CN116130607B - Preparation method and application of solid sulfur anode - Google Patents
Preparation method and application of solid sulfur anode Download PDFInfo
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Abstract
A preparation method and application of a solid sulfur positive electrode belong to the technical field of batteries. The specific scheme is as follows: preparation of a three-dimensional current collector attached with a photo-thermal conversion material, preparation of in-situ polymerization slurry, preparation of a photo-thermal conversion solid sulfur positive electrode, preparation of a lithium-philic/sodium-type three-dimensional negative electrode and preparation of an integrated solid metal-sulfur battery. The photo-thermal conversion solid sulfur positive electrode comprises a three-dimensional current collector attached with a photo-thermal conversion material and an in-situ cured polymer sulfur material embedded in the three-dimensional current collector, and can be applied to a solid metal-sulfur battery in a low-temperature environment through a photo-thermal conversion effect. Meanwhile, the lithium-philic/sodium-philic three-dimensional current collector and the solid-state battery are integrally prepared, so that the influence of dendrites on the battery performance is reduced, meanwhile, the discontinuous contact between electrode interfaces is greatly relieved, the internal stress of the solid-state battery is reduced, the circulation capacity of the solid-state metal-sulfur battery is greatly improved, and the progress of the solid-state metal-sulfur battery with high specific energy and long endurance is promoted.
Description
Technical Field
The invention belongs to the technical field of batteries, and particularly relates to a preparation method and application of a solid sulfur positive electrode.
Background
Among all batteries with commercial prospects, rechargeable "metal-sulfur" batteries have extremely high energy density, while the key component sulfur of "metal-sulfur" batteries is abundant in the crust and inexpensive, making "metal-sulfur" batteries a high cost advantage in most high specific energy batteries, and thus it is considered a promising class of energy storage technology. However, conventional liquid "metal-sulfur" generally has serious leakage and combustion safety problems, and its sharply reduced performance in cold regions (at low temperatures) further limits its wide application. More importantly, current liquid "metal-sulfur" batteries generally suffer from poor mechanical and chemical stability (e.g., sodium dendrites and interfacial side reactions), making it difficult to maintain long-term efficient operation of such batteries.
Solid state "metal-sulfur" batteries based on solid state electrolytes have many advantages over liquid state "metal-sulfur" batteries: very high energy density; high-current and high-power discharge can be realized; no self-discharge reaction, and the charge-discharge current efficiency is almost 100%; meanwhile, the shuttle effect in the traditional metal-sulfur battery can be eliminated, and the loss of active substances of the metal-sulfur battery caused by circulation is reduced. It also has significant disadvantages including dendrite and polysulfide formation and accumulation, allowing it to last only a few charge cycles, a short cycle life, and a discontinuous interface between the negative/positive electrode and the electrolyte that gives rise to adverse stress distribution at the electrode. Therefore, in order to accelerate the commercialization process of the metal-sulfur battery, it is needed to overcome the problems of low temperature application, discontinuous contact of negative dendrite and electrode interface, and the like of the solid metal-sulfur battery.
Disclosure of Invention
The invention provides a preparation method and integrated application of a photo-thermal conversion solid sulfur positive electrode, which are used for solving the problems of dendrite, interface contact and narrow working temperature of a solid metal-sulfur battery.
In order to achieve the above purpose, the present invention adopts the following technical scheme:
a preparation method of a photo-thermal conversion solid sulfur positive electrode comprises the following steps:
step one, electropolymerizing an imino-containing polymer monomer on a three-dimensional current collector I, adding the electropolymerized three-dimensional current collector I into an aqueous solution containing a silicone sheet for ultrasonic treatment, enabling siloxane to be attached to the three-dimensional current collector I through hydrogen bonds, filtering and drying to obtain the three-dimensional current collector I attached with the photothermal conversion material;
step two, fully mixing a polymer monomer containing C=C bonds, a polymer monomer containing ether bonds and metal salt I in an organic solvent to obtain a precursor solution of in-situ polymerization slurry; adding an initiator into a precursor solution of the in-situ polymerization slurry to obtain an in-situ polymerization slurry;
step three, the mass ratio is 1 at 170-200 ℃: 2-30, adding hyperbranched polymer precursor into molten sulfur, fully mixing to prepare polymer sulfur material, and mixing the polymer sulfur material with conductive carbon according to the proportion of 1-4: 1, fully grinding the mass ratio to obtain anode powder;
fourthly, in-situ polymerization slurry and positive electrode powder are mixed according to the following ratio of 1: mixing the materials in the mass ratio of 1 to 6 in succinonitrile, coating the mixed slurry on the three-dimensional current collector I attached with the photo-thermal conversion material obtained in the step one, and drying to obtain the photo-thermal conversion solid sulfur anode.
Further, in the first step, the specific step of electropolymerizing the imino-containing polymer monomer onto the three-dimensional current collector I comprises: the three-dimensional current collector I is used as an anode, a platinum sheet is used as a cathode, an aqueous solution of polymer monomer containing imino is used as an electrolyte solution, and the polymer monomer is electropolymerized on the three-dimensional current collector I under constant potential of 0.05-0.18V.
Further, the three-dimensional current collector I is one or more of foam nickel, foam aluminum, carbon cloth, porous nickel oxide and porous aluminum oxide; the polymer monomer containing imino is one or more of methoxyimino furan ammonium acetate, 4-acetamido phenylacetate, imide, iminodiacetic acid and (isocyano imino) triphenylphosphine.
Further, in the first step, the preparation step of the aqueous solution containing the silicone sheet includes: placing calcium silicide powder into concentrated acid, stirring for 5-10 days in an inert atmosphere at-30-0 ℃, washing with ethanol to neutrality, dispersing the obtained product into water, and performing ultrasonic treatment for 1-4 hours to obtain an aqueous solution containing the silicon oxide sheet.
Further, in the second step, the molar ratio of the c=c bond-containing polymer monomer, the ether bond-containing polymer monomer and the metal salt i is 1 to 2: 3-30: 1.
further, in step two, the c=c bond-containing polymer monomer includes one or more of pentaerythritol tetraacrylate, styrene, 4-methyl-1-pentene, propyl methacrylate, isothiazol-3-one, 2-sec-butyl-4, 6-dinitrophenol; the polymer monomer containing ether bond comprises one or more of 1, 3-dioxolane, tri (ethylene glycol) divinyl ether, ethylene carbonate, vinylene carbonate, carboxylic acid ester, 4-phenoxybenzoyl chloride and 1, 4-phenylene bis (thiourea); the metal salt I is lithium salt or sodium salt; when the corresponding negative electrode contains lithium, the metal salt I is lithium salt, and the lithium salt comprises LiTFSI, liFSI, liClO 4 、LiBOB、LiBF 4 、LiCF 3 SO 3 One or more of LiDFOB; when the corresponding negative electrode contains sodium, the metal salt I is sodium salt, and the sodium salt comprises one or more of sodium triflate, disodium sebacate, sodium hexafluorophosphate, sodium perchlorate and disodium hydrogen phosphate; the organic solvent is one or more of N-methyl pyrrolidone, succinonitrile, ethylene carbonate and diethyl carbonate; the initiator is one or more of ammonium persulfate, tert-butyl benzoyl peroxide, azodiisoheptonitrile and azodiisobutyronitrile.
Further, in step three, the hyperbranched polymer precursor comprises one or more combinations of pentaerythritol tetraacrylate, 1,3, 5-benzenetrithiol, acrylonitrile, tetramethyldithiothiuram, methacrylic acid, tetra-thio-2, 5- (1, 3, 4-thiadiazole); the conductive carbon is one or more of carbon nano tube, VGCF, carbon black, superP, keqin black and graphite.
The photo-thermal conversion solid sulfur positive electrode prepared by the preparation method is applied to a solid metal-sulfur battery.
Further, the preparation method of the solid metal-sulfur battery comprises the following steps:
step 1, the molar ratio is 1-3: 1 and 2, 5-dihydroxyterephthalic acid are dissolved in a mixed solution of N, N-dimethylformamide and methanol, then a three-dimensional current collector II is added and subjected to ultrasonic treatment, the three-dimensional current collector II reacts for 15 to 30 hours at the temperature of 100 to 150 ℃, the obtained three-dimensional current collector II growing with a metal organic framework is heated for 1 to 4 hours at the temperature of 500 to 900 ℃ in argon atmosphere after filtration and drying, the obtained three-dimensional current collector II growing with carbon-loaded lithium/sodium metal clusters is obtained, and the obtained three-dimensional current collector II growing with carbon-loaded lithium/sodium metal clusters is contacted with molten lithium/sodium in inert atmosphere, so that a lithium/sodium-loaded three-dimensional cathode is obtained;
step 2: and uniformly coating in-situ polymerization slurry on the lithium-philic/sodium-philic three-dimensional cathode in inert atmosphere, covering the photo-thermal conversion solid sulfur anode on the in-situ polymerization slurry, packaging the battery by using a light-transmitting material, and performing thermal polymerization to finally obtain the solid metal-sulfur battery.
Further, in the step 1, the metal salt ii includes one or more of magnesium salt, nickel salt, cobalt salt, and chromium salt; the magnesium salt comprises one or more of magnesium phthalocyanine, magnesium acrylate, magnesium hydrogen phosphate and magnesium citrate, the nickel salt comprises one or more of nickel phthalocyanine, nickel acetylacetonate, nickel benzoate and nickel naphthenate, the cobalt salt comprises one or more of cobalt carbonyl, cobalt thiocyanate, cobalt naphthenate and cobalt sulfamate, and the chromium salt comprises one or more of chromium hexacarbonyl, chromium acetylacetonate, chromium acyl chloride and chromium acetate; the three-dimensional current collector II comprises one or more of foam copper, carbon paper, a stainless steel mesh, a zinc oxide array and a titanium mesh; in the step 2, the light-transmitting material comprises one or more of a light-transmitting acrylic plate, a transparent organic glass, a sunlight plate and a polycarbonate plate, and the thickness is between 0.5 and 5 mm.
Compared with the prior art, the invention has the beneficial effects that:
(1) According to the invention, a layer of polymer containing imino is subjected to electro-polymerization on the three-dimensional current collector I in advance, and the siloxane with photo-thermal conversion effect and catalysis effect is tightly and uniformly attached to the three-dimensional current collector I through the hydrogen bond effect between the imino and the siloxane, so that the defects of uneven material distribution, local aggregation and the like in the traditional growth technology are avoided, meanwhile, the photo-thermal conversion effect under the natural illumination condition can be realized by the photo-thermal conversion three-dimensional positive electrode, the internal temperature of the battery is increased, the high reversible operation of the battery under the low-temperature environment is realized, in addition, the high load of positive sulfur can be realized by the positive three-dimensional current collector I through a thick framework, and the energy density and the catalytic reaction area of the battery are increased;
(2) The hyperbranched organic sulfur prepared by the strong interaction between the sulfur simple substance and the hyperbranched polymer can convert the traditional S 8 The aggregate is split into organic matters embedded by S-S single bonds, so that uniform distribution of reversible sulfur is realized, the defects of low conductivity of traditional elemental sulfur ions and electrons are overcome, shuttle of polysulfide in a positive electrode of a polymer system is greatly inhibited, stable electrochemical behavior is realized, meanwhile, excellent interface compatibility is realized between hyperbranched organic matters and in-situ polymerization slurry, solid positive electrode pores (figure 1) can be basically eliminated, an ion/electron transmission path in an electrode is shortened, and the energy efficiency and the service life of a battery are remarkably improved;
(3) The invention utilizes the three-dimensional current collector II with the carbon-loaded lithium/sodium metal clusters, can realize the high wettability of the current collector to lithium/sodium, reduces the local current density of the negative electrode, obviously relieves the dendrite of the negative electrode, simultaneously can realize the continuous contact of the solid electrolyte and a two-stage interface by in-situ polymerization of the solid electrolyte which is the same as that of the solid positive electrode on the three-dimensional negative electrode, eliminates the potential difference caused by different components between the positive electrode and the electrolyte interface, reduces the space charge layer of the electrode interface, and in addition, the integrated design of the battery can relieve the stress accumulation of the electrode interface in the charge-discharge process, reduces the use amount (thickness) of the electrolyte, and realizes the long-term reliable operation of the solid lithium/sodium-sulfur battery.
Drawings
FIG. 1 is a scanning electron microscope image of a photo-thermal conversion solid sulfur anode;
FIG. 2 is a scanning electron microscope image of a sodium philic three-dimensional negative electrode formed after contact with molten sodium;
FIG. 3 is a cycle chart of a solid state "sodium-sulfur" cell at low temperature (-10 ℃).
Detailed Description
The technical solutions of the present invention will be clearly and completely described below with reference to the accompanying drawings and examples, and it is apparent that the described examples are only some, but not all, of the examples of the invention, and all other examples obtained by those skilled in the art without making any inventive effort are within the scope of the present invention.
A preparation method and application of solid sulfur positive electrode, the concrete scheme is as follows: preparation of a three-dimensional current collector I attached with a photo-thermal conversion material, preparation of in-situ polymerization slurry, preparation of a photo-thermal conversion solid sulfur positive electrode, preparation of a lithium-philic/sodium-type three-dimensional negative electrode and preparation of an integrated solid metal-sulfur battery. The photo-thermal conversion solid sulfur positive electrode comprises a three-dimensional current collector I attached with a photo-thermal conversion material and an in-situ solidified polymer sulfur material embedded in the three-dimensional current collector I, and can be applied to a solid metal-sulfur battery in a low-temperature environment through a photo-thermal conversion effect. Meanwhile, the lithium-philic/sodium-philic three-dimensional current collector II and the solid-state battery are integrally prepared, so that the influence of dendrites on the battery performance is reduced, meanwhile, the discontinuous contact between electrode interfaces is greatly relieved, the internal stress of the solid-state battery is reduced, the circulation capacity of the solid-state metal-sulfur battery is greatly improved, and the progress of the solid-state metal-sulfur battery with high specific energy and long endurance is promoted.
The first embodiment is as follows:
a preparation method of a photo-thermal conversion solid sulfur positive electrode comprises the following steps:
step one: the preparation of the three-dimensional current collector I attached with the photo-thermal conversion material specifically comprises the following steps: electropolymerizing an imino-containing polymer monomer on the three-dimensional current collector I to obtain a polymer-coated three-dimensional current collector I;
placing calcium silicide powder into concentrated acid, stirring for 5-10 days in an inert atmosphere at the temperature of minus 30-0 ℃, washing with ethanol to be neutral, dispersing the obtained product into water, and carrying out ultrasonic treatment for 1-4 hours to obtain an aqueous solution containing the silicon oxide sheet; adding a three-dimensional current collector I coated by a polymer into the solution, continuing ultrasonic treatment for 10-30 min, enabling siloxane to be attached to the three-dimensional current collector through hydrogen bonds, filtering and drying to obtain the three-dimensional current collector I attached with the photothermal conversion material;
wherein the specific steps of electropolymerization of the imino-containing polymer monomer on the three-dimensional current collector I comprise: treating the three-dimensional current collector I serving as an anode, a platinum sheet serving as a cathode and an imino-containing polymer monomer solution serving as an electrolyte solution at a constant potential in the range of 0.05-0.18V for 5-30 min, and electropolymerizing the imino-containing polymer monomer on the three-dimensional current collector I;
the three-dimensional current collector I is one or more of foam nickel, foam aluminum, carbon cloth, porous nickel oxide and porous aluminum oxide;
the polymer monomer containing imino is one or more of methoxyimino furan ammonium acetate, 4-acetamido phenylacetate, imide, iminodiacetic acid and (isocyano imino) triphenylphosphine;
the concentrated acid is one or more of concentrated hydrochloric acid, concentrated sulfuric acid and concentrated nitric acid.
Step two: the preparation of the in-situ polymerization slurry specifically comprises the following steps:
the method comprises the steps of mixing a polymer monomer containing C=C bonds, a polymer monomer containing ether bonds and metal salt I according to a ratio of 1-2: 3-30: 1 in an organic solvent to obtain a precursor solution of in-situ polymerization slurry; adding 0.05 to 0.5wt.% of initiator into a precursor solution of the in-situ polymerization slurry within 1 to 5min before in-situ polymerization to obtain the in-situ polymerization slurry;
wherein the polymer monomer containing C=C bond is one or more of pentaerythritol tetraacrylate, styrene, 4-methyl-1-pentene, propyl methacrylate, isothiazol-3-ketone and 2-sec-butyl-4, 6-dinitrophenol;
the polymer monomer containing ether bond comprises one or more of 1, 3-dioxolane, tri (ethylene glycol) divinyl ether, ethylene carbonate, vinylene carbonate, carboxylic acid ester, 4-phenoxybenzoyl chloride and 1, 4-phenylene bis (thiourea);
the metal salt I comprises lithium salt or sodium salt; when the corresponding negative electrode contains lithium, the metal salt I is lithium salt, and the metal salt I comprises LiTFSI, liFSI, liClO 4 、LiBOB、LiBF 4 、LiCF 3 SO 3 One or more of LiDFOB; when the corresponding negative electrode contains sodium, the metal salt I is sodium salt, and the metal salt I comprises one or more of sodium trifluoromethanesulfonate, disodium sebacate, sodium hexafluorophosphate, sodium perchlorate and disodium hydrogen phosphate;
the organic solvent comprises one or more of N-methyl pyrrolidone, succinonitrile, ethylene carbonate and diethyl carbonate;
the initiator comprises one or more of ammonium persulfate, tert-butyl benzoyl peroxide, azodiisoheptonitrile and azodiisobutyronitrile.
Step three: the preparation of the photo-thermal conversion solid sulfur anode specifically comprises the following steps:
the mass ratio of the components is 1 at 170-200 ℃: 2-30, adding hyperbranched polymer precursor into molten sulfur, fully mixing to prepare polymer sulfur material, and mixing the polymer sulfur material with conductive carbon according to the proportion of 1-4: 1, fully grinding the mass ratio to obtain anode powder;
mixing the in-situ polymerization slurry obtained in the second step with the positive electrode powder obtained in the third step according to the proportion of 1: mixing the materials in the mass ratio of 1-6 in succinonitrile, coating the mixed slurry on the photo-thermal conversion three-dimensional current collector obtained in the step one, and drying to obtain the photo-thermal conversion solid sulfur anode;
wherein the hyperbranched polymer precursor is one or more of pentaerythritol tetraacrylate, 1,3, 5-benzene trithiophenol, acrylonitrile, tetramethyl dithiothiuram, methacrylic acid and tetrathio-2, 5- (1, 3, 4-thiadiazole);
the conductive carbon is one or more of carbon nano tube, VGCF, carbon black, superP, keqin black and graphite.
The second embodiment is as follows:
the use of a photothermal conversion solid state sulfur positive electrode according to one embodiment is used in an integrated solid state "metal-sulfur" battery. Preferably, the "metal-sulfur" battery is a "lithium-sulfur" battery or a "sodium-sulfur" battery.
And a third specific embodiment:
the preparation of the integrated solid state "metal-sulfur" battery of embodiment two comprises the steps of:
step 1: the preparation of the lithium-philic/sodium-type three-dimensional negative electrode specifically comprises the following steps:
the molar ratio is 1-3: 1 and 2, 5-dihydroxyterephthalic acid are dissolved in a volume ratio of 1:1, adding a three-dimensional current collector II into a mixed solution of N, N-dimethylformamide and methanol, performing ultrasonic treatment for 5-20 min, reacting for 15-30 h at the temperature of 100-150 ℃ in a reaction kettle, filtering and drying, heating the obtained three-dimensional current collector II growing with a metal organic framework for 1-4 h at the temperature of 500-900 ℃ in an argon atmosphere to obtain a three-dimensional current collector II growing with carbon-loaded lithium/sodium metal clusters, and contacting the obtained three-dimensional current collector II growing with carbon-loaded lithium/sodium metal clusters with molten lithium/sodium in an argon-filled glove box to obtain a lithium/sodium-loaded three-dimensional cathode;
wherein the metal salt II comprises one or more of magnesium salt, nickel salt, cobalt salt and chromium salt; the magnesium salt comprises one or more of magnesium phthalocyanine, magnesium acrylate, magnesium hydrogen phosphate and magnesium citrate, the nickel salt comprises one or more of nickel phthalocyanine, nickel acetylacetonate, nickel benzoate and nickel naphthenate, the cobalt salt comprises one or more of cobalt carbonyl, cobalt thiocyanate, cobalt naphthenate and cobalt sulfamate, and the chromium salt comprises one or more of chromium hexacarbonyl, chromium acetylacetonate, chromium chloride and chromium acetate;
the three-dimensional current collector II is one or more of foam copper, carbon paper, a stainless steel net, a zinc oxide array and a titanium net.
Step 2: the preparation of the integrated solid metal-sulfur battery specifically comprises the following steps:
uniformly coating 40-200 mu L of the in-situ polymerization slurry obtained in the step I in the specific embodiment on the lithium-philic/sodium three-dimensional cathode obtained in the step 1 in argon atmosphere, covering the photo-thermal conversion sulfur anode obtained in the step III in the specific embodiment on the coated in-situ polymerization slurry, packaging a battery by using a light-transmitting material, and carrying out thermal polymerization in an oven at 40-100 ℃ for 6-18 h to finally obtain the dendrite-free integrated solid metal-sulfur battery capable of running at low temperature;
the light-transmitting material is one or more of a light-transmitting acrylic plate, transparent organic glass, a sunlight plate and a polycarbonate plate, and the thickness is between 0.5 and 5 mm.
Example 1:
a preparation method and application of a photo-thermal conversion solid sulfur positive electrode comprise the following steps:
(1) Taking foam nickel as an anode, a platinum sheet as a cathode, and an imide solution as an electrolyte solution, and performing electropolymerization on the imide monomer on the foam nickel under constant potential of 0.15V for 10min to obtain polyimide coated foam nickel;
(2) Placing calcium silicide powder into concentrated hydrochloric acid, stirring for 6 days in nitrogen atmosphere at-20 ℃, repeatedly cleaning with ethanol to be neutral, dispersing the obtained product into water, and performing ultrasonic treatment for 2 hours to obtain an aqueous solution containing a silicone sheet;
(3) Adding polyimide coated foam nickel into the solution, continuing ultrasonic treatment for 20min, enabling siloxane to be attached to the polyimide coated foam nickel through hydrogen bonds, filtering and drying to obtain a three-dimensional current collector I attached with a silicone sheet;
(4) Pentaerythritol tetraacrylate, vinylene carbonate and sodium triflate are mixed according to a ratio of 2:12:1 in ethylene carbonate to obtain a precursor solution of in-situ polymerization slurry;
(5) Adding 0.1wt.% benzoyl peroxide to a precursor solution of an in-situ polymerization slurry within 5min before in-situ polymerization to obtain an in-situ polymerization slurry;
(6) The mass ratio of the components is 1 at 190 ℃:15, adding pentaerythritol tetraacrylate into molten sulfur, fully mixing to prepare a pentaerythritol tetraacrylate polymeric sulfur material, and mixing the pentaerythritol tetraacrylate polymeric sulfur material with VGCF according to a ratio of 3:1, fully grinding the mass ratio to obtain anode powder;
(7) Mixing the in-situ polymerization slurry obtained in the step (5) with the positive electrode powder obtained in the step (6) according to the following ratio of 1: mixing in succinonitrile at a mass ratio of 5, coating the mixed slurry on the three-dimensional current collector I attached with the silicone sheet obtained in the step (3), and drying to obtain the photo-thermal conversion solid sulfur anode;
(8) The molar ratio was set to 3:1 with 2, 5-dihydroxyterephthalic acid in a volume ratio of 1:1, adding carbon paper into a mixed solution of N, N-dimethylformamide and methanol, carrying out ultrasonic treatment for 10min, reacting for 20h at the temperature of 120 ℃ in a reaction kettle, filtering and drying, heating the obtained carbon paper growing with a metal-organic framework for 2h at the temperature of 700 ℃ in an argon atmosphere to obtain carbon paper growing with carbon-loaded sodium-philic metal clusters, and contacting the obtained carbon paper with molten sodium in an argon-filled glove box to obtain a sodium-philic three-dimensional anode;
(9) And (3) uniformly coating 80 mu L of the in-situ polymerization slurry obtained in the step (5) on the sodium-philic three-dimensional cathode obtained in the step (8) in argon atmosphere, covering the photo-thermal conversion sulfur anode obtained in the step (7) on the coated in-situ polymerization slurry, packaging the battery by using transparent organic glass with the thickness of 1mm, and keeping the battery in an oven at 60 ℃ for 12 hours for thermal polymerization to finally obtain the dendrite-free integrated solid sodium-sulfur battery capable of running at low temperature.
Example 2:
a preparation method and application of a photo-thermal conversion solid sulfur positive electrode comprise the following steps:
(1) Taking aluminum foam as an anode, a platinum sheet as a cathode, and an imide solution as an electrolyte solution, and performing electropolymerization on the imide monomer on the aluminum foam under constant potential of 0.18V for 8min to obtain polyimide coated aluminum foam;
(2) Placing calcium silicide powder into concentrated sulfuric acid, stirring for 6 days in a nitrogen atmosphere at the temperature of minus 10 ℃, repeatedly cleaning with ethanol to be neutral, dispersing the obtained product into water, and performing ultrasonic treatment for 2 hours to obtain an aqueous solution containing a silicone sheet;
(3) Adding polyimide coated foamed aluminum into the solution, continuing ultrasonic treatment for 20min, enabling siloxane to be attached to the polyimide coated foamed aluminum through hydrogen bonds, filtering and drying to obtain a three-dimensional current collector I attached with a silicone sheet;
(4) Propyl methacrylate, carboxylate and LiDFOB were prepared at 3:15:1 in ethylene carbonate to obtain a precursor solution of in-situ polymerization slurry;
(5) Adding 0.05wt.% of azobisisoheptonitrile to the precursor solution of the in situ polymerization slurry within 5min before in situ polymerization to obtain an in situ polymerization slurry;
(6) The mass ratio of the components is 1 at 190 ℃:12, adding acrylonitrile into the molten sulfur, fully mixing to prepare an acrylonitrile polymeric sulfur material, and mixing the acrylonitrile polymeric sulfur material and the carbon nano tube according to the ratio of 2:1, fully grinding the mass ratio to obtain anode powder;
(7) Mixing the in-situ polymerization slurry obtained in the step (5) with the positive electrode powder obtained in the step (6) according to the following ratio of 1:4, mixing the materials in succinonitrile, coating the mixed slurry on the three-dimensional current collector I attached with the silicone sheet obtained in the step (3), and drying to obtain the photo-thermal conversion solid sulfur anode;
(8) The molar ratio was set to 2:1 with 2, 5-dihydroxyterephthalic acid in a volume ratio of 1:1, adding a titanium mesh into a mixed solution of N, N-dimethylformamide and methanol, carrying out ultrasonic treatment for 10min, reacting for 24h at the temperature of 110 ℃ in a reaction kettle, filtering and drying, heating the obtained titanium mesh growing with a metal-organic framework for 2h at the temperature of 700 ℃ in an argon atmosphere to obtain a titanium mesh growing with carbon-loaded lithium-philic metal clusters, and contacting the obtained titanium mesh with molten lithium in an argon-filled glove box to obtain a lithium-philic three-dimensional anode;
(9) And (3) uniformly coating 100 mu L of the in-situ polymerization slurry obtained in the step (5) on the lithium-philic three-dimensional cathode obtained in the step (8) in argon atmosphere, covering the photo-thermal conversion sulfur anode obtained in the step (7) on the coated in-situ polymerization slurry, packaging the battery by using transparent organic glass with the thickness of 0.08mm, and keeping the battery in an oven at the temperature of 60 ℃ for 12 hours for thermal polymerization to finally obtain the dendrite-free integrated solid-state lithium sulfur battery capable of running at low temperature.
Comparative example 1:
the present comparative example is different from example 1 in that steps (1) to (3) are not performed, and the other conditions and parameters are exactly the same as example 1.
The invention constructs the three-dimensional photo-thermal conversion solid sulfur anode, and can realize the high-efficiency application of the battery in a low-temperature environment by utilizing the photo-thermal conversion effect on the premise of remarkably improving the active sulfur loading. Meanwhile, due to the design of the integrated solid metal-sulfur battery, the discontinuous contact between electrode interfaces is obviously reduced, the transfer efficiency of active ions between the anode and the cathode is improved, and the discharge capacity and the cycle time of the battery are obviously increased. As shown in fig. 1, the photo-thermal conversion solid sulfur cathode prepared in example 1 shows high loading of active sulfur and substantial elimination of voids. As shown in fig. 2, there is good interfacial wetting between the sodium-philic three-dimensional negative electrode and molten sodium. As shown in fig. 3, the solid sodium-sulfur battery prepared in example 1 significantly increased in cycle at low temperature as compared to comparative example 1.
Furthermore, it should be understood that although the present disclosure describes embodiments, not every embodiment is provided with a separate embodiment, and that this description is provided for clarity only, and that the disclosure is not limited to the embodiments described in detail below, and that the embodiments described in the examples may be combined as appropriate to form other embodiments that will be apparent to those skilled in the art.
Claims (10)
1. A preparation method of a photo-thermal conversion solid sulfur anode is characterized by comprising the following steps: the method comprises the following steps:
step one, electropolymerizing an imino-containing polymer monomer on a three-dimensional current collector I, adding the electropolymerized three-dimensional current collector I into an aqueous solution containing a silicone sheet for ultrasonic treatment, enabling siloxane to be attached to the three-dimensional current collector I through hydrogen bonds, filtering and drying to obtain the three-dimensional current collector I attached with the photothermal conversion material;
step two, fully mixing a polymer monomer containing C=C bonds, a polymer monomer containing ether bonds and metal salt I in an organic solvent to obtain a precursor solution of in-situ polymerization slurry; adding an initiator into a precursor solution of the in-situ polymerization slurry to obtain an in-situ polymerization slurry;
step three, the mass ratio is 1 at 170-200 ℃: 2-30, adding hyperbranched polymer precursor into molten sulfur, fully mixing to prepare polymer sulfur material, and mixing the polymer sulfur material with conductive carbon according to the proportion of 1-4: 1, fully grinding the mass ratio to obtain anode powder;
fourthly, in-situ polymerization slurry and positive electrode powder are mixed according to the following ratio of 1: mixing the materials in the mass ratio of 1 to 6 in succinonitrile, coating the mixed slurry on the three-dimensional current collector I attached with the photo-thermal conversion material obtained in the step one, and drying to obtain the photo-thermal conversion solid sulfur anode.
2. The method for preparing the photo-thermal conversion solid sulfur positive electrode according to claim 1, which is characterized in that: in step one, the specific step of electropolymerizing the imino-containing polymer monomer onto the three dimensional current collector I comprises: the three-dimensional current collector I is used as an anode, a platinum sheet is used as a cathode, an aqueous solution of polymer monomer containing imino is used as an electrolyte solution, and the polymer monomer is electropolymerized on the three-dimensional current collector I under constant potential of 0.05-0.18V.
3. The method for preparing the photo-thermal conversion solid sulfur positive electrode according to claim 1 or 2, which is characterized in that: the three-dimensional current collector I is one or more of foam nickel, foam aluminum, carbon cloth, porous nickel oxide and porous aluminum oxide; the polymer monomer containing imino is one or more of methoxyimino furan ammonium acetate, 4-acetamido phenylacetate, imide, iminodiacetic acid and (isocyano imino) triphenylphosphine.
4. The method for preparing the photo-thermal conversion solid sulfur positive electrode according to claim 1, which is characterized in that: in the first step, the preparation step of the aqueous solution containing the silicone sheet comprises the following steps: placing calcium silicide powder into concentrated acid, stirring for 5-10 days in an inert atmosphere at-30-0 ℃, washing with ethanol to neutrality, dispersing the obtained product into water, and performing ultrasonic treatment for 1-4 hours to obtain an aqueous solution containing the silicon oxide sheet.
5. The method for preparing the photo-thermal conversion solid sulfur positive electrode according to claim 1, which is characterized in that: in the second step, the molar ratio of the polymer monomer containing C=C bond, the polymer monomer containing ether bond and the metal salt I is 1-2: 3-30: 1.
6. the method for preparing the photo-thermal conversion solid sulfur positive electrode according to claim 1 or 5, wherein the method comprises the following steps: in the second step, the polymer monomer containing C=C bond comprises one or more of pentaerythritol tetraacrylate, styrene, 4-methyl-1-pentene, propyl methacrylate, isothiazol-3-ketone and 2-sec-butyl-4, 6-dinitrophenol; the polymer monomer containing ether bond comprises one or more of 1, 3-dioxolane, tri (ethylene glycol) divinyl ether, ethylene carbonate, vinylene carbonate, carboxylic ester and 4-phenoxybenzoyl chloride; the metal salt I is lithium salt or sodium salt; when the corresponding negative electrode contains lithium, the metal salt I is lithium salt, and the lithium salt comprises LiTFSI, liFSI, liClO 4 、LiBOB、LiBF 4 、LiCF 3 SO 3 One or more of LiDFOB; when the corresponding negative electrode contains sodium, the metal salt I is sodium salt, and the sodium salt comprises one or more of sodium triflate, disodium sebacate, sodium hexafluorophosphate, sodium perchlorate and disodium hydrogen phosphate; the organic solvent is one or more of N-methyl pyrrolidone, succinonitrile, ethylene carbonate and diethyl carbonate; the initiator is one or more of ammonium persulfate, tert-butyl benzoyl peroxide, azodiisoheptonitrile and azodiisobutyronitrile.
7. The method for preparing the photo-thermal conversion solid sulfur positive electrode according to claim 1, which is characterized in that: in the third step, the hyperbranched polymer precursor comprises one or a combination of more of pentaerythritol tetraacrylate, 1,3, 5-benzene trithiol, acrylonitrile, tetramethyl dithiothiuram and methacrylic acid; the conductive carbon is one or more of carbon nano tube, VGCF, carbon black, keqin black and graphite.
8. Use of a photothermal conversion solid sulfur anode prepared by the preparation method of any one of claims 1 to 7, characterized in that: the photo-thermal conversion solid sulfur positive electrode is applied to a solid metal-sulfur battery.
9. The use according to claim 8, characterized in that: the preparation method of the solid metal-sulfur battery comprises the following steps:
step 1, the molar ratio is 1-3: 1 and 2, 5-dihydroxyterephthalic acid are dissolved in a mixed solution of N, N-dimethylformamide and methanol, then a three-dimensional current collector II is added and subjected to ultrasonic treatment, the three-dimensional current collector II reacts for 15 to 30 hours at the temperature of 100 to 150 ℃, the obtained three-dimensional current collector II growing with a metal organic framework is heated for 1 to 4 hours at the temperature of 500 to 900 ℃ in argon atmosphere after filtration and drying, the obtained three-dimensional current collector II growing with carbon-loaded lithium/sodium metal clusters is obtained, and the obtained three-dimensional current collector II growing with carbon-loaded lithium/sodium metal clusters is contacted with molten lithium/sodium in inert atmosphere, so that a lithium/sodium-loaded three-dimensional cathode is obtained;
step 2: and uniformly coating in-situ polymerization slurry on the lithium-philic/sodium-philic three-dimensional cathode in inert atmosphere, covering the photo-thermal conversion solid sulfur anode on the in-situ polymerization slurry, packaging the battery by using a light-transmitting material, and performing thermal polymerization to finally obtain the solid metal-sulfur battery.
10. The use according to claim 9, characterized in that: in the step 1, the metal salt II comprises one or more of magnesium salt, nickel salt, cobalt salt and chromium salt; the magnesium salt comprises one or more of magnesium phthalocyanine, magnesium acrylate, magnesium hydrogen phosphate and magnesium citrate, the nickel salt comprises one or more of nickel phthalocyanine, nickel acetylacetonate, nickel benzoate and nickel naphthenate, the cobalt salt comprises one or more of cobalt carbonyl, cobalt thiocyanate, cobalt naphthenate and cobalt sulfamate, and the chromium salt comprises one or more of chromium hexacarbonyl, chromium acetylacetonate, chromium acyl chloride and chromium acetate; the three-dimensional current collector II comprises one or more of foam copper, carbon paper, a stainless steel mesh, a zinc oxide array and a titanium mesh; in the step 2, the light-transmitting material comprises one or more of a light-transmitting acrylic plate and a polycarbonate plate, and the thickness is between 0.5 and 5 mm.
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| CN108376773A (en) * | 2018-02-07 | 2018-08-07 | 成都新柯力化工科技有限公司 | A kind of the lithium-sulfur cell sulfur electrode material and preparation method of dissaving polymer network |
| CN109713402A (en) * | 2018-12-28 | 2019-05-03 | 南京大学 | It can be in the solar energy optical-thermal lithium battery and preparation method thereof that temperature range limit works |
| CN115064702A (en) * | 2022-07-22 | 2022-09-16 | 哈尔滨工业大学 | Sodium-philic 3D carbon current collector, preparation method and application thereof, and preparation method of non-negative solid sodium battery |
| CN115566251A (en) * | 2022-09-29 | 2023-01-03 | 重庆邮电大学 | Flexible all-solid-state photo-thermal lithium-sulfur battery capable of working at low temperature and preparation method thereof |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN108376773A (en) * | 2018-02-07 | 2018-08-07 | 成都新柯力化工科技有限公司 | A kind of the lithium-sulfur cell sulfur electrode material and preparation method of dissaving polymer network |
| CN109713402A (en) * | 2018-12-28 | 2019-05-03 | 南京大学 | It can be in the solar energy optical-thermal lithium battery and preparation method thereof that temperature range limit works |
| CN115064702A (en) * | 2022-07-22 | 2022-09-16 | 哈尔滨工业大学 | Sodium-philic 3D carbon current collector, preparation method and application thereof, and preparation method of non-negative solid sodium battery |
| CN115566251A (en) * | 2022-09-29 | 2023-01-03 | 重庆邮电大学 | Flexible all-solid-state photo-thermal lithium-sulfur battery capable of working at low temperature and preparation method thereof |
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