WO2018236046A1 - Batterie au lithium-soufre - Google Patents

Batterie au lithium-soufre Download PDF

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Publication number
WO2018236046A1
WO2018236046A1 PCT/KR2018/005189 KR2018005189W WO2018236046A1 WO 2018236046 A1 WO2018236046 A1 WO 2018236046A1 KR 2018005189 W KR2018005189 W KR 2018005189W WO 2018236046 A1 WO2018236046 A1 WO 2018236046A1
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Prior art keywords
lithium
sulfur battery
sulfur
radical
separator
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PCT/KR2018/005189
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English (en)
Korean (ko)
Inventor
김기현
김수현
양두경
진선미
이창훈
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주식회사 엘지화학
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Priority claimed from KR1020180051030A external-priority patent/KR102320325B1/ko
Application filed by 주식회사 엘지화학 filed Critical 주식회사 엘지화학
Priority to EP18821205.4A priority Critical patent/EP3624223B1/fr
Priority to JP2019568206A priority patent/JP7065893B2/ja
Priority to US16/624,750 priority patent/US11545720B2/en
Priority to CN201880035323.0A priority patent/CN110679010B/zh
Publication of WO2018236046A1 publication Critical patent/WO2018236046A1/fr

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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
    • H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
    • H01M50/40—Separators; Membranes; Diaphragms; Spacing elements inside cells
    • H01M50/409—Separators, membranes or diaphragms characterised by the material
    • 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
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/42—Methods or arrangements for servicing or maintenance of secondary cells or secondary half-cells
    • 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
    • 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
    • H01M4/38—Selection of substances as active materials, active masses, active liquids of elements or alloys
    • 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
    • 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

Definitions

  • the present invention relates to a lithium-sulfur battery including a radical compound having a nitroxyl radical functional group, and more particularly, To a lithium-sulfur battery in which the diffusion of lithium polysulfide is suppressed.
  • a lithium-sulfur (Li-S) battery is a secondary battery in which a sulfur-based material having a sulfur-sulfur bond is used as a cathode active material and lithium metal is used as an anode active material.
  • Sulfur the main material of the cathode active material, is very rich in resources, has no toxicity, and has a low atomic weight.
  • the theoretical energy density of the lithium-sulfur battery is 1675 mAh / g-sulfur and the theoretical energy density is 2,600 Wh / kg.
  • Ni-MH battery 450 Wh / , which is the most promising among the batteries that have been developed to date, because it is much higher than the FeS battery (480Wh / kg), Li-MnO 2 battery (1,000Wh / kg) and Na-S battery (800Wh / kg).
  • lithium polysulfide (Li 2 S x , usually x> 4) It melts easily. The lithium polysulfide dissolved in the electrolytic solution diffuses away from the anode where the lithium polysulfide is generated due to the difference in the concentration. Thus, the lithium polysulfide eluted from the anode is lost outside the positive electrode reaction region, and it is impossible to perform the stepwise reduction to lithium sulfide (Li 2 S).
  • the lithium polysulfide existing in a dissolved state from the anode and the cathode is not able to participate in the charge-discharge reaction of the battery, the amount of the sulfur material participating in the electrochemical reaction at the anode is reduced, which is a major factor in reducing the charge capacity and energy of the battery.
  • the lithium polysulfide diffused into the cathode causes a problem of corrosion of the lithium metal cathode because it reacts directly with lithium and is fixed in the form of Li 2 S on the surface of the cathode.
  • Patent Document 1 Korean Patent Laid-Open No. 10-2016-0146844 (2016.12.21), "lithium sulfur solid electrochemical cell having a long cycle life"
  • Non-Patent Document 1 Hongwei Chena, Changhong Wanga, Yafei Daib, Jun Gea, Wei Lua and Liwei Chen, In-situ activated polycation as a multifunctional additive for Li-S batteries. Nano Energy. 2016. 26. 43-49
  • the lithium-sulfur battery has a problem that capacity and life characteristics of the battery are deteriorated due to lithium polysulfide which is eluted and diffused from the anode.
  • the present inventors have found that a radical compound having a nitroxyl radical functional group, which is a stable free radical molecule, is effective in adsorbing lithium polysulfide, thereby completing the present invention.
  • an object of the present invention is to improve the capacity and lifetime characteristics of a battery by providing a separation membrane containing the polysulfide adsorption layer.
  • Still another object of the present invention is to provide a lithium-sulfur battery including the separator.
  • a positive electrode comprising a sulfur-carbon composite
  • a cathode arranged opposite to the anode
  • a lithium-sulfur battery including a separator interposed between the positive electrode and the negative electrode,
  • the separation membrane comprises a separation membrane body; And a lithium polysulfide adsorption layer formed on at least one side of the separator main body,
  • the adsorbent layer comprises a radical compound having a nitroxyl radical functional group.
  • the present invention also provides a method for producing a lithium-sulfur battery
  • the separation membrane comprising: i) preparing a separation membrane body; ii) preparing a solution by mixing a radical compound having a nitroxyl radical portion in a solvent; iii) coating the solution on at least one side of the membrane body; And iv) drying the coated separator to form a lithium polysulfide adsorption layer.
  • the method of manufacturing a lithium-sulfur battery includes:
  • the lithium polysulfide eluted from the positive electrode is adsorbed by the radical compound having the nitroxyl radical functional group, thereby preventing elution and diffusion of the lithium polysulfide, thereby improving the capacity and lifetime characteristics of the battery.
  • FIG. 1 is a cross-sectional view of a lithium-sulfur battery including a separator having an adsorption layer of lithium sulfide.
  • TEM 2 is a scanning electron microscope (TEM) of a separator coated with poly (2,2,6,6-tetramethyl-1-piperidinyloxy-4-ylmethacrylate (PTMA)), a radical compound having a nitroxyl radical functional group SEM) images.
  • TEM scanning electron microscope
  • SEM scanning electron microscope
  • Example 4 is a graph showing the battery life characteristics of the specific discharging capacity and the coulombic efficiency according to Example 1 and Comparative Example 1 of the present invention.
  • 5 is a graph showing the discharge capacity of the lithium-sulfur battery after 10 cycles.
  • 6 is a graph showing the discharge capacity of the lithium-sulfur battery after 30 cycles.
  • Example 8 is a graph showing the battery lifetime characteristics of specific discharging capacity and coulombic efficiency according to Example 1 and Comparative Example 2 of the present invention.
  • Example 9 is a graph showing the battery lifetime characteristics of specific discharging capacity and coulombic efficiency according to Example 1 and Comparative Example 3 of the present invention.
  • the present invention relates to a lithium polysulfide adsorption layer containing a radical compound having a nitrosyl radical functional group on at least one surface of a separator main body to prevent diffusion of lithium polysulfide and improve the capacity and lifetime of the battery, Thereby providing a separation membrane.
  • At least one surface of the separator main body is one surface or both surfaces necessarily including a surface facing the anode when assembling the electrode.
  • the radical compound having a nitroxyl radical functional group may be located on the surface or in the interior of the separation membrane and is preferably positioned on the surface of the separation membrane facing the anode in order to prevent the diffusion of lithium polysulfide produced in the anode of the lithium- can do.
  • the lithium-sulfur battery includes a cathode 200 and a cathode 300, and an electrolyte 400 and a separator 100 interposed therebetween.
  • a separation membrane 100 in which a separation membrane body 110 and an adsorption layer 120 are sequentially laminated.
  • the adsorption layer 120 may be formed on one side of the separation membrane body 110, and may be formed on both sides if necessary.
  • the separator main body 110 is not particularly limited in the present invention, and can be used without any particular limitation as long as it is physically separated from the electrode, has an electrolyte and ion permeability, and is used as a conventional separator.
  • the nonconductive or insulating material it is preferable that the material has low resistance to ion movement of the electrolytic solution and excellent electrolytic solution impregnation ability.
  • a porous polymer film such as a polyolefin-based polymer such as an ethylene homopolymer, a propylene homopolymer, an ethylene / butene copolymer, an ethylene / hexene copolymer and an ethylene / methacrylate copolymer
  • a nonwoven fabric made of conventional porous nonwoven fabric such as high melting point glass fiber or polyethylene terephthalate fiber can be used, but the present invention is not limited thereto .
  • the radical compound having a nitroxyl radical functional group contained in the adsorption layer 120 means a structure having a functional group represented by the following formula (1).
  • R 1 and R 2 may be aliphatic, aromatic, hydroxyl, alkoxy, aldehyde, carboxyl, amino, or a combination thereof, R 1 and R 2 may be different or the same.
  • radical compound provided in the present invention may be a polymer having an intramolecular nitrosyl radical functional group.
  • the polymer may be polymerized from a monomer containing any one functional group selected from the group consisting of (meth) acrylate, acrylonitrile, anhydride, styrene, epoxy, isocyanate and vinyl groups.
  • the polymer may be selected from the group consisting of poly (2,2,6,6-tetramethyl-1-piperidinyloxy-4-ylmethacrylate (PTMA), poly (2,2,6,6-tetramethyl- (PTVE), poly (TEMPO-substituted norbornene) (PTN), poly (2,2,5,5-tetramethylpyrrolidine-1-oxyl-3-yl ethylene oxide PTEB), poly (2,3-bis (2,2,6,6-tetramethylpiperidine-1-oxyl-4-oxyphenyl) -5- (PTAm), and combinations thereof.
  • the TEMPO may be at least one selected from the group consisting of (2,2,6,6-tetramethylpiperidin-1-yl) oxyl compound .
  • the radical compound having a nitroxyl radical functional group can form an adsorption layer by itself as a polymer
  • the content of the radical compound having a nitroxyl radical functional group in the present invention may be 80 wt% or more of the total weight of the adsorbent layer have.
  • the following formula (2) represents PTMA which is a kind of polymer formed by the polymerization reaction, which contains the nitroxyl radical functional group in the molecule provided by the present invention.
  • the monomer type of the PTMA is TEMPO (2,2,6,6-Tetramethylpiperidin-1-yl) oxyl) compound, which can be attached to a polymer backbone to form PTMA.
  • PTMA which is a radical compound proposed in the present invention can explain the stability of PTMA through the following formula (3) as a relatively stable compound by the phenomenon of dissociation of electrons from nitrogen to oxygen.
  • the PTMA in the state (B) is changed into the activated cation in the state (C), and the PTMA in the state (C) is changed to the polysulfide In 4 As shown in FIG.
  • PTMA which is a polymer is used. Since PTMA has a high molecular weight, it is advantageous that it can be coated on a separator without being dissolved in an electrolyte.
  • the adsorption layer 120 of the present invention may include a conductive material together with the above-described radical compound having a nitrosyl radical functional group in order to impart additional electrical conductivity to the lithium-sulfur battery.
  • sulfur which is a positive electrode active material of a lithium-sulfur battery, does not have conductivity by itself, it is generally made of a composite of a conductive carbon material and an anode 200 of a sulfur-carbon composite.
  • the adsorption layer 120 of the present invention may include a conductive material to provide additional sulfur reduction sites in addition to the anode reaction sites.
  • the conductive material of the adsorption layer 120 may additionally provide a reduction reaction site of the adsorbed lithium polysulfide 20 to increase the electrode efficiency.
  • the conductive material included in the adsorption layer 120 according to the present invention may be selected from the group consisting of a carbon-based conductive material, a conductive polymer, and a combination thereof.
  • the carbon-based conductive material is not limited in its kind but may be graphite such as natural graphite, artificial graphite, expanded graphite, Graphene, Super-P and Super-C. Active black carbon black, Channel black, Denka black, Furnace black, Thermal black, Contact black, Lamp black, Carbon black such as acetylene black; Carbon nanotubes such as a carbon fiber, a carbon nanotube (CNT), and a fullerene, and combinations thereof.
  • the carbon nanotube may include a super- Can be used.
  • the conductive polymer may be selected from the group consisting of polyaniline, polypyrrole, polythiophene, polyazulene, polypyridine, polyindole, polycarbazole, Polycarbazole, Polyazine, Polyquinone, Polyacetylene, Polyselenophene, Polytellurophene, Poly-p-phenylene, Poly And may include one selected from the group consisting of polyphenylene vinylene, polyphenylene sulfide, polyethylene dioxythiophene, polyethylene glycol, and combinations thereof.
  • the weight ratio of the radical compound having a nitrosyl radical functional group and the conductive material is controlled within a range of 3: 1 to 7: 1 for the above-described lithium polysulfide diffusion preventing effect and the conductivity imparting effect for providing the lithium polysulfide reduction reaction site It is possible. If an excess amount of a radical compound having a nitrosyl radical functional group is used in excess of the above-mentioned range, it acts as a resistive layer to deteriorate battery performance. On the contrary, when an excess amount of conductive material is used, a radical having a nitrosyl radical functional group It is difficult to secure the effect due to the radical compound because the content of the compound is decreased. Therefore, it is preferable to appropriately use the compound in the above range.
  • the adsorption layer 120 may be formed on the separation membrane body 110 to have a thickness of 0.1 to 10 ⁇ , preferably 0.1 to 5 ⁇ , in order to secure the above-mentioned effect. If the thickness is less than the above range, the effect of adsorbing lithium polysulfide is insufficient. On the other hand, if the thickness exceeds the above range, the lithium ion conductivity is lowered to cause problems in electrode performance. Therefore, .
  • a cathode comprising the sulfur-carbon composite of the present invention; A cathode arranged opposite to the anode; And a separator interposed between the anode and the cathode.
  • the lithium-sulfur battery includes tetramethylpiperidine N-oxyl in a part of the separator. At this time, the tetramethylpiperidine N-oxyl contained in the separator may be dissolved in the electrolyte during discharging and charging of the battery.
  • the separation membrane of the lithium-sulfur battery according to the present invention comprises i) preparing a separator main body; ii) preparing a solution by mixing a radical compound having a nitroxyl radical portion in a solvent; iii) coating the solution on at least one side of the membrane body; And iv) drying the coated separator to form a lithium polysulfide adsorption layer.
  • the separation membrane body 110 is not particularly limited in the present invention, and any one of the separation membrane bodies described above can be selected, and it is possible to purchase or use a commercially available separation membrane.
  • a radical compound having a nitrosyl radical functional group is dispersed in a predetermined solvent to prepare a radical compound solution.
  • a solvent which can uniformly disperse the radical compound and is easily evaporated and can be dried.
  • NMP N-methyl-2-pyrrolidone
  • acetonitrile acetonitrile
  • methanol ethanol
  • Tetrahydrofuran water
  • isopropyl alcohol and the like
  • the mixing for the preparation of the radical compound solution may be carried out by a conventional method using a conventional mixer such as a paste mixer, a high-speed shear mixer, a homomixer or the like.
  • the prepared solution is coated on one surface of the separator main body 110.
  • one surface of the separator main body 110 is one surface of the separator main body 110 which is assembled opposite to the anode 200 at the time of later electrode assembly.
  • a method of coating the slurry for example, a doctor blade coating, a dip coating, a gravure coating, a slit die coating, a spin coating, a comma
  • a reverse coating method, a screen coating method, a cap coating method, and the like, may be used as a method of coating the slurry.
  • the drying process is a process of removing the solvent and moisture in the adsorption layer 120 coated on the separation membrane.
  • the drying temperature and time may vary depending on the solvent used. Generally, the drying process is performed in a vacuum oven at 50 to 200 ° C within 48 hours Drying is preferred.
  • the radical compound having a nitrosyl radical functional group according to the present invention can form an adsorption layer by itself as the polymer, the content of the radical compound is not less than 80% by weight of the total weight of the adsorption layer .
  • a positive electrode comprising a sulfur-carbon composite; A cathode arranged opposite to the anode; And a separator interposed between the anode and the cathode, wherein the separator comprises a separator main body; And a lithium polysulfide adsorbent layer formed on at least one side of the separator main body, wherein the adsorbent layer comprises a radical compound having a nitrosyl radical functional group.
  • the separation membrane 100 may be interposed between the anode 200 and the cathode 300, and may be a separator of the lithium-sulfur battery, At this time, when the adsorption layer 120 is coated on only one surface, the adsorption layer 120 is preferably arranged to face the anode 200 in order to prevent diffusion of lithium polysulfide.
  • the anode 200 may include a sulfur element (S 8 ) as a cathode active material, a sulfur-based compound, or a mixture thereof. Since the sulfur element alone does not have electrical conductivity, the anode 200 may be used in combination with a conductive material .
  • a sulfurized poly-acrylonitrile (SPAN) anode with good lifetime characteristics can be used as the anode of the lithium-sulfur battery.
  • the average operating voltage of the SPAN anode is 1.7 V and the energy Since the density is low and the content of sulfur in the SPAN anode is also about 40% smaller than that in the sulfur-carbon composite anode, the anode of the lithium-sulfur battery is limited to the anode of the sulfur-carbon composite.
  • the conductive material may be porous. Therefore, any conductive material having porosity and conductivity may be used without limitation, and for example, a carbon-based material having porosity may be used. Examples of the carbon-based material include carbon black, graphite, graphene, activated carbon, carbon fiber, and carbon nanotube (CNT). Further, metallic fibers such as metal mesh; Metallic powder such as copper, silver, nickel, and aluminum; Or an organic conductive material such as a polyphenylene derivative can also be used. The conductive materials may be used alone or in combination.
  • the negative electrode 300 is a negative electrode active material that can reversibly intercalate or deintercalate lithium ions Li + , a material capable of reversibly reacting with lithium ions to form a lithium-containing compound, lithium A metal or a lithium alloy can be used.
  • the material capable of reversibly storing or releasing lithium ions (Li &lt ; + & gt ; ) may be, for example, crystalline carbon, amorphous carbon, or a mixture thereof.
  • the material capable of reacting with the lithium ion (Li &lt ; + & gt ; ) to reversibly form a lithium-containing compound may be, for example, tin oxide, titanium nitride or silicon.
  • the lithium alloy includes, for example, lithium (Li), sodium (Na), potassium (K), rubidium (Rb), cesium (Cs), francium (Fr), beryllium (Be), magnesium (Mg) Ca, Sr, Ba, Ra, Al, Si, and Sn.
  • the metal may be an alloy of a metal selected from the group consisting of Ca, Sr, Ba,
  • Inactive sulfur is sulfur in which sulfur can not participate in the electrochemical reaction of the anode after various electrochemical or chemical reactions.
  • Inactive sulfur formed on the surface of the lithium anode is a protective film of the lithium anode layer as well.
  • the electrolyte 400 impregnated into the anode 200, the cathode 300 and the separator 100 is a non-aqueous electrolyte containing a lithium salt and is composed of a lithium salt and an electrolyte.
  • the organic solid electrolyte and the inorganic solid electrolyte Etc. may be used.
  • the lithium salt of the present invention can be dissolved in a non-aqueous organic solvent, for example, LiCl, LiBr, LiI, LiClO 4 , LiBF 4 , LiB 10 Cl 10 , LiB (Ph) 4 , LiPF 6 , LiCF 3 SO 3 , LiCF 3 CO 2, LiAsF 6, LiSbF 6, LiAlCl 4, LiSO 3 CH 3, LiSO 3 CF 3, LiSCN, LiC (CF 3 SO 2) 3, LiN (CF 3 SO 2) 2, LiNO 3, chloroborane lithium , Lower aliphatic carboxylic acid lithium, lithium 4-phenylborate, and imide.
  • a non-aqueous organic solvent for example, LiCl, LiBr, LiI, LiClO 4 , LiBF 4 , LiB 10 Cl 10 , LiB (Ph) 4 , LiPF 6 , LiCF 3 SO 3 , LiCF 3 CO 2, LiAsF 6, LiSbF 6, LiAlCl 4, LiSO 3 CH 3, Li
  • the concentration of the lithium salt may be 0.2 to 4 M according to various factors such as the precise composition of the electrolyte mixture, the solubility of the salt, the conductivity of the dissolved salt, the charging and discharging conditions of the battery, the working temperature and other factors known to the lithium battery To 0.3 M, more specifically 0.3 M to 1.5 M, for example. If it is used at less than 0.2 M, the conductivity of the electrolyte may be lowered and electrolyte performance may be deteriorated. If it is used in excess of 4 M, the viscosity of the electrolyte may increase and the mobility of lithium ion (Li + ) may be decreased.
  • non-aqueous organic solvent of the present invention examples include N-methyl-2-pyrrolidinone, propylene carbonate, ethylene carbonate, butylene carbonate, dimethyl carbonate, di Ethyl carbonate, ethyl methyl carbonate, gamma-butylolactone, 1,2-dimethoxyethane, 1,2-diethoxyethane, tetrahydroxyfuran, 2-methyltetrahydrofuran, dimethylsulfoxide, Diethyl ether, formamide, dimethyl formamide, dioxolane, acetonitrile, nitromethane, methyl formate, methyl acetate, phosphoric acid triester, trimethoxymethane , A dioxolane derivative, an aprotic organic solvent such as sulfolane, methylsulfolane, 1,3-dimethyl-2-imidazolidinone, propylene carbonate derivative, tetrahydrofuran derivative, ether, methyl propionat
  • organic solid electrolyte examples include a polymer electrolyte such as a polyethylene derivative, a polyethylene oxide derivative, a polypropylene oxide derivative, a phosphate ester polymer, an agitation lysine, a polyester sulfide, a polyvinyl alcohol, a polyvinylidene fluoride, A polymer including a group can be used.
  • a polymer electrolyte such as a polyethylene derivative, a polyethylene oxide derivative, a polypropylene oxide derivative, a phosphate ester polymer, an agitation lysine, a polyester sulfide, a polyvinyl alcohol, a polyvinylidene fluoride, A polymer including a group can be used.
  • Examples of the inorganic solid electrolyte of the present invention include Li 3 N, LiI, Li 5 NI 2 , Li 3 N-LiI-LiOH, LiSiO 4 , LiSiO 4 -LiI-LiOH, Li 2 SiS 3 , Li 4 SiO 4 , Nitrides, halides and sulfates of Li such as Li 4 SiO 4 -LiI-LiOH and Li 3 PO 4 -Li 2 S-SiS 2 can be used.
  • the electrolyte of the present invention may be added to the electrolyte for the purpose of improving charge / discharge characteristics, flame retardancy, etc., for example, pyridine, triethylphosphite, triethanolamine, cyclic ether, ethylenediamine, glyme, hexaphosphoric triamide, Benzene derivatives, sulfur, quinone imine dyes, N-substituted oxazolidinones, N, N-substituted imidazolidines, ethylene glycol dialkyl ethers, ammonium salts, pyrrole, 2-methoxyethanol, .
  • a halogen-containing solvent such as carbon tetrachloride, ethylene trifluoride or the like may be further added to impart nonflammability.
  • carbon dioxide gas may be further added.
  • the lithium-sulfur battery according to the present invention may include additives commonly used in the lithium-sulfur battery field, and preferably, it may be vinylene carbonate (VC) or ethylene carbonate (EC).
  • VC vinylene carbonate
  • EC ethylene carbonate
  • the separator 100 cut to a predetermined size corresponding to the positive electrode plate and the negative electrode plate is interposed between the positive electrode plate and the negative electrode plate obtained by cutting the positive electrode 200 and the negative electrode 300 to a predetermined size, Can be produced.
  • two or more positive plates and negative plates may be arranged on the separator sheet so that the positive electrode 200 and the negative electrode 300 face each other with the separator 100 sheet therebetween, or the two or more positive and negative plates may be stacked with the separator interposed therebetween Stacked and folded electrode assemblies can be manufactured by arranging two or more unit cells on the separator sheet, winding the separator sheet, or bending the separator sheet to the size of the electrode plate or unit cell.
  • the battery pack including the lithium-sulfur battery includes an electric vehicle (EV), a hybrid electric vehicle (HEV), a plug-in hybrid electric vehicle (PHEV) And can be used as a power source of a storage device.
  • EV electric vehicle
  • HEV hybrid electric vehicle
  • PHEV plug-in hybrid electric vehicle
  • PTMA was dissolved in N-methyl-2-pyrrolidone (NMP) to prepare a 1 wt% PTMA solution.
  • NMP N-methyl-2-pyrrolidone
  • the solution was coated on a polypropylene separator having a thickness of 20 ⁇ m using a bar coater, followed by vacuum drying to prepare a 0.5 ⁇ m PTMA-coated separator.
  • SBR is styrene butadiene rubber
  • CMC is carboxymethyl cellulose.
  • Lithium foil having a thickness of 150 mu m was used as a cathode.
  • 70 ⁇ l of an electrolytic solution obtained by mixing 1M LiN (CF 3 SO 2 ) 2 dissolved in dimethoxyethane and dioxolane in a volume ratio of 1: 1 was introduced into the separator prepared in the above Preparation Example, To produce an electrode assembly.
  • the electrode assembly was housed in a battery case to prepare a lithium-sulfur battery coin cell.
  • a separator was prepared in the same manner as in the above preparation example, except that a polypropylene film having a thickness of 20 ⁇ in which no PTMA solution was coated was used as a separator instead of the separator in which the PTFE solution was coated on the polypropylene.
  • a coin cell was fabricated in the same manner as in Example 1, except that the separation membrane of Comparative Production Example 1 was used instead of the separation membrane in which the PTMA solution was coated on the polypropylene in Example 1.
  • PTMA was not coated on the separator but mixed with 70 wt% of a cathode active material prepared by mixing carbon and sulfur at a weight ratio of 9: 1, 20 wt% of Denka black as a conductive material and 9 wt% of SBR / CMC (weight ratio of 1: 1) And 1% by weight of PTMA were added to DI water to prepare a positive electrode slurry and then coated on an aluminum current collector to prepare a positive electrode.
  • a lithium-sulfur battery coin cell was prepared in the same manner as in Example 1, .
  • Example 2 In the same manner as in Example 1, except that the PTFE-coated polypropylene separator membrane in Example 1 was used, and a separator membrane impregnated with PTMA to the interior of the separator membrane was carried by PTMA solution for 1 minute, Cells were prepared.
  • the separation membrane surfaces of the preparation examples and comparative preparation examples were confirmed by scanning electron microscopy (SEM).
  • the rate of charge / discharge was evaluated at 0.1C for the initial 3 cycles, then at 0.2C for 3 cycles and then at 0.5C (evaluated at 0.2C for 3 cycles every 10 cycles)
  • Example 1 which is a lithium-sulfur battery using a PTMA-coated separator, exhibits remarkably improved capacity retention and coulon efficiency as compared with Comparative Example 1.
  • Example 8 shows that the capacity retention rate and the coulombic efficiency of the battery of Comparative Example 2, in which the PTMA is not coated on the separator but applied to the binder of the lithium-sulfur battery, are lower than those of Example 1.
  • the lithium-sulfur battery of Example 1 exhibited a better 890 mAh / g level than Comparative Example 1 after 10 cycles, 30 cycles, and 60 cycles due to the adsorption effect of polysulfide by PTMA Respectively.
  • the lithium-sulfur battery of the present invention suppresses the diffusion of polysulfide, thereby improving electrode loading and initial discharge capacity, and ultimately increasing the energy density of the lithium-sulfur battery.
  • the lithium-sulfur battery is preferably applicable as a high-density battery or a high-performance battery.

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  • Secondary Cells (AREA)

Abstract

La présente invention concerne une batterie au lithium-soufre contenant une membrane de séparation dans laquelle une couche d'adsorption comprenant un composé radicalaire ayant une région de radical nitroxyle est formée, et plus particulièrement, une batterie au lithium-soufre dans laquelle une couche d'adsorption, qui contient un matériau conducteur et un composé radicalaire ayant une région de radical nitroxyle, est appliquée sur une surface d'une membrane de séparation pour supprimer l'élution du polysulfure de lithium. Dans la batterie au lithium-soufre selon la présente invention, non seulement l'élution et la diffusion du polysulfure de lithium qui s'élue à partir d'une électrode positive sont empêchées par adsorption par un composé radicalaire qui est un composé radicalaire stable ayant une région de radical nitroxyle, mais des sites de réaction de matériau actif d'électrode positive sont fournis par apport d'une conductivité électrique supplémentaire. Par conséquent, les propriétés de capacité et de durée de vie de la batterie sont améliorées.
PCT/KR2018/005189 2017-06-20 2018-05-04 Batterie au lithium-soufre WO2018236046A1 (fr)

Priority Applications (4)

Application Number Priority Date Filing Date Title
EP18821205.4A EP3624223B1 (fr) 2017-06-20 2018-05-04 Batterie au lithium-soufre
JP2019568206A JP7065893B2 (ja) 2017-06-20 2018-05-04 リチウム－硫黄電池
US16/624,750 US11545720B2 (en) 2017-06-20 2018-05-04 Lithium-sulfur battery
CN201880035323.0A CN110679010B (zh) 2017-06-20 2018-05-04 锂硫电池

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KR10-2017-0077983 2017-06-20
KR20170077983 2017-06-20
KR1020180051030A KR102320325B1 (ko) 2017-06-20 2018-05-03 리튬-황 전지
KR10-2018-0051030 2018-05-03

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CN113555646A (zh) * 2021-08-10 2021-10-26 大连理工大学 一种凝剂型锂硫电池正极侧隔层材料的制备方法
CN114976482A (zh) * 2022-04-28 2022-08-30 清华大学山西清洁能源研究院 锂硫电池隔膜、其制备方法及锂硫电池

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CN113555646A (zh) * 2021-08-10 2021-10-26 大连理工大学 一种凝剂型锂硫电池正极侧隔层材料的制备方法
CN113555646B (zh) * 2021-08-10 2022-04-19 大连理工大学 一种凝剂型锂硫电池正极侧隔层材料的制备方法
CN114976482A (zh) * 2022-04-28 2022-08-30 清华大学山西清洁能源研究院 锂硫电池隔膜、其制备方法及锂硫电池

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