CN112802988B - Electrode with chromatographic membrane structure for lithium-sulfur battery and application thereof - Google Patents
Electrode with chromatographic membrane structure for lithium-sulfur battery and application thereof Download PDFInfo
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Abstract
The invention discloses an electrode with a chromatographic membrane structure for a lithium-sulfur battery and application thereof in the lithium-sulfur battery. The electrode with the structure has the advantages of simple preparation method, environment-friendly materials and process, controllable electrode thickness and controllable crosslinking degree, and can realize accurate sulfur resistance. Compared with the traditional electrode preparation process, the electrode prepared by the gel method has simple preparation process and instant forming, and the electrode is prevented from being damaged in the preparation or transfer process; meanwhile, the marine polysaccharide is used as a binder to replace a common organic polymer resin binder, and the marine polysaccharide-containing organic polymer resin binder is wide in source, easy to prepare, low in cost, degradable and environment-friendly.
Description
Technical Field
The invention relates to an electrode with a chromatographic membrane structure, which is prepared by a gel method for a lithium-sulfur battery.
In commercializationAmong secondary batteries, the lithium ion battery is the secondary battery with the highest energy density at present, but the theoretical specific capacity of the lithium ion battery based on the 'de-intercalation' theory is less than 300mA h g at present-1Actual energy density of less than 200Wh kg-1And the requirement of people on the 500km endurance of the electric automobile can not be met. As a new electrochemical energy storage secondary battery, the lithium-sulfur battery is different from the traditional lithium ion 'de-intercalation' type material, and in the discharging process, sulfur and metallic lithium generate two electronic reactions and can release high specific capacity (1675mAh g)-1) The theoretical specific energy is also as high as 2600Wh kg-1Meanwhile, the active substance sulfur has the advantages of large natural abundance, low cost, low toxicity, environmental friendliness and the like, so that the lithium-sulfur battery is considered to be one of novel secondary batteries capable of replacing the lithium ion battery, and has a good application prospect.
However, in the discharging process of the lithium-sulfur battery, lithium metal loses electrons and is converted into lithium ions, and the lithium ions are diffused to the positive electrode through the electrolyte and are combined with elemental sulfur in the positive electrode to form lithium sulfide. While the positive electrode intermediate product of the lithium sulfur battery is polysulfide lithium (Li)2SnN is more than or equal to 3) is easy to dissolve in the liquid ether electrolyte, and in the charging process: the short-chain polysulfide lithium is electrochemically oxidized into long-chain polysulfide lithium at the positive electrode; after being dissolved in the electrolyte, the long-chain polysulfide lithium migrates to the negative electrode and is chemically reduced into short-chain polysulfide lithium by the metal lithium; the short-chain polysulfide lithium generated by the negative electrode can migrate to the positive electrode along with the electrolyte and is electrochemically oxidized again at the positive electrode. Thus, the polysulfide lithium shuttles back and forth between the anode and the cathode to generate a shuttle flying effect. On one hand, the shuttle effect causes the coulomb efficiency of the battery to be greatly reduced; on the other hand, irreversible loss of the active material of the battery is caused, and the cycle life of the battery is shortened. Therefore, how to inhibit the polysulfide lithium from transferring from the positive electrode to the negative electrode and directly contacting with the lithium sheet is a key scientific problem to be solved urgently in the process of developing the lithium-sulfur battery.
The prior art has seen that the use of marine polysaccharides as binders for preparing electrodes for use in lithium sulfur batteries (CN201510827982.6) differs from the prior art in that the present invention achieves a layer-by-layer sulfur barrier effect through crosslinking treatment.
Disclosure of Invention
The invention aims to provide an electrode with a chromatographic membrane structure prepared by a gel method and application thereof.
In order to achieve the purpose, the technical scheme adopted by the invention is as follows:
the positive electrode structure for the lithium-sulfur battery is characterized in that one or more than two kinds of marine polysaccharides are mixed with a carbon/sulfur compound, and the marine polysaccharides are crosslinked by utilizing the gel property of the marine polysaccharides to obtain an electrode with a layer-by-layer sulfur-blocking structure.
The marine polysaccharide comprises one or more than two of Agar (Agar), Carrageenan (Carrageenan), Sodium alginate (Sodium alginate) and other alginates. The number average molecular weight is 1000-5000000, preferably 30000-5000000.
The carbon/sulfur compound is one or more than two compounds of carbon materials and sulfur. The carbon material is one or more than two of carbon nano tube, graphene, carbon nano fiber, BP2000, KB600, KB300, XC-72, Super-P, acetylene black, activated carbon or carbon materials modified or activated by the carbon nano tube, the graphene, the carbon nano fiber, the BP2000, the KB600, the KB300, the XC-72, the Super-P, the acetylene black and the activated carbon.
The layer sulfur-blocking structure electrode is 10-800 mu m, wherein the thickness of the polymer compact film which is wrapped on the surface and distributed inside is 0.1-20 mu m. The polymer film accounts for 1-60 wt% of the electrode.
The carbon-sulfur composite electrode with the layer-by-layer sulfur-blocking structure has the particle size of 20-100 nm, and the mass of sulfur accounts for 20-80 wt% of the total mass.
The preparation method of the carbon film comprises the following steps:
(1) dissolving marine polysaccharide or marine polysaccharide grafted with photo-crosslinking groups in deionized water, and stirring at 10-100 ℃ for 0.5-2 h to form a high-molecular solution; the grafted photocrosslinking group is one or more than two of groups with C ═ C double bonds or S ═ S double bonds
2) Adding a carbon/sulfur compound into the solution, and fully stirring for 2-10 hours at the temperature of 20-50 ℃ to finally prepare a blending solution; wherein the solid content is 5-30 wt%;
(3) pouring the blending solution prepared in the step (2) on an aluminum foil substrate, and forming a whole after blade coating;
(4) and (3) carrying out cross-linking treatment on the whole formed in the step (3):
if glutaraldehyde steam crosslinking is adopted, the whole body is exposed in glutaraldehyde atmosphere with the constant temperature of 20-60 ℃ for 2-48 h;
if divalent or trivalent cation crosslinking is adopted, the whole is placed in divalent or trivalent salt solution with the mass fraction of 0.1-10% for crosslinking for 0-60 min; (preferred embodiment)
If photo-crosslinking is adopted, in the step (1), the marine polysaccharide grafted with the photo-crosslinking group is used as a binder, a photo-crosslinking initiator is added into the blending solution, and the whole is exposed in ultraviolet light for 0.5-48 h; the photoinitiator is one or two of free radical polymerization photoinitiator or cationic polymerization photoinitiator.
(5) Then, the whole is subjected to freeze drying for 4-24 hours, and is taken out and dried for 2-24 hours at the temperature of 20-80 ℃ to obtain an electrode, wherein the thickness of the electrode is 10-800 mu m; the freeze drying temperature is-50-0 ℃, and the vacuum degree is 0.1-1;
the application of the electrode with the chromatographic membrane structure can be used in a lithium-sulfur battery.
The beneficial results of the invention are:
(1) the electrode prepared by the gel method has simple preparation process, and the prepared gel electrolyte porous electrode can be formed instantly, so that the electrode is prevented from being damaged in the preparation or transfer process;
(2) the electrode binder with the chromatographic membrane structure prepared by the invention has the advantages of wide source, easy preparation, degradability, environmental friendliness and low cost.
(3) The electrode with the chromatographic membrane structure prepared by the invention uses a water-based binder, does not need to be dissolved in an organic solvent, avoids the emission of a toxic organic solvent to the atmosphere in the drying process, and is energy-saving and environment-friendly;
(4) the electrode with the chromatographic membrane structure prepared by the invention forms a compact polymer membrane in the cross-linking process, and tightly coats the carbon/sulfur compound in the polymer membrane, so that the bonding property of the binder electrode is improved, and the electrode can be used for high-energy-density (high-sulfur-loading) lithium-sulfur batteries;
(5) the electrode with the chromatographic membrane structure provided by the invention is internally provided with the polymer membrane layer by layer, so that the shuttle of polysulfide can be inhibited layer by layer.
The electrode with the chromatographic membrane structure prepared by the invention has the advantages of simple preparation process, environmental friendliness and low cost, and the layer-by-layer sulfur blocking structure is beneficial to inhibiting polysulfide shuttle flying and polymer wrapping, thereby being beneficial to improving the cohesiveness and the electrode carrying capacity. The electrode with the chromatographic membrane structure is used as a positive electrode material of the lithium-sulfur battery, and the battery shows good comprehensive performance and has good application prospect.
The marine polysaccharide is used as a binder to replace a common organic polymer resin binder, and the marine polysaccharide binder has the advantages of wide source, easiness in preparation, low cost, degradability and environmental friendliness; the marine polysaccharide belongs to a water-based adhesive, organic solvents (such as N-methyl pyrrolidone, N, N-dimethylformamide, dimethylacetamide and the like) used for preparing the traditional slurry are not needed, and the emission of toxic organic solvents to the atmosphere is avoided in the electrode drying process, so that the energy is saved and the environment is protected; secondly, the adhesive forms a compact polymer film in the cross-linking process, and tightly coats the carbon/sulfur compound in the polymer film, so that the adhesion of the electrode is improved, and the polymer film can be used for high-energy-density (high-sulfur-loading) lithium-sulfur batteries; the dense polymer films distributed layer by layer in the electrode can prevent polysulfide from diffusing out of the anode layer by layer, in addition, the binder has polarity, can adsorb polysulfide in polarity and inhibit the polysulfide from flying, and the cycle performance and the service life of the battery are improved under the combined action of the two.
In conclusion, when the electrode with the chromatographic membrane structure prepared by the gel method is used as the positive electrode of the lithium-sulfur battery, the electrode has great advantages in the aspects of electrode preparation process, environmental protection, economy, preparation of high-load batteries, improvement of battery cycle performance and the like, and has good application prospects.
Drawings
FIG. 1: surface SEM image (left) of example 1, surface SEM image (middle) of comparative example 1 and surface SEM image (right) of comparative example 2;
FIG. 2: example 1 cross-sectional SEM images;
FIG. 3: surface SEM image of example 3 (left) and comparative example 3 (right);
FIG. 4: example 4 surface SEM image (left) and cross-sectional SEM image (right);
FIG. 5: rheological test curve of sodium alginate cation gelation;
FIG. 6: cycling stability testing of lithium sulfur batteries assembled with comparative examples 1,2 and example 1.
Detailed Description
Comparative example 1
10g of commercial KB600 was placed in a tube furnace under protection of Ar gas at 5 ℃ for min-1Heating to 900 deg.C, introducing steam for activation for 1.5h, wherein the flow rate of steam is 600mL min-1The activated carbon material was designated A-KB 600. Mixing 5g A-KB600 and 10g S, heating to 155 deg.C in a tube furnace at a heating rate of 1 deg.C for min-1And keeping the temperature for 20h to obtain the product which is marked as S/A-KB 600.
Dissolving 0.1g of polyvinylidene fluoride (PVDF) in 14g N-methylpyrrolidone (NMP), stirring for 0.5h, adding 0.7g of S/A-KB600, stirring for 5h, blade-coating on an aluminum film to form a film, adjusting a scraper to 600 mu m, blade-coating, and drying at 60 ℃ overnight to obtain an electrode which is bonded on an aluminum foil and has more cracks, and meanwhile, the powder can be dropped off by slight shaking.
Electrode preparation and battery assembly: cutting into 10mm small round pieces, weighing, vacuum drying at 60 deg.C for 2 hr, and making into positive electrode (sulfur loading per piece is about 2mg cm)-2) Taking a lithium sheet as a negative electrode, a clegard2325 as a diaphragm, and adding LiNO with the mass concentration of 1% into 1M lithium bis (trifluoromethylsulfonyl) imide solution (LiTFSI)3As an electrolyte solution, a mixed solution of 1, 3-Dioxolane (DOL) and ethylene glycol dimethyl ether (DME) (volume ratio v/v of 1:1) was used as a solvent, and a battery was assembled and subjected to a battery cycle performance test at a 0.2C rate.
The initial specific capacity under 0.2C multiplying power is 903mA h g-1The capacity retention after 100 cycles was 69.3%.
Comparative example 2 (uncrosslinked)
Dissolving 0.1g of Sodium Alginate (SA) in 14g of deionized water, stirring for 0.5h, adding 0.7g of S/A-KB600, stirring for 5h, blade-coating on an aluminum film to form a film, adjusting a scraper to 600 mu m, blade-coating at 60 ℃, drying at night, and bonding the obtained electrode on an aluminum foil with certain cracks, wherein powder can be dropped off by shaking forcibly.
Subsequent electrode preparation and cell assembly were the same as in comparative example 1.
The initial specific capacity under 0.2C multiplying power is 920mA h g-1The capacity retention after 100 cycles was 72.3%.
Comparative example 3 (uncrosslinked)
Dissolving 0.1g of carrageenan in 14g of deionized water, stirring for 0.5h, adding 0.7g of S/A-KB600, stirring for 5h, blade-coating an aluminum film to form a film, adjusting a scraper to 600 mu m, blade-coating at 60 ℃ overnight, and drying to obtain an electrode which is bonded on an aluminum foil and has a certain crack and simultaneously has powder falling by shaking forcefully. And the appearance of the electrode was observed under SEM.
Example 1
Dissolving 0.1g of Sodium Alginate (SA) in 14g of deionized water, stirring for 0.5h, adding 0.7g of S/A-KB600, stirring for 5h, blade-coating on an aluminum film to form a film, adjusting a scraper to 600 mu m, and blade-coating the whole on CaCl with the mass concentration of 1%2After 10min of medium cross-linking, the mixture is taken out, put into a refrigerator for freezing overnight, then freeze-dried for 10h, and taken out and dried at 60 ℃ overnight. The resulting electrode was a self-supporting electrode, one-piece, free of cracks, and shaken vigorously without powder falling.
The electrode is formed by wrapping a carbon/sulfur compound by a sodium alginate polymer film layer, the thickness of the sodium alginate polymer film layer is 0.1-20 mu m, the carbon/sulfur compound is positioned between the polymer film layers, and the number of the polymer film layers from one side surface to the other side surface of the electrode is 2-100. Subsequent electrode preparation and cell assembly were the same as in comparative example 1.
The initial specific capacity under 0.2C multiplying power is 951mA h g-1The capacity retention after 100 cycles was 89.8%.
Example 2
Dissolving 0.1g Sodium Alginate (SA) in 14g deionized water, stirring for 0.5h, adding 0.7g S/A-KB600, stirring for 5h, blade-coating on aluminum film to form film, adjusting the blade to 600 μm, and coating the whole onCaCl with mass concentration of 1%2After 10s of medium cross-linking, the mixture is taken out, placed into a refrigerator for freezing overnight, then freeze-dried for 10h, and taken out and dried at 60 ℃ overnight. The resulting electrode was a self-supporting electrode, as a whole, with no cracks, and no powder falling off with vigorous shaking.
Subsequent electrode preparation and cell assembly were the same as in comparative example 1.
The initial specific capacity under 0.2C multiplying power is 1001mA h g-1The capacity retention after 100 cycles was 82.1%.
Example 3
Dissolving 0.1g of carrageenan in 14g of deionized water, stirring for 0.5h, adding 0.7g of S/A-KB600, stirring for 5h, blade-coating an aluminum film to form a film, adjusting a scraper to 600 mu m, blade-coating the whole on CaCl with the mass concentration of 1%2After 10s of medium cross-linking, the mixture is taken out, placed into a refrigerator for freezing overnight, then freeze-dried for 10h, and taken out and dried at 60 ℃ overnight. The resulting electrode was a self-supporting electrode, as a whole, with no cracks, and no powder falling off with vigorous shaking.
Example 4
Dissolving 0.1g of Sodium Alginate (SA) in 14g of deionized water, stirring for 0.5h, adding 0.7g of S/A-KB600, stirring for 5h, blade-coating an aluminum film to form a film, adjusting a scraper to 600 mu m, crosslinking the whole in a glutaraldehyde atmosphere with constant temperature of 37 ℃ for 3h, taking out, and drying at 60 ℃ overnight. The resulting electrode was a self-supporting electrode, as a whole, with no cracks, and no powder falling off with vigorous shaking.
Compared with SEM images of the surfaces of comparative examples 1 and 2 and example 1, the surface of example 1 is flat, and a polymer film is attached to the surface layer, so that the flying shuttle of polysulfide is favorably blocked, and the bonding property is favorably improved; in the comparative example, the surface of the electrode was cracked seriously due to the thermal shrinkage of the polymer resin during the drying process. From the cross-sectional view of example 1, the polymer film is distributed in a laminar form inside the electrode, which structure is advantageous for blocking polysulfides and suppressing their shuttles.
From the comparison of the SEM images of the surfaces of comparative example 3 and example 3, it can be seen that, compared with the non-crosslinked electrode, example 3 has a flat surface and a thin polymer film is attached to the surface layer, which is similar to example 1, and this is advantageous for blocking the shuttle of polysulfide and for improving the adhesive property; in contrast, in comparative example 3, the surface of the electrode was cracked seriously due to thermal shrinkage of the polymer resin during the drying process.
From the SEM images of the surface and cross-section of example 4, it can be seen that the electrode prepared by glutaraldehyde cross-linking also has the same morphology and structure.
Rheological frequency sweeps were performed on examples 1 and 2 before drying, and the nature of the intermediate state was determined by storing the relationship of modulus G' and loss modulus G ". It can be seen that the crosslinked slurry became a gel. And as the crosslinking time increases, the gel strength increases and the entanglement sites increase, as evidenced by increased polysulfide inhibition.
Based on the above characteristics of the electrode with the layer-by-layer sulfur-resistant structure, as shown in fig. 6, in the battery using the example 1-2 as the positive electrode material, the initial specific discharge capacity at 0.1C was 1200mAh g-1The batteries using examples 1-2 as the positive electrode material had better cycle stability than comparative example 2, because the electrode surface was flat and no cracks occurred, and the multilayer polymer was formed on and in the electrode surface, which was advantageous in blocking the shuttle of polysulfide and reducing the loss of active material. Meanwhile, the battery of the comparative example 2 has better cycling stability than that of the comparative example 1 because the SA molecular chain has polarity and can fix sulfur through chemical adsorption, so that the capacity retention rate is better.
Claims (9)
1. An electrode having a chromatographic membrane structure for a lithium sulfur battery, characterized in that:
the electrode with the layer-by-layer sulfur-blocking structure is prepared by mixing one or more than two kinds of marine polysaccharides and a carbon/sulfur compound through a cross-linked gel method, wherein the mass of the marine polysaccharides accounts for 1-60 wt% of the total mass of the electrode;
the electrode is formed by wrapping a carbon/sulfur compound by a seaweed polysaccharide polymer film layer, a network-shaped structure formed by interlacing crosslinked flaky seaweed polysaccharide polymer film layers is arranged in the electrode, the thickness of a polymer compact film wrapped on the surface and distributed in the electrode is 0.1-20 mu m, the carbon/sulfur compound is positioned between the polymer film layers, the number of the polymer film layers from one side surface to the other side surface of the electrode is gradually increased along with the increase of crosslinking time, and the number of the polymer film layers is 2-100;
the marine polysaccharide comprises one or more than two of agar, carrageenan and sodium alginate, and the number average molecular weight of the marine polysaccharide is 1000-5000000.
2. The electrode with a chromatography membrane structure according to claim 1, characterized in that:
the carbon/sulfur compound is one or more than two of carbon material and sulfur compound, the particle size is 20-100 nm, and the mass of the sulfur in the carbon/sulfur compound accounts for 20-95 wt% of the total mass;
the carbon material is one or more than two of carbon nano tube, graphene, carbon nano fiber, BP2000, KB600, KB300, XC-72, SuperP, acetylene black and activated carbon.
3. The electrode with a chromatography membrane structure according to claim 1, characterized in that:
the preparation process utilizes the gel property of the algal polysaccharide, which can form gel through cross-linking; the crosslinking method comprises one or more than two of photocrosslinking, ethanol and/or isopropanol non-solvent phase conversion, glutaraldehyde steam crosslinking, divalent or trivalent cation crosslinking or standing crosslinking.
4. An electrode having a chromatographic membrane structure according to any one of claims 1 to 3, wherein: the electrode with the chromatographic membrane structure is prepared by the following process,
(1) dissolving marine polysaccharide or marine polysaccharide grafted with photo-crosslinking groups in deionized water, and stirring at 10-100 ℃ for 0.5-2 h to form a high-molecular solution; the grafted photocrosslinking group is one or more than two of groups with C = C double bond or S = S double bond;
(2) adding a carbon/sulfur compound into the solution, and fully stirring for 2-10 hours at the temperature of 20-50 ℃ to finally prepare a blending solution; wherein the solid content is 5-30 wt%;
(3) pouring the blending solution prepared in the step (2) on an aluminum foil substrate, and blade-coating to form a whole;
(4) and (4) carrying out cross-linking treatment on the whole formed in the step (3):
the marine polysaccharide comprises one or more of agar, carrageenan and sodium alginate;
if the marine polysaccharide is sodium alginate, performing glutaraldehyde steam crosslinking, and exposing the whole to glutaraldehyde atmosphere at the constant temperature of 20-60 ℃ for 2-48 h;
or if the marine polysaccharide is one or two of sodium alginate or carrageenan, and divalent or trivalent cation crosslinking is adopted, the whole is placed in divalent or trivalent salt solution with the mass fraction of 0.1-10% for crosslinking for 5 s-60 min;
or, if the marine polysaccharide is the marine polysaccharide grafted with the photo-crosslinking group, and photo-crosslinking is adopted, the marine polysaccharide grafted with the photo-crosslinking group is used as a binder in the step (1), a photo-crosslinking initiator is added into the blending solution, the whole is exposed in ultraviolet light for 0.5-48 h, and the photo-initiator is one or two of a free radical polymerization photo-initiator or a cationic polymerization photo-initiator;
or, if the marine polysaccharide is agar, adopting standing for crosslinking;
(5) then, the whole formed in the step (4) is freeze-dried for 4-24 hours, and is taken out and dried for 2-24 hours at 20-80 ℃ to obtain an electrode, wherein the thickness of the electrode is 10-800 micrometers; the freeze drying temperature is-50-0 ℃, and the vacuum degree is 0.1-1.
5. The electrode with a chromatography membrane structure according to claim 4, characterized in that:
the free radical polymerization photoinitiator or cationic polymerization photoinitiator is one or more than two of I-250, I-160 and I-2529;
the divalent or trivalent salt solution is Ca2+,Ba2+,Ni2+,Fe2+,Zn2+,Cu2+,Mg2+,Fe3+,Al3+One or more than two soluble salts of (a).
6. An electrode having a chromatography membrane structure according to claim 1, characterized in that:
the mass of the marine polysaccharide accounts for 5-30% of the total mass of the electrode.
7. The electrode with a chromatography membrane structure according to claim 1, characterized in that:
the number average molecular weight of the marine polysaccharide is 30000-5000000.
8. The electrode with a chromatography membrane structure according to claim 2, characterized in that:
the mass of sulfur in the carbon/sulfur compound accounts for 50-95% of the total mass.
9. Use of an electrode having a chromatographic membrane structure according to any one of claims 1 to 3 and 5 to 6, wherein: the electrode having a chromatographic membrane structure is used in a lithium sulfur battery.
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