CN116072963B - Preparation method of biomass-derived carbon/polymer gel electrolyte and application of biomass-derived carbon/polymer gel electrolyte in sodium-sulfur battery - Google Patents

Preparation method of biomass-derived carbon/polymer gel electrolyte and application of biomass-derived carbon/polymer gel electrolyte in sodium-sulfur battery Download PDF

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CN116072963B
CN116072963B CN202210485260.7A CN202210485260A CN116072963B CN 116072963 B CN116072963 B CN 116072963B CN 202210485260 A CN202210485260 A CN 202210485260A CN 116072963 B CN116072963 B CN 116072963B
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derived carbon
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CN116072963A (en
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潘虹
黄鑫
唐鑫垚
汪建新
李少斌
王超会
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Qiqihar University
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    • H01—ELECTRIC ELEMENTS
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    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/056—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes
    • H01M10/0564—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes the electrolyte being constituted of organic materials only
    • H01M10/0565—Polymeric materials, e.g. gel-type or solid-type
    • 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
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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
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Abstract

A preparation method of biomass-derived carbon/polymer gel electrolyte and application thereof in sodium-sulfur batteries relate to an electrolyte and a preparation method and application thereof. Aims to solve the problems of phase separation and poor uniformity of inorganic filler particles in gel electrolyte, and the preparation method comprises the following steps: 1. preparation and activation treatment of biomass-derived carbon: 2. activating treatment of polyvinylidene fluoride: 3. graft polymerization of vinylidene fluoride: 4. preparation of carbon/polymer composite: 5. and (3) preparation of a gel electrolyte. Application: preparing a sodium-sulfur secondary battery by using the biomass-derived carbon/polymer gel electrolyte, and assembling the anode, the cathode and the biomass-derived carbon/polymer gel electrolyte into the sodium-sulfur secondary battery in an inert atmosphere. The biomass-derived carbon/polymer gel electrolyte has high ionic conductivity and high mechanical strength, and can effectively inhibit the shuttle effect of the anode when being applied to a sodium-sulfur battery. Effectively solves the problems of phase separation and inorganic filler particle dispersion.

Description

Preparation method of biomass-derived carbon/polymer gel electrolyte and application of biomass-derived carbon/polymer gel electrolyte in sodium-sulfur battery
Technical Field
The invention relates to a preparation method and application of a biomass-derived carbon/polymer gel electrolyte.
Background
The sodium-sulfur battery takes metal sodium as a negative electrode and elemental sulfur as a positive electrode active substance, has a long research history, has high theoretical capacity, has energy density far higher than that of a lithium ion battery commonly used at present, can make up for the problem of insufficient lithium resources, and is a battery system with a very good development prospect. However, in ether electrolytes, when sulfur undergoes a reduction reaction, a series of soluble sodium polysulfide Na is produced 2 S x (4.ltoreq.x.ltoreq.8), these intermediatesThe product can cross the diaphragm and react with negative metallic sodium, thereby generating a serious shuttle effect, and the cycle stability of the battery can be influenced while the specific discharge capacity of the battery is reduced. In addition, the metal sodium atoms of the negative electrode can be unevenly deposited in the cyclic charge and discharge process, so that sodium dendrites are generated, and if the sodium dendrites penetrate through the diaphragm, safety problems can be caused.
Solid state electrolytes are an effective strategy to address the shuttling effect because solid state electrolytes can limit shuttling of polysulfides with their dense physical barriers. Solid electrolyte inorganic materials studied at this stage are the most. The reason is that the inorganic electrolyte has strong mechanical properties and can resist the growth of sodium dendrites. However, inorganic solid state electrolytes have poor ionic conductivity and, during repeated cycling, the interface with the negative electrode can create serious interface mismatch problems. In contrast to inorganic solid state electrolytes, gel polymer electrolytes have high ionic conductivity of liquid electrolytes with no interfacial problems. Because lithium ions can be transported in gel polymer electrolytes both by movement of the polymer chains and by the swollen gel or liquid phase. Gel polymers are therefore considered as the best candidates for replacing commercial liquid electrolytes.
However, the gel electrolyte has poor puncture resistance compared to the inorganic solid electrolyte, and thus, a mode of adding an inorganic filler to the organic gel is often adopted to increase mechanical strength, and at the same time, higher thermal stability can be obtained. However, such a composite electrolyte has a problem in that the inorganic phase is separated from the polymer to cause a phase separation phenomenon, and the dispersion uniformity of the inorganic filler particles in the polymer is poor.
Disclosure of Invention
The invention aims to provide a preparation method of a biomass-derived carbon in-situ combined polymer gel electrolyte and application of the biomass-derived carbon in sodium-sulfur battery, which solve the problems of phase separation and poor uniformity of inorganic filler particles and achieve the effect of improving the performance of the sodium-sulfur battery.
The preparation method of the biomass-derived carbon/polymer gel electrolyte comprises the following steps:
1. preparation and activation treatment of biomass-derived carbon:
isolating the biomass material from air for heat treatment to obtain a porous biomass carbon material; the obtained porous biomass carbon material is placed in concentrated nitric acid for activation or is placed in alkali solution for activation, so that activated biomass derived carbon is obtained;
2. activating treatment of polyvinylidene fluoride:
stirring and soaking the polyvinylidene fluoride in a strong alkali solution for 30min-2h, keeping the temperature at 60-90 ℃ during soaking, and washing the soaked polyvinylidene fluoride to be neutral by deionized water after the soaking is finished to obtain polyvinylidene fluoride with C=C bonds;
3. graft polymerization of vinylidene fluoride:
dissolving the obtained polyvinylidene fluoride with C=C bond and the reactive monomer in a solvent, adding an initiator, and stirring for 2-12 h at 40-90 ℃ to obtain polymer gel;
4. preparation of carbon/polymer composite:
cutting activated biomass-derived carbon into sheets of 0.5-2mm in a cutting direction perpendicular to the length direction of through holes in the activated biomass-derived carbon, mixing the obtained polymer gel with the cut activated biomass-derived carbon sheets, and heating, hydrothermal or hot-pressing; the gel is filled in the pore structure of the biomass derived carbon after heating, hydrothermal or hot pressing; drying at 40-80 deg.c to obtain carbon/polymer compound; at the moment, active groups on the surface of carbon react with carboxyl, sulfonic groups and the like in the side chain of the monomer, so that the carbon and the polymer are combined in situ;
5. preparation of gel electrolyte:
and immersing the obtained carbon/polymer composite in electrolyte used by the sodium-sulfur battery to obtain the biomass-derived carbon/polymer gel electrolyte.
The use of the above biomass-derived carbon/polymer gel electrolyte in sodium-sulfur secondary batteries: preparing a sodium-sulfur secondary battery by using the biomass-derived carbon/polymer gel electrolyte, and assembling the anode, the cathode and the biomass-derived carbon/polymer gel electrolyte into the sodium-sulfur secondary battery in an inert atmosphere.
Compared with the prior art, the invention has the following beneficial effects:
1. in the biomass-derived carbon/polymer gel electrolyte prepared by the invention, the biomass-derived carbon is provided with through holes which are arranged in an oriented way, the pore size of the through holes is 30-60 mu m, and the surfaces of the inner walls of the pore canals are provided with functional groups such as hydroxyl groups, carboxyl groups and the like; the polymer gel is a graft copolymer of vinylidene fluoride and a reactive monomer, wherein the reactive monomer is provided with carboxyl, sulfonic acid group, anhydride group and the like. The biomass-derived carbon and the polymer are combined by chemical bonds, and the polymer is filled in the pore canal of the biomass-derived carbon, and the bonding mode is that the hydroxyl or carboxyl provided by the biomass-derived carbon and the carboxyl, sulfonic acid, hydroxyl or anhydride group provided by the polymer are combined by esterification reaction. The polymer gel has high ionic conductivity, and the framework structure of biomass derived carbon can strengthen the gel structure and improve the mechanical strength of the polymer gel, so that the growth and penetration of sodium dendrites can be prevented, and the growth of negative sodium dendrites can be inhibited; the biomass-derived carbon/polymer gel electrolyte is semi-solid, can reduce polysulfide dissolution, and can effectively inhibit the shuttle effect of the anode when applied to sodium-sulfur batteries. The inorganic carbon and the polymer are combined through chemical bonds, so that the problem of phase separation can be effectively solved; and because the inorganic carbon and the polymer have rich chemical bonds, the inorganic filler particles can be uniformly dispersed in the polymer due to the plurality of bonding sites.
2. The circulation stability of the battery anode is improved due to the effective inhibition of the shuttle effect and the sodium dendrite by the biomass-derived carbon/polymer gel electrolyte; the gel electrolyte has a high-conductivity carbon skeleton, so that the electrochemical reaction polarization is low, and the utilization rate of active substances is improved, so that the sodium-sulfur battery assembled by the biomass-derived carbon/polymer gel electrolyte prepared by the invention has the advantages of high discharge specific capacity, good cycling stability and the like; the sodium-sulfur battery can stably circulate for 1000 circles, has coulomb efficiency of more than 98 percent and has excellent multiplying power performance. The preparation method of the material applied by the invention is simple, convenient and feasible, safe and low in cost, and the preparation of the quasi-solid electrolyte of the sodium-sulfur battery is realized by a simpler method.
3. The synthesis method of the biomass-derived carbon/polymer gel electrolyte is simple, the sources of raw materials are wide, the price is low, the reaction conditions are mild, the operation is simple and convenient, and the mass production is easy.
Drawings
FIG. 1 is an SEM image of activated biomass-derived carbon of example 1;
FIG. 2 is a graph of the cycling performance of the biomass-derived carbon/polymer gel (polyvinylidene fluoride-methacrylic acid) electrolyte in sodium sulfur secondary batteries of example 1;
fig. 3 is a constant current charge and discharge plot of a biomass-derived carbon/polymer gel (polyvinylidene fluoride-methacrylic acid) electrolyte in sodium sulfur secondary batteries in example 1:
FIG. 4 is an SEM image of activated biomass-derived carbon of example 2;
FIG. 5 is an infrared spectrum of a birch-derived carbon/polyvinylidene fluoride-2-acrylamido-2-methylpropanesulfonic acid gel of example 2;
FIG. 6 is a graph of the cycling performance of the biomass-derived carbon/polymer gel (polyvinylidene fluoride-2-acrylamido-2-methylpropanesulfonic acid) electrolyte in sodium sulfur secondary batteries of example 2;
FIG. 7 is a constant current charge and discharge plot of a biomass-derived carbon/polymer gel (polyvinylidene fluoride-2-acrylamido-2-methylpropanesulfonic acid) electrolyte in sodium sulfur secondary batteries in example 2;
FIG. 8 is an SEM image of activated biomass-derived carbon of example 3;
FIG. 9 is a graph of the cycling performance of the biomass-derived carbon/polymer gel (polyvinylidene fluoride-maleic anhydride) electrolyte in sodium sulfur secondary batteries of example 4;
fig. 10 is a constant current charge and discharge plot of a biomass-derived carbon/polymer gel (polyvinylidene fluoride-maleic anhydride) electrolyte in sodium sulfur secondary batteries in example 4.
Detailed Description
The technical scheme of the invention is not limited to the specific embodiments listed below, and also comprises any reasonable combination of the specific embodiments.
The first embodiment is as follows: the preparation method of the biomass-derived carbon/polymer gel electrolyte in the embodiment is carried out according to the following steps:
1. preparation and activation treatment of biomass-derived carbon:
isolating the biomass material from air for heat treatment to obtain a porous biomass carbon material; the obtained porous biomass carbon material is placed in concentrated nitric acid for activation or is placed in alkali solution for activation, so that activated biomass derived carbon is obtained;
2. activating treatment of polyvinylidene fluoride:
stirring and soaking the polyvinylidene fluoride in a strong alkali solution for 30min-2h, keeping the temperature at 60-90 ℃ during soaking, and washing the soaked polyvinylidene fluoride to be neutral by deionized water after the soaking is finished to obtain polyvinylidene fluoride with C=C bonds;
3. graft polymerization of vinylidene fluoride:
dissolving the obtained polyvinylidene fluoride with C=C bond and the reactive monomer in a solvent, adding an initiator, and stirring for 2-12 h at 40-90 ℃ to obtain polymer gel;
4. preparation of carbon/polymer composite:
cutting activated biomass-derived carbon into sheets of 0.5-2mm in a cutting direction perpendicular to the length direction of through holes in the activated biomass-derived carbon, mixing the obtained polymer gel with the cut activated biomass-derived carbon sheets, and heating, hydrothermal or hot-pressing; the gel is filled in the pore structure of the biomass derived carbon after heating, hydrothermal or hot pressing; drying at 40-80 deg.c to obtain carbon/polymer compound; at the moment, active groups on the surface of carbon react with carboxyl, sulfonic groups and the like in the side chain of the monomer, so that the carbon and the polymer are combined in situ;
5. preparation of gel electrolyte:
and immersing the obtained carbon/polymer composite in electrolyte used by the sodium-sulfur battery to obtain the biomass-derived carbon/polymer gel electrolyte.
The present embodiment has the following advantageous effects:
1. in the biomass-derived carbon/polymer gel electrolyte prepared by the embodiment, the biomass-derived carbon is provided with through holes which are arranged in an oriented manner, the pore size of the through holes is 30-60 mu m, and the surfaces of the inner walls of the pore canals are provided with functional groups such as hydroxyl groups, carboxyl groups and the like; the polymer gel is a graft copolymer of vinylidene fluoride and a reactive monomer, wherein the reactive monomer is provided with carboxyl, sulfonic acid group, anhydride group and the like. The biomass-derived carbon and the polymer are combined by chemical bonds, and the polymer is filled in the pore canal of the biomass-derived carbon, and the bonding mode is that the hydroxyl or carboxyl provided by the biomass-derived carbon and the carboxyl, sulfonic acid, hydroxyl or anhydride group provided by the polymer are combined by esterification reaction. The polymer gel has high ionic conductivity, and the framework structure of biomass derived carbon can strengthen the gel structure and improve the mechanical strength of the polymer gel, so that the growth and penetration of sodium dendrites can be prevented, and the growth of negative sodium dendrites can be inhibited; the biomass-derived carbon/polymer gel electrolyte is semi-solid, can reduce polysulfide dissolution, and can effectively inhibit the shuttle effect of the anode when applied to sodium-sulfur batteries. The inorganic carbon and the polymer are combined through chemical bonds, so that the problem of phase separation can be effectively solved; and because the inorganic carbon and the polymer have rich chemical bonds, the inorganic filler particles can be uniformly dispersed in the polymer due to the plurality of bonding sites.
2. The circulation stability of the battery anode is improved due to the effective inhibition of the shuttle effect and the sodium dendrite by the biomass-derived carbon/polymer gel electrolyte; the gel electrolyte has a high-conductivity carbon skeleton, so that the electrochemical reaction polarization is low, and the utilization rate of active substances is improved, so that the sodium-sulfur battery assembled by the biomass-derived carbon/polymer gel electrolyte prepared by the embodiment has the advantages of high discharge specific capacity, good cycling stability and the like; the sodium-sulfur battery can stably circulate for 1000 circles, has coulomb efficiency of more than 98 percent and has excellent multiplying power performance. The preparation method of the material applied in the embodiment is simple, convenient and feasible, safe and low in cost, and the preparation of the quasi-solid electrolyte of the sodium-sulfur battery is realized by a relatively simple method.
3. The synthesis method of the biomass-derived carbon/polymer gel electrolyte is simple, the sources of raw materials are wide, the price is low, the reaction conditions are mild, the operation is simple and convenient, and the mass production is easy.
The second embodiment is as follows: the first difference between this embodiment and the specific embodiment is that: the time of the heat treatment for isolating the air in the step one is at least 3 hours, and the temperature is 300-800 ℃.
And a third specific embodiment: this embodiment differs from the first or second embodiment in that: in the first step, the biomass material is wood, such as birch, pine, poplar and the like. The biomass material is carbonized and activated, and then has through holes in directional arrangement, and the activated biomass derived carbon obtained after carbonization has enough thickness to ensure the integrity of the hole structure during slicing.
The specific embodiment IV is as follows: this embodiment differs from one of the first to third embodiments in that: step one, placing the porous biomass carbon material into concentrated nitric acid for activation at a temperature of 80-90 ℃ for at least 30min; an activated carbon with hydroxyl and carboxyl groups is obtained. The biomass-derived carbon is stirred for 12 to 48 hours when being placed in an alkali solution for activation, so as to obtain activated carbon with hydroxyl and carboxyl; the alkali solution is NaOH solution or KOH solution, and the concentration is 5-10mol/L.
Fifth embodiment: this embodiment differs from one to four embodiments in that: and step two, the strong alkali solution is NaOH solution or KOH solution, and the concentration is 0.5-2.5mol/L.
Specific embodiment six: this embodiment differs from one of the first to fifth embodiments in that: the reactive monomers in the third step are methacrylic acid, maleic anhydride, 2-acrylamide-2-methylpropanesulfonic acid and the like; the solvent is nitrogen methyl pyrrolidone or dimethyl sulfoxide; the initiator is ammonium persulfate.
Seventh embodiment: this embodiment differs from one of the first to sixth embodiments in that: the volume ratio of the mass of the initiator to the solvent in the third step is (0.1-10) g/100mL; the mass ratio of the polyvinylidene fluoride with a C=C bond to the reactive monomer is 1: (0.1-3).
Eighth embodiment: this embodiment differs from one of the first to seventh embodiments in that: and step four, heating, hydrothermal or hot-pressing at 180-250 ℃ for 10-24 hours.
Detailed description nine: this embodiment differs from one to eight of the embodiments in that: the mass ratio of the activated biomass-derived carbon to the polymer gel in the step four is 1 (1-10).
Detailed description ten: application of gel electrolyte: the positive electrode, the negative electrode and the biomass-derived carbon/polymer gel electrolyte are assembled into a sodium-sulfur secondary battery in an inert atmosphere.
The active material of the positive electrode is sulfur;
the negative electrode is sodium metal or sodium-containing alloy;
the inert atmosphere is any one or a mixture of more than one of argon, nitrogen and helium, and is preferably argon.
Example 1:
(1) Preparation and activation treatment of biomass-derived carbon: isolating birch with the length of 3cm multiplied by the width of 3cm multiplied by the height of 3cm from air at 300 ℃ for 5 hours to obtain a porous biomass carbon material, then placing the porous biomass carbon material in concentrated nitric acid with the concentration of 68% (mass fraction), stirring for 30min at 80 ℃, and activating to obtain activated biomass derived carbon;
(2) Activating treatment of polyvinylidene fluoride: and (3) stirring and soaking the polyvinylidene fluoride in 2.5mol/L NaOH solution for 0.5h, keeping the temperature at 60 ℃, and washing with deionized water to be neutral to obtain the polyvinylidene fluoride with C=C bonds.
(3) Graft polymerization of vinylidene fluoride: the resulting polyvinylidene fluoride and methacrylic acid monomers having c=c bonds were dissolved in azomethylpyrrolidone, ammonium persulfate was added as an initiator (the amount of ammonium persulfate was 10 per ml of solvent -3 g) Stirring for 2h at 40 ℃ to obtain the prepared polymer gel;
the mass ratio of the polyvinylidene fluoride monomer with C=C bond to the methacrylic acid monomer is 10:1, a step of;
(4) Preparation of carbon/polymer composite:
cutting activated biomass-derived carbon into 0.5mm slices, wherein the cutting direction is perpendicular to the length direction of a through hole in the activated biomass-derived carbon, adding the slices into the obtained polymer gel, heating to 180 ℃ and preserving heat for 10 hours, softening and filling the heated polymer gel into the pore structure of a carbon material, and drying at 80 ℃;
the mass ratio of the activated biomass-derived carbon to the polymer gel is 1:1;
(5) Preparation of gel electrolyte: immersing the obtained carbon/polymer composite in a common organic liquid electrolyte selected from ethylene carbonate, propylene carbonate, fluoroethylene carbonate (FEC) and NaClO 4 Mixing to obtain the final gel electrolyte;
(6) The positive electrode with pure sulfur as an active material, the negative electrode with metallic sodium as a negative electrode, and the substance derived carbon/polymer gel electrolyte prepared by the method as an electrolyte are assembled into a battery in an argon atmosphere, and electrochemical performance tests are carried out.
FIG. 1 is an SEM image of activated biomass-derived carbon of example 1; it can be seen that the activated biomass-derived carbon has an oriented arrangement of through-holes. FIG. 2 is a graph of the cycling performance of the biomass-derived carbon/polymer gel (polyvinylidene fluoride-methacrylic acid) electrolyte in sodium sulfur secondary batteries of example 1; it can be seen that the battery has a higher initial discharge capacity and longer cycling stability. Fig. 3 is a constant current charge and discharge plot of a biomass-derived carbon/polymer gel (polyvinylidene fluoride-methacrylic acid) electrolyte in sodium sulfur secondary batteries in example 1: the charge and discharge characteristics of the sodium-sulfur battery can be seen to be double-discharge platform, and the cycle reversibility is good.
Example 2:
(1) Preparation and activation treatment of biomass-derived carbon: performing air-insulated heat treatment on pine wood with the length of 3cm multiplied by the width of 3cm multiplied by the height of 3cm for 4 hours at 300 ℃ to obtain a porous biomass carbon material, then placing the porous biomass carbon material in concentrated nitric acid with the concentration of 68% (mass fraction), stirring for 30min at 80 ℃, and activating to obtain activated biomass derived carbon;
(2) Activating treatment of polyvinylidene fluoride: and (3) stirring and soaking the polyvinylidene fluoride in 2mol/L NaOH solution for 1h, keeping the temperature at 60 ℃, and washing with deionized water to be neutral to obtain the polyvinylidene fluoride with C=C bonds.
(3) Graft polymerization of vinylidene fluoride: the polyvinylidene fluoride having c=c bond and 2-acrylamido-2-methylpropanesulfonic acid monomer obtained were dissolved in azomethylpyrrolidone, ammonium persulfate was added as an initiator (the amount of ammonium persulfate added was 10 per ml of solvent -3 g) Stirring for 2h at 40 ℃ to obtain the prepared polymer gel;
the mass ratio of the polyvinylidene fluoride monomer with C=C bond to the methacrylic acid monomer is 10:1, a step of;
(4) Preparation of carbon/polymer composite:
cutting activated biomass-derived carbon into 0.5mm slices, wherein the cutting direction is perpendicular to the length direction of a through hole in the activated biomass-derived carbon, adding the slices into the obtained polymer gel, heating to 180 ℃ and preserving heat for 10 hours, softening and filling the heated polymer gel into the pore structure of a carbon material, and drying at 80 ℃;
the mass ratio of the activated biomass-derived carbon to the polymer gel is 1:1;
(5) Preparation of gel electrolyte: immersing the obtained carbon/polymer composite in a common organic liquid electrolyte selected from ethylene carbonate, propylene carbonate, fluoroethylene carbonate (FEC) and NaClO 4 Mixing to obtain the final gel electrolyte;
(6) The positive electrode taking pure sulfur as an active material, the metal sodium as a negative electrode, and the substance derived carbon/polymer gel electrolyte prepared by the method as an electrolyte are assembled into a battery in an argon atmosphere, and electrochemical performance test is carried out;
FIG. 4 is an SEM image of activated biomass-derived carbon of example 2; it can be seen that the activated biomass-derived carbon has an oriented arrangement of through-holes. FIG. 5 is a schematic view of a displayAn infrared spectrum of a birch-derived carbon/polyvinylidene fluoride-2-acrylamido-2-methylpropanesulfonic acid gel in example 2. As can be seen, it is located at 1155 and 1115cm -1 is-SO 3 The strong absorption peak at the absorption peak band of H indicates that AMPS has been grafted onto the polyvinylidene fluoride backbone. FIG. 6 is a graph of the cycling performance of the biomass-derived carbon/polymer gel (polyvinylidene fluoride-2-acrylamido-2-methylpropanesulfonic acid) electrolyte in sodium sulfur secondary batteries of example 2; it can be seen that the battery has a higher initial discharge capacity and longer cycling stability. FIG. 7 is a constant current charge and discharge plot of a biomass-derived carbon/polymer gel (polyvinylidene fluoride-2-acrylamido-2-methylpropanesulfonic acid) electrolyte in sodium sulfur secondary batteries in example 2; the charge and discharge characteristics of the sodium-sulfur battery can be seen to be double-discharge platform, and the cycle reversibility is good. The battery obtained in example 2 had a first discharge capacity of 1100mAh g at a current density of 0.2C -1 About 600mAh g is maintained after 1000 cycles -1 Is a function of the capacity of the battery.
Example 3:
(1) Preparation and activation treatment of biomass-derived carbon: insulating poplar with the length of 3cm multiplied by the width of 3cm multiplied by the height of 3cm from air at 800 ℃ for heat treatment for 3 hours to obtain a porous biomass carbon material, and then placing the porous biomass carbon material in 10mol/L NaOH solution for stirring for 12 hours to obtain activated biomass derived carbon;
(2) Activating treatment of polyvinylidene fluoride: stirring and soaking the polyvinylidene fluoride in 0.5mol/L NaOH solution for 2 hours, keeping the temperature at 90 ℃, and washing the mixture to be neutral by deionized water to obtain polyvinylidene fluoride with C=C bonds;
(3) Graft polymerization of vinylidene fluoride: dissolving the obtained polyvinylidene fluoride and maleic anhydride monomer with C=C bond in nitrogen methyl pyrrolidone, adding ammonium persulfate as an initiator (the dosage of ammonium persulfate is 0.1g per milliliter of solvent), and stirring for 10 hours at 90 ℃ to obtain the prepared polymer gel;
the mass ratio of the polyvinylidene fluoride monomer with C=C bond to the methacrylic acid monomer is 1:3, a step of;
(4) Preparation of carbon/polymer composite:
cutting activated biomass-derived carbon into 0.5mm slices, wherein the cutting direction is perpendicular to the length direction of a through hole in the activated biomass-derived carbon, adding the slices into the obtained polymer gel, heating to 250 ℃ and preserving heat for 20 hours, softening and filling the heated polymer gel into the pore structure of a carbon material, and drying at 40 ℃;
the mass ratio of the activated biomass-derived carbon to the polymer gel is 1:2;
(5) Preparation of gel electrolyte: immersing the obtained carbon/polymer composite in a common organic liquid electrolyte selected from ethylene carbonate, propylene carbonate, fluoroethylene carbonate (FEC) and NaClO 4 Mixing to obtain the final gel electrolyte;
(6) The positive electrode taking pure sulfur as an active material, the metal sodium as a negative electrode, and the substance derived carbon/polymer gel electrolyte prepared by the method as an electrolyte are assembled into a battery in an argon atmosphere, and electrochemical performance test is carried out;
FIG. 8 is an SEM image of activated biomass-derived carbon of example 3; it can be seen that the activated biomass-derived carbon has an oriented arrangement of through-holes. The battery obtained in example 3 had a first discharge capacity of 1300mAh g at a current density of 0.2C -1 About 750mAh g is maintained after 1000 cycles -1 Is a function of the capacity of the battery.
Example 4:
(1) Preparation and activation treatment of biomass-derived carbon: performing heat treatment on pine wood with the length of 3cm multiplied by the width of 3cm multiplied by the height of 3cm at 800 ℃ for 3 hours in an air-isolated manner to obtain a porous biomass carbon material, and then placing the porous biomass carbon material in a 5mol/L NaOH solution for stirring for 24 hours to obtain activated biomass derived carbon;
(2) Activating treatment of polyvinylidene fluoride: stirring and soaking the polyvinylidene fluoride in 2mol/L NaOH solution for 1h, keeping the temperature at 90 ℃, and washing with deionized water to be neutral to obtain polyvinylidene fluoride with C=C bonds;
(3) Graft polymerization of vinylidene fluoride: dissolving the obtained polyvinylidene fluoride and maleic anhydride monomer with C=C bond in nitrogen methyl pyrrolidone, adding ammonium persulfate as an initiator (the dosage of ammonium persulfate is 0.1g per milliliter of solvent), and stirring at 90 ℃ for 12 hours to obtain the prepared polymer gel;
the mass ratio of the polyvinylidene fluoride monomer with C=C bond to the methacrylic acid monomer is 1:3, a step of;
(4) Preparation of carbon/polymer composite:
cutting activated biomass-derived carbon into 0.5mm slices, wherein the cutting direction is perpendicular to the length direction of a through hole in the activated biomass-derived carbon, adding the slices into the obtained polymer gel, heating to 180 ℃ and preserving heat for 24 hours, softening and filling the heated polymer gel into the pore structure of a carbon material, and drying at 60 ℃;
the mass ratio of the activated biomass-derived carbon to the polymer gel is 1:10;
(5) Preparation of gel electrolyte: immersing the obtained carbon/polymer composite in a common organic liquid electrolyte selected from ethylene carbonate, propylene carbonate, fluoroethylene carbonate (FEC) and NaClO 4 Mixing to obtain the final gel electrolyte;
(6) The positive electrode taking pure sulfur as an active material, the metal sodium as a negative electrode, and the substance derived carbon/polymer gel electrolyte prepared by the method as an electrolyte are assembled into a battery in an argon atmosphere, and electrochemical performance test is carried out;
FIG. 9 is a graph of the cycling performance of the biomass-derived carbon/polymer gel (polyvinylidene fluoride-maleic anhydride) electrolyte in sodium sulfur secondary batteries of example 4; it can be seen that the battery has a higher initial discharge capacity and longer cycling stability. FIG. 10 is a constant current charge and discharge plot of a biomass-derived carbon/polymer gel (polyvinylidene fluoride-maleic anhydride) electrolyte in sodium sulfur secondary batteries in example 4; the charge and discharge characteristics of the sodium-sulfur battery can be seen to be double-discharge platform, and the cycle reversibility is good. The battery obtained in example 4 had a first discharge capacity of 1250mAh g at a current density of 0.2C -1 About 800mAh g is maintained after 1000 cycles -1 Is a function of the capacity of the battery.

Claims (7)

1. A method for preparing a biomass-derived carbon/polymer gel electrolyte, which is characterized by comprising the following steps: the preparation method of the biomass-derived carbon/polymer gel electrolyte comprises the following steps:
1. preparation and activation treatment of biomass-derived carbon:
isolating the biomass material from air for heat treatment to obtain a porous biomass carbon material; the obtained porous biomass carbon material is placed in concentrated nitric acid for activation or is placed in alkali solution for activation, so that activated biomass derived carbon is obtained;
the biomass material is wood, and the wood is birch, pine or poplar;
step one, placing a porous biomass carbon material into concentrated nitric acid for activation at a temperature of 80-90 ℃ for at least 30min to obtain activated carbon with hydroxyl and carboxyl; placing biomass-derived carbon in an alkali solution for activation, and stirring for 12-48 hours to obtain activated carbon with hydroxyl and carboxyl; the alkali solution is NaOH solution or KOH solution, and the concentration is 5-10 mol/L;
2. activating treatment of polyvinylidene fluoride:
stirring and soaking the polyvinylidene fluoride in a strong alkali solution for 30min-2h, keeping the temperature at 60-90 ℃ during soaking, and washing the soaked polyvinylidene fluoride to be neutral by deionized water after the soaking is finished to obtain polyvinylidene fluoride with C=C bonds;
3. graft polymerization of vinylidene fluoride:
dissolving the obtained polyvinylidene fluoride with C=C bond and the reactive monomer in a solvent, adding an initiator, and stirring for 2-12 h at 40-90 ℃ to obtain polymer gel;
the reactive monomer is methacrylic acid, maleic anhydride or 2-acrylamido-2-methylpropanesulfonic acid; the solvent is nitrogen methyl pyrrolidone or dimethyl sulfoxide; the initiator is ammonium persulfate;
4. preparation of carbon/polymer composite:
cutting activated biomass-derived carbon into sheets of 0.5-2mm in a cutting direction perpendicular to the length direction of through holes in the activated biomass-derived carbon, mixing the obtained polymer gel with the cut activated biomass-derived carbon sheets, and heating, hydrothermal or hot-pressing; drying at 40-80 deg.c to obtain carbon/polymer compound;
5. preparation of gel electrolyte:
and immersing the obtained carbon/polymer composite in electrolyte used by the sodium-sulfur battery to obtain the biomass-derived carbon/polymer gel electrolyte.
2. The method of preparing a biomass-derived carbon/polymer gel electrolyte according to claim 1, characterized in that: the time of the heat treatment for isolating the air in the step one is at least 3 hours, and the temperature is 300-800 ℃.
3. The method of preparing a biomass-derived carbon/polymer gel electrolyte according to claim 1, characterized in that: and step two, the strong alkali solution is NaOH solution or KOH solution, and the concentration is 0.5-2.5mol/L.
4. The method of preparing a biomass-derived carbon/polymer gel electrolyte according to claim 1, characterized in that: the volume ratio of the mass of the initiator to the solvent in the third step is (0.1-10) g/100mL; the mass ratio of the polyvinylidene fluoride with a C=C bond to the reactive monomer is 1: (0.1-3).
5. The method of preparing a biomass-derived carbon/polymer gel electrolyte according to claim 1, characterized in that: and step four, heating, hydrothermal or hot-pressing at 180-250 ℃ for 10-24 hours.
6. The method of preparing a biomass-derived carbon/polymer gel electrolyte according to claim 1, characterized in that: the mass ratio of the activated biomass-derived carbon to the polymer gel in the step four is 1 (1-10).
7. Use of the gel electrolyte prepared by the method of claim 1, wherein: the positive electrode, the negative electrode and the biomass-derived carbon/polymer gel electrolyte are assembled into a sodium-sulfur secondary battery in an inert atmosphere.
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