WO2020091479A1 - Électrode au lithium et batterie secondaire au lithium la comprenant - Google Patents

Électrode au lithium et batterie secondaire au lithium la comprenant Download PDF

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Publication number
WO2020091479A1
WO2020091479A1 PCT/KR2019/014641 KR2019014641W WO2020091479A1 WO 2020091479 A1 WO2020091479 A1 WO 2020091479A1 KR 2019014641 W KR2019014641 W KR 2019014641W WO 2020091479 A1 WO2020091479 A1 WO 2020091479A1
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Prior art keywords
lithium
protective layer
ion
electrically conductive
electrolyte
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PCT/KR2019/014641
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English (en)
Korean (ko)
Inventor
박은경
장민철
정보라
윤석일
손병국
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주식회사 엘지화학
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Application filed by 주식회사 엘지화학 filed Critical 주식회사 엘지화학
Priority to PL19877644.5T priority Critical patent/PL3745506T3/pl
Priority to EP19877644.5A priority patent/EP3745506B1/fr
Priority to ES19877644T priority patent/ES2925381T3/es
Priority to CN201980012939.0A priority patent/CN111712949B/zh
Priority to US16/975,333 priority patent/US11978852B2/en
Priority claimed from KR1020190137931A external-priority patent/KR102388263B1/ko
Publication of WO2020091479A1 publication Critical patent/WO2020091479A1/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
    • H01M10/42—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
    • H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
    • H01M4/134—Electrodes based on metals, Si 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 electrode having a protective layer capable of preventing the growth of lithium dendrites and a lithium secondary battery comprising the same.
  • Lithium metal compared to other electrochemical systems with lithium intercalated carbon anodes, and nickel or cadmium electrodes, for example, reducing the energy density of the cell by increasing the weight and volume of the anode in the presence of a non-electroactive material Since it has low weight and high capacity characteristics, it is very interesting as an anode active material for electrochemical cells.
  • a lithium metal negative electrode, or a negative electrode mainly containing lithium metal provides an opportunity to construct a lighter and higher energy density battery than a battery such as a lithium-ion, nickel metal hydride, or nickel-cadmium battery.
  • lithium ion batteries have an energy density of 700 wh / l using graphite as a cathode and lithium cobalt oxide (LCO) as a cathode.
  • LCO lithium cobalt oxide
  • a field requiring a high energy density has been expanded, and the need to increase the energy density of a lithium ion battery has been continuously raised. For example, it is necessary to increase the energy density to increase the mileage to 500 km or more per charge of an electric vehicle.
  • lithium electrodes are increasing to increase the energy density of lithium ion batteries.
  • lithium metal is a metal that is highly reactive and difficult to handle, which is difficult to handle in a process.
  • a lithium metal When a lithium metal is used as the negative electrode of a lithium secondary battery, the lithium metal reacts with impurities such as an electrolyte, water or an organic solvent, and a lithium salt to form a solid electrolyte interphase (SEI).
  • SEI solid electrolyte interphase
  • Such a passivation layer causes a difference in the current density on the local area to promote the formation of dendritic dendrites by lithium metal during charging, and gradually grows during charging and discharging to cause an internal short circuit between the anode and the cathode.
  • dendrites have mechanically weak necks (bottle neck) to form inert lithium (dead lithium) that loses electrical contact with the current collector during discharge, thereby reducing the capacity of the battery, shortening the cycle life, and stability of the battery. Has a bad effect on
  • Korean Patent Publication No. 2018-0032168 relates to a negative electrode including a multiple protective layer, and a protective layer that protects a lithium metal layer and maintains an interface with the lithium metal layer, a protective layer that physically suppresses the growth of dendrites And by forming a multiple protective layer including a protective layer for supporting the structure of the protective layer, it is disclosed that the problem of volume expansion of the cell due to lithium dendrites can be solved.
  • Patent Document 1 Korean Patent Publication No. 2018-0032168
  • Patent Document 2 Korean Patent Publication No. 2018-0036564
  • the present inventors formed a protective layer on the lithium electrode, but sequentially from the surface of the lithium metal, a first protective layer having excellent ion conductivity and excellent electrical conductivity and physical strength A multiple protective layer including a second protective layer was formed on the lithium electrode.
  • the multiple layers of protection can suppress the growth of lithium dendrites in the lithium electrode and minimize the growth of lithium dendrites even when defects occur.
  • an object of the present invention is to provide a lithium electrode having multiple protective layers.
  • Another object of the present invention is to provide a lithium secondary battery including a lithium electrode having a multiple protective layer as described above.
  • the present invention lithium metal; And a protective layer formed on at least one surface of the lithium metal, wherein the protective layer comprises: a first protective layer formed on at least one surface of the lithium metal; And a second protective layer formed on the first protective layer, wherein the first protective layer includes an ion conductive electrolyte, and the second protective layer includes an electrically conductive matrix and a crosslinked ion conductive electrolyte. electrode.
  • the present invention also provides a lithium secondary battery comprising a lithium electrode comprising the lithium electrode.
  • the lithium electrode is formed of multiple protective layers including first and second protective layers sequentially formed on the surface of the lithium metal, and the lithium metal during charging and discharging by the first protective layer in contact with the lithium metal It can prevent the volume change.
  • the first protective layer since the second protective layer is in the form of an ion conductive electrolyte cross-linked inside and on the surface of the electrically conductive matrix, the first protective layer has a higher ion conductivity than the second protective layer, and thus is formed from the lithium metal.
  • the growth of lithium dendrites can be suppressed by preventing electrons from being focused with the lithium dendrites.
  • the second protective layer is formed on the first protective layer, and is electrically connected to lithium metal as charging and discharging proceeds, so that lithium dendrites are included only inside the first protective layer, and lithium outside the lithium electrode. Dendrites can be prevented from growing.
  • the second protective layer may further enhance the lithium dendrite growth suppression effect by mechanically suppressing the growth of lithium dendrites due to its excellent strength.
  • FIG. 1 is a schematic diagram of a lithium electrode according to an embodiment of the present invention.
  • FIG. 2 is a schematic view showing the principle of preventing the growth of lithium dendrites in a lithium electrode according to an embodiment of the present invention.
  • the present invention is a lithium metal; And it relates to a lithium electrode including a multiple protective layer formed on the lithium metal, the multiple protective layer includes a first protective layer and a second protective layer sequentially stacked on at least one surface of the lithium metal.
  • the second protective layer 22 may appear to have two layers formed, but as will be described later, a cross-linked ion conductive electrolyte is also formed inside the electrically conductive matrix, and an ion conductive electrolyte is also formed on the surface to form two layers. It is to be seen only, reference numeral 22 in the illustrated drawing refers to one layer called the second protective layer.
  • FIG. 1 is a schematic diagram of a lithium electrode according to an embodiment of the present invention.
  • a lithium electrode 1 includes a lithium metal 10; A first protective layer 21 formed on one surface of the lithium metal 10; And a second protective layer 22 formed on the first protective layer 21.
  • the first protective layer 21 and the second protective layer 22 including the multiple protective layer 20 are referred to.
  • FIG. 2 is a schematic view showing the principle of preventing the growth of lithium dendrites in a lithium electrode according to an embodiment of the present invention.
  • lithium dendrites 11 are formed on one surface of the lithium metal 10 to be in electrical contact with the second protective layer 22.
  • the electrons (e ⁇ ) of the second protective layer 22 having excellent electrical conductivity are uniformly transmitted to the entire surface and the ionic conductivity of the first protective layer 21 is higher than that of the second protective layer 22, lithium ions It is reduced in the first protective layer 21 rich in (Li + ), so that the lithium dendrites 11 are formed only inside the first protective layer 21 and the lithium dendrites grow outside the lithium electrode 1. Can be prevented.
  • the first protective layer is formed on at least one surface of the lithium metal, it is possible to prevent the phenomenon of depletion of lithium ions on the surface of the lithium metal.
  • the first protective layer may include an ion conductive electrolyte, and the ion conductive electrolyte may include an ion conductive polymer.
  • the ion-conducting polymer includes polyethylene oxide (Poly (ethylene oxide): PEO), polypropylene oxide (Poly (polypropylene oxide: PPO), polyacrylonitrile (PAN)) and polyvinylidene fluoride (Poly ( vinylidene fluoride): PVDF).
  • the ion-conducting electrolyte may be in a liquid, gel or solid phase, and preferably in a solid phase.
  • the ion-conducting electrolyte may include an ion-conducting polymer and a lithium salt, and if necessary, an additive may be further included.
  • the lithium salt and the additive are as described below in the description related to the second protective layer.
  • the weight ratio of the monomer constituting the ion-conducting polymer and lithium may be 10 to 30: 1, preferably 15 to 25: 1, and when the weight ratio is satisfied, an excellent ion conductivity and a lithium dendrite suppression effect may be best.
  • the ion-conducting polymer may have a weight ratio of 10 to 30: 1 of ethyl oxide and lithium.
  • the ion conductivity of the first protective layer may be 10 -5 to 10 -2 S / cm, preferably 10 -4 to 10 -3 S / cm. If the amount is less than the above range, lithium ion may be depleted on the surface of the lithium metal, and thus battery performance may be deteriorated. If the ion conductivity is increased, battery performance is not further improved.
  • the second protective layer is formed on the first protective layer, and electrons are transferred to the surface of the lithium metal having a relatively large amount of lithium ions compared to the second protective layer, that is, the first protective layer.
  • the electrons By preventing the electrons from being focused on the lithium dendrites generated in the first protective layer, it serves to suppress the growth of lithium dendrites.
  • the second protective layer may include an electrically conductive matrix and a crosslinked ion conductive electrolyte.
  • the electrically conductive matrix may be in the form of a three-dimensional structure in which an internal space is formed.
  • the interior space may be referred to as pore.
  • An ion conductive electrolyte may be filled in the inner space of the electrically conductive matrix, and the electrically conductive matrix is enclosed by the crosslinked ion conductive electrolyte, that is, the crosslinked ion conductive electrolyte on the surface of the electrically conductive matrix It may be formed.
  • the electrical conductivity can be made uniform on the surface of the lithium electrode, thereby suppressing the growth of lithium dendrites.
  • the growth of lithium dendrites can be suppressed, thereby preventing the occurrence of dead lithium in electrical contact.
  • the weight ratio of the ion conductive polymer contained in the ion conductive electrolyte cross-linked with the electrically conductive matrix may be 3: 7 to 7: 3.
  • the electrically conductive matrix exceeds the prescribed weight range as described above, the content of the ion-conducting polymer is relatively reduced, so the Li ion conductivity of the protective layer is very low, and more Li grows on the protective layer, resulting in the growth of Li dendrites. It is difficult to suppress.
  • the electrically conductive matrix is outside the prescribed weight range as described above and is smaller than the appropriate weight, vertical / horizontal electrical conductivity may be lowered and uniform electron transfer to the electrode surface may be difficult.
  • the crosslinked ion-conducting electrolyte may be in a solid phase, and the ion-conducting electrolyte may include 25 to 50% by weight of the remaining components excluding the solvent in the electrolyte together with the ion-conducting polymer. In other words, compared to 100% by weight of the ion conductive polymer, the content of the remaining components excluding the solvent in the electrolyte may be 25 to 50% by weight. At this time, the remaining components other than the solvent in the electrolyte may be a lithium salt and an additive.
  • the weight ratio of the monomer constituting the ion-conducting polymer and lithium may be 10 to 30: 1, preferably 15 to 25: 1, and when the weight ratio is satisfied, an excellent electrical conductivity and a lithium dendrite suppression effect may be best.
  • the ion-conducting polymer may have a weight ratio of 10 to 30: 1 of ethyl oxide and lithium.
  • the crosslinked ion conductive electrolyte may include a crosslinking agent, and the crosslinking agent is polyethylene glycol diacrylate (PEGDA), polyethylene glycol dimethacrylate (PEGDMA). ), Polypropylene glycol diacrylate (Poly (propylene glycol) diacrylate: PPGDA) and polypropylene glycol dimethacrylate (Poly (propylene glycol) dimethacrylate: PPGDMA).
  • PEGDA polyethylene glycol diacrylate
  • PEGDMA polyethylene glycol dimethacrylate
  • PPGDA polypropylene glycol diacrylate
  • PPGDMA polypropylene glycol dimethacrylate
  • the weight ratio of the ion conductive polymer and the crosslinking agent may be 70 to 90: 10 to 30, and when the weight ratio range is satisfied, a crosslinked ion conductive electrolyte layer that is effective in suppressing lithium dendrite growth may be formed because of excellent modulus.
  • the ion conductive electrolyte exhibits a crosslinked form as described above, so that the ion conductivity is lower than that of the first protective layer including the non-crosslinked ion conductive electrolyte.
  • the sheet resistance of the second protective layer is 5 x 10 -2 ⁇ / sq. To 1000 ⁇ / sq., Preferably 1 ⁇ 10 -2 ⁇ / sq. To about 500 ⁇ / sq, more preferably from 1 x 10 -. 2 ⁇ / sq. To 300 ⁇ / sq. If it is less than the above range, it is difficult to suppress the growth of Li dendrites because there is more Li growing on the protective layer, and if it is above the range, the life characteristics of the battery may be deteriorated by acting as a large resistance layer.
  • the ion conductivity of the second protective layer is 1x10 -6 S / cm to 1x10 -2 S / cm at room temperature, preferably 1x10 -5 S / cm to 1x10 -2 S / cm, more preferably May be 1x10 -4 S / cm to 1x10 -2 S / cm. If it is less than the above range, the ion conductivity is not good, so there is more Li growing on the protective layer, so it is difficult to suppress the growth of Li dendrites, and a protective layer exceeding the above range cannot be formed.
  • the ion conductivity of the second protective layer may mean vertical lithium ion conductivity.
  • the ionic conductivity of the first protective layer is higher than the ionic conductivity of the second protective layer.
  • the electrically conductive material included in the electrically conductive matrix is uniformly distributed while forming a three-dimensional structure throughout the electrically conductive matrix, so that the protective layer can exhibit uniform electrical conductivity.
  • the electrically conductive material may be at least one selected from the group consisting of electrically conductive metals, semiconductors, and electrically conductive polymers.
  • the electrically conductive metal may be at least one selected from the group consisting of copper, gold, silver, aluminum, nickel, zinc, carbon, tin and indium.
  • the semiconductor may be one or more selected from the group consisting of silicon and germanium.
  • the electrically conductive polymer is PEDOT (poly (3,4-ethylenedioxythiophene)), polyaniline, polypyrrole, polythiophene, polyacetylene, polyphenylene and polyphenylene It may be at least one selected from the group consisting of poly (thienylene vinylene).
  • the ion conductive electrolyte contained in the electrically conductive matrix may include an ion conductive polymer.
  • the ion-conducting polymer includes polyethylene oxide (Poly (ethylene oxide): PEO), polypropylene oxide (Poly (polypropylene oxide: PPO), polyacrylonitrile (PAN)) and polyvinylidene fluoride (Poly ( vinylidene fluoride): PVDF).
  • the ion-conducting electrolyte may be in a liquid, gel or solid phase.
  • the form of such an ion-conducting electrolyte may be determined according to the properties of the ion-conducting polymer.
  • the liquid or gel electrolyte contained in the liquid or gel ion conductive electrolyte may further include a lithium salt, a non-aqueous solvent, and additional additives.
  • the solid phase ion conductive electrolyte may further include a lithium salt and additional additives.
  • the lithium salt is LiCl, LiBr, LiI, LiNO 3 , 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 carboxylate, 4-phenyl lithium borate And it may be one or more selected from the group consisting of lithium imide.
  • non-aqueous solvent included in the ion conductive electrolyte those commonly used in electrolytes for lithium secondary batteries can be used without limitation, for example, ether, ester, amide, linear carbonate, cyclic carbonate, etc., respectively, alone or It can be used by mixing two or more kinds. Among them, a cyclic carbonate, a linear carbonate, or a carbonate compound that is a slurry thereof may be included.
  • cyclic carbonate compound examples include ethylene carbonate (EC), propylene carbonate (PC), 1,2-butylene carbonate, 2,3-butylene carbonate, 1,2-pentylene carbonate, 2,3-pentylene carbonate, vinylene carbonate, vinyl ethylene carbonate, and any one selected from the group consisting of halides, or a slurry of two or more of them.
  • halides include, but are not limited to, fluoroethylene carbonate (FEC).
  • linear carbonate compound may be any one selected from the group consisting of dimethyl carbonate (DMC), diethyl carbonate (DEC), dipropyl carbonate, ethylmethyl carbonate (EMC), methylpropyl carbonate and ethylpropyl carbonate or these Among them, two or more kinds of slurries may be used, but are not limited thereto.
  • the carbonate-based organic solvents ethylene carbonate and propylene carbonate, which are cyclic carbonates, are high-viscosity organic solvents and have a high dielectric constant, so that lithium salts in the electrolyte can be better dissociated, such as dimethyl carbonate and diethyl carbonate.
  • a low-viscosity, low-permittivity linear carbonate is mixed and used in an appropriate ratio, an electrolyte having a higher electrical conductivity can be prepared.
  • any one selected from the group consisting of dimethyl ether, diethyl ether, dipropyl ether, methylethyl ether, methylpropyl ether and ethylpropyl ether, or two or more of them may be used. , But is not limited thereto.
  • esters include methyl acetate, ethyl acetate, propyl acetate, methyl propionate, ethyl propionate, propyl propionate, ⁇ -butyrolactone, ⁇ -valerolactone, and ⁇ -caprolactone.
  • ⁇ -valerolactone and ⁇ -caprolactone any one selected from the group or two or more of them may be used, but is not limited thereto.
  • the additive included in the ion conductive electrolyte may be at least one selected from the group consisting of fluoroethylene carbonate (FEC), 1,3-propanesultone (1,3-PS) and vinyl ethylene carbonate (VEC), , Preferably fluoroethylene carbonate (FEC).
  • the content of the additive may be 2 to 13% by weight, preferably 3 to 10% by weight, more preferably 4 to 8% by weight based on the total weight of the electrolyte. If it is within the above range, the life characteristics of the lithium secondary battery can be improved, and the thickness expansion rate of the lithium secondary battery can be reduced.
  • the present invention also relates to a method of manufacturing a lithium electrode, (A) forming a first protective layer on a lithium metal; (B) forming a second protective layer on the release film; And (C) transferring the second protective layer on the first protective layer.
  • a first protective layer may be formed on the lithium metal.
  • the first protective layer includes an ion conductive electrolyte as described above, and the ion conductive electrolyte includes an ion conductive polymer.
  • a mixed solution is formed and applied onto the release film to form an ion-conductive electrolyte layer, and then transferred to lithium metal to form a first protective layer.
  • the ion-conductive polymer may be dissolved in an electrolyte solution to form a mixed solution, and applied to a lithium electrode to form a first protective layer.
  • the concentration of the mixed solution may be 15 to 35% by weight based on the weight of the solid content, in this case, the first protective layer forming process can be made smoothly, and the defective rate of the manufactured first protective layer can also be reduced. have.
  • the material and thickness of the release film are not particularly limited, and various films may be used.
  • a polyethylene terephthalate (PET) film, a polyethylene (PE) film, a polypropylene (PP) film, a silicone-based release film, etc. can be used, and the release film thickness is, for example, 12 ⁇ m to 80 ⁇ m.
  • the coating method may be solution casting, spray casting, spraying or rolling, but is not limited thereto.
  • the first protective layer may be in the form of a layer or a film, and an initiator may be used together so that such a form is well formed.
  • the initiators are azobisisobutyronitrile, benzoyl peroxide, t-butylperoxy-2-ethyl-hexanoate, cumyl peroxide, t-butyl peroxide and 1,1-di (t-butylperoxy) It may be one or more selected from the group consisting of cyclohexane.
  • a second protective layer may be formed on the release film.
  • the second protective layer is in a form including an electrically conductive matrix and a crosslinked ion conductive electrolyte.
  • the manufacturing method of the second protective layer (b1) forming a crosslinked ion conductive electrolyte layer by coating a release film with a mixture of an ion conductive polymer, a crosslinking agent, and a lithium salt; And (b2) depositing an electrically conductive material on the crosslinked ion conductive electrolyte layer to form a second protective layer including an electrically conductive matrix and a crosslinked ion conductive electrolyte.
  • an ion conductive polymer and a crosslinking agent are dissolved in an electrolyte solution in a release film to form a mixed solution and coated on the release film to form a crosslinked ion conductive electrolyte layer.
  • the concentration of the mixed solution may be 15 to 35% by weight based on the weight of the solid content, in this case, the first protective layer forming process can be made smoothly, and the defective rate of the prepared second protective layer can also be reduced. have.
  • the material and thickness of the release film are not particularly limited, and various films may be used.
  • a polyethylene terephthalate (PET) film, a polyethylene (PE) film, a polypropylene (PP) film, a silicone-based release film, etc. can be used, and the release film thickness is, for example, 12 ⁇ m to 80 ⁇ m.
  • the coating method may be solution casting, spray casting, spraying or rolling, but is not limited thereto.
  • an initiator may be used together to form the crosslinked ion conductive electrolyte layer.
  • the initiators are azobisisobutyronitrile, benzoyl peroxide, t-butylperoxy-2-ethyl-hexanoate, cumyl peroxide, t-butyl peroxide and 1,1-di (t-butylperoxy) It may be one or more selected from the group consisting of cyclohexane.
  • an electrically conductive material may be deposited on the crosslinked ion conductive electrolyte layer to form a second protective layer including an electrically conductive matrix and a crosslinked ion conductive electrolyte.
  • particles of the electrically conductive material penetrate into the cross-linked ion conductive electrolyte layer during deposition, and particles of the electrically conductive material are inserted into the cross-linked ion conductive electrolyte layer.
  • the particles of the electrically conductive material inserted into the crosslinked ion conductive electrolyte layer may be in the form of an island or may be connected to each other to form a skeleton of a three-dimensional structure to form an electrically conductive matrix.
  • the island shape and the 3D structure may be formed together.
  • a cross-linked ion conductive electrolyte may be included in the inner space of the electrically conductive matrix, or a cross-linked ion conductive electrolyte may be formed on the surface of the electrically conductive matrix to surround the electrically conductive matrix.
  • a lithium electrode may be formed by transferring the second protective layer on the first protective layer.
  • the lithium metal may be formed on a current collector.
  • the current collector is not particularly limited as long as it has conductivity without causing a chemical change in the battery.
  • the current collector may be one or more selected from the group consisting of copper, stainless steel, aluminum, nickel, titanium, and calcined carbon.
  • the present invention also relates to a lithium secondary battery comprising a lithium electrode as described above.
  • the lithium electrode may be included as a negative electrode, and the lithium secondary battery may include an electrolyte solution provided between the negative electrode and the positive electrode.
  • the shape of the lithium secondary battery is not limited, and may be, for example, coin, flat, cylindrical, horn, button, sheet or stacked.
  • the lithium secondary battery may further include a tank for storing the positive electrode electrolyte and the negative electrode electrolyte, and a pump that moves each electrolyte solution to the electrode cell, and may be manufactured as a flow battery.
  • the electrolyte solution may be an electrolyte solution impregnated with the negative electrode and the positive electrode.
  • the lithium secondary battery may further include a separator provided between the negative electrode and the positive electrode.
  • the separator positioned between the negative electrode and the positive electrode may be used as long as it separates or insulates the negative electrode and the positive electrode from each other and enables ion transport between the negative electrode and the positive electrode.
  • it may be a non-conductive porous film or an insulating porous film. More specifically, a polymer nonwoven fabric such as a nonwoven fabric of polypropylene material or a nonwoven fabric of polyphenylene sulfide material; Alternatively, a porous film of an olefin-based resin such as polyethylene or polypropylene can be exemplified, and it is also possible to use two or more of these together.
  • the lithium secondary battery may further include a positive electrode electrolyte on the positive electrode side and a negative electrode electrolyte on the negative electrode side separated by a separator.
  • the positive electrode electrolyte and the negative electrode electrolyte may each include a solvent and an electrolytic salt.
  • the positive electrode electrolyte and the negative electrode electrolyte may be the same as or different from each other.
  • the electrolyte solution may be an aqueous electrolyte solution or a non-aqueous electrolyte solution.
  • the aqueous electrolyte solution may include water as a solvent
  • the non-aqueous electrolyte solution may include a non-aqueous solvent as a solvent.
  • the non-aqueous solvent may be selected to be generally used in the art, and is not particularly limited, for example, carbonate-based, ester-based, ether-based, ketone-based, organosulfur-based, organophosphorous ), Aprotic solvent, and combinations thereof.
  • the electrolytic salt refers to dissociation into a cation and an anion in a water or non-aqueous organic solvent, and is not particularly limited as long as it can deliver lithium ions in a lithium secondary battery, and can be selected generally used in the art.
  • the concentration of the electrolytic salt in the electrolytic solution may be 0.1 M or more and 3 M or less. In this case, charge and discharge characteristics of the lithium secondary battery can be effectively expressed.
  • the electrolyte may be a solid electrolyte membrane or a polymer electrolyte membrane.
  • the solid electrolyte membrane and the polymer electrolyte membrane are not particularly limited, and those generally used in the art may be employed.
  • the solid electrolyte membrane may include a composite metal oxide
  • the polymer electrolyte membrane may be a membrane provided with a conductive polymer inside the porous substrate.
  • the positive electrode means an electrode that accepts electrons and reduces lithium-containing ions when the battery is discharged from a lithium secondary battery. Conversely, when the battery is charged, it acts as a negative electrode (oxidizing electrode), oxidizing the positive electrode active material to release electrons and lose lithium-containing ions.
  • the positive electrode may include a positive electrode current collector and a positive electrode active material layer formed on the positive electrode current collector.
  • the material of the positive electrode active material of the positive electrode active material layer is not particularly limited as long as it is applied to a lithium secondary battery together with the negative electrode to reduce lithium-containing ions during discharge and oxidize during charging.
  • the lithium secondary battery may be a lithium-sulfur battery, and the composite material based on sulfur (S) is not particularly limited, and in the art. It is possible to select and apply a commonly used anode material.
  • the present specification provides a battery module including the lithium secondary battery as a unit battery.
  • the battery module may be formed by stacking with a bipolar plate provided between two or more lithium secondary batteries according to one embodiment of the present specification.
  • the bipolar plate may be porous to supply air supplied from the outside to the positive electrode included in each lithium air battery.
  • the bipolar plate may include porous stainless steel or porous ceramic.
  • the battery module may be specifically used as a power source for electric vehicles, hybrid electric vehicles, plug-in hybrid electric vehicles, or power storage devices.
  • a first protective layer including an ion conductive electrolyte layer was formed on one surface of a lithium metal having a thickness of 20 ⁇ m.
  • a cross-linked ion conductive electrolyte layer was formed on one surface of a silicone-based release film (SKC Hass).
  • Cu was deposited on one surface of the crosslinked ion conductive electrolyte layer. As the Cu is vacuum-deposited on one surface of the ion-conducting electrolyte layer, Cu particles penetrate the ion-conducting electrolyte layer and go inside, where the Cu particles are electrically connected to each other inside the ion-conducting electrolyte layer, so that a space is formed therein.
  • a second protective layer was prepared by forming a Cu matrix in the form of a three-dimensional structure.
  • a lithium electrode was manufactured by transferring the second protective layer on the first protective layer.
  • Li / Li Symmetric Cell was prepared. Since the first protective layer and the second protective layer function as a separator, a separate separator was not used.
  • a lithium electrode and a lithium secondary battery were manufactured in the same manner as in Example 1, except that only the ion conductive nitrile layer (first protective layer) was formed on the lithium electrode.
  • a lithium electrode and a lithium secondary battery were prepared in the same manner as in Example 1, except that only the ion conductive electrolyte layer crosslinked on the lithium electrode (unformed Cu matrix in the second protective layer) was formed.
  • a lithium electrode and a lithium secondary battery were manufactured in the same manner as in Example 1, except that the protective layer was not formed.
  • the lithium secondary battery was charged and discharged at a current of 0.5 mA / cm 2 and a capacity of 1 mAh / cm 2 at 60 ° C. to measure life characteristics.
  • a modulus was measured at 60 ° C using a dynamic viscoelasticity measuring device (DMA, PerkinElmer DMA 8000) (E ': Storage modulus, E' ': Loss modulus, tan ⁇ (E '' / E ').
  • DMA dynamic viscoelasticity measuring device
  • Table 1 shows the results of measuring the life characteristics and modulus of elasticity.

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  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Electrochemistry (AREA)
  • General Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Manufacturing & Machinery (AREA)
  • Materials Engineering (AREA)
  • Secondary Cells (AREA)

Abstract

La présente invention concerne une électrode au lithium et une batterie secondaire au lithium la comprenant, et plus particulièrement une première et une seconde couche de protection empilées de manière séquentielle sur au moins une surface d'un métal au lithium, la seconde couche de protection comprenant une matrice électriquement conductrice et un électrolyte conducteur d'ions réticulé formé sur l'intérieur et la surface de la matrice électroconductrice, et ainsi la première couche de protection présentant une conductivité ionique supérieure à celle de la seconde couche de protection. Par conséquent, la présente invention peut supprimer la croissance de dendrites de lithium en empêchant les électrons de se floquer aux dendrites de lithium formées par le métal lithium, et peut supprimer physiquement la croissance des dendrites de lithium par la seconde couche de protection en même temps.
PCT/KR2019/014641 2018-10-31 2019-10-31 Électrode au lithium et batterie secondaire au lithium la comprenant WO2020091479A1 (fr)

Priority Applications (5)

Application Number Priority Date Filing Date Title
PL19877644.5T PL3745506T3 (pl) 2018-10-31 2019-10-31 Elektroda litowa i zawierający ją akumulator litowy
EP19877644.5A EP3745506B1 (fr) 2018-10-31 2019-10-31 Électrode au lithium et batterie secondaire au lithium la comprenant
ES19877644T ES2925381T3 (es) 2018-10-31 2019-10-31 Electrodo de litio y batería secundaria de litio que comprende el mismo
CN201980012939.0A CN111712949B (zh) 2018-10-31 2019-10-31 锂电极以及包含该锂电极的锂二次电池
US16/975,333 US11978852B2 (en) 2018-10-31 2019-10-31 Lithium electrode and lithium secondary battery comprising same

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KR20180131652 2018-10-31
KR10-2018-0131652 2018-10-31
KR10-2019-0137931 2019-10-31
KR1020190137931A KR102388263B1 (ko) 2018-10-31 2019-10-31 리튬 전극 및 이를 포함하는 리튬 이차전지

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CN113789074A (zh) * 2021-07-28 2021-12-14 南京同宁新材料研究院有限公司 锂负极保护层及其制备方法和应用

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KR20190137931A (ko) 2017-05-22 2019-12-11 닛산 지도우샤 가부시키가이샤 차량의 자동 주차 제어 방법 및 자동 주차 제어 장치

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KR20180131652A (ko) 2017-05-30 2018-12-11 중부대학교 산학협력단 진세노사이드 Rd, Rg3 및 Rg5 함량이 강화된 효소처리 백삼 추출물 및 이의 제조방법

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CN113789074A (zh) * 2021-07-28 2021-12-14 南京同宁新材料研究院有限公司 锂负极保护层及其制备方法和应用
CN113789074B (zh) * 2021-07-28 2022-08-26 南京同宁新材料研究院有限公司 锂负极保护层及其制备方法和应用

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