolonifer, xylaria, mucor.
Preferably, the constant-temperature shaking culture time in the step (2) is 12-24h, the rotating speed is 160-220 rad/min, and the constant-temperature standing culture time is 2-5 days.
Preferably, the wood hypha symbiotic material in the step (4) is placed on a hot press, the temperature is raised at a constant speed, the wood hypha symbiotic material is pre-carbonized at a low temperature for a period of time, the pressure is 0.1-1.0Mpa, the temperature raising rate is 2-3 ℃/min, and the temperature is kept for 1h at 200-300 ℃.
Preferably, the rotation speed of the middle rotating table is 50 to 300rad/min, and the Li is contained 2 S 8 In a mixed solution of DOL/DME of (1) 2 S 8 The concentration of (b) is 0.05-0.2 g/mL, and the dropping volume is 20-60 mu L.
Preferably, the laminated stacking ensures that two cathodes are positioned at the outermost side, the anodes are inserted into the inner sides of the cathodes, 1-8 layers of anodes are stacked according to the designed capacity specification of the battery, additional cathodes need to be added between the two anodes, and a polypropylene diaphragm needs to be added between each two anodes; size-compliant diaphragm>Negative electrode>A positive electrode; dropwise adding a lithium-sulfur specific electrolyte between layers to a solution containing 1M LiTFSI and 1.0% LiNO 3 The volume of the DOL/DME mixed solution (2) is 5 to 20. Mu.L/mg(s).
Has the advantages that:
the invention provides a preparation method of a wood hypha symbiotic biomass derived carbon skeleton and application of the wood hypha symbiotic biomass derived carbon skeleton as an energy storage anode of a lithium-sulfur battery after sulfur loading, and the preparation method has the following beneficial effects:
(1) The invention adopts a biological culture method, prepares the composite biomass in one step, has simple preparation method, no introduction of harmful reagents, low production cost, wide sources and good biocompatibility, uses renewable biological materials as a sustainable effective mode, and brings brightness for the development and application of the lithium-sulfur battery;
(2) The method not only utilizes the natural wood pore channel structure to be beneficial to loading high-density active substances, provides a high-efficiency channel for the transmission and ion diffusion of electrolyte, can improve the electrochemical performance of the lithium-sulfur battery, but also utilizes the hypha network structure to fill the wood pore channel, and realizes the loading with ultrahigh specific surface area;
(3) The wood hypha symbiotic biomass derived carbon skeleton is a conductive network which is communicated into a whole, has a multi-channel structure, and is not coated and blocked by insulated elemental sulfur or lithium sulfide in the charging and discharging processes due to multiple active sites, so that sufficient electrons can be provided for the electrochemical reaction to supply the electrochemical reaction efficiency;
(4) The wood hypha symbiotic biomass derived carbon skeleton is beneficial to physically confining lithium polysulfide in the positive electrode through physical action and can synergistically inhibit the shuttle effect by matching with the chemical polar adsorption action of nitrogen, oxygen, phosphorus, sulfur and other heteroatoms contained in a biomass carbon material;
(5) Compared with the traditional slurry coating electrode, the self-supporting electrode designed by the invention simplifies the electrode preparation process, avoids the addition of extra binder, conductive agent and current collector, and improves the energy density of the battery.
Drawings
FIG. 1 is a composite biomass high definition picture obtained by inoculating Penicillium chrysogenum in culture solution containing Barsha wood according to an embodiment of the present invention;
FIG. 2 shows rate capability of a composite biomass carbon-based positive electrode obtained by inoculating Penicillium chrysogenum in a culture solution containing Baker Sasa in an embodiment of the invention;
FIG. 3 shows that the sulfur-carrying amount of the composite biomass carbon-based positive electrode obtained by inoculating Penicillium chrysogenum in culture solution containing Barsha wood in the embodiment of the invention is about 4.48mg/cm 2 Cycle performance plot of 100 cycles at 0.1C;
FIG. 4 is a composite biomass high definition picture obtained by inoculating Rhizopus stolonifer to a culture solution containing Baer sanders in an embodiment of the invention;
FIG. 5 is a graph showing rate capability of a composite biomass carbon-based positive electrode obtained by inoculating Rhizopus stolonifer into a culture solution containing Baer sanders in an embodiment of the present invention;
FIG. 6 shows that the sulfur loading of the composite biomass carbon-based positive electrode obtained by inoculating Rhizopus stolonifer to a culture solution containing Barr sanders in the embodiment of the invention is about 4.48mg/cm 2 Cycle performance plot of 100 cycles at 0.1C.
Detailed Description
The technical solutions in the embodiments of the present invention will be clearly and completely described below with reference to fig. 1 to 6 in the embodiments of the present invention, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all of the embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
Example 1
Step (1): cutting Barbados into strips, keeping the height direction as the wood growth direction, cutting the wood into slices with the thickness of 2mm perpendicular to the height direction, soaking the wood slices in deionized water, keeping the temperature at 70 ℃ until the wood slices sink, soaking the wood slices in diluted potato dextrose water culture solution, heating, boiling, and sterilizing.
Step (2): selecting a yellow mould producing strain, and obtaining a biomass symbiotic material for growing hypha fibers in wood pores based on a microbial culture technology, wherein the biomass symbiotic material specifically comprises the following components: inoculating the activated penicillium chrysogenum strain into the potato glucose aqueous culture solution containing the wood chips in the step (1), shaking for a period of time at a constant temperature of 25-30 ℃, then transferring to a constant-temperature incubator, standing and culturing for a period of time, and collecting a wood hypha symbiotic precursor;
and (3): repeatedly washing the wood hypha symbiotic precursor obtained in the step (2) with deionized water, then soaking the wood hypha symbiotic precursor into 0.1-1 mol/L NaOH solution for 2h in a water bath at the temperature of 70-80 ℃, then controlling the vacuum degree by using a suction filtration method, washing the wood hypha symbiotic precursor with the deionized water until the pH value is about =7.0, then placing the wood hypha symbiotic precursor into liquid nitrogen for quick freezing, and then freezing and drying the wood hypha symbiotic precursor for 48h at the temperature of-50 ℃ to obtain the wood hypha symbiotic material.
And (4): and (3) placing the wood hypha symbiotic material obtained in the step (3) on a hot press, raising the temperature at a constant speed, pre-carbonizing at a low temperature for a period of time, then pressing the pre-carbonized sheet between two layers of graphite plates, raising the temperature to 800-1100 ℃ at a speed of 5 ℃/min in a nitrogen atmosphere furnace, and preserving the heat for 3 hours to obtain the carbon skeleton derived from the wood hypha symbiotic material.
And (5): symbiotic wood hyphaSending the biomass derived carbon skeleton into a dry chamber or a glove box, fixing the biomass derived carbon skeleton on a rotating table, and dropwise adding Li while rotating 2 S 8 And (3) carrying out a plurality of drops of DOL/DME mixed solution, standing to obtain the wood hypha symbiotic material derived carbon skeleton sulfur-carrying self-supporting anode.
And (6): and respectively welding lugs on a sulfur-carrying self-supporting positive electrode of the derived carbon skeleton made of the wood hypha symbiotic material and a lithium foil negative electrode, separating by using a polypropylene diaphragm, stacking in a laminated manner, dropwise adding a lithium sulfur special electrolyte between layers, respectively welding a positive lug cluster and a negative lug cluster, and sealing by using an aluminum plastic shell to obtain the soft-packaged lithium sulfur battery adopting the sulfur-carrying self-supporting positive electrode of the derived carbon skeleton made of the wood hypha symbiotic material.
The material prepared in example 1 was put into a glove box, placed on a spin coater, and 20. Mu.L of 0.05g/mL Li-containing solution was added dropwise 2 S 8 The DOL/DME mixed solution is used as a self-supporting positive electrode, a soft package lithium sulfur battery is assembled, and an electrochemical performance test is carried out, wherein the results are as follows:
fig. 1 shows a high-definition picture obtained by inoculating penicillium chrysogenum in a culture solution soaked with balsa wood and culturing for a period of time, and it can be seen that the surfaces of wood chips are covered by compact hypha fibers to form an integrated composite biomass material with hypha growing in wood pores, the hypha fibers not only grow along vertical pores of the wood and extend to the periphery, but also decompose lignin, cellulose and hemicellulose, thereby forming rich gaps, and inducing the hypha fibers to be interwoven in the pores and assembled with the wood into a composite biomass with a compact structure. After carbonizing the lithium sulfide battery, loading active substances, assembling the lithium sulfide battery with soft packages, and testing the rate capability as shown in fig. 2. Under the current density of 0.1C, the initial discharge specific capacity reaches 1289mAh/g, the average discharge specific capacities under 0.2C,0.5C and 1C are 1037mAh/g,923mAh/g and 800mAh/g respectively, when the current density returns to 0.1C again, the capacity can still be recovered to more than 1000mAh/g, and the composite biomass electrode shows excellent rate capability.
Example 2
Step (1): cutting Barbados into strips, keeping the height direction as the wood growth direction, cutting the wood into slices with the thickness of 2mm perpendicular to the height direction, soaking the wood slices in deionized water, keeping the temperature at 70 ℃ until the wood slices sink, soaking the wood slices in diluted potato dextrose water culture solution, heating, boiling, and sterilizing.
Step (2): selecting a yellow mould producing strain, and obtaining a biomass symbiotic material for growing hypha fibers in wood pores based on a microbial culture technology, wherein the biomass symbiotic material specifically comprises the following components: inoculating the activated fungus strain into the potato dextrose water culture solution containing the wood chips in the step (1), shaking for a period of time at a constant temperature of 25-30 ℃, then transferring to a constant temperature incubator for standing culture for a period of time, and collecting a wood hypha symbiotic precursor;
and (3): repeatedly washing the wood hypha symbiotic precursor obtained in the step (2) with deionized water, then soaking the wood hypha symbiotic precursor into 0.1-1 mol/L NaOH solution for 2h in a water bath at the temperature of 70-80 ℃, then controlling the vacuum degree by using a suction filtration method, washing the wood hypha symbiotic precursor with the deionized water until the pH value is about =7.0, then placing the wood hypha symbiotic precursor into liquid nitrogen for quick freezing, and then freezing and drying the wood hypha symbiotic precursor for 48h at the temperature of-50 ℃ to obtain the wood hypha symbiotic material.
And (4): and (3) placing the wood hypha symbiotic material obtained in the step (3) on a hot press, raising the temperature at a constant speed, pre-carbonizing at a low temperature for a period of time, then pressing the pre-carbonized sheet between two layers of graphite plates, raising the temperature to 800-1100 ℃ at a speed of 5 ℃/min in a nitrogen atmosphere furnace, and preserving the heat for 3 hours to obtain the carbon skeleton derived from the wood hypha symbiotic material.
And (5): sending the wood hypha symbiotic biomass derived carbon skeleton into a dry chamber or a glove box, fixing the skeleton on a rotating table, and dropwise adding Li while rotating 2 S 8 And (3) carrying out standing on a plurality of drops of DOL/DME mixed solution to obtain the wood hypha symbiotic material derived carbon skeleton sulfur-loaded self-supporting anode.
And (6): and respectively welding lugs on a sulfur-carrying self-supporting positive electrode of the derived carbon skeleton made of the wood hypha symbiotic material and a lithium foil negative electrode, separating by using a polypropylene diaphragm, stacking in a laminated manner, dropwise adding a lithium sulfur special electrolyte between layers, respectively welding a positive lug cluster and a negative lug cluster, and sealing by using an aluminum plastic shell to obtain the soft-packaged lithium sulfur battery adopting the sulfur-carrying self-supporting positive electrode of the derived carbon skeleton made of the wood hypha symbiotic material.
To implementationThe material prepared in example 2 was placed in a glove box, placed on a spin coater, and 60. Mu. L0.05g/mL Li-containing solution was added dropwise 2 S 8 The DOL/DME mixed solution can easily realize 4.48mg/cm 2 Then used as a self-supporting positive electrode, assembled into a cell and tested for electrochemical performance, with the following results: as shown in FIG. 3, at 4.48mg/cm 2 Exhibits excellent long cycle performance at a current density of 0.1C. The first discharge specific capacity can reach 879mAh/g, the capacity attenuation is relatively slow along with the circulation, and the capacity can be kept 697mAh/g after 100 times of circulation.
Example 3
Step (1): cutting Barbados into strips, keeping the height direction as the wood growth direction, cutting the wood into slices with the thickness of 2mm perpendicular to the height direction, soaking the wood slices in deionized water, keeping the temperature at 70 ℃ until the wood slices sink, soaking the wood slices in diluted potato dextrose water culture solution, heating, boiling, and sterilizing.
Step (2): selecting rhizopus stolonifer strains, and obtaining a biomass symbiotic material for growing hypha fibers in wood holes based on a microbial culture technology, wherein the biomass symbiotic material specifically comprises the following components: inoculating the activated fungus strain into the potato dextrose water culture solution containing the wood chips in the step (1), shaking for a period of time at a constant temperature of 25-30 ℃, then transferring to a constant temperature incubator for standing culture for a period of time, and collecting a wood hypha symbiotic precursor;
and (3): repeatedly washing the wood hypha symbiotic precursor obtained in the step (2) with deionized water, then soaking the wood hypha symbiotic precursor into 0.1-1 mol/L NaOH solution for 2h in a water bath at the temperature of 70-80 ℃, then controlling the vacuum degree by using a suction filtration method, washing the wood hypha symbiotic precursor with the deionized water until the pH value is about =7.0, then placing the wood hypha symbiotic precursor into liquid nitrogen for quick freezing, and then freezing and drying the wood hypha symbiotic precursor for 48h at the temperature of-50 ℃ to obtain the wood hypha symbiotic material.
And (4): and (3) placing the wood hypha symbiotic material obtained in the step (3) on a hot press, raising the temperature at a constant speed, pre-carbonizing at a low temperature for a period of time, then pressing the pre-carbonized sheet between two layers of graphite plates, raising the temperature to 800-1100 ℃ at a speed of 5 ℃/min in a nitrogen atmosphere furnace, and preserving the heat for 3 hours to obtain the carbon skeleton derived from the wood hypha symbiotic material.
And (5): sending the wood hypha symbiotic biomass derived carbon skeleton into a dry chamber or a glove box, fixing the skeleton on a rotating table, and dropwise adding Li while rotating 2 S 8 And (3) carrying out a plurality of drops of DOL/DME mixed solution, standing to obtain the wood hypha symbiotic material derived carbon skeleton sulfur-carrying self-supporting anode.
And (6): respectively welding lugs on a sulfur-carrying self-supporting positive electrode of a wood hypha symbiotic material derived carbon skeleton and a lithium foil negative electrode, then separating by using a polypropylene diaphragm, stacking in a laminated manner, dropwise adding a lithium-sulfur special electrolyte between layers, respectively welding a positive lug cluster and a negative lug cluster, and then sealing by using an aluminum-plastic shell, thus obtaining the soft package lithium-sulfur battery adopting the sulfur-carrying self-supporting positive electrode of the wood hypha symbiotic derived carbon skeleton.
The material prepared in example 3 was placed in a glove box, placed on a spin coater, and 20. Mu. L0.05g/mL of Li-containing solution was added dropwise 2 S 8 Then the cell is assembled and tested for electrochemical performance by taking the DOL/DME mixed solution as a self-supporting positive electrode, and the results are as follows: FIG. 3 shows high definition pictures of Rhizopus stolonifer inoculated in culture medium soaked with Baer sanders and cultured for a period of time. After the composite biomass porous carbon-based self-supporting electrode is processed and carbonized, an active substance is loaded, the lithium-sulfur battery is assembled, and the rate performance test is shown in figure 5, so that the composite biomass porous carbon-based self-supporting electrode shows excellent rate performance. The specific discharge capacity reaches 1156mAh/g,1028mAh/g,882mAh/g and 681mAh/g respectively at the current density of 0.1C,0.2C,0.5C and 1C, and the capacity can be recovered to 1012mAh/g when the current density returns to 0.1C again.
Example 4
Step (1): cutting Barbados into strips, keeping the height direction as the wood growth direction, cutting the wood into slices with the thickness of 2mm perpendicular to the height direction, soaking the wood slices in deionized water, keeping the temperature at 70 ℃ until the wood slices sink, soaking the wood slices in diluted potato dextrose water culture solution, heating, boiling, and sterilizing.
Step (2): selecting rhizopus stolonifer strain, and obtaining a biomass symbiotic material for growing hypha fibers in wood holes based on a microbial culture technology, wherein the biomass symbiotic material comprises the following components: inoculating the activated fungus strain into the potato dextrose water culture solution containing the wood chips in the step (1), shaking for a period of time at a constant temperature of 25-30 ℃, then transferring to a constant temperature incubator for standing culture for a period of time, and collecting a wood hypha symbiotic precursor;
and (3): repeatedly washing the wood hypha symbiotic precursor obtained in the step (2) with deionized water, then soaking the wood hypha symbiotic precursor into 0.1-1 mol/L NaOH solution for 2h in a water bath at the temperature of 70-80 ℃, then controlling the vacuum degree by using a suction filtration method, washing the wood hypha symbiotic precursor with the deionized water until the pH value is about =7.0, then placing the wood hypha symbiotic precursor into liquid nitrogen for quick freezing, and then freezing and drying the wood hypha symbiotic precursor for 48h at the temperature of-50 ℃ to obtain the wood hypha symbiotic material.
And (4): and (3) placing the wood hypha symbiotic material obtained in the step (3) on a hot press, raising the temperature at a constant speed, pre-carbonizing at a low temperature for a period of time, then pressing the pre-carbonized sheet between two layers of graphite plates, raising the temperature to 800-1100 ℃ at a speed of 5 ℃/min in a nitrogen atmosphere furnace, and preserving the heat for 3 hours to obtain the carbon skeleton derived from the wood hypha symbiotic material.
And (5): sending the wood hypha symbiotic biomass derived carbon skeleton into a dry chamber or a glove box, fixing the skeleton on a rotating table, and dropwise adding Li while rotating 2 S 8 And (3) carrying out a plurality of drops of DOL/DME mixed solution, standing to obtain the wood hypha symbiotic material derived carbon skeleton sulfur-carrying self-supporting anode.
And (6): and respectively welding lugs on a sulfur-carrying self-supporting positive electrode of the derived carbon skeleton made of the wood hypha symbiotic material and a lithium foil negative electrode, separating by using a polypropylene diaphragm, stacking in a laminated manner, dropwise adding a lithium sulfur special electrolyte between layers, respectively welding a positive lug cluster and a negative lug cluster, and sealing by using an aluminum plastic shell to obtain the soft-packaged lithium sulfur battery adopting the sulfur-carrying self-supporting positive electrode of the derived carbon skeleton made of the wood hypha symbiotic material.
The material prepared in example 4 was placed in a glove box, placed on a spin coater, and 60. Mu. L0.05g/mL of Li-containing solution was added dropwise 2 S 8 The DOL/DME mixed solution is used as a self-supporting positive electrode, a battery is assembled, and electrochemical performance tests are carried out, wherein the cycle performance test results are as follows: FIG. 6 shows a signal at 4.48mg/cm 2 Exhibits excellent long cycling at a current density of 0.1CAnd (4) performance. The first discharge specific capacity can reach 948mAh/g, the capacity attenuation is relatively slow along with the circulation, and the capacity can be kept at 525mAh/g after 100 times of circulation.
It is noted that, herein, relational terms such as first and second, and the like may be used solely to distinguish one entity or action from another entity or action without necessarily requiring or implying any actual such relationship or order between such entities or actions. Also, the terms "comprises," "comprising," or any other variation thereof, are intended to cover a non-exclusive inclusion, such that a process, method, article, or apparatus that comprises a list of elements does not include only those elements but may include other elements not expressly listed or inherent to such process, method, article, or apparatus. Without further limitation, an element defined by the phrase "comprising a … …" does not exclude the presence of another identical element in a process, method, article, or apparatus that comprises the element.
Although embodiments of the present invention have been shown and described, it will be appreciated by those skilled in the art that changes, modifications, substitutions and alterations can be made in these embodiments without departing from the principles and spirit of the invention, the scope of which is defined in the appended claims and their equivalents.

Claims (6)

1. A method for preparing a carbon skeleton by using a wood hypha symbiotic material is characterized by comprising the following steps:
step (1): cutting wood into strips, keeping the height direction as the growth direction of the wood, cutting the wood into slices with the thickness of 2mm vertical to the height direction, soaking the wood slices in deionized water, preserving the temperature at 70 ℃ until the wood slices sink, soaking the wood slices in a diluted potato dextrose water culture solution, heating and boiling, and sterilizing;
step (2): selecting fungus strains capable of growing fibrous hyphae, and obtaining a biomass symbiotic material for growing hyphae fibers in wood pores based on a microbial culture technology, wherein the method specifically comprises the following steps: inoculating the activated fungus strains into the potato dextrose water culture solution containing the wood chips in the step (1), shaking for a period of time at a constant temperature under the condition of 25-30 ℃, then transferring to a constant-temperature incubator for standing culture for a period of time, and collecting wood hypha symbiotic precursors;
and (3): repeatedly washing the wood hypha symbiotic precursor obtained in the step (2) with deionized water, then soaking the wood hypha symbiotic precursor into 0.1-1 mol/L NaOH solution for 2 hours in a water bath at the temperature of 70-80 ℃, then controlling the vacuum degree by using a suction filtration method, washing the wood hypha symbiotic precursor with the deionized water until the pH value is about =7.0, then placing the wood hypha symbiotic precursor into liquid nitrogen for quick freezing, and then freezing and drying the wood hypha symbiotic precursor for 48 hours at the temperature of-50 ℃ to obtain a wood hypha symbiotic material;
and (4): placing the wood hypha symbiotic material obtained in the step (3) on a hot press, heating at a constant speed, pre-carbonizing at a low temperature for a period of time, then pressing a pre-carbonized sheet between two layers of graphite plates, heating to 800-1100 ℃ at a speed of 5 ℃/min in a nitrogen atmosphere furnace, and preserving heat for 3 hours to obtain a carbon skeleton derived from the wood hypha symbiotic material;
and (5) placing the wood hypha symbiotic material on a hot press in the step (4), raising the temperature at a constant speed, pre-carbonizing at a low temperature for a period of time, wherein the pressure is 0.1-1.0Mpa, the temperature raising rate is 2-3 ℃/min, and keeping the temperature at 200-300 ℃ for 1h.
2. The method for preparing a carbon skeleton by using a wood hyphal symbiotic material according to claim 1, wherein the wood in the step (1) comprises linden americana, poplar wood and balsa wood, and the fungus strains capable of growing fibrous hyphae in the step (1) comprise penicillium chrysogenum, rhizopus stolonifer, xylaria and mucor.
3. The method for preparing a carbon skeleton by using a wood hypha symbiotic material according to claim 1, wherein the constant-temperature shaking culture time in the step (2) is 12-24h, the rotating speed is 160-220 rad/min, and the constant-temperature standing culture time is 2-5 days.
4. The application of the wood hypha symbiotic material in preparing the sulfur-carrying energy storage of the carbon skeleton according to any one of claims 1 to 3, wherein the carbon skeleton comprises the following components in percentage by weight:
sending the wood hypha symbiotic biomass derived carbon skeleton into a dry chamber or a glove box, fixing on a rotating table, and dropwise adding Li while rotating 2 S 8 The DOL/DME mixed solution is dripped, and the derived carbon skeleton sulfur-carrying self-supporting anode of the wood hypha symbiotic material is obtained after standing;
and respectively welding lugs on a sulfur-carrying self-supporting positive electrode of the derived carbon skeleton made of the wood hypha symbiotic material and a lithium foil negative electrode, separating by using a polypropylene diaphragm, stacking in a laminated manner, dropwise adding a lithium sulfur special electrolyte between layers, respectively welding a positive lug cluster and a negative lug cluster, and sealing by using an aluminum plastic shell to obtain the soft-packaged lithium sulfur battery adopting the sulfur-carrying self-supporting positive electrode of the derived carbon skeleton made of the wood hypha symbiotic material.
5. The application of the sulfur-carrying energy storage in preparing carbon skeleton from wood hypha symbiotic material as claimed in claim 4, wherein the rotation speed of the rotating platform is 50-300 rad/min, and the rotating platform contains Li 2 S 8 In a mixed solution of DOL/DME of (1) 2 S 8 The concentration of (b) is 0.05-0.2 g/mL, and the dropping volume is 20-60 mu L.
6. The application of the sulfur-carrying energy storage for preparing the carbon skeleton from the wood hypha symbiotic material according to claim 4, wherein the two negative electrodes are stacked in a laminated manner, the outermost negative electrodes are arranged, the inner sides of the two negative electrodes are inserted into the positive electrodes, 1-8 layers of positive electrodes are stacked according to the design capacity specification of the battery, additional negative electrodes are required to be added between the two positive electrodes, and a polypropylene diaphragm is required to be added between each two positive electrodes; size-compliant membrane>Negative electrode>A positive electrode; dropwise adding a lithium-sulfur specific electrolyte between layers to a solution containing 1M LiTFSI and 1.0% LiNO 3 The volume of the DOL/DME mixed solution (2) is 5 to 20. Mu.L/mg(s).
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