WO2016052932A1 - 애노드, 이를 포함하는 리튬 이차 전지, 상기 리튬 이차 전지를 포함하는 전지 모듈 및 애노드의 제조방법 - Google Patents
애노드, 이를 포함하는 리튬 이차 전지, 상기 리튬 이차 전지를 포함하는 전지 모듈 및 애노드의 제조방법 Download PDFInfo
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- WO2016052932A1 WO2016052932A1 PCT/KR2015/010117 KR2015010117W WO2016052932A1 WO 2016052932 A1 WO2016052932 A1 WO 2016052932A1 KR 2015010117 W KR2015010117 W KR 2015010117W WO 2016052932 A1 WO2016052932 A1 WO 2016052932A1
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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
- H01M10/42—Methods or arrangements for servicing or maintenance of secondary cells or secondary half-cells
- H01M10/4235—Safety or regulating additives or arrangements in electrodes, separators or electrolyte
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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
- H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/13—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
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/362—Composites
- H01M4/366—Composites as layered products
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/38—Selection of substances as active materials, active masses, active liquids of elements or alloys
- H01M4/381—Alkaline or alkaline earth metals elements
- H01M4/382—Lithium
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/38—Selection of substances as active materials, active masses, active liquids of elements or alloys
- H01M4/386—Silicon or alloys based on silicon
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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
- H01M2220/00—Batteries for particular applications
- H01M2220/30—Batteries in portable systems, e.g. mobile phone, laptop
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- 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
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- 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
- Y02T—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO TRANSPORTATION
- Y02T10/00—Road transport of goods or passengers
- Y02T10/60—Other road transportation technologies with climate change mitigation effect
- Y02T10/70—Energy storage systems for electromobility, e.g. batteries
Definitions
- the present specification relates to an anode, a lithium secondary battery including the same, a battery module including the lithium secondary battery, and a method of manufacturing the anode.
- Lithium secondary batteries have been put to practical use as small, light weight and high capacity rechargeable batteries, and are used in portable electronic devices and communication devices such as small video cameras, mobile phones, and notebook computers.
- Lithium secondary batteries are energy storage devices having high energy and power, and have an advantage of higher capacity and operating voltage than other batteries.
- a high energy is a problem of the safety of the battery has a risk of explosion or fire.
- such a hybrid car has been in the spotlight, so high energy and output characteristics are required such safety can be seen more important.
- a lithium secondary battery is composed of a cathode, an anode, and an electrolyte, and transfers energy while reciprocating both electrodes such that lithium ions from the cathode active material are inserted into the anode active material, ie, carbon particles, and desorbed upon discharge by the first charge. Since it plays a role, it becomes possible to charge and discharge.
- the present specification provides an anode, a lithium secondary battery including the same, a battery module including the lithium secondary battery, and a method of manufacturing the anode.
- the present specification is a current collector; A lithium metal layer provided on the current collector; And it provides an anode comprising a silicon layer or a silicon oxide layer provided on the lithium metal layer.
- the present specification is a current collector; A lithium metal layer provided on the current collector; And a lithium-silicon composite layer provided on the lithium metal layer and containing a lithium-silicon composite in which silicon or silicon oxide is alloyed with lithium.
- the present specification provides a lithium secondary battery including the anode and the cathode, and including an electrolyte provided between the anode and the cathode.
- the present disclosure provides a battery module including the lithium secondary battery as a unit cell.
- the anode according to one embodiment of the present specification improves the chemical stability and safety of lithium metal.
- Figure 1 shows that the protective layer (passivation layer) is peeled off because the volume of the lithium metal changes with the charge and discharge of the battery.
- FIG. 3 shows that the metal layer or the metal oxide layer is not peeled from the lithium metal layer when repeatedly charging and discharging a battery including an anode according to another exemplary embodiment of the present specification.
- FIG. 5 shows that the lithium metal layer and the silicon layer do not peel off when the battery including the anode according to another exemplary embodiment of the present disclosure is repeatedly charged and discharged.
- 6 to 7 is a structure of the anode according to another embodiment of the present specification.
- a lithium metal layer a metal layer or a metal oxide layer provided on the lithium metal layer and containing a metal or metal oxide capable of alloying with lithium.
- the thickness of the anode may be 1 micrometer or more and 1,000 micrometers or less.
- the anode may be used in a battery, and the anode means an electrode which emits electrons when the battery is discharged.
- the anode may be used in a secondary battery, and the anode may refer to an electrode that emits electrons based on discharge of the battery, and may serve as a cathode (reduction electrode) when charging the battery.
- the lithium metal layer means a layer containing a lithium metal element.
- the material of the lithium metal layer may be lithium alloy, lithium metal, oxide of lithium alloy or lithium oxide.
- the lithium metal layer may be a layer composed only of lithium metal.
- a part of the lithium metal layer may be altered by oxygen or moisture or include impurities.
- Lithium metal of the lithium metal layer is a metal having a standard reduction potential of -3.040 V, and is a metal having a strong tendency to oxidize. When such lithium metal encounters a heterogeneous material that tends to oxidize, such as oxygen, sulfur, or polysulfide, oxidation (corrosion) of the lithium metal proceeds rapidly.
- a dendritic phase is formed on the surface of the lithium metal, thereby reducing the reactivity of the lithium metal.
- lithium salts having relatively stable lithium ions were used as electrode materials, as batteries of high capacity continue to be required, the necessity of stably using high capacity lithium metal as electrode materials is increasing.
- the metal layer or metal oxide layer may be a layer containing a metal or metal oxide capable of alloying with lithium.
- the metal layer or metal oxide layer may contain a metal or metal oxide that expands in volume by reacting with lithium.
- the metal layer may be a layer containing a metal capable of alloying with lithium.
- the metal layer may be a layer made of only metal capable of alloying with lithium.
- the metal oxide layer may be a layer containing a metal oxide capable of alloying with lithium.
- the metal oxide layer may be a layer made of only an oxide of a metal capable of alloying with lithium.
- the metal contained in the metal layer or the metal oxide layer is not particularly limited as long as it can be alloyed with lithium.
- the metal oxide is not particularly limited as long as the metal oxide contains at least one of silicon (Si), tin (Sn), germanium (Ge), and cobalt (Co).
- the metal layer or the metal oxide layer is any one of silicon, tin and germanium; Two or more alloys; Or at least one oxide.
- the metal layer or the metal oxide layer may be a silicon layer or a silicon oxide layer containing a silicon element as a metal capable of alloying with the lithium.
- the lithium metal layer may further include a lithium-metal composite layer provided between the metal layer or the metal oxide layer.
- the lithium-metal composite layer may be a lithium-metal composite or a lithium-metal oxide composite in which a lithium metal element of a lithium metal layer and a metal element of a metal layer or a metal oxide layer are formed at an interface between the lithium metal layer and the metal layer or metal oxide layer. It may include.
- the metal layer or the metal oxide layer is a silicon layer or a silicon oxide layer containing a silicon element as a metal capable of alloying with the lithium, the lithium metal layer and the silicon layer or silicon oxide layer It may further comprise a lithium-silicon composite layer provided between.
- the content of the lithium-metal composite formed by alloying the metal or metal oxide with lithium may be influenced by the content of the metal or metal oxide capable of alloying with lithium. Some or all of the metal or metal oxide that is alloyable with lithium included in the anode may be alloyed with lithium to form a lithium-metal composite.
- the metal layer or the metal oxide layer is a silicon layer or a silicon oxide layer containing silicon as a metal or metal oxide capable of alloying with the lithium
- the weight ratio of the lithium element and the silicon element in the anode is 100: 1 to 1 50 may be.
- the content of the lithium-silicon composite formed by alloying the silicon with lithium may be affected according to the content of silicon. Some or all of the silicon contained in the anode may be alloyed with lithium to form a lithium-silicon composite.
- the lithium-silicon composite layer may include a lithium-silicon composite or a lithium-silicon oxide composite.
- the lithium-silicon composite layer may include a lithium-silicon composite represented by the following Chemical Formula 1 or a lithium-silicon oxide composite represented by the following Chemical Formula 2.
- x is a real number of 1.0 to 4.0
- o is a real number of 0.3 to 4.0
- p is a real number of 0.1 to 2.0, respectively.
- the metal layer or the metal oxide layer may include a lithium-metal composite bonded to the metal element of the metal layer or the metal oxide layer by receiving ions containing lithium metal from the interface or electrolyte of the lithium metal layer.
- some of the metal elements of the metal layer or the metal oxide layer may combine with the received lithium-containing ions to form a lithium-metal composite or a lithium-metal oxide composite.
- the metal layer or the metal oxide layer may be formed of a lithium-metal composite or a lithium-metal oxide composite that receives lithium-containing ions from an interface or electrolyte of the lithium metal layer and is bonded to the metal element of the metal layer or the metal oxide layer.
- all of the metal elements of the metal layer or the metal oxide layer may combine with the received lithium-containing ions to form a lithium-metal composite or a lithium-metal oxide composite.
- the metal layer or the metal oxide layer is a silicon layer or silicon oxide layer containing a silicon element as a metal or metal oxide capable of alloying with the lithium
- the silicon layer or silicon oxide layer is a lithium-silicon composite or It may comprise a lithium-silicon oxide composite.
- the metal layer or the metal oxide layer is a silicon layer or a silicon oxide layer containing a silicon element as a metal or metal oxide capable of alloying with the lithium
- the silicon layer or the silicon oxide layer is an interface of the lithium metal layer or It may include a lithium-silicon composite or a metal-silicon oxide composite coupled with the silicon element of the silicon layer by receiving ions containing lithium metal from the electrolyte.
- some of the silicon elements of the silicon layer or the silicon oxide layer may be combined with the received lithium-containing ions to form a lithium-silicon composite or a metal-silicon oxide composite.
- the metal layer or the metal oxide layer is a silicon layer or silicon oxide layer containing a silicon element as a metal or metal oxide capable of alloying with the lithium
- the silicon layer or silicon oxide layer is a lithium-silicon composite or It may be made of a metal-silicon oxide composite.
- all of the silicon elements of the silicon layer may be combined with ions containing the received lithium metal to form a lithium-silicon composite or a metal-silicon oxide composite.
- lithium metal is a material having high reactivity with moisture
- the surface of the lithium metal electrode may be altered or dendritic crystals may be formed on the surface of the lithium metal electrode by reacting with moisture.
- a protective film can be formed on the lithium metal electrode, but lithium metal is lithium metal because the volume changes while repeating the charging and discharging of the battery
- the protective film provided on the garment may be peeled off.
- the anode of the present specification has the advantage that the protective metal layer or the metal oxide layer is not peeled off by the volume change of the lithium metal layer by repeated charging and charging.
- the protective metal layer or the metal oxide layer includes a metal or a metal oxide capable of alloying with lithium.
- a lithium-metal composite layer may be formed between the phosphorus metal layer or the metal oxide layer so that the interface between the lithium metal layer and the metal layer or the metal oxide layer may be maintained without peeling. Accordingly, there is an advantage that the chemical safety and stability of the lithium metal is improved.
- the metal layer or the metal oxide layer is a silicon layer containing a silicon element as a metal or metal oxide capable of alloying with the lithium
- the volume of the lithium metal layer is consumed as shown in FIGS. 4 and 5.
- the silicon element which can be alloyed with lithium of the silicon layer or the silicon oxide layer, reacts with the lithium metal element of the lithium metal layer even though it is reduced, to form a lithium-silicon composite layer at the interface between the lithium metal layer and the silicon layer or the silicon oxide layer.
- the interface between the silicon layers can be maintained without peeling off.
- Initial charge and discharge efficiency of the battery to which the anode according to an embodiment of the present disclosure can be improved. Since the interface between the lithium metal layer and the metal or metal oxide layer is maintained without peeling, the initial and cycle efficiency is improved.
- the anode may further include a current collector.
- the anode may include a current collector, a lithium metal layer provided on the current collector, and a metal layer or a metal oxide layer provided on the lithium metal layer.
- the current collector may be any material having electrical conductivity as the current collector of the anode, and may be manufactured using materials and methods generally used in the art. For example, one, two or more selected from the group consisting of carbon, stainless, nickel, aluminum, iron, and titanium may be used.
- the shape of the current collector may be various forms such as a film, a sheet, a foil, a net, a porous body, a foam, or a nonwoven fabric, respectively.
- the present specification is a current collector; A lithium metal layer provided on the current collector; And it provides an anode comprising a silicon layer or a silicon oxide layer provided on the lithium metal layer.
- the anode may further include a lithium-silicon composite layer provided between the lithium metal layer and the silicon layer or silicon oxide layer.
- the silicon layer or silicon oxide layer may include a lithium-silicon composite or a lithium-silicon oxide composite in which the silicon or silicon oxide is alloyed with lithium.
- the weight ratio of the lithium element and the silicon element in the anode may be 100: 1 to 50.
- the lithium-silicon composite layer may include a lithium-silicon composite represented by Chemical Formula 1 or a lithium-silicon oxide composite represented by Chemical Formula 2.
- a lithium metal layer a lithium metal layer; And a lithium-metal composite layer provided on the lithium metal layer and capable of alloying with lithium, the lithium-metal composite layer containing a lithium-metal composite or a lithium-metal oxide composite alloyed with lithium.
- the lithium-metal composite layer may be formed of a lithium-metal composite or a lithium-metal oxide composite by combining all of metal elements capable of alloying with lithium of the metal layer or metal oxide layer with ions containing lithium metal.
- the anode is a lithium metal layer; And a lithium-metal composite layer on the lithium metal layer.
- the lithium-metal composite layer may be a lithium-silicon composite layer containing a silicon element as a metal or metal oxide capable of alloying with lithium.
- all of the silicon elements of the silicon layer or the silicon oxide layer may be combined with ions containing lithium metal to form a lithium-silicon composite or a lithium-silicon oxide composite.
- the anode includes a lithium metal layer; And it may include a lithium-silicon composite layer on the lithium metal layer.
- the lithium-silicon composite layer may include a lithium-silicon composite represented by the following Formula 1 or a lithium-silicon oxide composite represented by the following Formula 2.
- x is a real number of 1.0 to 4.0
- o is a real number of 0.3 to 4.0
- p is a real number of 0.1 to 2.0, respectively.
- the present specification is a current collector; A lithium metal layer provided on the current collector; And a lithium-silicon composite layer provided on the lithium metal layer and containing a lithium-silicon composite in which silicon or silicon oxide is alloyed with lithium.
- the lithium-silicon composite layer may include a lithium-silicon composite represented by Chemical Formula 1 or a lithium-silicon oxide composite represented by Chemical Formula 2.
- the anode comprises a cathode, it provides a lithium secondary battery comprising an electrolyte provided between the anode and the cathode.
- the shape of the lithium secondary battery is not limited, and may be, for example, coin type, flat plate type, cylindrical type, horn type, button type, sheet type, or stacked type.
- the lithium secondary battery may be a lithium air battery.
- the cathode of the lithium secondary battery may be an air electrode.
- the lithium secondary battery may further include a tank for storing a cathode electrolyte and an anode electrolyte, and a pump for moving each electrolyte to an electrode cell, thereby manufacturing a flow battery.
- the electrolyte may be an electrolyte solution in which the anode and the cathode are impregnated.
- the lithium secondary battery may further include a separator provided between the anode and the cathode.
- the separator located between the anode and the cathode may be used as long as it separates or insulates the anode and the cathode from each other and enables ion transport between the anode and the cathode.
- it may be a non-conductive porous membrane or an insulating porous membrane. More specifically, nonwoven fabrics such as polypropylene nonwoven fabric or polyphenylene sulfide nonwoven fabric; Or the porous film of olefin resin, such as polyethylene and a polypropylene, can be illustrated, It is also possible to use these 2 or more types together.
- the lithium secondary battery may further include a cathode electrolyte on the cathode side and an anode electrolyte on the anode side separated by a separator.
- the cathode electrolyte and the anode electrolyte may each include a solvent and an electrolyte salt.
- the cathode electrolyte and the anode electrolyte may include the same or different solvents.
- the electrolyte solution may be an aqueous electrolyte solution or a non-aqueous electrolyte solution.
- the aqueous electrolyte may include water as a solvent
- the non-aqueous electrolyte may include a non-aqueous solvent as a solvent.
- the non-aqueous solvent may be selected generally used in the art, and is not particularly limited, for example, carbonate-based, ester-based, ether-based, ketone-based, organosulfur-based, organophosphorous ), Aprotic solvents, and combinations thereof.
- the electrolytic salt refers to dissociation into cations and anions in water or a non-aqueous organic solvent, and is not particularly limited as long as it can transfer lithium ions in a lithium secondary battery, and may be generally used in the art.
- the concentration of the electrolyte salt in the electrolyte solution may be 0.1 M or more and 3 M or less. In this case, the charge and discharge characteristics of the lithium secondary battery may be effectively expressed.
- the electrolyte may be a solid electrolyte membrane or a polymer electrolyte membrane.
- the material of the solid electrolyte membrane and the polymer electrolyte membrane is 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 having a conductive polymer inside the porous substrate.
- the cathode refers to an electrode that accepts electrons and reduces lithium-containing ions when the battery is discharged in a lithium secondary battery. On the contrary, when the battery is charged, the cathode active material is oxidized to emit electrons and lose lithium-containing ions.
- the cathode may include a cathode current collector and a cathode active material layer formed on the cathode current collector.
- the material of the cathode active material of the cathode active material layer is not particularly limited as long as it is applied to a lithium secondary battery together with the anode to reduce lithium-containing ions during discharge and to be oxidized during charging.
- the present specification provides a battery module including the lithium secondary battery as a unit cell.
- the battery module may be formed by stacking 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 cathode included in each of the lithium air batteries.
- it may comprise porous stainless steel or porous ceramics.
- the battery module may be used as a power source for an electric vehicle, a hybrid electric vehicle, a plug-in hybrid electric vehicle, or a power storage device.
- the metal layer or the metal oxide layer may be a silicon layer or a silicon oxide layer containing a silicon element as a metal or metal oxide capable of alloying with the lithium.
- the method of attaching the lithium metal layer and the metal layer or the metal oxide layer may be compressed by pressure or thermocompressed by heat and pressure.
- the metal layer or the metal oxide layer may be a silicon layer or a silicon oxide layer containing a silicon element as a metal or metal oxide capable of alloying with the lithium.
- the method of forming a metal layer or a metal oxide layer on the lithium metal layer may be formed by depositing a metal or metal oxide on the lithium metal layer or applying a composition including the metal or metal oxide on the lithium metal layer.
- composition including the metal or metal oxide may further include a binder resin.
- the composition may include silicon or silicon oxide, a binder resin and a solvent.
- the binder resin may include polyvinylidene fluoride (PVdF).
- the content of the binder resin may be 5 parts by weight to 20 parts by weight.
- the metal layer or the metal oxide layer may be a silicon layer or a silicon oxide layer containing a silicon element as a metal or metal oxide capable of alloying with the lithium.
- a lithium metal layer may be formed by depositing lithium metal, applying soft lithium metal, or sputtering.
- the metal layer or the metal oxide layer is a silicon layer or silicon oxide layer containing a silicon element as a metal or metal oxide capable of alloying with the lithium
- the silicon layer or silicon oxide layer is formed by depositing silicon, or a silane-based It can be prepared by depositing or applying a compound to form a layer and reducing it.
- the silane-based compound may include an organic compound in which silicon hydride (Si n H 2n +2 ) and hydrogen atoms of the silicon hydride are substituted with a hydrocarbon group, a halogen group, an alkoxy group, a hydroxy group, and the like.
- Chlorosilane, dichlorosilane, trichlorosilane, tetraalkylsilane, chlorotrialkylsilane, dichlorodialkylsilane and trichloroalkylsilane may include, but are not limited to.
- the hydrocarbon group is a functional group of an organic compound consisting of only carbon and hydrogen, and the hydrocarbon group is any one or two of linear or branched alkyl, alkenyl, fluorene, cycloalkyl and aryl groups. The group mentioned above may be connected.
- the halogen group may be fluorine, chlorine, bromine, iodine or the like, but is not limited thereto.
- the alkoxy group preferably has 1 to 12 carbon atoms, more specifically methoxy, ethoxy, isopropyloxy, and the like, but is not limited thereto.
- the alkyl group may be linear or branched chain, carbon number is not particularly limited, but is preferably 1 to 12. Specific examples include, but are not limited to, methyl, ethyl, propyl, isopropyl, butyl, t-butyl, pentyl, hexyl, heptyl, and the like.
- the alkenyl group may be linear or branched chain, carbon number is not particularly limited, but is preferably 2 to 12. Specific examples thereof include butenyl group; Pentenyl group; Or alkenyl group, such as a stilbenyl group (stylbenyl), styrenyl group (styrenyl) is connected, but is not limited thereto.
- the fluorenyl group is a structure in which two ring organic compounds are connected through one atom, for example Etc.
- the fluorenyl group includes a structure of an open fluorenyl group, wherein the open fluorenyl group is a structure in which one ring compound is disconnected in a structure in which two ring compounds are connected through one atom, For example Etc.
- the cycloalkyl group may be monocyclic or polycyclic, and the number of carbon atoms is not particularly limited, but is preferably 6 to 40. Specific examples include, but are not limited to, cyclopropyl group, cyclobutyl group, cyclopentyl group, cyclohexyl group, cycloheptyl group, and the like.
- the aryl group may be monocyclic or polycyclic, and the carbon number is not particularly limited, but is preferably 6 to 40.
- the monocyclic aryl group include phenyl group, biphenyl group, terphenyl group, stilbene, and the like.
- the polycyclic aryl group include naphthyl group, anthracenyl group, phenanthrene group, pyrenyl group, perrylenyl group, and cryo. Although a cenyl group, a fluorene group, etc. are mentioned, It is not limited to this.
- the description of the lithium metal layer and the metal layer or metal oxide layer may be cited above.
- the anode was manufactured by forming a passivation layer by coating a composition including silicon and PVdF in a 90:10 weight ratio on a lithium foil by 10 ⁇ m.
- An anode was prepared by forming a protective layer having a thickness of 10 ⁇ m using a lithium phosphorous oxynitride (LiPON) as a sputter instead of the protective layer of Example 1 on a lithium foil.
- LiPON lithium phosphorous oxynitride
- the efficiency of the battery was constituted by the battery cell under the following conditions, and the cycle efficiency characteristics were measured. The results are shown in Table 1 below.
- Electrolyte Carbonate-based electrolyte and solvent containing lithium salt
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Abstract
Description
Claims (12)
- 집전체;상기 집전체 상에 구비된 리튬금속층; 및상기 리튬금속층 상에 구비된 실리콘층 또는 실리콘옥사이드층을 포함하는 애노드.
- 청구항 1에 있어서, 상기 리튬금속층과 상기 실리콘층 또는 실리콘옥사이드층 사이에 구비된 리튬-실리콘 복합체층을 더 포함하는 것인 애노드.
- 청구항 1에 있어서, 상기 실리콘층 또는 실리콘옥사이드층은 상기 실리콘 또는 실리콘옥사이드가 리튬과 합금화된 리튬-실리콘 복합체를 포함하는 것인 애노드.
- 청구항 1에 있어서, 상기 애노드 중 리튬 원소와 규소 원소의 중량비는 100: 1 내지 50인 것인 애노드.
- 청구항 2에 있어서, 상기 리튬-실리콘 복합체층은 하기 화학식 1로 표시되는 리튬-실리콘 복합체 또는 하기 화학식 2로 표시되는 리튬-실리콘옥사이드 복합체를 포함하는 것인 애노드:[화학식 1]LixSi[화학식 2]LioSiOp상기 화학식 1 및 2에서, x는 1.0 내지 4.0인 실수이고, o는 각각 0.3 내지 4.0인 실수이며, p는 각각 0.1 내지 2.0인 실수이다.
- 집전체;상기 집전체 상에 구비된 리튬금속층; 및상기 리튬금속층 상에 구비되고 실리콘 또는 실리콘옥사이드가 리튬과 합금화된 리튬-실리콘 복합체를 함유하는 리튬-실리콘 복합체층을 포함하는 애노드.
- 청구항 6에 있어서, 상기 리튬-실리콘 복합체층은 하기 화학식 1로 표시되는 리튬-실리콘 복합체 또는 하기 화학식 2로 표시되는 리튬-실리콘옥사이드 복합체를 포함하는 것인 애노드:[화학식 1]LixSi[화학식 2]LioSiOp상기 화학식 1 및 2에서, x는 1.0 내지 4.0인 실수이고, o는 각각 0.3 내지 4.0인 실수이며, p는 각각 0.1 내지 2.0인 실수이다.
- 청구항 1 내지 7 중 어느 한 항에 따른 애노드; 및 캐소드를 포함하고,상기 애노드와 캐소드 사이에 구비된 전해질을 포함하는 것인 리튬 이차 전지.
- 청구항 8에 있어서, 상기 전해질은 상기 애노드 및 캐소드가 함침된 전해질액인 것인 리튬 이차 전지.
- 청구항 9에 있어서, 상기 리튬 이차 전지는 상기 애노드와 캐소드 사이에 구비된 분리막을 더 포함하는 것인 리튬 이차 전지.
- 청구항 8에 있어서, 상기 전해질은 고체 전해질막 또는 고분자 전해질막인 것인 리튬 이차 전지.
- 청구항 8의 리튬 이차 전지를 단위 전지로 포함하는 전지 모듈.
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CN201580052138.9A CN106716686B (zh) | 2014-09-29 | 2015-09-24 | 负极、包含该负极的锂二次电池、包含该锂二次电池的电池模块以及制造该负极的方法 |
US15/510,813 US10199693B2 (en) | 2014-09-29 | 2015-09-24 | Anode, lithium secondary battery comprising same, battery module comprising the lithium secondary battery, and method for manufacturing anode |
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