WO2018030686A1 - 폴리이미드를 포함하는 양극 활물질, 이의 제조방법 및 이를 포함하는 리튬-황 전지 - Google Patents
폴리이미드를 포함하는 양극 활물질, 이의 제조방법 및 이를 포함하는 리튬-황 전지 Download PDFInfo
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- WO2018030686A1 WO2018030686A1 PCT/KR2017/008135 KR2017008135W WO2018030686A1 WO 2018030686 A1 WO2018030686 A1 WO 2018030686A1 KR 2017008135 W KR2017008135 W KR 2017008135W WO 2018030686 A1 WO2018030686 A1 WO 2018030686A1
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Definitions
- the present invention relates to a positive electrode active material for a lithium-sulfur battery including a polyimide, and more particularly, to a positive electrode active material in which a complex of polyimide and carbon-based secondary particles is complexed with sulfur particles, a method for preparing the same, and a lithium- Relates to a sulfur battery.
- a lithium-sulfur (Li-S) battery is a secondary battery using a sulfur-based material having an SS bond (Sulfur-sulfur bond) as a positive electrode active material and using lithium metal as a negative electrode active material.
- Sulfur the main material of the positive electrode active material, is very rich in resources, has no toxicity, and has an advantage of having a low weight per atom.
- the theoretical discharge capacity of the lithium-sulfur battery is 1675 mAh / g-sulfur, and the theoretical energy density is 2,600 Wh / kg, and the theoretical energy density of other battery systems currently being studied (Ni-MH battery: 450 Wh / kg, Li- FeS cells: 480 Wh / kg, Li-MnO 2 cells: 1,000 Wh / kg, Na-S cells: 800 Wh / kg) is very high compared to the most promising battery that has been developed to date.
- a reduction reaction in a cyclic S 8 so that the lithium polysulfide is completely Reduction will eventually lead to the formation of lithium sulfide (Lithium sulfide, Li 2 S).
- Discharge behavior of the lithium-sulfur battery by the process of reduction to each lithium polysulfide is characterized by showing the discharge voltage step by step unlike the lithium ion battery.
- lithium polysulfides such as Li 2 S 8 , Li 2 S 6 , Li 2 S 4 , and Li 2 S 2
- lithium polysulfide (Li 2 S x , usually x> 4) having a high number of sulfur oxides is used in a hydrophilic electrolyte solution. Easily melts Lithium polysulfide dissolved in the electrolyte is diffused away from the positive electrode where lithium polysulfide is formed due to the difference in concentration. The lithium polysulfide eluted from the positive electrode is lost out of the positive electrode reaction region, so that stepwise reduction to lithium sulfide (Li 2 S) is impossible.
- lithium polysulfide which is present in the dissolved state outside the positive electrode and the negative electrode, cannot participate in the charge / discharge reaction of the battery, the amount of sulfur material participating in the electrochemical reaction at the positive electrode decreases, and eventually lithium-sulfur It is a major factor causing a decrease in the charge capacity and energy of the battery.
- lithium polysulfide diffused to the negative electrode in addition to being suspended or precipitated in the electrolyte, is directly reacted with lithium and fixed in the form of Li 2 S on the surface of the negative electrode, causing a problem of corrosion of the lithium metal negative electrode.
- lithium polysulfide may be formed by using carbon containing nitrogen or oxygen, which is known as a lithium polysulfide adsorption material, or by coating or adding a polymer to an electrode or a composite. Although studies have been conducted to induce adsorption, it is insufficient to completely solve the problem of dissolution of lithium polysulfide.
- Patent Document 1 Republic of Korea Patent Publication No. 10-1637983 "Surface-coated positive electrode active material, its manufacturing method, and a lithium secondary battery comprising the same"
- Non-Patent Document 1 Manthiram et al., Adv. Mat. 2015, 27, 1980.
- the lithium-sulfur battery has a problem in that the capacity and life characteristics of the battery decrease as the charge / discharge cycle progresses due to lithium polysulfide eluted from the positive electrode.
- Another object of the present invention is to provide a lithium-sulfur battery including the cathode active material.
- the present invention is a plurality of carbon-based primary particles are agglomerated porous carbon-based secondary particles; A coating layer in which pores of the carbon-based secondary particles are coated with polyimide; It provides a polyimide-carbon-sulfur composite (hereinafter PI / C / S composite) comprising; and sulfur (S) supported in the pores of the carbon-based secondary particles.
- PI / C / S composite polyimide-carbon-sulfur composite
- the present invention 1) preparing a carbon-based material (C) as secondary particles; 2) mixing the carbon-based secondary particles and the polyimide precursor solution; 3) imidizing the polyimide precursor to prepare a polyimide-carbon composite; And 4) preparing polyimide-carbon-sulfur composite by supporting sulfur in the polyimide-carbon composite.
- the present invention provides a cathode for a lithium-sulfur battery comprising the cathode active material, a conductive material and a binder resin.
- the present invention provides a lithium-sulfur battery comprising the positive electrode.
- the lithium-sulfur battery including the PI / C composite of the polyimide and the carbon-based material according to the present invention and the PI / C / S composite in which sulfur particles are complexed is applied to the lithium-sulfur battery, it is possible to suppress the dissolution of polysulfide. Therefore, lifespan characteristics and energy efficiency are improved.
- Example 2 is data showing the life characteristics and energy efficiency of the lithium-sulfur battery according to Example 1 and Comparative Example 1 of the present invention.
- the present invention is a plurality of carbon-based primary particles are assembled by agglomerated porous carbon-based secondary particles; Polyimide (PI) coating layer for coating the inside, the outside of the pores of the carbon-based secondary particles; It provides a polyimide-carbon-sulfur composite (hereinafter PI / C / S composite) comprising; and sulfur (S) supported in the pores of the carbon-based secondary particles.
- PI polyimide-carbon-sulfur composite
- Polyimide is a polymer having a large amount of nitrogen atoms (N) and oxygen atoms (O) in the molecular structure, the nitrogen and oxygen atoms effectively attract polysulfide ions due to the high electronegativity, thereby the poly present in the electrode active material
- the sulfide ions (S x 2 ⁇ ) are effectively adsorbed (or fixed), thereby suppressing the elution of the polysulfide into the electrolyte.
- this effect cannot be predicted in the simple mixed form of the conductive material and the polyimide as in the prior US patent (2014-0322614).
- the polyimide of the PI / C / S composite may be present in various forms, for example, the polyimide forms a continuous simple coating layer or a discontinuous coating layer (eg, island form or partial coating) on the carbon-based secondary particle surface.
- the porous coating layer may be formed while maintaining the pores.
- the form is not limited in the present invention as long as it does not lower the high electrical conductivity function which is a function of the carbon-based material itself while increasing the adsorption of ions of the polysulfide.
- polysulfide ions when the polyimide forms a continuous simple coating layer, polysulfide ions can be adsorbed in a large area, thereby effectively suppressing the dissolution of polysulfide.
- forming a discontinuous coating layer allows the adsorption of polysulfide ions while maintaining the electronic conductivity of the carbon-based material.
- This type of control can be achieved by controlling the concentration of the polyimide precursor solution used in the preparation of the polyimide at the time of production, and at low concentrations can form a discontinuous coating layer, the higher the concentration can form a continuous coating layer.
- Carbon-based secondary particles are formed by agglomeration of carbon-based primary particles.
- the carbon-based primary particles may be in powder form, and when the primary particles in powder form aggregate, voids may be formed between the primary particles. Therefore, the carbon-based secondary particles formed by aggregation of the carbon-based primary particles have a porous particle form.
- the carbon-based material constituting the carbon-based secondary particles is not limited in its kind, but natural graphite, artificial graphite, expanded graphite, graphene (Graphene), graphene oxide (Graphene oxide), Super-P ), Graphite-based such as Super-C; Active carbon system; Denka black, Ketjen black, Channel black, Furnace black, Thermal black, Contact black, Lamp black, Acetylene Carbon black system such as black (Acetylene black); Carbon nano structures such as carbon fiber-based, carbon nanotubes (CNT), and fullerenes; And it may include one selected from the group consisting of a combination thereof, preferably using a carbon black system.
- the carbon-based secondary particles preferably have an average particle diameter of 1 to 50 ⁇ m. If the average particle diameter exceeds the above range, the porosity between secondary particles increases, so that tap density decreases, and slurry mixing and sedimentation occur gradually, which is not preferable. Since it can not be prepared by adjusting to the above range.
- the carbon-based secondary particles in addition to the pores possessed by the primary particles have pores (Textural pores) generated during the aggregation between the primary particles (pore), which can be measured by BET analysis.
- the pore volume thus measured is in the range of about 0.2-4.0 cm 3 / g, and the specific surface area may be 100-2000 m 2 / g.
- the weight ratio of the polyimide and the carbon-based secondary particles is preferably contained in 5: 95 to 20: 80.
- the polyimide is included in less than the above range it is difficult to ensure the effect of inhibiting the dissolution of lithium polysulfide due to the polyimide desired in the present invention, when included in the above range, the weight of the carbon-based material is relatively reduced It is difficult to ensure sufficient electrical conductivity.
- the content of sulfur in the PI / C / S composite may be adjusted to include 30 to 90% by weight relative to the total weight of the composite.
- the above range is a content range capable of sufficiently performing the function as an electrode active material, and ensuring the electronic conductivity by the carbon-based material (C). If the sulfur content is less than the above range, it cannot function as an active material. On the contrary, if the sulfur is used in excess of the above range, sulfur is melted and sulfur which is not bonded to carbon aggregates among them. It is difficult to receive and thus is difficult to directly participate in the electrode reaction, which may cause degradation of battery performance.
- the positive electrode (ie, the sulfur electrode) of the lithium-sulfur battery including the PI / C / S composite polysulfide ions dissolved from the electrode are adsorbed to the PI, so that the diffusion of the polysulfide is suppressed to reduce the active material loss. Also, since the polysulfide ions near the electrode are involved in the discharge reaction, the charge and discharge efficiency and the cycle performance can be improved. In addition, since there is a kinetic synergy effect by the solid-liquid reaction, it is possible to secure a high reaction activity compared to the solid surface (solid surface).
- a cathode active material for a lithium-sulfur battery according to the present invention comprises the following steps: I) preparing a PI / C composite to synthesize polyimide on a carbon-based material; And II) a PI / C / S composite manufacturing step of complexing the PI / C complex and sulfur particles.
- step I) the PI / C complex manufacturing step of step I) is specifically,
- the carbonaceous material is prepared as secondary particles.
- Spray drying is the most preferred method for preparing carbonaceous materials into secondary particles.
- a carbon-based material is selected, mixed with a predetermined solvent to prepare a spray liquid, and the spray liquid is prepared in the form of secondary particles by spraying the nano-sized fine droplets.
- the spray drying equipment may be used spray drying equipment commonly used, for example, ultrasonic spray drying apparatus, air nozzle spray drying apparatus, ultrasonic nozzle spray drying apparatus, filter expansion droplet generator or electrostatic spray drying apparatus, etc. May be used, but is not limited thereto.
- the solvent for diluting the carbon-based powder may be any one of water, methanol, ethanol, isopropyl alcohol, and acetone, but is not limited thereto. Any solvent may be used to uniformly disperse the carbon-based powder. In addition to this, a predetermined dispersant may be further added for strengthening the binding force between the primary particles and dispersing the primary particles.
- the content of solids contained in the spray liquid is 0.5 to 40% by weight, more preferably 15 to 30% by weight. It can be produced by adjusting appropriately according to the carbon material of the primary particles.
- the drying temperature may vary depending on the solvent used, and may be, for example, 100 to 220 ° C. for water, and the spray pressure may be 1.5 to 3 bar, but is not limited thereto.
- the rate of supplying the spray liquid is adjustable up to 10 mL / min, which may vary depending on the size of the pressure to be reduced.
- a carbonization process of about 2 to 10 hours at 400 to 900 ° C. may be further performed to enhance the binding force between the primary particles and to remove the dispersant used for dispersing the primary particles.
- the carbon-based secondary particles and the polyimide precursor solution thus prepared are mixed.
- the polyimide precursor may be a polyamic acid (PAA), a polyamic ester, a polyamic acid ester or other reaction product according to the selection of the starting material, preferably polyamic acid is applied.
- the polyamic acid may be prepared by polymerizing an aromatic anhydride and an aromatic diamine.
- the polyamic acid may be prepared by solution polymerization of the aromatic anhydride and an aromatic diamine, and then imidized by ring closure dehydration at a high temperature.
- aromatic anhydride components examples include biphenyl dianhydride (3,3 ', 4,4'-Biphenyltetracarboxylic Dianhydride, BPDA), pyromellitic dianhydride (1,2,4,5-benzenetetracarboxylic dianhydride, PMDA), and the like. This is available.
- aromatic diamine component Oxydianiline (ODA), p-phenylenediamine (para-Phenylene Diamine, pPDA), m-phenylenediamine (meta-Phenylene Diamine, mPDA), methylene dianiline (Methylenedianiline, MDA), bisaminophenyl hexafluoropropane (HFDA) and the like can be used.
- ODA aromatic diamine component
- pPDA para-Phenylene Diamine
- mPDA m-phenylenediamine
- MDA methylene dianiline
- HFDA bisaminophenyl hexafluoropropane
- the aromatic anhydride component and the aromatic diamine component may be used in an organic solvent in a molar ratio of 1: 0.99 to 0.99: 1 so as to have almost the same molar amount.
- One or more types of anhydrides and aromatic diamines may be used, two or more aromatic anhydrides may be used, one or more aromatic diamines may be used, or two or more aromatic diamines may be used, and one or more aromatic anhydrides may be used.
- the organic solvent for the polymerization reaction of the polyamic acid solution is not particularly limited as long as it is a solvent in which the polyamic acid is dissolved.
- Known reaction solvents selected from m-cresol, N-methyl-2-pyrrolidone (NMP), dimethylformamide (DMF), dimethylacetamide (DMAc), dimethyl sulfoxide (DMSO), acetone, diethyl acetate
- NMP N-methyl-2-pyrrolidone
- DMF dimethylformamide
- DMAc dimethylacetamide
- DMSO dimethyl sulfoxide
- acetone diethyl acetate
- low boiling point solutions such as tetrahydrofuran (THF), chloroform or low absorbing solvents such as ⁇ -butyrolactone may be used.
- the reaction temperature is preferably -20 to 80 ° C, and the reaction time is preferably 2 to 48 hours.
- an inert atmosphere such as reaction of argon (Ar) or nitrogen (N 2).
- the polyamic acid is, for example, pyromellitic dianhydride (PMDA), which is an aromatic anhydride, and 4,4'-oxydianiline (4,4'-oxydianiline, ODA), which is an aromatic diamine.
- PMDA pyromellitic dianhydride
- ODA 4,4'-oxydianiline
- Dimethyl acetamide (DMAc) can be prepared as a coating solution in a nitrogen atmosphere, wherein the molar fraction of PMDA / ODA of the coating solution can be 1/1 to 1 / 1.05, and the polyamic acid is 0.1 to 5 weight. It is preferably included in the% content, more preferably contained in the 0.5 to 2% by weight content.
- the secondary particles of a carbon-based material such as denka black
- the secondary particles of a carbon-based material are immersed in the prepared polyamic acid solution, followed by room temperature (about 15 to 30 ° C.).
- room temperature about 15 to 30 ° C.
- the temperature range and the rotational speed range may be a condition in which the denka black may be smoothly dispersed in the organic solvent in which the polyamic acid is diluted. If the temperature is excessively high, the polyimide reaction in which the polyamic acid is converted to polyimide is performed. There is a risk of progressing early.
- the dispersion is filtered and dried to prepare a composite of a polyimide precursor and a carbonaceous material.
- the denka black is filtered through the filter in the dispersion and dried for 5 to 10 hours at 75 to 95 ° C. to prepare a composite of the coated polyamic acid and denka black.
- the polyimide precursor is then imidized and converted into a polyimide.
- an imidation method for converting the said polyimide precursor into polyimide it can apply in combination with the thermal imidation method, the chemical imidation method, or the thermal imidation method and the chemical imidation method.
- the chemical imidization method is a method of injecting an imidization catalyst represented by a dehydrating agent represented by acid anhydrides such as acetic anhydride and tertiary amines such as isoquinoline, ⁇ -picolin and pyridine into a polyamic acid solution.
- the heating conditions of the polyamic acid solution may vary depending on the kind of the polyamic acid solution, the thickness of the polyimide to be produced, and the like.
- thermal imidization may be performed.
- stepwise heat treatment in order to have a uniform and continuous coating on the denka black secondary particle surface. That is, the polyamic acid-coated denka black may be sequentially heated to 60 ° C. to 400 ° C. to perform heat treatment.
- the PI / C composite prepared above may be complexed with sulfur according to a conventional method.
- sulfur may be repeated several times by dissolving sulfur in an organic solvent to fill the pore volume of the PI / C composite and drying the solvent.
- sulfur powder is first prepared and mixed with the PI / C composite prepared above using a wet ball mill or a dry jet mill method to uniform particle size.
- after adjusting the size of the particles prior to mixing may further comprise the step of dispersing using an organic solvent.
- the usable organic solvents are ethanol, toluene, benzene, N-methyl-2-pyrrolidone (NMP), dimethylsulfoxide (DMSO), acetone, chloroform, dimethylformamide, cyclohexane, tetrahydrofuran and methylene chloride.
- the mixing method may be performed by putting in a powder mixer for a certain time.
- pores between the sulfur particles and the PI / C composite may be reduced.
- the sulfur particles may be melted through the melting process to increase the bonding strength with the PI / C composite.
- the PI / C / S composite as described above may be used as the positive electrode composition
- the PI / C / S composite may be used alone or, if necessary, in addition to the PI / C / S composite, a conductive material and a binder , Fillers and the like may be further added.
- the positive electrode composition of the lithium-sulfur battery according to the present invention may further include a conductive material for imparting electronic conductivity in addition to the PI / C / S composite that is a positive electrode active material.
- the conductive material electrically connects the electrolyte and the positive electrode active material to play a role of allowing lithium ions (Li + ) dissolved in the electrolyte to move to sulfur and react. It also serves as a path for electrons to move to sulfur from the current collector.
- the amount of the conductive material is not sufficient or does not perform the role properly, the portion of the sulfur in the electrode that does not react increases, eventually causing a decrease in capacity.
- high rate discharge characteristics and charge and discharge cycle life are adversely affected. Therefore, the addition of a suitable conductive material is necessary.
- the content of the conductive material is preferably added within the range of 0.01 to 30% by weight based on the total weight of the positive electrode composition.
- the conductive material is not particularly limited as long as it has conductivity without causing chemical change in the battery.
- graphite Carbon blacks such as denka black, acetylene black, ketjen black, channel black, furnace black, lamp black and summer black
- Conductive fibers such as carbon fibers and metal fibers
- Metal powders such as carbon fluoride powder, aluminum powder and nickel powder
- Conductive whiskers such as zinc oxide and potassium titanate
- Conductive metal oxides such as titanium oxide
- Conductive materials such as polyphenylene derivatives and the like
- Specific examples of commercially available conductive materials include Chevron Chemical Company, Denka Singapore Private Limited, Gulf Oil Company, Ketjenblack and EC Armak, which are acetylene black series. Company (Armak Company), Vulcan XC-72 Cabot Company, Super P (manufactured by Timcal), and the like can be used.
- the binder is a component that assists the bonding of the active material and the conductive material to the current collector, and is generally added in an amount of 1 to 50 wt% based on the total weight of the mixture including the electrode active material.
- the content of the binder resin is less than 1% by weight, the physical properties of the positive electrode may be lowered, so that the positive electrode active material and the conductive material may be dropped, and when the content of the binder resin exceeds 50% by weight, the ratio of the active material and the conductive material in the positive electrode may be relatively reduced. Battery capacity can be reduced.
- the binder applicable to the present invention may be all binders known in the art, and specifically, a fluororesin binder including polyvinylidene fluoride (PVdF) or polytetrafluoroethylene (PTFE) ; Rubber-based binders including styrene-butadiene rubber, acrylonitrile-butadiene rubber and styrene-isoprene rubber; Cellulose-based binders including carboxymethyl cellulose (CMC), starch, hydroxypropyl cellulose, regenerated cellulose; Poly alcohol-based binders; Polyolefin-based binders including polyethylene and polypropylene; Polyimide-based binders, polyester-based binders, silane-based binders; may be one or a mixture of two or more selected from the group consisting of, but is not limited thereto.
- PVdF polyvinylidene fluoride
- PTFE polytetrafluoroethylene
- Rubber-based binders
- the filler is not particularly limited as long as it is a fibrous material without causing chemical change in the battery.
- the filler include olefinic polymers such as polyethylene and polypropylene; Fibrous materials, such as glass fiber and carbon fiber, are used.
- the positive electrode as described above may be prepared according to a conventional method, and specifically, a positive electrode composition prepared by mixing a positive electrode active material, a conductive material, and a binder on an organic solvent, is coated and dried on a current collector, and optionally, an electrode density. It can be manufactured by compression molding on the current collector for the purpose of improvement.
- the organic solvent may uniformly disperse the positive electrode active material, the binder, and the conductive material, and preferably evaporates easily. Specifically, acetonitrile, methanol, ethanol, tetrahydrofuran, water, isopropyl alcohol, etc. are mentioned.
- the current collector may be generally made of a thickness of 3 ⁇ 500 ⁇ m, and is not particularly limited as long as it has a high conductivity without causing chemical changes in the battery.
- a conductive material such as stainless steel, aluminum, copper, titanium, or the like may be used, and more specifically, a carbon-coated aluminum current collector may be used.
- the use of an aluminum substrate coated with carbon has an advantage in that the adhesion to the active material is excellent, the contact resistance is low, and the corrosion of polysulfide of aluminum is prevented, compared with the non-carbon coated aluminum substrate.
- the current collector may be in various forms such as film, sheet, foil, net, porous body, foam or nonwoven fabric.
- Lithium-sulfur battery according to the present invention is a positive electrode comprising a PI / C / S composite of the present invention; A negative electrode comprising a lithium metal or a lithium alloy; A separator interposed between the anode and the cathode; And electrolytes.
- the positive electrode including the PI / C / S composite suppresses the dissolution of lithium polysulfide, thereby improving electrode loading and initial discharge capacity, and finally 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.
- the negative electrode active material of the lithium-sulfur battery according to the present invention may be one selected from the group consisting of lithium metal, lithium alloy, lithium metal composite oxide, lithium-containing titanium composite oxide (LTO), and combinations thereof.
- the lithium alloy may be an alloy consisting of lithium and at least one metal selected from Na, K, Rb, Cs, Fr, Be, Mg, Ca, Sr, Ba, Ra, Al and Sn.
- the lithium metal composite oxide is any one metal (Me) oxide (MeO x ) selected from the group consisting of lithium and Si, Sn, Zn, Mg, Cd, Ce, Ni, and Fe, for example, Li x Fe 2 O 3 (0 ⁇ x ⁇ 1) or Li x WO 2 (0 ⁇ x ⁇ 1).
- the separator of the lithium-sulfur battery according to the present invention is a physical separator having a function of physically separating an electrode, and can be used without particular limitation as long as it is used as a conventional separator, and is particularly resistant to ion migration of the electrolyte. It is preferable that the moisture content is excellent.
- the separator enables the transport of lithium ions between the positive electrode and the negative electrode while separating or insulating the positive electrode and the negative electrode from each other.
- a separator may be made of a porous and nonconductive or insulating material.
- the separator may be an independent member such as a film or a coating layer added to the anode and / or the cathode.
- a porous polymer film made of a polyolefin-based polymer such as ethylene homopolymer, propylene homopolymer, ethylene / butene copolymer, ethylene / hexene copolymer and ethylene / methacrylate copolymer may be used alone. It may be used as a lamination or or a conventional porous non-woven fabric, for example, a non-woven fabric made of glass fibers, polyethylene terephthalate fibers of high melting point, etc. may be used, but is not limited thereto.
- the electrolyte of the lithium-sulfur battery according to the present invention comprises a lithium salt and an electrolyte as a non-aqueous electrolyte containing a lithium salt, and a non-aqueous organic solvent, an organic solid electrolyte and an inorganic solid electrolyte are used as the electrolyte.
- Lithium salt of the present invention is a good material to dissolve 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, chloroborane lithium, lower aliphatic
- 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, Li
- the concentration of the lithium salt is 0.2-2 M, depending on several factors, such as the exact composition of the electrolyte mixture, the solubility of the salt, the conductivity of the dissolved salt, the charging and discharging conditions of the cell, the operating temperature and other factors known in the lithium battery art. 0.6 to 2M, and more specifically 0.7 to 1.7M. If the amount is less than 0.2M, the conductivity of the electrolyte may be lowered, and thus the performance of the electrolyte may be lowered. If the concentration is more than 2M, the viscosity of the electrolyte may be increased, thereby reducing the mobility of lithium ions (Li + ).
- the non-aqueous organic solvent must dissolve lithium salts well, and as the non-aqueous organic solvent of the present invention, for example, N-methyl-2-pyrrolidinone, propylene carbonate, ethylene carbonate, butylene carbonate , Dimethyl carbonate, diethyl carbonate, ethylmethyl carbonate, gamma-butylo lactone, 1,2-dimethoxy ethane, 1,2-diethoxy ethane, tetrahydroxy franc, 2-methyl Tetrahydrofuran, dimethyl sulfoxide, 1,3-dioxolon, 4-methyl-1,3-dioxene, diethyl ether, formamide, dimethylformamide, dioxorone, acetonitrile, nitromethane, methyl formate Methyl acetate, phosphate triester, trimethoxy methane, dioxorone derivative, sulfolane, methyl sulfolane, 1,3-d
- organic solid electrolyte examples include polyethylene derivatives, polyethylene oxide derivatives, polypropylene oxide derivatives, phosphate ester polymers, poly etchation lysine, polyester sulfides, polyvinyl alcohol, polyvinylidene fluoride, and ionic dissociation. Polymers containing groups and the like 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, sulfates, and the like of Li, such as Li 4 SiO 4 —LiI-LiOH, Li 3 PO 4 —Li 2 S-SiS 2 , and the like, may be used.
- Secondary particles of denka black were prepared by introducing a spray drying process.
- Example 1 shows the results of thermal gravimetric analysis (TGA) of the PI / C composite prepared in Example 1 and the PI / C / S composite in a nitrogen atmosphere, wherein 11 wt% of PI was synthesized on denka black; After removing the polyimide (PI) and sulfur (S) in the PI / C / S composite was confirmed that the carbon (C) is about 30wt%.
- TGA thermal gravimetric analysis
- the coin cell test was performed after discharge / charging 2.5 cycles at 0.1C condition after 12 hours of REST, and then at 0.3C charge / 0.5C discharge condition. As shown in FIG. 2, which is an experimental result, it can be seen that the coulombic efficiency of the lithium-sulfur battery of Comparative Example 1 is rapidly decreased, but the coulombic efficiency of the lithium-sulfur battery of Example 1 is improved. You can check it.
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Abstract
Description
Claims (16)
- 복수의 탄소계 1차 입자가 조립되어 응집된 다공성 탄소계 2차 입자;상기 탄소계 2차 입자의 기공 내,외부가 폴리이미드로 코팅된 코팅층; 및상기 탄소계 2차 입자의 기공에 담지되는 황(S);을 포함하는 폴리이미드-탄소-황 복합체.
- 제1항에 있어서,상기 폴리이미드 코팅층은 다공성 탄소계 2차 입자의 표면상에 연속적 또는 불연속적으로 코팅층을 형성하거나, 기공을 유지하며 다공성 코팅층을 형성하는 것을 특징으로 하는 폴리이미드-탄소-황 복합체.
- 제1항에 있어서,상기 폴리이미드와 탄소계 2차 입자의 중량비는 5 : 95 ~ 20 : 80인 것을 특징으로 하는 폴리이미드-탄소-황 복합체.
- 제1항에 있어서,상기 탄소계 2차 입자는 천연 흑연, 인조 흑연, 팽창 흑연, 그래핀(Graphene), 그래핀 옥사이드(Graphene oxide), 슈퍼-피(Super-P), 슈퍼-씨(Super-C)를 포함하는 흑연(Graphite)계; 활성탄(Active carbon)계; 덴카 블랙(Denka black), 케첸 블랙(Ketjen black), 채널 블랙(Channel black), 퍼니스 블랙(Furnace black), 써말 블랙(Thermal black), 컨택트 블랙(Contact black), 램프 블랙(Lamp black), 아세틸렌 블랙(Acetylene black)을 포함하는 카본 블랙(Carbon black)계; 탄소 섬유(Carbon fiber)계, 탄소나노튜브(Carbon nanotube: CNT), 풀러렌(Fullerene)을 포함하는 탄소나노구조체; 및 이들의 조합으로 이루어진 군으로부터 선택된 1종 이상에서 선택된 것을 특징으로 하는 폴리이미드-탄소-황 복합체.
- 제1항에 있어서,상기 탄소계 2차 입자의 평균 입경은 1 내지 50 ㎛인 것을 특징으로 하는 폴리이미드-탄소-황 복합체.
- 제1항에 있어서,상기 탄소계 2차 입자의 기공 부피는 약 0.2 ~ 4.0 cm3/g인 것을 특징으로 하는 폴리이미드-탄소-황 복합체.
- 제1항에 있어서,상기 탄소계 2차 입자의 비표면적은 100 ~ 2000 m2/g인 것을 특징으로 하는 폴리이미드-탄소-황 복합체.
- 제1항에 있어서,상기 황은 황 원소(elemental sulfur, S8), 고체 Li2Sn(n ≥1), Li2Sn(n ≥ 1)가 용해된 캐쏠라이트, 유기황 화합물 및 탄소-황 폴리머[(C2Sx)n, x = 2.5 내지 50, n ≥2]로 이루어진 군에서 선택된 1종 이상인 것을 특징으로 하는 폴리이미드-탄소-황 복합체.
- 제1항에 있어서,상기 황의 함량은 전체 복합체 중량 대비 30 내지 90 중량%로 포함되는 것을 특징으로 하는 폴리이미드-탄소-황 복합체.
- 1) 탄소계 물질을 2차 입자로 제조하는 단계;2) 상기 탄소계 2차 입자와 폴리이미드 전구체 용액을 혼합하는 단계;3) 상기 폴리이미드 전구체를 이미드화(imidization) 하여 폴리이미드-탄소 복합체를 제조하는 단계; 및4) 폴리이미드-탄소 복합체에 황을 담지하여 폴리이미드-탄소-황 복합체를 제조하는 단계;를 포함하여 제조하는 것을 특징으로 하는 폴리이미드-탄소-황 복합체의 제조방법.
- 제10항에 있어서,상기 1) 단계의 2차 입자는 탄소계 물질이 포함된 용액을 분무건조(Spray drying)하여 제조하는 것을 특징으로 하는 폴리이미드-탄소-황 복합체의 제조방법.
- 제10항에 있어서,상기 2) 단계의 폴리이미드 전구체는 폴리아믹산(Polyamic acid: PAA)인 것을 특징으로 하는 폴리이미드-탄소-황 복합체의 제조방법.
- 제10항에 있어서,상기 3) 단계의 이미드화는 60 ~ 400℃ 범위 내에서 단계적으로 승온하여 열처리하는 것을 특징으로 하는 폴리이미드-탄소-황 복합체의 제조방법.
- 제1항 내지 제9항의 폴리이미드-탄소-황 복합체를 포함하는 리튬-황 전지용 양극.
- 제14항에 있어서,상기 리튬-황 전지용 양극은 바인더 수지, 도전재, 첨가제로 이루어진 군에서 선택된 1종 이상을 더 포함하는 것을 특징으로 하는 리튬-황 전지용 양극.
- 양극; 음극; 이들 사이에 개재되는 분리막 및 전해질을 포함하고,상기 양극은 제14항의 양극인 것을 특징으로 하는 리튬-황 전지.
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US16/080,610 US10756333B2 (en) | 2016-08-10 | 2017-07-28 | Cathode active material comprising polyimide, manufacturing method thereof, and lithium-sulfur battery comprising same |
EP17839704.8A EP3419088B1 (en) | 2016-08-10 | 2017-07-28 | Cathode active material comprising polyimide, manufacturing method thereof, and lithium-sulfur battery comprising same |
JP2018562497A JP6671730B2 (ja) | 2016-08-10 | 2017-07-28 | リチウム−硫黄電池用正極、これを含むリチウム−硫黄電池、及びポリイミド−炭素−硫黄複合体の製造方法 |
CN201780025825.0A CN109075328B (zh) | 2016-08-10 | 2017-07-28 | 包含聚酰亚胺的正极活性材料、其制造方法和包含其的锂-硫电池 |
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EP3419088B1 (en) | 2020-07-08 |
EP3419088A1 (en) | 2018-12-26 |
US20190067682A1 (en) | 2019-02-28 |
KR102003304B1 (ko) | 2019-07-24 |
JP2019509613A (ja) | 2019-04-04 |
EP3419088A4 (en) | 2019-05-01 |
KR20180017724A (ko) | 2018-02-21 |
JP6671730B2 (ja) | 2020-03-25 |
US10756333B2 (en) | 2020-08-25 |
CN109075328B (zh) | 2021-07-20 |
CN109075328A (zh) | 2018-12-21 |
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