CN112133919B - Sulfide-carbon in-situ composite material, electrode, preparation method of electrode and battery - Google Patents

Sulfide-carbon in-situ composite material, electrode, preparation method of electrode and battery Download PDF

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CN112133919B
CN112133919B CN202011009299.9A CN202011009299A CN112133919B CN 112133919 B CN112133919 B CN 112133919B CN 202011009299 A CN202011009299 A CN 202011009299A CN 112133919 B CN112133919 B CN 112133919B
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sulfide
carbon
electrode
battery
composite material
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CN112133919A (en
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叶瑛
夏天
张楚青
张平萍
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Hangzhou Yilaike Technology Co ltd
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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/58—Selection of substances as active materials, active masses, active liquids of inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy; of polyanionic structures, e.g. phosphates, silicates or borates
    • H01M4/581—Chalcogenides or intercalation compounds thereof
    • H01M4/5815—Sulfides
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/052—Li-accumulators
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
    • H01M4/136—Electrodes based on inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
    • H01M4/139—Processes of manufacture
    • H01M4/1397—Processes of manufacture of electrodes based on inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
    • H01M4/624—Electric conductive fillers
    • H01M4/625—Carbon or graphite
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
    • H01M4/628—Inhibitors, e.g. gassing inhibitors, corrosion inhibitors
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M2004/026—Electrodes composed of, or comprising, active material characterised by the polarity
    • H01M2004/027—Negative electrodes
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/10—Energy storage using batteries

Abstract

The invention discloses a sulfide-carbon in-situ composite material, an electrode, a preparation method thereof and a battery. In the preparation method, a sulfide precursor and a carbon precursor are prepared into a completely mutually soluble solution, the precursors are sequentially separated out through heating and distillation, and a rudiment crystal structure is kept under the dispersion action of the residual solution to form an inlaid structure. And evaporating the solvent to dryness to obtain a solid phase mixture of two precursors, and performing pyrolysis to obtain the sulfide-carbon in-situ composite material. The composite material powder can be prepared into an electrode based on the sulfide-carbon in-situ composite material through bonding, secondary forming and carbonization. The electrode has the advantages of large specific surface area, high electrochemical activity, high conductivity and the like. The electrode is used as an anode, is matched with a metal cathode, and is matched with a corresponding electrolyte solution to obtain the sulfur-magnesium and sulfur lithium battery, and the sulfur-magnesium and sulfur lithium battery has wide application prospect in the field of high-capacity batteries.

Description

Sulfide-carbon in-situ composite material, electrode, preparation method of electrode and battery
Technical Field
The invention belongs to the field of energy sources, and particularly relates to a sulfide-carbon in-situ composite material, an electrode, a preparation method of the electrode and a battery.
Background
The magnesium sulfide and the lithium sulfide are anode materials with great application potential, and have the advantages of high energy density, low comprehensive cost and the like. However, sulfide anode materials and polysulfides formed after charging have poor conductivity and have problems of volume expansion and the like, so that the charge-discharge cycle life of the sulfide anode materials is short, and the performance of the battery cannot reach a theoretical value easily. These disadvantages have prevented its widespread use to date.
By combining the sulfide with carbon by doping, coating, or the like, the conductivity of the sulfide or polysulfide to electrons or ions can be improved. The conventional preparation method comprises the steps of ball-milling and mixing sulfide (or precursor) and carbon black (or carbon-containing precursor), and then calcining to obtain a mixture of sulfide and carbon. The mechanical ball milling is difficult to ensure that sulfide and carbon carriers can form micro-scale combination, and the technical defects enable carbon-based magnesium sulfide and carbon-based lithium sulfide to be not commercially applied in the field of electrode materials.
Disclosure of Invention
The invention aims to overcome the defects in the prior art and provides a sulfide-carbon in-situ composite material, an electrode, a preparation method of the electrode and a battery.
The invention adopts the following specific technical scheme:
in a first aspect, the sulfide-carbon in-situ composite material provided by the invention is a uniform mixture formed by embedding microcrystalline sulfide and carbon particles.
The sulfide is one of magnesium sulfide and lithium sulfide.
The invention provides a preparation method of the composite material, which comprises the following steps:
1) dissolving the sulfide precursor in an alcohol solvent to obtain a solution with the concentration of 10-20%. Preferably, ethanol is recommended.
The sulfide precursor is one of magnesium thiocyanate and lithium thiocyanate.
2) Polystyrene powder is dissolved in benzene, toluene or xylene to give a solution with a concentration of 15% to 25%. Toluene is preferably recommended.
3) Mixing the two solutions, and stirring to obtain a mixed solution. The weight ratio of the sulfide precursor to the polystyrene in the mixed solution is 1:1 to 1: 1.5.
due to the intersolubility of the solvents, the sulfide precursor solution and the polystyrene solution can be mixed to obtain a uniform mixed solution.
4) Heating the mixed solution while stirring to evaporate the solvent to be nearly dry, transferring the material into a crucible, putting the crucible into a vacuum oven, vacuumizing, and heating to 80-120 ℃ until the solvent is completely evaporated to obtain a solid-phase mixture.
5) And putting the obtained solid phase mixture and a crucible into a muffle furnace, heating to 450-600 ℃ under the protection of high-purity nitrogen or argon, keeping the temperature for 4-6 hours, cooling to room temperature, taking out the crucible, and grinding the product to obtain the powdery sulfide-carbon in-situ composite material.
In a second aspect, the present invention provides a sulfide-carbon in-situ composite electrode, comprising an electrode body and carbon fibers; the electrode main body is formed by putting sulfide-carbon in-situ composite powder into a mold for processing, the carbon fiber is arranged in the electrode main body and is used as a conductor connected with an external circuit, and the sulfide-carbon in-situ composite powder is obtained by grinding the sulfide-carbon in-situ composite material.
The sulfide is one of magnesium sulfide and lithium sulfide.
The invention provides a preparation method of a sulfide-carbon in-situ composite material electrode, which comprises the following steps:
1) polyacrylonitrile powder is dissolved in Dimethylformamide (DMF) to obtain a solution with a concentration of 20% to 25% as a binder.
2) Adding the sulfide-carbon in-situ composite powder into a binder, wherein the solid-to-liquid ratio is 1: 0.8-1: 1.5, and uniformly stirring to obtain a mixture with plasticity and no rheology.
3) Filling the mixture into a mold to 50% filling degree, putting a bundle of carbon fibers as an external lead after compacting, continuously adding the mixture to fill the mold, and evaporating the solvent in a vacuum oven after compacting to obtain an electrode blank.
4) Putting the mold and the electrode blank into a muffle furnace, heating to 160-200 ℃ under the protection of high-purity nitrogen or argon, keeping the temperature for 2-3 hours, heating to 600-900 ℃, keeping the temperature for 4-6 hours, cooling to room temperature, taking out, and demolding to obtain the sulfide-carbon in-situ composite material electrode.
In a third aspect, the invention provides a battery using the sulfide-carbon in-situ composite material electrode, wherein the battery is internally provided with one or more groups of metal cathodes and an anode consisting of the sulfide-carbon in-situ composite material electrode, the cathode and the anode are separated by an ion diaphragm, the battery is filled with electrolyte solution, and the battery is sealed after being vacuumized; the metal cathode and the anode which is composed of the sulfide-carbon in-situ composite material electrode are connected with an external electric field by a conductor penetrating through the seal; the battery is a secondary battery, and the battery can be recharged and reused after being discharged.
The metal cathode is made of a metal magnesium sheet or a metal lithium sheet, and the shape and the size of the metal cathode are matched with those of the metal magnesium sheet or the metal lithium sheet.
The ionic membrane is a membrane of a lithium ion battery and is a commercial product.
The electrolyte solution is an electrolyte solution of a sulfur-magnesium battery or a sulfur-lithium battery, can be a commercial product, and can also be prepared by self.
Compared with the prior art, the invention has the following beneficial effects:
the sulfide-carbon in-situ composite material provided by the invention is prepared by the steps of co-dissolving two precursors (namely thiocyanate and polystyrene) in the preparation method, forming a tightly interwoven structure by the precursors of the two substances in the process of evaporating a solvent, and obtaining a mixture in which microcrystalline sulfide and carbon particles are tightly embedded after in-situ decomposition. The composition of the sulfide and the carbon particles on a microscopic scale overcomes the defect of low conductivity of an intermediate product of the sulfide in the charge-discharge process, and effectively improves the charge-discharge cycle performance of magnesium sulfide and lithium sulfide. The composite electrode, the electrode and the battery based on the material provided by the invention are superior to other magnesium ion batteries and lithium ion batteries used at present in energy density and comprehensive performance. Has wide application prospect in the field of high-capacity batteries.
Detailed Description
The invention will be further illustrated and described with reference to specific examples. The technical features of the various implementations may be combined without conflict with each other and do not constitute a limitation to the present invention.
In a first aspect, the present invention provides a sulfide-carbon in-situ composite material which is a homogeneous mixture of microcrystalline sulfide embedded with carbon particles.
The sulfide precursor is one of magnesium thiocyanate and lithium thiocyanate.
The interweaving and embedding of the microcrystalline sulfide and the carbon particles on the microscopic scale overcomes the defect of low conductivity of an intermediate product of the sulfide in the charging and discharging process, and effectively improves the charging and discharging cycle performance of magnesium sulfide and lithium sulfide. The composite powder is suitable for being used as anode materials of sulfur-magnesium batteries and sulfur-lithium batteries.
The invention provides a preparation method of the sulfide-carbon in-situ composite material, which comprises the following steps:
1) dissolving the sulfide precursor in an alcohol solvent to obtain a solution with the concentration of 10-20%.
The sulfide is one of magnesium sulfide and lithium sulfide.
The sulfide precursor is one of magnesium thiocyanate and lithium thiocyanate. They are readily soluble in alcohols, and because of their low toxicity and suitable boiling point, ethanol is preferred.
Magnesium thiocyanate and lithium thiocyanate usually contain crystal water, alcoholic solvents also often contain trace amounts of water, and it is recommended to add granular calcium oxide to the solvent to remove water and then filter to remove the solid phase to obtain an anhydrous solution of the sulfide precursor. The purpose of removing water is to prevent the formation of oxides and hydroxides during thermal decomposition of magnesium thiocyanate and lithium thiocyanate.
2) Polystyrene powder is dissolved in benzene, toluene or xylene to give a solution with a concentration of 15% to 25%.
Polystyrene is easily soluble in aromatic hydrocarbons, and toluene, which has high solubility in polystyrene and is less toxic to the human body, is preferably used. Polystyrene is used as a precursor of carbon because it does not agglomerate after high temperature carbonization, and loose powder can be obtained.
3) Mixing the two solutions, and stirring to obtain a mixed solution. The weight ratio of the sulfide precursor to the polystyrene in the mixed solution is 1:1 to 1: 1.5.
because of the mutual solubility of the two preferred recommended solvents, ethanol and toluene, the two solutions dissolve into each other after mixing to form a homogeneous mixed solution. The method is characterized in that a precursor of sulfide (thiocyanate) and a precursor of carbon (polystyrene) are dissolved in the same solution system, and the method is a prerequisite for preparing a uniform sulfide-carbon in-situ composite material.
The weight ratio of the two precursors in the mixed solution determines the weight ratio of sulfide to carbon in the final product. The proportion of sulfide is increased, which is beneficial to improving the content of active ions in the composite material, thereby improving the energy density, but reducing the conductivity and the charge-discharge life; increased carbon content increases conductivity, increases service life, but decreases energy density. The recommended proportion is an optimized parameter.
4) Heating the mixed solution while stirring to evaporate the solvent to be nearly dry, transferring the material into a crucible, putting the crucible into a vacuum oven, vacuumizing, and heating to 80-120 ℃ until the solvent is completely evaporated to obtain a solid-phase mixture.
Because the boiling points of the methanol and the ethanol are lower than those of the toluene and the xylene, the methanol and the ethanol are firstly evaporated in the heating process, and the thiocyanate in the mixed solution is precipitated along with the evaporation of the methanol or the ethanol. The thiocyanate crystallites are dispersed in toluene, xylene solution of polystyrene, the dispersion of the organic solution inhibits the growth and agglomeration of the crystallites, so that the crystallites of thiocyanate can be uniformly dispersed in the solution. After methanol and ethanol are evaporated, with the evaporation of toluene and xylene, polystyrene takes thiocyanate crystal as a core for precipitation and wraps the crystal to form a solid phase mixture formed by interweaving and inlaying two substances.
5) And putting the obtained solid phase mixture and a crucible into a muffle furnace, heating to 450-600 ℃ under the protection of high-purity nitrogen or argon, keeping the temperature for 4-6 hours, cooling to room temperature, taking out the crucible, and grinding the product to obtain the powdery sulfide-carbon in-situ composite material.
The thiocyanate decomposes during heating calcination to produce sulfide and volatile gases; the polystyrene decomposes to produce carbon particles and gas. Since the precursors of sulfide and carbon (i.e. thiocyanate and polystyrene) are solid mixtures of interlaced and mosaic compositions, they retain their original microstructure when decomposed by heat, preventing recrystallization and agglomeration during calcination. The obtained product has a loose structure and is slightly ground to obtain a powdery product.
The preparation method is characterized in that a sulfide precursor and a carbon precursor are prepared into solutions respectively, and then the two solutions are mixed to obtain a mixed solution; in the process of evaporating the solution, the sulfide precursor forms a primary crystal firstly, and the residual solution and the dissolved polystyrene (carbon precursor) play a role of a dispersing agent, so that the growth and agglomeration of the primary crystal are inhibited. And evaporating the solution to dryness to obtain a solid phase mixture of the sulfide precursor and the polystyrene. The interweaving mosaic structure of the solid phase mixture is retained in the high temperature carbonization process, and the sulfide and the carbon particles have the characteristics of mutual embedding and in-situ compounding.
In a second aspect, the present invention provides a sulfide-carbon in-situ composite electrode, comprising an electrode body and carbon fibers; the electrode main body is formed by putting sulfide-carbon in-situ composite powder into a mold for processing, the carbon fiber is arranged in the electrode main body and is used as a conductor connected with an external circuit, and the sulfide-carbon in-situ composite powder is obtained by grinding the sulfide-carbon in-situ composite material.
The sulfide is one of magnesium sulfide and lithium sulfide. The sulfide-carbon in-situ composite material is prepared according to the method. The mold uses a common technique and carbon fiber is a commercial product.
The invention provides a preparation method of a sulfide-carbon in-situ composite material electrode, which comprises the following steps:
1) polyacrylonitrile powder is dissolved in Dimethylformamide (DMF) to obtain a solution with a concentration of 20% to 25% as a binder.
The polyacrylonitrile solution is used as the adhesive because the polyacrylonitrile is not melted at high temperature but is directly carbonized, and the carbonized product can keep the original shape and maintain higher strength.
Polyacrylonitrile is dissolved in polar organic solvents, and besides DMF, dimethylacetamide, dimethyl sulfoxide and ethylene carbonate can be used as solvents. Because of the different molecular weights, polyacrylonitrile has different solubilities in these solvents, and it is recommended to use DMF as the solvent.
2) Adding the sulfide-carbon in-situ composite powder into a binder, wherein the solid-to-liquid ratio is 1: 0.8-1: 1.5, and uniformly stirring to obtain a mixture with plasticity and no rheology.
The amount of binder used affects the shape of the mixture and also the physical properties of the final product (electrode) such as strength and conductivity.
3) Filling the mixture into a mold to 50% filling degree, putting a bundle of carbon fibers as an external lead after compacting, continuously adding the mixture to fill the mold, and evaporating the solvent in a vacuum oven after compacting to obtain an electrode blank.
The function of the mould is to enable the plastic mixture to be pressed into round, square or rectangular sheets, or other desired shapes. The technique used is a conventional general technique.
Carbon fibers are commercial products. The carbon fiber is used as a lead wire for connecting an external circuit because it has electrical conductivity not inferior to that of a metal material, and has good chemical stability and can be used in an electrolyte solution for a long time without being corroded.
4) And putting the mold and the electrode blank into a muffle furnace, heating to 160-200 ℃ under the protection of high-purity nitrogen or argon, keeping the temperature for 2-3 hours, heating to 600-900 ℃, keeping the temperature for 4-6 hours, cooling to room temperature, taking out, and demolding to obtain the sulfide-carbon in-situ composite material electrode.
Heating the electrode blank in two stages, wherein in the first stage, the electrode blank is heated to 160-200 ℃ and is kept at the constant temperature for 2-3 hours, and in the first stage, the solvent is evaporated, and the sulfide precursor is decomposed; in the second stage, the temperature is raised to 600-900 ℃, the temperature is kept constant for 4-6 hours, the polyacrylonitrile is carbonized in the second stage, and amorphous carbon is recrystallized to form microcrystals. The carbonized product agglutinates the sulfide-carbon in-situ composite powder together to form a conduction network among powder particles; the carbonized product is in close contact with the carbon fiber used as a lead, communicating the connection of the electrode with an external circuit.
In a third aspect, the invention provides a battery using the sulfide-carbon in-situ composite material electrode, wherein the battery is internally provided with one or more groups of metal cathodes and an anode consisting of the sulfide-carbon in-situ composite material electrode, the cathode and the anode are separated by an ion diaphragm, the battery is filled with electrolyte solution, and the battery is sealed after being vacuumized; the metal cathode and the sulfide-carbon in-situ composite material electrode anode pass through the seal through a conductor to be connected with an external electric field; the battery is a secondary battery, and the battery can be recharged and reused after being discharged.
The metal cathode is made of a metal magnesium sheet or a metal lithium sheet, and the shape and the size of the metal cathode are matched with those of the sulfide-carbon in-situ composite material electrode anode.
The ionic membrane is a membrane of a lithium ion battery and is a commercial product.
The electrolyte solution is an electrolyte solution of a sulfur-magnesium battery or a sulfur-lithium battery, can be a commercial product, and can also be prepared by self.
In the practical application process, the lithium metal can be used as a cathode material and matched with a lithium sulfide-carbon in-situ composite material electrode anode to obtain a lithium sulfur battery; the magnesium metal is used as a cathode material and is matched with a magnesium sulfide-carbon in-situ composite material electrode anode to obtain the sulfur-magnesium battery. The common characteristics of the materials are that the materials have high electrochemical activity and energy density, and have good charge and discharge performance when being matched with a sulfide-carbon in-situ composite material electrode. In consideration of the safety and comprehensive performance of the battery, the magnesium-sulfur battery with the metal magnesium cathode matched with the magnesium sulfide-carbon in-situ composite material electrode anode is preferentially recommended, the energy density of the magnesium-sulfur battery is not much different from that of a lithium-sulfur battery, but the magnesium-sulfur battery is obviously superior to the lithium-sulfur battery in the aspects of safety, cost performance and the like.
The diaphragm positioned between the metal magnesium and lithium cathode and the sulfide-carbon in-situ composite material electrode anode is an insulating material and also an ion semi-permeable material, and has the functions of separating the positive electrode and the negative electrode in the battery and preventing the two electrodes from being contacted and short-circuited on one hand; on the other hand, allows metal cations to pass through, while other components in the electrolyte solution cannot. The requirements for separator materials are the same as for lithium ion batteries and other ionic batteries, namely: permeability to cations, barrier properties to anions, corrosion resistance and wettability to an electrolytic solution, and sufficient strength and heat resistance. As the radiuses of magnesium ions and lithium ions are similar and the electrochemical properties are similar, the lithium-sulfur battery and the sulfur-magnesium battery provided by the invention can both use lithium ion battery diaphragms, and belong to mature commercial products.
The electrolyte solution functions as an ionic conductor, i.e., conducts metal cations between the cathode and anode during charging and discharging, wherein the cation concentration is maintained in dynamic equilibrium and the total amount is maintained stable. The used electrolyte solution is a sulfur magnesium battery or a sulfur lithium battery electrolyte solution matched with the electrode type, and can be a commercial product or be prepared by self.
The solute of the recommended magnesium thiocyanate battery electrolyte solution is a mixture of magnesium thiocyanate and 1-ethyl-3-methylimidazole thiocyanate, and the ratio of the magnesium thiocyanate to the 1:1 to 1: 3; the solvent is a mixture of dimethyl sulfoxide and dimethylformamide or dimethylacetamide, and the ratio of the dimethyl sulfoxide to the dimethylformamide to the dimethylacetamide is 9: 1-2: 1; the total concentration of solutes in the solution is 30% to 50%.
The lithium sulfur battery electrolyte solution recommended to be used has a solute of lithium bistrifluoromethylsulfonate imide (LiTFSI) with a concentration of 25% to 30% in a solvent; the solvent is ethylene glycol dimethyl ether (DME) and 1, 3-Dioxolane (DOL), and the weight ratio of the two solvents is l: 1. lithium nitrate as synergist is added into the solvent in the amount of 1-3 wt% of solute.
The electrolyte solution should be kept at a constant temperature above the boiling point of water for 1-2 hours before filling the battery to completely remove water. Before sealing, the battery shell needs to be vacuumized so as to discharge air in the sulfide-carbon in-situ composite material electrode and the micropores inside the ion diaphragm, so that the electrolyte solution is fully contacted with the electrode and the diaphragm, and the conduction of cations is prevented from being blocked by micro-bubbles.
After the battery is assembled, a sulfide-carbon in-situ composite material electrode (anode) is connected to the positive electrode of an external circuit, a metal lithium or metal magnesium electrode (cathode) is connected to the negative electrode of the external circuit, and when the external circuit is switched on for charging, metal cations in sulfides on the anode are released into an electrolyte solution under the action of an external electric field, namely:
Li2S→S+2Li++2e-(Positive electrode reaction) (1)
MgS→S+Mg2++2e-(Positive electrode reaction) (1')
The metal cations reach the cathode and precipitate on the metal cathode by transfer through the electrolyte solution:
Li++e-→Li0(negative electrode reaction) (2)
Mg2++2e-→Mg0(negative electrode reaction) (2')
When the external circuit is switched on for discharging, the anode of the battery obtains electrons through the external circuit and obtains ions from the electrolyte solution to form sulfide:
S+2Li++2e-＝Li2s (Positive pole reaction) (3)
S+Mg2++2e-MgS (Positive electrode reaction) (3')
The metal cathode loses electrons, dissolving the metal, releasing metal cations:
Li0→Li++e-(negative electrode reaction) (4)
Mg0→Mg2++2e-(negative electrode reaction) (4')
The overall cell reaction is:
Figure BDA0002697038960000081
Figure BDA0002697038960000082
the present invention will be described in detail with reference to examples.
Embodiments 1 to 3 respectively prepare a sulfide-carbon in-situ composite material, which specifically comprises the following steps:
example 1
1) 10 g of magnesium thiocyanate and 90 g of anhydrous methanol are weighed and stirred until the magnesium thiocyanate and the anhydrous methanol are completely dissolved to obtain a solution with the concentration of 10%.
2) 15 g of polystyrene powder and 85 g of xylene were weighed and stirred until completely dissolved, giving a 10% strength solution.
3) Mixing the two solutions, and stirring to obtain a mixed solution.
4) And (3) heating the mixed solution while stirring to evaporate the solvent to be nearly dry, transferring the material into a crucible, putting the crucible into a vacuum oven, vacuumizing, and heating to 120 ℃ until the solvent is completely evaporated to obtain a solid-phase mixture.
5) And putting the obtained solid phase mixture and a crucible into a muffle furnace, heating to 600 ℃ under the protection of high-purity nitrogen or argon, keeping the temperature for 4 hours, cooling to room temperature, taking out the crucible, and grinding the product to obtain the powdery magnesium sulfide-carbon in-situ composite material.
Example 2
1) 20 g of lithium thiocyanate and 80 g of absolute ethyl alcohol are weighed and stirred until the lithium thiocyanate and the absolute ethyl alcohol are completely dissolved, so that a solution with the concentration of 20% is obtained.
2) 20 g of polystyrene powder and 80 g of toluene were weighed and stirred until completely dissolved, giving a 20% strength solution.
3) Mixing the two solutions, and stirring to obtain a mixed solution.
4) And (3) heating the mixed solution while stirring to evaporate the solvent to be nearly dry, transferring the material into a crucible, putting the crucible into a vacuum oven, vacuumizing, and heating to 100 ℃ until the solvent is completely evaporated to obtain a solid-phase mixture.
5) And putting the obtained solid phase mixture and a crucible into a muffle furnace, heating to 450 ℃ under the protection of high-purity nitrogen or argon, keeping the temperature for 6 hours, cooling to room temperature, taking out the crucible, and grinding the product to obtain the powdery lithium sulfide-carbon in-situ composite material.
Example 3
1) 20 g of magnesium thiocyanate and 80 g of absolute ethyl alcohol are weighed and stirred until the magnesium thiocyanate and the absolute ethyl alcohol are completely dissolved, so that a solution with the concentration of 20% is obtained.
2) 25 g of polystyrene powder and 75 g of benzene were weighed and stirred until completely dissolved, giving a 25% strength solution.
3) Mixing the two solutions, and stirring to obtain a mixed solution.
4) And (3) heating the mixed solution while stirring to evaporate the solvent to be nearly dry, transferring the material into a crucible, putting the crucible into a vacuum oven, vacuumizing, and heating to 80 ℃ until the solvent is completely evaporated to obtain a solid-phase mixture.
5) And putting the obtained solid phase and the crucible together into a muffle furnace, heating to 500 ℃ under the protection of high-purity nitrogen or argon, keeping the temperature for 5 hours, cooling to room temperature, taking out the crucible, and grinding the product to obtain the powdery magnesium sulfide-carbon in-situ composite material.
Embodiments 4 to 6 respectively prepare a sulfide-carbon in-situ composite electrode, which specifically comprises the following steps:
example 4
1) 2.5 g of polyacrylonitrile powder and 7.5 g of the powder were dissolved in Dimethylformamide (DMF) to obtain a 25% solution as a binder.
2) Adding the magnesium sulfide-carbon in-situ composite powder into the adhesive with the solid-to-liquid ratio of 1:0.8, and uniformly stirring to obtain a mixture with plasticity and no rheology.
3) Filling the mixture into a mold to 50% filling degree, putting a bundle of carbon fibers as an external lead after compacting, continuously adding the mixture to fill the mold, and evaporating the solvent in a vacuum oven after compacting to obtain an electrode blank.
4) And putting the mold and the electrode blank into a muffle furnace, heating to 160 ℃ under the protection of high-purity nitrogen or argon, keeping the temperature for 3 hours, heating to 900 ℃ again, keeping the temperature for 4 hours, cooling to room temperature, taking out, and demolding to obtain the magnesium sulfide-carbon in-situ composite material electrode.
Example 5
1) 2.0 g of polyacrylonitrile powder was weighed and 8.0 g of polyacrylonitrile powder was dissolved in dimethyl sulfoxide (DMSO) to obtain a 20% solution as a binder.
2) Adding the lithium sulfide-carbon in-situ composite powder into the binder, wherein the solid-to-liquid ratio is 1:1.5, and uniformly stirring to obtain a mixture with plasticity and no rheology.
3) Filling the mixture into a mold to 50% filling degree, putting a bundle of carbon fibers as an external lead after compacting, continuously adding the mixture to fill the mold, and evaporating the solvent in a vacuum oven after compacting to obtain an electrode blank.
4) And putting the mold and the electrode blank into a muffle furnace, heating to 200 ℃ under the protection of high-purity nitrogen or argon, keeping the temperature for 3 hours, heating to 600 ℃, keeping the temperature for 6 hours, cooling to room temperature, taking out, and demolding to obtain the lithium sulfide-carbon in-situ composite material electrode.
Example 6
1) 2.5 g of polyacrylonitrile powder and 7.5 g of polyacrylonitrile powder were dissolved in Dimethylacetamide (DEF) to obtain a 25% solution as a binder.
2) Adding the magnesium sulfide-carbon in-situ composite powder into a binder, wherein the solid-to-liquid ratio is 1:1, and uniformly stirring to obtain a mixture with plasticity and no rheology.
3) Filling the mixture into a mold to 50% filling degree, putting a bundle of carbon fibers as an external lead after compacting, continuously adding the mixture to fill the mold, and evaporating the solvent in a vacuum oven after compacting to obtain an electrode blank.
4) And putting the mold and the electrode blank into a muffle furnace, heating to 180 ℃ under the protection of high-purity nitrogen or argon, keeping the temperature for 4 hours, heating to 800 ℃, keeping the temperature for 8 hours, cooling to room temperature, taking out, and demolding to obtain the magnesium sulfide-carbon in-situ composite material electrode.
Embodiments 7 to 10 respectively prepare a laminate polymer battery of a sulfide-carbon in-situ composite electrode, specifically as follows:
example 7
1) 90 g of dimethyl sulfoxide was mixed with 10 g of dimethylformamide to obtain a solvent.
2) Adding 60 g of 1-ethyl-3-methylimidazolium thiocyanate into a solvent, stirring until the 1-ethyl-3-methylimidazolium thiocyanate is completely dissolved, adding 30 g of magnesium thiocyanate, stirring until the magnesium thiocyanate is completely dissolved, keeping the temperature of the solution at 120 ℃ for 5 hours, and cooling the solution to room temperature in a dryer to obtain an electrolyte solution. And obtaining the electrolyte solution of the sulfur-magnesium battery.
3) The lithium ion membrane interlayer is arranged in the aluminum-plastic composite bag, so that the plastic bag is divided into two parts which are separated by the lithium ion membrane and are not communicated with each other.
4) Putting a magnesium sulfide-carbon in-situ composite material electrode with the diameter of 50 multiplied by 3mm into one part of the plastic bag as a battery anode, wherein the anode is provided with built-in carbon fibers; the other part is put into a magnesium sheet with the thickness of 50 multiplied by 1mm as a cathode, and a copper lead is welded on the magnesium sheet.
5) And putting the anode and the lithium sheet cathode packaged in the lithium ion membrane small bag into an aluminum-plastic composite membrane bag, adding a proper amount of electrolyte solution, and vacuumizing to keep the electrodes in the bag to be fully wet.
6) And (3) thermally shrinking/pressing and sealing the aluminum-plastic composite film packaging bag after vacuumizing, and enabling a carbon fiber lead and a copper lead for connecting an external circuit to penetrate through a seal to obtain the sulfur-magnesium soft package battery adopting the magnesium sulfide-carbon in-situ composite material electrode.
Example 8
1) 60 g of dimethyl sulfoxide are mixed with 30 g of dimethylacetamide to obtain a solvent
2) Adding 22.5 g of 1-ethyl-3-methylimidazole thiocyanate into a solvent, stirring until the 1-ethyl-3-methylimidazole thiocyanate is completely dissolved, adding 22.5 g of magnesium thiocyanate, stirring until the magnesium thiocyanate is completely dissolved, keeping the temperature of the solution at 150 ℃ for 2 hours, and cooling the solution to room temperature in a dryer to obtain the magnesium sulfate battery electrolyte solution.
3) The lithium ion membrane interlayer is arranged in the aluminum-plastic composite bag, so that the plastic bag is divided into two parts which are separated by the lithium ion membrane and are not communicated with each other.
4) Putting a magnesium sulfide-carbon in-situ composite material electrode with the diameter of 50 multiplied by 3mm into one part of the plastic bag as a battery anode, wherein the anode is provided with built-in carbon fibers; the other part is put into a magnesium sheet with the thickness of 50 multiplied by 1mm as a cathode, and a copper lead is welded on the magnesium sheet.
5) And putting the anode and the lithium sheet cathode packaged in the lithium ion membrane small bag into an aluminum-plastic composite membrane bag, adding a proper amount of electrolyte solution, and vacuumizing to keep the electrodes in the bag to be fully wet.
6) And (3) thermally shrinking/pressing and sealing the aluminum-plastic composite film packaging bag after vacuumizing, and enabling a carbon fiber lead and a copper lead for connecting an external circuit to penetrate through a seal to obtain the sulfur-magnesium soft package battery adopting the magnesium sulfide-carbon in-situ composite material electrode.
Example 9
1) Taking 37.5 g of ethylene glycol dimethyl ether (DME) and 37.5 g of 1, 3-Dioxolane (DOL), mixing to obtain a mixed solvent, dissolving 25 g of lithium bistrifluoromethylsulfonimide and 0.75 g of lithium nitrate in the mixed solvent, keeping the temperature of the solution at 120 ℃ for 5 hours, drying the solution, and cooling the solution to room temperature to obtain an electrolyte solution.
2) The lithium ion membrane interlayer is arranged in the aluminum-plastic composite bag, so that the plastic bag is divided into two parts which are separated by the lithium ion membrane and are not communicated with each other.
3) Putting a lithium sulfide-carbon in-situ composite material electrode with the diameter of 50 multiplied by 3mm into one part of the plastic bag as a battery anode, wherein the anode is provided with built-in carbon fibers; the other part is put into a lithium sheet with the thickness of 50 multiplied by 1mm as a cathode, and a copper wire is welded on the lithium sheet.
4) And putting the anode and the lithium sheet cathode packaged in the lithium ion membrane small bag into an aluminum-plastic composite membrane bag, adding a proper amount of electrolyte solution, and vacuumizing to keep the electrodes in the bag to be fully wet.
5) And (3) thermally shrinking/pressing and sealing the aluminum-plastic composite film packaging bag after vacuumizing, and enabling a carbon fiber lead and a copper lead for connecting an external circuit to penetrate through a seal to obtain the lithium-sulfur soft package battery adopting the lithium sulfide-carbon in-situ composite material electrode.
Example 10
1) 35 g of ethylene glycol dimethyl ether (DME) and 35 g of 1, 3-Dioxolane (DOL) were mixed to obtain a mixed solvent, 30 g of lithium bistrifluoromethylsulfonate imide and 6 g of lithium nitrate were dissolved in the mixed solvent, and the solution was kept at a constant temperature of 130 ℃ for 4 hours, dried, and cooled to room temperature. So as to obtain the electrolyte solution, and the electrolyte solution,
2) the lithium ion membrane interlayer is arranged in the aluminum-plastic composite bag, so that the plastic bag is divided into two parts which are separated by the lithium ion membrane and are not communicated with each other.
3) Putting a lithium sulfide-carbon in-situ composite material electrode with the diameter of 50 multiplied by 3mm into one part of the plastic bag as a battery anode, wherein the anode is provided with built-in carbon fibers; the other part is put into a lithium sheet with the thickness of 50 multiplied by 1mm as a cathode, and a copper wire is welded on the lithium sheet.
4) And putting the anode and the lithium sheet cathode packaged in the lithium ion membrane small bag into an aluminum-plastic composite membrane bag, adding a proper amount of electrolyte solution, and vacuumizing to keep the electrodes in the bag to be fully wet.
5) And (3) thermally shrinking/pressing and sealing the aluminum-plastic composite film packaging bag after vacuumizing, and enabling a carbon fiber lead and a copper lead for connecting an external circuit to penetrate through a seal to obtain the lithium-sulfur soft package battery adopting the lithium sulfide-carbon in-situ composite material electrode.
The above-described embodiments are merely preferred embodiments of the present invention, which should not be construed as limiting the invention. Various changes and modifications may be made by one of ordinary skill in the pertinent art without departing from the spirit and scope of the present invention. Therefore, the technical scheme obtained by adopting the mode of equivalent replacement or equivalent transformation is within the protection scope of the invention.

Claims (6)

1. The preparation method of the sulfide-carbon in-situ composite material is characterized by comprising the following steps of:
1) dissolving a sulfide precursor in an alcohol solvent to obtain a solution with the concentration of 10-20%; the sulfide precursor is one of magnesium thiocyanate and lithium thiocyanate;
2) dissolving polystyrene powder in benzene, toluene or xylene to obtain a solution with the concentration of 15-25%;
3) mixing the two solutions, and stirring to obtain a mixed solution; the weight ratio of the sulfide precursor to the polystyrene in the mixed solution is 1:1 to 1: 1.5;
4) heating the mixed solution while stirring to evaporate the solvent to be nearly dry, then transferring the material into a crucible and putting the crucible into a vacuum oven, vacuumizing and heating to 80-120 ℃ until the solvent is completely evaporated to obtain a solid-phase mixture;
5) and putting the obtained solid phase mixture and a crucible into a muffle furnace, heating to 450-600 ℃ under the protection of high-purity nitrogen or argon, keeping the temperature for 4-6 hours, cooling to room temperature, taking out the crucible, and grinding the product to obtain the powdery sulfide-carbon in-situ composite material.
2. A sulfide-carbon in-situ composite material electrode is characterized by comprising an electrode main body and carbon fibers; the electrode main body is formed by putting sulfide-carbon in-situ composite powder into a mold, the carbon fiber is arranged in the electrode main body and is used as a conductor connected with an external circuit, and the sulfide-carbon in-situ composite powder is prepared by the method of claim 1.
3. The preparation method of the sulfide-carbon in-situ composite material electrode based on the claim 2 is characterized by comprising the following steps:
1) dissolving polyacrylonitrile powder in Dimethylformamide (DMF) to obtain a solution with the concentration of 20-25% as a binder;
2) adding the sulfide-carbon in-situ composite powder into a binder, wherein the solid-to-liquid ratio is 1: 0.8-1: 1.5, and uniformly stirring to obtain a mixture with plasticity and no rheology;
3) filling the mixture into a mold to 50% filling degree, putting a bundle of carbon fibers as an external lead after compacting, continuously adding the mixture to fill the mold, and evaporating the solvent in a vacuum oven after compacting to obtain an electrode blank;
4) and putting the mold and the electrode blank into a muffle furnace, heating to 160-200 ℃ under the protection of high-purity nitrogen or argon, keeping the temperature for 2-3 hours, heating to 600-900 ℃, keeping the temperature for 4-6 hours, cooling to room temperature, taking out, and demolding to obtain the sulfide-carbon in-situ composite material electrode.
4. A battery using the sulfide-carbon in-situ composite material electrode as claimed in claim 3, wherein the battery is provided with one or more groups of metal cathodes and an anode formed by the sulfide-carbon in-situ composite material electrode, the cathodes and the anode are separated by an ion diaphragm, the battery is filled with electrolyte solution, and the battery is sealed after being vacuumized; the cathode and the anode are connected with an external electric field through a conductor penetrating through the seal; the battery is a secondary battery, and the battery can be recharged and reused after being discharged.
5. The cell of claim 4 wherein the metal cathode is formed from a sheet of magnesium metal or lithium metal and is shaped and sized to match the anode.
6. The battery of claim 4, wherein the ionic separator is a lithium ion battery separator and is a commercial product.
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