WO2017074116A1 - Électrolyte polymère à structure multicouche, et batterie tout solide le comprenant - Google Patents

Électrolyte polymère à structure multicouche, et batterie tout solide le comprenant Download PDF

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WO2017074116A1
WO2017074116A1 PCT/KR2016/012283 KR2016012283W WO2017074116A1 WO 2017074116 A1 WO2017074116 A1 WO 2017074116A1 KR 2016012283 W KR2016012283 W KR 2016012283W WO 2017074116 A1 WO2017074116 A1 WO 2017074116A1
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polymer electrolyte
solid
lithium
polymer
layer
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PCT/KR2016/012283
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English (en)
Korean (ko)
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고동욱
양두경
박은경
채종현
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주식회사 엘지화학
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Priority to CN201680033253.6A priority Critical patent/CN107636880B/zh
Priority to JP2017558637A priority patent/JP6450030B2/ja
Priority to EP16860299.3A priority patent/EP3285324B1/fr
Priority to US15/572,851 priority patent/US10522872B2/en
Priority claimed from KR1020160141786A external-priority patent/KR101930477B1/ko
Publication of WO2017074116A1 publication Critical patent/WO2017074116A1/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
    • 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
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/056—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes
    • H01M10/0564—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes the electrolyte being constituted of organic materials only
    • H01M10/0565—Polymeric materials, e.g. gel-type or solid-type
    • 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
    • H01M10/056—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes
    • H01M10/0564—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes the electrolyte being constituted of organic materials only
    • H01M10/0566—Liquid materials
    • H01M10/0568—Liquid materials characterised by the solutes
    • 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
    • H01M10/058—Construction or manufacture
    • H01M10/0585—Construction or manufacture of accumulators having only flat construction elements, i.e. flat positive electrodes, flat negative electrodes and flat separators
    • 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
    • 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
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P70/00—Climate change mitigation technologies in the production process for final industrial or consumer products
    • Y02P70/50—Manufacturing or production processes characterised by the final manufactured product

Definitions

  • the present invention relates to a polymer electrolyte for an all-solid-state battery having a multi-layer structure, and more specifically, the EO: Li molar ratio of a polyethylene oxide (PEO) -based polymer and a lithium salt is A multi-layered polymer electrolyte comprising different first polymer electrolyte layers and second polymer electrolyte layers.
  • PEO polyethylene oxide
  • secondary batteries have been increasing in demand for various applications as power sources for PCs, video cameras, mobile phones, and the like, or as power sources for electric vehicles and power storage media.
  • the secondary batteries especially lithium-based secondary batteries have higher capacity density than other secondary batteries and can operate at high voltage, and thus are used in information-related devices and communication devices as secondary batteries for compact and lightweight, and have recently been used for electric vehicles and hybrid vehicles.
  • the development of high power and high capacity lithium-based secondary batteries is in progress.
  • a typical lithium-based secondary battery is composed of an electrolyte containing a positive electrode (positive electrode, cathode), a negative electrode (negative electrode, anode) and a lithium salt interposed therebetween, and such an electrolyte is a non-aqueous liquid electrolyte or a solid electrolyte.
  • a non-aqueous liquid electrolyte is used for the electrolyte, since the electrolyte penetrates into the positive electrode, an interface between the positive electrode active material constituting the positive electrode and the electrolyte tends to be formed, and thus has high electrical performance.
  • a lithium secondary battery uses a flammable organic solvent in the liquid electrolyte, it is necessary to install a safety device in order to prevent ignition and rupture that may occur due to overcurrent due to a short circuit. It is also built. In addition, in order to prevent such a phenomenon, there may be a restriction in selecting a battery material or designing a battery structure.
  • an all-solid-state battery which uses a solid electrolyte instead of a liquid electrolyte is advanced. Since an all-solid-state battery does not contain a flammable organic solvent, it has the advantage of simplifying a safety device, and is recognized as a battery excellent in manufacturing cost and productivity. Moreover, since it is easy to stack a junction structure including a pair of electrode layers including an anode (positive electrode) layer and a cathode (negative electrode) layer and a solid electrolyte layer sandwiched between these electrode layers, it is stable and has a high capacity, In addition, it is expected as a technology that can produce a battery of high power.
  • LiNbO 3 LiNbO 3 -coated LiCoO 2 as cathode material for all solid-state lithium secondary batteries
  • Electrochemistry Communications 9 (2007), 1486 ⁇ 1490 is applied to the surface of LiCoO 2 (anode active material).
  • LiNbO 3 Lithium niobate
  • This technique is to obtain a high power battery in such a manner as to reduce the interface resistance between the surface of LiCoO 2 is coated with LiNbO 3, LiCoO 2 as solid by suppressing the reaction between the electrolyte material, the solid electrolyte material and LiCoO 2.
  • Japanese Laid-Open Patent Publication No. 2004-206942 discloses a second solid electrolyte layer which does not chemically react with the first solid electrolyte and has lower ion conductivity than the first solid electrolyte layer (sulfide-based solid electrolyte material).
  • an all-solid-state battery formed between the first solid electrolyte layer and a cathode made of metallic lithium. This is to suppress the reaction between the first solid electrolyte layer and the metal lithium through the formation of a second solid electrolyte layer having low ion conductivity.
  • Patent Document 1 Korean Unexamined Patent Publication No. 2012-0092918 "Polymer composite electrolyte for lithium secondary battery and lithium secondary battery comprising same"
  • Patent Document 2 Japanese Unexamined Patent Publication No. 2004-206942 "All-solid-state lithium battery”
  • Non-Patent Document 1 Qian, Jiangfeng, et al. "High rate and stable cycling of lithium metal anode.” Nature communications 6 (2015)
  • Non-Patent Document 2 LiNbO3-coated LiCoO2 as cathode material for all solid-state lithium secondary batteries
  • Electrochemistry Communications 9 (2007), 1486-1490 Electrochemistry Communications 9 (2007), 1486-1490.
  • An all-solid-state battery to which a solid polymer electrolyte is applied is hard to express sufficient output or capacity at room temperature but also at 60 ° C or 80 ° C.
  • the reasons for this are firstly low ionic conductivity of the polymer electrolyte and secondly, interfacial resistance between lithium and the polymer electrolyte.
  • an object of the present invention is to provide a polymer electrolyte for an all-solid-state battery which significantly lowers the interface resistance between lithium and a polymer electrolyte.
  • the present invention provides a polymer electrolyte layer having a molar ratio of EO: Li of a polyethylene oxide (PEO) -based polymer and a lithium salt of 1: 1 to 7: 1; And
  • It provides a polymer electrolyte for an all-solid-state battery comprising a multi-layer structure.
  • the thickness of the first polymer electrolyte layer may be 1 to 5 ⁇ m.
  • the thickness of the second polymer electrolyte layer may be 5 ⁇ 50 ⁇ m.
  • the weight average molecular weight (Mw) of the polyethylene oxide polymer may be 1,000,000 to 8,000,000.
  • the lithium salt is LiCl, LiBr, LiI, LiClO 4 , LiBF 4 , LiB 10 Cl 10 , LiPF 6 , LiCF 3 SO 3 , LiCF 3 CO 2 , LiAsF 6 , LiSbF 6 , LiAlCl 4 , CH 3 SO 3 Li , CF 3 SO 3 Li, LiSCN, LiC (CF 3 SO 2 ) 3 , (CF 3 SO 2 ) 2 NLi, (FSO 2 ) 2 NLi, chloroborane lithium, lower aliphatic carbonate, lithium 4-phenyl borate, It may include one selected from imides and combinations thereof.
  • the second polymer electrolyte layer may be cross-linked by a crosslinkable monomer to form a semi-interpenetrating polymer network (semi-IPN).
  • a crosslinkable monomer to form a semi-interpenetrating polymer network (semi-IPN).
  • the crosslinkable monomer may include a — (CH 2 —CH 2 —O) —repeating unit.
  • the crosslinkable monomer may include 2 to 8 alkylenically unsaturated bonds at the terminals.
  • the crosslinkable monomer may be included in an amount of 5 to 50 wt% based on the polyethylene oxide polymer and the lithium salt.
  • the present invention is an all-solid-state battery comprising a positive electrode, a negative electrode and a solid polymer electrolyte interposed therebetween,
  • the solid polymer electrolyte provides an all-solid-state battery, which is a polymer electrolyte for an all-solid-state battery having the multilayer structure.
  • the first polymer electrolyte layer may be disposed to face the cathode.
  • the solid polymer electrolyte of the present invention When the solid polymer electrolyte of the present invention is applied to an all-solid-state battery, the interfacial resistance with lithium and the discharge overvoltage are significantly reduced, resulting in sufficient discharge capacity and improved output characteristics and energy density.
  • FIG. 1 is a graph showing the interfacial resistance of a lithium metric battery according to Comparative Example 1.
  • FIG. 2 is a graph showing the interfacial resistance of the lithium symmetric battery according to Example 1.
  • Example 3 is a cross-sectional comparison diagram of the all-solid-state battery according to Comparative Example 2 (a) and Example 2 (b).
  • Example 4 is a graph comparing discharge capacities of all-solid-state batteries according to Comparative Example 2 (a) and Example 2 (b).
  • the solid polymer electrolyte applied to an all-solid-state battery includes a polyethylene oxide (PEO) -based polymer and a lithium salt
  • the EO: Li molar ratio of the polyethylene oxide-based polymer and the lithium salt is A multi-layered polymer electrolyte comprising a different first polymer electrolyte layer and a second polymer electrolyte layer is disclosed.
  • the first polymer electrolyte layer is applied to lower the interfacial resistance
  • the EO: Li molar ratio of the polyethylene oxide polymer and the lithium salt is selected and prepared within the range of 1: 1 to 7: 1.
  • the lithium salt is doped at a high rate and thinned to a thickness of 1 to 5 ⁇ m, the ion conductivity is slightly lowered, but the interface resistance can be significantly lowered.
  • the second polymer electrolyte layer is applied to prevent the phenomenon caused by the generation of dendrite by increasing the mechanical strength, and the molar ratio of EO: Li of the polyethylene oxide polymer and the lithium salt is 30: 1 to 8: 1 It selects and manufactures in the range.
  • the thickness of the second polymer electrolyte layer may be 5 to 50 ⁇ m.
  • the second polymer electrolyte layer may be crosslinked by a crosslinkable monomer to form a semi-interpenetrating polymer network (semi-IPN) structure.
  • the semi-IPN structure can increase the strength of the solid polymer electrolyte, and the higher the strength, the more physically it can suppress the generation of lithium dendrites on the electrode surface.
  • the weight average molecular weight (Mw) of the polyethylene oxide-based polymer may form a more dense semi-IPN structure when a relatively high molecular weight is applied within the range of 1,000,000 to 8,000,000.
  • the crosslinkable monomer may be a bifunctional or more than one polyfunctional monomer, and may include a-(CH 2 -CH 2 -O) -repeat unit, and may form an alkylenically unsaturated bond within the range of 2 to 8 polymerizable at both ends. It is preferable to include.
  • the alkylenically unsaturated bond is a hydrocarbon group including at least one carbon-carbon double bond or triple bond, an ethenyl group, 1-propenyl group, 2-propenyl group, 2-methyl-1-propenyl group, 1-butenyl group, 2-butenyl group, ethynyl group, 1-propynyl group, 1-butynyl group, 2-butynyl group, and the like, but are not limited thereto.
  • Such alkylenically unsaturated bonds act as a crosslinking point to form a semi-IPN structure by crosslinking the polyethylene oxide polymer through a polymerization process.
  • the crosslinkable monomer may include polyethylene glycol diacrylate (PEGDA), polyethylene glycol dimethacrylate (PEGDMA), polypropylene glycol diacrylate (Poly ( propylene glycol diacrylate: PPGDA), poly (propylene glycol) dimethacrylate (PPGDMA) and combinations thereof, and preferably polyethylene glycol diacrylate (PEGDA).
  • PEGDA polyethylene glycol diacrylate
  • PEGDMA polyethylene glycol dimethacrylate
  • PPGDA polypropylene glycol diacrylate
  • PPGDMA poly (propylene glycol) dimethacrylate
  • PEGDA polyethylene glycol diacrylate
  • crosslinkable monomer is preferably included in the range of 5 to 50 wt% based on the weight of the polyethylene oxide-based polymer to form a semi-IPN structure suitable for the purpose of the present invention.
  • Lithium salts commonly applied to the first polymer electrolyte layer and the second polymer electrolyte layer according to the present invention may be dissociated into lithium ions to penetrate into the first polymer electrolyte layer and the second polymer electrolyte layer and move freely.
  • any lithium salt can be used as long as it is commonly used in lithium batteries, but preferably LiCl, LiBr, LiI, LiClO 4 , LiBF 4 , LiB 10 Cl 10 , LiPF 6 , LiCF 3 SO 3 , LiCF 3 CO 2 , LiAsF 6 , LiSbF 6 , LiAlCl 4 , CH 3 SO 3 Li, CF 3 SO 3 Li, LiSCN, LiC (CF 3 SO 2 ) 3 , (CF 3 SO 2 ) 2 NLi, (FSO 2 ) 2 NLi, chloroborane lithium, lower aliphatic lithium carbonate, lithium 4-phenyl borate, imide and combinations thereof, but more preferably Lithium bis (fluorosulfonyl) imide (LiFSI), preferably represented by (FSO 2 ) 2 NLi, is possible.
  • LiFSI Lithium bis (fluorosulfonyl) imide
  • the manufacturing method of the first polymer electrolyte layer or the second polymer electrolyte layer of the present invention is not limited in the present invention, and a mixing and molding process may be used by a wet or dry method as is known.
  • the thickness of the solid polymer electrolyte of the present invention may be selectively prepared within the range of 1 to 50 ⁇ m.
  • an all-solid-state battery including the solid polymer electrolyte of the present invention interposed between a positive electrode and a negative electrode will be described an all-solid-state battery in which the first polymer electrolyte layer faces the negative electrode and the interface resistance is significantly reduced.
  • the electrode active material may be a positive electrode active material when the electrode proposed in the present invention is a positive electrode, a negative electrode active material when the negative electrode.
  • each electrode active material can be any active material applied to a conventional electrode, and is not particularly limited in the present invention.
  • the positive electrode or negative electrode active material used in the present invention varies depending on the type of conductive ions of the intended all-solid-state battery.
  • the all-solid-state battery according to the present invention is an all-solid lithium secondary battery
  • the positive or negative electrode active material occludes or releases lithium ions.
  • the positive electrode or negative electrode active material used in the present invention can generally react with the solid electrolyte material described above to form a high resistance portion.
  • the positive electrode active material may vary depending on the use of the lithium secondary battery, and the specific composition uses a known material. For example, any one selected from the group consisting of lithium-phosphate-iron compound, lithium cobalt-based oxide, lithium manganese-based oxide, lithium copper oxide, lithium nickel-based oxide and lithium manganese composite oxide, lithium-nickel-manganese-cobalt-based oxide And lithium transition metal oxides.
  • M is at least one selected from metals of Groups 2 to 12
  • X is F
  • the negative electrode active material 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).
  • a conductive material, a polymer electrolyte, a binder, a filler, and the like may be further added to the active material, and the conductive material is not particularly limited as long as it has conductivity without causing chemical changes to the battery.
  • the conductive material is not particularly limited as long as it has conductivity without causing chemical changes to the battery.
  • graphite Carbon blacks such as carbon 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 whiskeys such as zinc oxide and potassium titanate
  • Conductive metal oxides such as titanium oxide
  • Conductive materials such as polyphenylene derivatives and the like can be used.
  • 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 in bonding 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.
  • binders include polyvinylidene fluoride, polyvinyl alcohol, carboxymethyl cellulose (CMC), starch, hydroxypropyl cellulose, regenerated cellulose, polyvinylpyrrolidone, tetrafluoroethylene, polyethylene, poly Propylene, ethylene-propylene-diene terpolymer (EPDM), sulfonated EPDM, styrene butylene rubber, fluorine rubber, various copolymers, and the like.
  • 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 first polymer electrolyte layer is disposed to face the negative electrode, and a second polymer electrolyte layer is formed thereon, and an anode is formed thereon. If the stacking order of the first and second polymer electrolyte layers is reversed, the resistance of the battery may increase and the discharge capacity may decrease, which is not preferable.
  • the interfacial resistance may increase and the discharge capacity may be lowered, and if the second polymer electrolyte layer is out of the above range, the resistance of the electrolyte-separation membrane layer may increase. Discharge capacity may be lowered, which is undesirable.
  • the manufacture of an all-solid-state battery is a dry compression process in which an electrode and a solid electrolyte are prepared in powder form, and then put into a predetermined mold and pressed, or a slurry coating is prepared after coating and drying in the form of a slurry composition containing an active material, a solvent, and a binder. It is manufactured through the process.
  • the production of the all-solid-state battery having the above configuration is not particularly limited in the present invention, and a known method can be used.
  • a solid electrolyte is disposed between the positive electrode and the negative electrode and then compression molded to assemble the cell.
  • the assembled cell is installed in an outer packaging material and sealed by heat compression.
  • laminate packs such as aluminum and stainless steel and cylindrical or rectangular metal containers are very suitable.
  • the method of coating the electrode slurry on the current collector is a method of distributing the electrode slurry on the current collector and then uniformly dispersing it using a doctor blade or the like, die casting, comma coating. , Screen printing, and the like.
  • the electrode slurry may be bonded to the current collector by pressing or lamination after molding on a separate substrate. At this time, by adjusting the concentration of the slurry solution, or the number of coating, it is possible to control the coating thickness to be finally coated.
  • the drying process is a process of removing the solvent and water in the slurry to dry the slurry coated on the metal current collector, and may vary depending on the solvent used. In one example, it is carried out in a vacuum oven at 50 ⁇ 200 °C.
  • a drying method the drying method by irradiation with warm air, hot air, low humidity wind, vacuum drying, (far) infrared rays, an electron beam, etc. are mentioned, for example. Although it does not specifically limit about drying time, Usually, it carries out in 30 second-24 hours.
  • a cooling process may be further included, and the cooling process may be slow cooling to room temperature so that the recrystallized structure of the binder is well formed.
  • a pressing process may be performed in which the electrode is passed between two hot-heated rolls and compressed to a desired thickness.
  • the said rolling process is not specifically limited in this invention, A well-known rolling process is possible. In one example, it is passed between the rotating rolls or performed using a flat plate press.
  • n represents the number of moles of PEO corresponding to 1 mol of Li of the lithium salt
  • X is a semi-IPN structure in what is referred to as 'PEO n -lithium salt-X' It means crosslinked with.
  • a 3 ⁇ m polymer electrolyte membrane and a PEO 5 -LiFSI membrane were prepared by a solution casting method.
  • a 20 ⁇ m polymer electrolyte membrane and a PEO 20 -LiFSI membrane were prepared by a solution casting method.
  • initiator BPO Benzoyl peroxide
  • a 20 ⁇ m polymer electrolyte membrane and a PEO 20 -LiFSI-X membrane were prepared by a solution casting method using the mixed solution.
  • a 3 ⁇ m polymer electrolyte membrane and a PEO 2 -LiFSI membrane were prepared by a solution casting method.
  • a 10 ⁇ m polymer electrolyte membrane and a PEO 12 -LiFSI membrane were prepared by a solution casting method.
  • a lithium symmetric cell is applied by applying the PEO 5 -LiFSI film of Preparation Example 1 to the surface of a lithium metal and applying the PEO 20 -LiFSI-X film of Preparation Example 3 therebetween.
  • a lithium symmetric cell is applied by applying the PEO 5 -LiFSI film of Preparation Example 1 to the surface of a lithium metal and applying the PEO 20 -LiFSI-X film of Preparation Example 3 therebetween.
  • a lithium symmetric cell was fabricated by applying the PEO 20 —LiFSI-X film of Preparation Example 3 between lithium.
  • a positive electrode having a porosity of 10% or less and a loading of 2 mAh / cm 2 was prepared by mixing LFP (LiFePO 4 ) active material, a conductive material, and a polymer electrolyte to a size of 10.6 cm 2 .
  • the positive electrode prepared in step 1 was stacked on the second polymer electrolyte to prepare an all-solid-state battery as shown in FIG. 3 (b).
  • a positive electrode having a porosity of 10% or less and a loading of 2 mAh / cm 2 was prepared by mixing LFP (LiFePO 4 ) active material, a conductive material, and a polymer electrolyte to a size of 10.6 cm 2 .
  • An all-solid-state battery was manufactured by stacking the positive electrode prepared in step 1 on the second polymer electrolyte.
  • a positive electrode having a porosity of 10% or less and a loading of 2 mAh / cm 2 was prepared by mixing LFP (LiFePO 4 ) active material, a conductive material, and a polymer electrolyte to a size of 10.6 cm 2 .
  • step 3 The positive electrode prepared in step 1 was stacked to produce an all-solid-state battery as shown in FIG.
  • a positive electrode having a porosity of 10% or less and a loading of 2 mAh / cm 2 was prepared by mixing LFP (LiFePO 4 ) active material, a conductive material, and a polymer electrolyte to a size of 10.6 cm 2 .
  • the first polymer electrolyte of PEO 5 -LiFSI of Preparation Example 1 was mounted on the second polymer electrolyte.
  • An all-solid-state battery was manufactured by stacking the positive electrode prepared in step 1 on the first polymer electrolyte.
  • a positive electrode having a porosity of 10% or less and a loading of 2 mAh / cm 2 was prepared by mixing LFP (LiFePO 4 ) active material, a conductive material, and a polymer electrolyte to a size of 10.6 cm 2 .
  • a second polymer electrolyte of PEO 20 -LiFSI of Preparation Example 2 was mounted on the second polymer electrolyte.
  • An all-solid-state battery was manufactured by stacking the positive electrode prepared in step 1 on the second polymer electrolyte.
  • Example 1 and Comparative Example 1 and the all-solid-state cells of Example 3 and Comparative Examples 3 and 4 were measured by electrochemical impedance spectroscopy (EIS) measurement.
  • EIS electrochemical impedance spectroscopy
  • the resistance of the cell to which only PEO 20 -LiFSI-X, which is Comparative Example 1 shown in FIG. 1, is 350 ⁇
  • the battery applied as an interlayer was found to have a very low resistance of about 130 ⁇ despite the increase in thickness of 6 ⁇ m. Therefore, it can be seen that the PEO 5 -LiFSI film has a very low interfacial resistance with lithium.
  • the resistance of the all-solid-state battery in which PEO 2 -LiFSI and PEO 20 -LiFSI based on the lithium negative electrode of Example 3 were sequentially applied was 200 ⁇
  • Comparative Example 3 which changed the positions of the first polymer and the second polymer, was used.
  • a negative electrode based on PEO and PEO 5 20 -LiFSI -LiFSI was the resistance of the all-solid battery are applied sequentially appeared as 350 ⁇
  • the resistance of the all-solid-state battery sequentially applied was 2200 ⁇ .
  • the interfacial resistance of the battery in which the lithium negative electrode reference first polymer electrolyte layer is disposed facing lithium and the second polymer electrolyte layer is disposed thereon is lower, and that the first polymer electrolyte layer is the first polymer electrolyte layer than the battery using only the second polymer electrolyte layer. It can be seen that the interface resistance of the battery using the polymer electrolyte layer and the second polymer electrolyte layer at the same time is lower.
  • an all-solid-state battery (Comparative Example 2, (a)) using only PEO 20 -LiFSI-X has a high positive electrode loading and a high interfacial resistance with lithium, so that the discharge capacity is 130 mAh / g. It was not expressed.
  • an all-solid-state battery (Examples 2 and (b)) in which the PEO 5 -LiFSI polymer electrolyte membrane of the present invention is applied between the lithium anode and the second polymer electrolyte PEO 20 -LiFSI-X (Interlayer) is lithium. It was confirmed that the interfacial resistance with and the discharge overvoltage is reduced significantly, and sufficient discharge capacity of 155 mAh / g is implemented. Therefore, when the PEO 5 -LiFSI polymer electrolyte membrane, which is the first polymer electrolyte, is applied to a battery, output characteristics and energy density can be improved.

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Abstract

La présente invention porte sur un électrolyte polymère pour batterie tout solide présentant une structure multicouche, et plus précisément sur un électrolyte polymère présentant une structure multicouche qui comprend une première couche d'électrolyte polymère et une deuxième couche d'électrolyte polymère, le rapport molaire EO : Li entre un polymère à base de poly(oxyde d'éthylène) (PEO) et un sel de lithium (Li) étant différent entre les première et deuxième couches d'électrolyte polymère. L'application de l'électrolyte polymère solide de la présente invention à la batterie tout solide peut réduire de façon remarquable la résistance interfaciale avec le lithium et la surtension de décharge, ce qui permet d'obtenir une capacité de décharge suffisante, et peut améliorer les caractéristiques de sortie et la densité d'énergie.
PCT/KR2016/012283 2015-10-30 2016-10-28 Électrolyte polymère à structure multicouche, et batterie tout solide le comprenant WO2017074116A1 (fr)

Priority Applications (4)

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CN201680033253.6A CN107636880B (zh) 2015-10-30 2016-10-28 具有多层结构的聚合物电解质及包含其的全固体电池
JP2017558637A JP6450030B2 (ja) 2015-10-30 2016-10-28 多層構造のポリマー電解質及びこれを含む全固体電池
EP16860299.3A EP3285324B1 (fr) 2015-10-30 2016-10-28 Électrolyte polymère à structure multicouche, et batterie tout solide le comprenant
US15/572,851 US10522872B2 (en) 2015-10-30 2016-10-28 Polymer electrolyte having multi-layer structure, and all-solid battery comprising same

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Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN111566866A (zh) * 2018-10-31 2020-08-21 株式会社Lg化学 具有差异离子电导率的电解质和包含该电解质的锂二次电池
EP3944388A1 (fr) * 2020-07-22 2022-01-26 ETH Zurich Procédé, dispositif de revêtement et préparation de formation de couches fonctionnelles d'un dispositif de stockage électrochimique
CN114006033A (zh) * 2021-10-12 2022-02-01 东南大学 固态电解质表面盐包聚合物界面保护层及其制备方法

Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH05298915A (ja) * 1992-04-16 1993-11-12 Japan Energy Corp 電解質複合体
KR960027037A (ko) * 1994-12-30 1996-07-22 이정성 복합 고분자 전해질을 갖는 전지(電池)
KR20100098548A (ko) * 2007-12-21 2010-09-07 바티움 캐나다 인크. 리튬 폴리머 배터리용 전해질
KR20130042513A (ko) * 2013-03-08 2013-04-26 주식회사 아모그린텍 다성분계 나노 복합산화물 분말을 이용한 박막 전지 및 그 제조방법
KR20150101235A (ko) * 2014-02-26 2015-09-03 서강대학교산학협력단 고체 고분자 전해질 조성물 및 이를 포함하는 리튬 이차전지

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH05298915A (ja) * 1992-04-16 1993-11-12 Japan Energy Corp 電解質複合体
KR960027037A (ko) * 1994-12-30 1996-07-22 이정성 복합 고분자 전해질을 갖는 전지(電池)
KR20100098548A (ko) * 2007-12-21 2010-09-07 바티움 캐나다 인크. 리튬 폴리머 배터리용 전해질
KR20130042513A (ko) * 2013-03-08 2013-04-26 주식회사 아모그린텍 다성분계 나노 복합산화물 분말을 이용한 박막 전지 및 그 제조방법
KR20150101235A (ko) * 2014-02-26 2015-09-03 서강대학교산학협력단 고체 고분자 전해질 조성물 및 이를 포함하는 리튬 이차전지

Cited By (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN111566866A (zh) * 2018-10-31 2020-08-21 株式会社Lg化学 具有差异离子电导率的电解质和包含该电解质的锂二次电池
US20210066752A1 (en) * 2018-10-31 2021-03-04 Lg Chem, Ltd. Electrolyte having differential ion conductivity and lithium secondary battery comprising same
EP3736898A4 (fr) * 2018-10-31 2021-06-09 Lg Chem, Ltd. Électrolyte présentant une conductivité ionique différentielle, et batterie secondaire au lithium le comprenant
US11705578B2 (en) 2018-10-31 2023-07-18 Lg Energy Solution, Ltd. Electrolyte having differential ion conductivity and lithium secondary battery comprising same
CN111566866B (zh) * 2018-10-31 2024-01-05 株式会社Lg新能源 具有差异离子电导率的电解质和包含该电解质的锂二次电池
EP3944388A1 (fr) * 2020-07-22 2022-01-26 ETH Zurich Procédé, dispositif de revêtement et préparation de formation de couches fonctionnelles d'un dispositif de stockage électrochimique
WO2022018190A1 (fr) * 2020-07-22 2022-01-27 Eth Zurich Procédé, dispositif de revêtement et préparation de formation de couches fonctionnelles d'un dispositif de stockage électrochimique
CN114006033A (zh) * 2021-10-12 2022-02-01 东南大学 固态电解质表面盐包聚合物界面保护层及其制备方法
CN114006033B (zh) * 2021-10-12 2023-10-27 东南大学 固态电解质表面盐包聚合物界面保护层及其制备方法

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