WO2018034526A1 - 다중 보호층을 포함하는 음극 및 이를 포함하는 리튬 이차전지 - Google Patents
다중 보호층을 포함하는 음극 및 이를 포함하는 리튬 이차전지 Download PDFInfo
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- WO2018034526A1 WO2018034526A1 PCT/KR2017/008995 KR2017008995W WO2018034526A1 WO 2018034526 A1 WO2018034526 A1 WO 2018034526A1 KR 2017008995 W KR2017008995 W KR 2017008995W WO 2018034526 A1 WO2018034526 A1 WO 2018034526A1
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- 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
- H01M4/133—Electrodes based on carbonaceous material, e.g. graphite-intercalation compounds or CFx
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- 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
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- 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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- 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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- 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
- H01M4/139—Processes of manufacture
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- H—ELECTRICITY
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- 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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- 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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- 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
- H01M4/40—Alloys based on alkali metals
- H01M4/405—Alloys based on lithium
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- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/64—Carriers or collectors
- H01M4/66—Selection of materials
- H01M4/661—Metal or alloys, e.g. alloy coatings
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- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
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- H01M4/64—Carriers or collectors
- H01M4/66—Selection of materials
- H01M4/665—Composites
- H01M4/667—Composites in the form of layers, e.g. coatings
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- H—ELECTRICITY
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- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
- H01M50/40—Separators; Membranes; Diaphragms; Spacing elements inside cells
- H01M50/46—Separators, membranes or diaphragms characterised by their combination with electrodes
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- H—ELECTRICITY
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- 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
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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
- H01M2004/026—Electrodes composed of, or comprising, active material characterised by the polarity
- H01M2004/027—Negative electrodes
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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
Definitions
- the present invention relates to a negative electrode including a multiple protective layer and a lithium secondary battery including the same. More specifically, it is possible to effectively inhibit the growth of dendrite (Dendrite), to prevent degradation of the battery performance and stability when driving the battery
- the present invention relates to a negative electrode including a multiple protective layer capable of securing a lithium secondary battery including the same.
- the electrochemical device is the field that is receiving the most attention in this respect, and the development of secondary batteries that can be charged and discharged among them is the focus of attention, and in recent years to improve the capacity density and energy efficiency in the development of such R & D on the design of new electrodes and batteries is ongoing.
- lithium secondary batteries developed in the early 1990s have a higher operating voltage and a higher energy density than conventional batteries such as Ni-MH, Ni-Cd, and sulfuric acid-lead batteries that use an aqueous electrolyte solution. I am in the spotlight.
- the lithium secondary battery has a structure in which an electrode assembly including a positive electrode, a negative electrode, and a separator interposed between the positive electrode and the negative electrode is stacked or wound, and the electrode assembly is embedded in a battery case and a nonaqueous electrolyte is injected into the inside. do.
- the lithium secondary battery produces electrical energy by oxidation and reduction reactions when lithium ions are inserted / desorbed from the positive electrode and the negative electrode.
- lithium metal, carbon, and the like are used as active materials for a negative electrode of a lithium secondary battery
- lithium oxide, transition metal oxide, metal chalcogenide, conductive polymer, and the like are used as active materials for a positive electrode.
- lithium secondary batteries using lithium metal as a negative electrode attach lithium foil on a copper current collector or use a lithium metal sheet itself as an electrode.
- Lithium metal has attracted great attention as a high capacity cathode material due to its low potential and large capacity.
- lithium metal When lithium metal is used as a negative electrode, electron density nonuniformity may occur on the surface of lithium metal due to various factors when the battery is driven.
- the lithium dendrite in the form of twigs is formed on the surface of the electrode, so that protrusions are formed or grown on the surface of the electrode, thereby making the electrode surface very rough.
- These lithium dendrites along with deterioration of the cell, cause severe damage to the separator and short circuit of the cell. As a result, there is a risk of explosion and fire of the battery due to an increase in the battery temperature.
- Patent Document 1 Korean Patent Publication No. 10-1486130 "Lithium metal electrode modified with conductive polymer, manufacturing method thereof and lithium metal battery using the same"
- Patent Document 2 Korean Unexamined Patent Publication No. 10-2002-0057577 "A lithium battery negative electrode and a lithium battery comprising the same"
- lithium dendrites of the lithium secondary battery are precipitated on the surface of the negative electrode, thereby causing volume expansion of the cell. Accordingly, the present inventors have conducted various studies, and have found a way to solve the problem caused by the dendrite through the structural modification of the electrode and completed the present invention.
- an object of the present invention is to solve the problem of volume expansion of the cell due to lithium dendrites through the modification of the electrode structure, and to provide a lithium secondary battery with improved battery performance.
- the present invention is a lithium metal layer
- the protective layer is a first protective layer comprising a composite material of carbon nanotube-ion conductive polymer
- a negative electrode for a lithium secondary battery comprising a; a second protective layer comprising a composite material of carbon nanotube-electrically conductive polymer.
- the protective layer may have two or more layers in which the first protective layer and the second protective layer are alternately stacked.
- the first protective layer may have a thickness of 0.01 ⁇ 10 ⁇ m.
- the second protective layer may have a thickness of 0.01 ⁇ 10 ⁇ m.
- the composite material of the carbon nanotube-ion conductive polymer may include 0.5 to 20 parts by weight of carbon nanotubes based on 100 parts by weight of the ion conductive polymer.
- the ion conductive polymer is polyethylene oxide, polyethylene glycol, polypropylene glycol, polypropylene oxide, polyethylene succinate, polyethylene adipate, polyethylene imine, poly epichlorohydrin, poly ⁇ -propiolactone, poly N-propyl aziri Dean, polyethylene glycol diacrylate, polypropylene glycol diacrylate, polyethylene glycol dimethacrylate and polypropylene glycol dimethacrylate may include one or more selected from the group consisting of.
- the composite material of the carbon nanotube-electrically conductive polymer may include 0.5-20 parts by weight of carbon nanotubes based on 100 parts by weight of the electrically conductive polymer.
- the electrically conductive polymer may be polyaniline, polyethylenedioxythiophene, polyphenylenevinylene, polyacetylene, poly (p-phenylene), polythiophene, poly (3-alkylthiophene), poly (3-alkoxyti).
- the present invention is a lithium metal layer
- the temporary protective metal may form an alloy with lithium metal or may diffuse into lithium metal,
- the protective layer is a first protective layer comprising a composite material of carbon nanotube-ion conductive polymer
- a negative electrode for a lithium secondary battery comprising a; a second protective layer comprising a composite material of carbon nanotube-electrically conductive polymer.
- the temporary protective metal may include one or more selected from the group consisting of copper, magnesium, aluminum, silver, gold, lead, cadmium, bismuth, indium, germanium, gallium, zinc, tin, and platinum.
- the present invention provides a lithium secondary battery including the negative electrode.
- the multi-layer protective layer according to the present invention prevents lithium dendrite from growing on the surface of the electrode, and the protective layer itself does not act as a resistive layer and thus does not take overvoltage during charging and discharging, thereby preventing deterioration of battery performance and stability when driving the battery. Can be secured.
- the lithium electrode including the multiple protective layer of the present invention is preferably applicable as a negative electrode of a lithium secondary battery, which is a large-capacity energy storage device from most small electronic devices using various devices, for example, lithium metal as a negative electrode. Applicable to the back.
- FIG. 1 is a schematic view of a negative electrode for a lithium secondary battery according to an embodiment of the present invention.
- FIG. 2 is a schematic view of a negative electrode for a lithium secondary battery according to an embodiment of the present invention.
- FIG 3 is a schematic view of a lithium secondary battery negative electrode according to an embodiment of the present invention.
- Figure 4 is a SEM photograph of the lithium metal prepared in (a) Example 1, (b) Example 2, (c) Example 3 and (d) Example 4.
- Figure 5 is a SEM photograph of the lithium metal prepared in (e) Example 5, (f) Example 6, (g) Example 7 and (h) Example 8.
- Figure 6 is a SEM photograph of the lithium metal prepared in (i) Comparative Example 1, (j) Comparative Example 2, (k) Comparative Example 3 and (l) Comparative Example 4.
- Figure 8 shows the charge and discharge test results of the negative electrode prepared in Examples 2, 3 and Comparative Example 2.
- a layer is referred to herein as "on" another layer or substrate, it may be formed directly on another layer or substrate, or a third layer may be interposed therebetween.
- the directional expression of the upper part, the upper part, and the upper part may be understood as meanings of the lower part, the lower part, the lower part, and the like according to the criteria.
- the expression of the spatial direction should be understood as a relative direction and should not be construed as limiting the absolute direction.
- the present invention is a lithium metal layer 110;
- the protective layer includes a first protective layer 120 including a composite material of carbon nanotube-ion conductive polymer
- a negative electrode 100 for a lithium secondary battery comprising a; a second protective layer (130) comprising a composite material of carbon nanotube-electrically conductive polymer.
- lithium metal when used as a battery negative electrode, the following problems exist.
- a passivation layer is formed by reacting with electrolyte, water, impurities in a battery, lithium salt, and the like, and this layer causes a local current density difference to form dendritic lithium dendrite.
- the dendrite thus formed may grow and cause an internal short circuit directly between the anode and the pores of the separator, thereby causing the battery to explode.
- the first protective layer 120 including the composite material of carbon nanotube-ion conductive polymer and the second protective layer including the composite material of carbon nanotube-electrically conductive polymer on the lithium metal layer 110 By forming the 130, the growth of the dendrites can be prevented.
- FIG. 1 and 2 are views showing a negative electrode 100 for a lithium secondary battery according to an embodiment of the present invention, respectively.
- a first protective layer 120 including a composite material of carbon nanotube-ion conductive polymer and a composite material of carbon nanotube-electrically conductive polymer are formed on the lithium metal layer 110.
- the second protective layer 130 is alternately stacked in order, and the two protective layers are stacked in reverse order in the lithium secondary battery negative electrode 100 of FIG. 2.
- the first protective layer 120 and the second protective layer 130 are formed only on one surface of the lithium metal layer 110, but are not limited thereto and may be formed on both surfaces.
- the lithium metal layer 110 may use a plate-shaped lithium metal, the width can be adjusted according to the shape of the electrode to facilitate electrode production.
- the center of the tube of the carbon nanotubes is empty and the multi-walled carbon nanotubes composed of several to several tens of graphite surfaces are possible. You may.
- the first protective layer 120 including the composite material of the carbon nanotube-ion conductive polymer and the second protective layer 130 including the composite material of the carbon nanotube-electrically conductive polymer are electrolytes of the lithium metal layer 110. Or it blocks from moisture in the electrolyte and serves to suppress the production of dendrites.
- the two protective layers may be prepared as a polymer solution dispersed in a solvent to be coated on the lithium metal layer 110 through a wet process.
- the polymer or monomer may be mixed with a solvent coating solution and then formed by employing microgravure coating, comma coating, slot die coating, spray coating, dip coating, flow coating, and the like, but is not limited thereto.
- the protective layer After the protective layer is prepared by applying the composition to a glass substrate, curing and separating, but not limited thereto, the protective layer may be attached to the lithium metal layer 110 by using an adhesive component such as polydopamine, olefin elastomer, silicone elastomer, acrylic elastomer, or the like. Alternatively, the composition may be directly applied to the lithium metal layer 110 and cured.
- an adhesive component such as polydopamine, olefin elastomer, silicone elastomer, acrylic elastomer, or the like.
- the composition may be directly applied to the lithium metal layer 110 and cured.
- the protective layer includes carbon nanotubes to improve both mechanical strength and electrical conductivity, and includes an ion conductive polymer or an electrically conductive polymer for improving ion conductivity, electrical conductivity or weakening resistance, and in addition to the above configuration, a protective layer Materials that can enhance the effect of may be additionally included. As described above, since both the protective layer including the composite material of the ion conductive polymer and the protective layer including the composite material of the electrically conductive polymer are laminated, there is an effect of improving both the ion conductivity and the electrical conductivity of the protective layer.
- the first protective layer 120 may have a thickness of 0.01 ⁇ m to 10 ⁇ m.
- the thickness of the first protective layer 120 is smaller than the above range, it may be difficult to perform a function as a protective layer, and if the thickness is large, the interfacial resistance may be increased to deteriorate battery characteristics.
- the second protective layer 130 may have a thickness of 0.01 ⁇ m to 10 ⁇ m.
- the thickness of the second protective layer 130 is smaller than the above range, it may be difficult to perform a function as a protective layer, and when the thickness is large, the interface resistance may be increased to cause deterioration of battery characteristics.
- the composite material of the carbon nanotube-ion conductive polymer refers to a composite material including the carbon nanotube and the ion conductive polymer, and may further include an additional material which may improve materials or physical properties necessary for manufacturing.
- the ion conductive polymer may have a plurality of electron donor atoms or atomic groups capable of forming coordination bonds with lithium ions in the polymer chain, and may move lithium ions between coordination positions by local movement of the polymer chain segment. Which may mean a polymer.
- the composite material of the carbon nanotube-ion conductive polymer may include 0.5 to 20 parts by weight of carbon nanotubes based on 100 parts by weight of the ion conductive polymer.
- the ion conductivity may decrease. If too little carbon nanotubes are included, the mechanical strength of the protective layer may be reduced.
- the ion conductive polymer may be polyethylene oxide, polyethylene glycol, polypropylene glycol, polypropylene oxide, polyethylene succinate, polyethylene adipate, polyethyleneimine, poly epichlorohydrin, poly ⁇ -propiolactone, polyN-propylaziridine, It may include one or more selected from the group consisting of polyethylene glycol diacrylate, polypropylene glycol diacrylate, polyethylene glycol dimethacrylate and polypropylene glycol dimethacrylate.
- the ion conductive polymer may have a weight average molecular weight of 1,000,000 ⁇ 5,000,000. If the molecular weight is less than the above range, the polymer protective film may have a low strength and may dissolve upon contact with the electrolytic solution. On the contrary, if the molecular weight exceeds the above range, lithium ions may be inhibited from moving to lower the performance of the battery. use.
- the ion conductive polymer may further include a lithium salt.
- the polymer membrane in which high concentration of lithium salt is dissociated is used, the polymer membrane does not act as a resistive layer because of high ionic conductivity, and does not take overpotential during charging and discharging. It can be used more advantageously.
- the lithium salt may be any one used as the lithium salt in the battery field, and typically, LiCl, LiBr, LiI, LiClO 4 , LiBF 4 , LiB 10 Cl 10 , LiPF 6 , LiAsF 6 , LiSbF 6 , LiAlCl 4 , LiSCN, Li (FSO 2 ) 2 N, LiCF 3 CO 2 , LiCH 3 SO 3 , LiCF 3 SO 3 , LiN (SO 2 CF 3 ) 2 , LiN (SO 2 C 2 F 5 ) 2 , LiC 4 F 9 SO At least one selected from the group consisting of 3 , LiC (CF 3 SO 2 ) 3 , (CF 3 SO 2 ) 2 NLi, lithium chloroborane, lower aliphatic lithium carbonate, lithium phenyl borate imide, and combinations thereof
- Li (FSO 2 ) 2 N can be used.
- Lithium salts have different ionic conductivity depending on their type, and the interaction between lithium ions and the polymer chain can make the ionic mobility stronger or weaker, using PEO and Li (FSO 2 ) 2 N together. In this case, the optimum effect can be obtained.
- the ion conductive polymer forms an ion crosslinking network structure if necessary.
- the crosslinked network structure increases the strength of the polymer protective film, and the higher the strength, the more physically it can suppress the generation of lithium dendrites on the electrode surface, the electrolyte penetrates into the polymer film more effectively to dissolve the polymer film, etc. You can prevent it.
- the strength is increased too much, the polymer protective film becomes harder and more fragile, causing a problem that the polymer protective film is damaged by the volume change of the surface of the lithium negative electrode during charging / discharging. Therefore, in the present invention, a flexible polymer is used, and a specific polymer is selected and used so that lithium ions can move smoothly.
- This crosslinked network structure may be a bifunctional or more than one multifunctional monomer for crosslinking, preferably using an alkylene glycol diacrylate monomer.
- the composite material of the carbon nanotube-electrically conductive polymer is a composite material including the carbon nanotube and the electrically conductive polymer, and may further include an additional material that may improve materials or physical properties necessary for manufacturing.
- the electrically conductive polymer may be a polymer having a conjugated structure in which carbon-carbon single bonds and double bonds are alternately repeated, or a conjugated structure coupled with a hetero atom providing a p-orbital, and expanded ⁇ in the main chain. - May mean conductive and semiconducting organics having a conjugated system.
- the electrically conductive polymer may be doped to have charge carriers by various methods such as chemical doping, electrochemical doping, light doping, charge injection doping and non-redox doping.
- the composite material of the carbon nanotube-electrically conductive polymer may include 0.5-20 parts by weight of carbon nanotubes based on 100 parts by weight of the electrically conductive polymer. If too much carbon nanotubes are included in the above range, the interfacial resistance may be increased. If too little carbon nanotubes are included, the mechanical strength of the protective layer may be reduced.
- the electrically conductive polymer may be polyaniline, polyethylenedioxythiophene, polyphenylenevinylene, polyacetylene, poly (p-phenylene), polythiophene, poly (3-alkylthiophene), poly (3-alkoxythiophene) , Poly (crownetherthiophene), polypyrrole, poly (dialkyl-2,2'-bipyridine), polypyridine, polyalkylpyridine, poly (2,2'-bipyridine), poly (dialkyl-2, 2'-bipyridine), polypyrimidine, polydihydrophenanthrene, polyquinoline, polyisoquinoline, poly (1,2,3-benzothiadiazole), poly (benzimidazole), poly (quinoxaline) , Poly (2,3-diarylquinoxaline), poly (1,5-naphthyridine), poly (1,3-cyclohexadiene), poly (anthraquinone), poly (Z-methyl
- the electrically conductive polymer may have a weight average molecular weight of 1,000,000 ⁇ 5,000,000. If the molecular weight is less than the above range, the polymer protective film may have a low strength and may dissolve upon contact with the electrolytic solution. On the contrary, if the molecular weight exceeds the above range, lithium ions may be inhibited from moving to lower the performance of the battery. use.
- the protective layer according to the present invention may be configured by stacking two or more layers of the first protective layer 120 and the second protective layer 130, and these may be formed on the lithium metal layer 110 by the first protective layer 120 /.
- the second protective layer 130, or the second protective layer 130 / the first protective layer 120 may be stacked in this order, or alternately stacked. That is, the protective layer has a configuration of at least two layers and can be at most ten layers or less.
- the thickness of the polymer protective film having the above composition is not limited in the present invention, but has a range that does not increase the internal resistance of the battery while securing the above effects, and may be, for example, 2 to 50 ⁇ m. If the thickness is less than the above range, it may not function as a protective film. On the contrary, if the thickness exceeds the above range, stable interfacial properties may be imparted, but initial interface resistance may increase, resulting in an increase in internal resistance during battery manufacturing.
- the negative electrode 100 for a lithium secondary battery according to the present invention may have various widths and lengths depending on the shape of the battery. If necessary, the lithium secondary battery negative electrode 100 manufactured in various widths may be wound and cut as necessary.
- the present invention is a lithium metal layer 110;
- the temporary protective metal may form an alloy with lithium metal or may diffuse into lithium metal,
- the protective layer includes a first protective layer 120 including a composite material of carbon nanotube-ion conductive polymer
- a negative electrode 100 for a lithium secondary battery comprising a; a second protective layer (130) comprising a composite material of carbon nanotube-electrically conductive polymer.
- the temporary protective metal may include one or more selected from the group consisting of copper, magnesium, aluminum, silver, gold, lead, cadmium, bismuth, indium, germanium, gallium, zinc, tin, and platinum.
- the temporary protective metal layer 140 forms an alloy with the lithium metal layer 110, is dissolved in, blended with, or diffused into the negative electrode including lithium metal.
- the active layer can be obtained.
- Lithium metal is known to form alloys with certain metals, and has also been observed to alloy with or diffuse into thin films of certain other metals such as, for example, copper.
- the metal of the temporary protective metal layer 140 forms an alloy with the lithium metal layer 110.
- the metal of the temporary protective metal layer 140 is diffused into lithium metal. Interdiffusion or alloying can be assisted by heating the cathode assembly.
- the temporary protective metal layer 140 may improve characteristics of the battery by forming an alloy with the lithium metal layer 110 when charging and discharging the battery, and the two protective layers may inhibit dendrite formation and the like. The efficiency of the battery can be maximized.
- FIG 3 is a view showing a negative electrode 100 for a lithium secondary battery according to an embodiment of the present invention.
- a temporary protective metal layer 140 is stacked on the lithium metal layer 110, and the first protective layer 120 including a composite material of carbon nanotube-ion conductive polymer thereon.
- a second protective layer 130 including a composite material of a carbon nanotube-electrically conductive polymer are alternately stacked.
- the second protective layer 130 may be stacked on the temporary protective metal layer 140, and the first protective layer 120 may be stacked thereon.
- the present invention provides a lithium secondary battery comprising the negative electrode.
- Lithium secondary battery according to the present invention can be manufactured through a known technique carried out by those skilled in the art for the remaining configuration except for the structure and characteristics of the above-described negative electrode, will be described in detail below.
- Common lithium secondary battery is a negative electrode; anode; Separation membrane interposed between them; And an electrolyte; and the negative electrode of the lithium secondary battery of the present invention may include a negative electrode including the multiple protective layer of the present invention.
- the positive electrode may be manufactured in the form of a positive electrode by forming a composition including a positive electrode active material, a conductive material, and a binder on a positive electrode current collector.
- the conductive material is a component for further improving the conductivity of the positive electrode active material.
- the conductive material include graphite such as natural graphite and artificial 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 whiskers 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.
- the binder maintains a positive electrode active material in a positive electrode current collector and has a function of organically connecting the positive electrode active materials.
- PVDF polyvinylidene fluoride
- PVA polyvinyl alcohol
- CMC carboxymethyl cellulose
- starch hydroxypropyl cellulose, regenerated cellulose
- polyvinylpyrrolidone tetrafluoroethylene
- polyethylene polypropylene
- EPDM ethylene-propylene-diene polymer
- sulfonated-EPDM styrene-butadiene rubber
- fluorine Rubber these various copolymers, etc.
- the positive electrode current collector is the same as described above in the negative electrode current collector, and generally, a thin aluminum plate may be used for the positive electrode current collector.
- the positive electrode composition may be coated on a positive electrode current collector using a conventional method known in the art, and for example, a dipping method, a spray method, a roll court method, and a gravure printing method.
- a conventional method known in the art, and for example, a dipping method, a spray method, a roll court method, and a gravure printing method.
- Various methods may be used, such as a bar court method, a die coating method, a comma coating method, or a mixture thereof.
- the positive electrode and the positive electrode composition which have undergone such a coating process are then dried through evaporation of a solvent or a dispersion medium, compactness of the coating film and adhesion between the coating film and the current collector. At this time, the drying is carried out according to a conventional method, which is not particularly limited.
- the separator is not particularly limited in material, and physically separates the positive electrode and the negative electrode, and has electrolyte and ion permeability, and can be used without particular limitation as long as they are commonly used as separators in electrochemical devices, but are porous and visionary.
- As the conductive or insulating material it is particularly desirable to have low resistance to ion migration of the electrolyte solution and excellent electrolyte electrolyte moisture content.
- a polyolefin-based porous membrane or a nonwoven fabric may be used, but is not particularly limited thereto.
- polyolefin-based porous membrane examples include polyethylene, polypropylene, polybutylene, polypentene, such as high density polyethylene, linear low density polyethylene, low density polyethylene, ultra high molecular weight polyethylene, respectively, or a mixture thereof There is a curtain.
- the nonwoven fabric is, for example, polyphenyleneoxide, polyimide, polyamide, polycarbonate, polyethyleneterephthalate, polyethylenenaphthalate in addition to the aforementioned polyolefin-based nonwoven fabric.
- Polybutyleneterephthalate, polyphenylenesulfide, polyacetal, polyethersulfone, polyetheretherketone, polyester, etc. alone or in combination
- a nonwoven fabric formed of a polymer mixed therewith is possible, and the nonwoven fabric is a fiber form forming a porous web, and includes a spunbond or meltblown form composed of long fibers.
- the thickness of the separator is not particularly limited, but is preferably in the range of 1 to 100 ⁇ m, more preferably in the range of 5 to 50 ⁇ m. If the thickness of the separator is less than 1 ⁇ m can not maintain the mechanical properties, if the separator exceeds 100 ⁇ m the separator acts as a resistive layer to deteriorate the performance of the battery.
- the pore size and porosity of the separation membrane is not particularly limited, but the pore size is 0.1 to 50 ⁇ m, porosity is preferably 10 to 95%.
- the separator acts as a resistive layer, and the mechanical properties cannot be maintained when the pore size exceeds 50 ⁇ m or the porosity exceeds 95%. .
- the electrolyte may be a nonaqueous electrolyte or a solid electrolyte which does not react with lithium metal, but is preferably a nonaqueous electrolyte and includes an electrolyte salt and an organic solvent.
- the electrolyte salt contained in the nonaqueous electrolyte is a lithium salt.
- the lithium salt may be used without limitation those conventionally used in the lithium secondary battery electrolyte.
- For example is the above lithium salt anion F -, Cl -, Br - , I -, NO 3 -, N (CN) 2 -, BF 4 -, ClO 4 -, PF 6 -, (CF 3) 2 PF 4 -, (CF 3) 3 PF 3 -, (CF 3) 4 PF 2 -, (CF 3) 5 PF -, (CF 3) 6 P -, CF 3 SO 3 -, CF 3 CF 2 SO 3 - , (CF 3 SO 2) 2 N -, (FSO 2) 2 N -, CF 3 CF 2 (CF 3) 2 CO -, (CF 3 SO 2) 2 CH -, (SF 5) 3 C -, (CF 3 SO 2) 3 C - from the group consisting of -, CF 3 (CF
- organic solvent included in the non-aqueous electrolyte those conventionally used in the lithium secondary battery electrolyte may be used without limitation, and for example, ethers, esters, amides, linear carbonates, and cyclic carbonates may be used alone or in combination of two or more. Can be used. Among them, carbonate compounds which are typically cyclic carbonates, linear carbonates, or mixtures 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, vinylethylene carbonate and any one selected from the group consisting of halides thereof or mixtures of two or more thereof.
- halides include, for example, fluoroethylene carbonate (FEC), but are not limited thereto.
- 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. Mixtures of two or more of them may be representatively used, but are not limited thereto.
- ethylene carbonate and propylene carbonate which are cyclic carbonates among the carbonate-based organic solvents, have high dielectric constants and may dissociate lithium salts in the electrolyte more efficiently.
- low viscosity, low dielectric constant linear carbonate mixed in an appropriate ratio it can be made an electrolyte having a higher electrical conductivity.
- any one selected from the group consisting of dimethyl ether, diethyl ether, dipropyl ether, methylethyl ether, methylpropyl ether, and ethylpropyl ether, or a mixture of two or more thereof may be used. It is not limited to this.
- esters in the organic solvent include methyl acetate, ethyl acetate, propyl acetate, methyl propionate, ethyl propionate, propyl propionate, ⁇ -butyrolactone, ⁇ -valerolactone, ⁇ -caprolactone, ⁇
- One or more mixtures selected from the group consisting of -valerolactone and ⁇ -caprolactone may be used, but is not limited thereto.
- the injection of the nonaqueous electrolyte may be performed at an appropriate step in the manufacturing process of the electrochemical device, depending on the manufacturing process and the required physical properties of the final product. That is, it may be applied before the electrochemical device assembly or the final step of the electrochemical device assembly.
- the lithium secondary battery according to the present invention may be a lamination (stacking) and folding (folding) process of the separator and the electrode in addition to the winding (winding) which is a general process.
- the case of the battery may be cylindrical, square, pouch type or coin type.
- the lithium secondary battery including the negative electrode according to the present invention stably exhibits excellent discharge capacity, output characteristics, and capacity retention ratio, and therefore, portable devices such as mobile phones, laptop computers, digital cameras, and hybrid electric vehicles. It is useful for electric vehicle field such as vehicle, HEV) and the like.
- Example 1-8 Preparation of a negative electrode for a lithium secondary battery of the present invention Double layer )
- polyaniline (PANI) monomer and carbon nanotube (CNT) were dissolved in the same amount as the composition of Table 1 and uniformly dispersed using ultrasonic dispersion.
- a solution of carbon nanotubes and polyethylene oxide (PEO) dissolved in an acetonitrile solution in the same content as in Table 1 was uniformly mixed using ultrasonic dispersion, and the electrolyte was added at twice the weight of the polymer for 2 hours. Stirred.
- the two polymer solutions were sequentially coated on a lithium metal surface using a spin coater, and the process was performed in a dry room at room temperature in order to minimize the influence of moisture and active gases in the air.
- Comparative example 1-4 Fabrication of Anode for Comparative Lithium Secondary Battery Double layer )
- PVdF-HFP polyvinylidene fluoride-hexafluoropropylene
- the negative electrode was prepared in the same manner to form a protective layer.
- a lithium metal battery was manufactured using the negative electrodes for lithium secondary batteries, the organic electrolyte solution, and the LiCoO 2 positive electrode of Examples 1 to 8 and Comparative Examples 1 to 7.
- poly (vinylidene fluoride) polyvinylidene fluoride, PVdF
- Super-P carbon and LiCoO 2 which are conductive materials, are quantified in the mixed solution. Stirred. At this time, the weight ratio of the positive electrode active material, the conductive material, and the binder was 85: 7.5: 7.5.
- the slurry solution with complete mixing was applied to an aluminum current collector and dried, followed by a lamination process using a roll press. This is to improve the mutual bonding force of the active material / conductive material / binder and to effectively bind these materials to the current collector.
- an electrode of an appropriate size was prepared through an altar process, and dried in a vacuum oven at 110 ° C. for at least 24 hours.
- the lithium metal layers having the protective layers of Examples 1 to 8 and Comparative Examples 1 to 7 were laminated on copper foils, respectively.
- Celgard 3501 was used as a separator. All electrodes were prepared in a dry room, and the battery was fabricated in a glove box in which an argon atmosphere was maintained.
- lithium secondary battery including the negative electrodes prepared in Examples 1 to 8 and Comparative Examples 1 to 7 was performed 10 times charging and discharging under the condition of 0.5mA. Then, in order to confirm the formation of lithium dendrites, lithium metal (cathode) was separated from the battery.
- FIG. 4 shows (a) Example 1, (b) Example 2, (c) Example 3 and (d) Example 4, and FIG. 5 shows (e) Example 5, (f) Example 6, ( g) Example 7 and (h) Example 8, FIG. 6 shows (i) Comparative Example 1, (j) Comparative Example 2, (k) Comparative Example 3 and (l) Comparative Example 4, and FIG. m) SEM pictures of the lithium metal prepared in Comparative Example 5, (n) Comparative Example 6 and (o) Comparative Example 7.
- the lithium metals of Examples 1 to 3 and Example 6 having a protective film formed thereon according to the present invention showed a very smooth shape, whereas Comparative Examples 5 to 7 using a single protective film.
- a large pores of dendrite was formed.
- the battery including the negative electrodes of Examples 1 to 8 shows a lower overall resistance than the battery containing the negative electrodes of Comparative Examples 1 to 4. This means that the reaction between the lithium metal and the organic electrolyte is suppressed by the conductive polymer coated on the lithium metal, thereby suppressing the growth of the passivation layer on the lithium electrode. It also means that the conductivity of PEO on lithium metal is better than that of PVDF-HFP.
- Comparative Examples 5 to 7 using only a single protective layer the initial resistance is low, but the interface resistance increases with time, and thus it is difficult to apply to driving a battery. In other words, the coating of the conductive polymer plays a positive role in stabilizing the lithium cathode-electrolyte interface.
- Example 2 As shown in FIG. 8, it can be seen that the charge and discharge performance of Example 2 is superior to that of Example 3 having a low initial interface resistance, so that there is an appropriate content of carbon nanotubes.
- the comparative evaluation of PEO and PVDF-HFP also showed that PEO has not only low resistance but also excellent life performance. From this result, it can be seen that the protective film according to the present invention is excellent in ion transfer performance as well as suppression performance of lithium dendrites.
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Abstract
Description
혼합물 | 제1층 | 제2층 | ||
PANI(g) | CNT(g) | PEO(g) | CNT(g) | |
실시예 1 | 100 | 0.5 | 100 | 0.5 |
실시예 2 | 1 | 1 | ||
실시예 3 | 5 | 5 | ||
실시예 4 | 10 | 10 | ||
실시예 5 | 10 | 0.5 | ||
실시예 6 | 5 | 1 | ||
실시예 7 | 1 | 5 | ||
실시예 8 | 0.5 | 10 |
혼합물 | 제1층 | 제2층 | |||
PANI(g) | CNT(g) | PVDP-HFP(g) | CNT(g) | 전해액(g) | |
비교예 1 | 100 | 0.5 | 100 | 0.5 | 200 |
비교예 2 | 1 | ||||
비교예 3 | 5 | ||||
비교예 4 | 10 |
혼합물 | PEO(g) | PANI(g) | CNT(g) | 전해액(g) |
비교예 5 | 100 | 0 | 0 | 200 |
비교예 6 | 0 | 100 | 0 | |
비교예 7 | 50 | 50 | 5 |
초기 계면 저항(Ω/cm2) | 10일 후 계면 저항(Ω/cm2) | 증가율(%) | |
실시예 1 | 22.47 | 23.37 | 4.01 |
실시예 2 | 8.16 | 8.83 | 8.21 |
실시예 3 | 5.14 | 12.74 | 147.86 |
실시예 4 | 35.17 | 40.22 | 14.36 |
실시예 5 | 34.48 | 41.16 | 19.37 |
실시예 6 | 17.75 | 19.73 | 11.15 |
실시예 7 | 38.37 | 41.95 | 9.33 |
실시예 8 | 11.29 | 17.8 | 52.17 |
비교예 1 | 384.2 | 434.2 | 13.01 |
비교예 2 | 190.7 | 216.4 | 13.48 |
비교예 3 | 296.2 | 330.5 | 11.58 |
비교예 4 | 411.2 | 451.7 | 9.85 |
비교예 5 | 38.86 | 105.4 | 171.23 |
비교예 6 | 17.75 | 57.98 | 226.65 |
비교예 7 | 24.46 | 102.49 | 319.01 |
Claims (11)
- 리튬 금속층; 및상기 리튬 금속층 상에 형성된 다층 구조의 보호층;을 구비하되,상기 보호층은 탄소나노튜브-이온 전도성 고분자의 복합재료를 포함하는 제1보호층; 및탄소나노튜브-전기 전도성 고분자의 복합재료를 포함하는 제2보호층;을 포함하는 것을 특징으로 하는 리튬 이차전지용 음극.
- 제1항에 있어서,상기 보호층은 제1보호층과 제2보호층이 번갈아 적층된 2층 이상의 층을 갖는 것을 특징으로 하는 리튬 이차전지용 음극.
- 제1항에 있어서,상기 제1보호층은 두께가 0.01~10㎛인 것을 특징으로 하는 리튬 이차전지용 음극.
- 제1항에 있어서,상기 제2보호층은 두께가 0.01~10㎛인 것을 특징으로 하는 리튬 이차전지용 음극.
- 제1항에 있어서,상기 탄소나노튜브-이온 전도성 고분자의 복합재료는 이온 전도성 고분자 100중량부에 대하여 탄소나노튜브 0.5~20중량부를 포함하는 것을 특징으로 하는 리튬 이차전지용 음극.
- 제1항에 있어서,상기 이온 전도성 고분자는 폴리에틸렌옥사이드, 폴리에틸렌글리콜, 폴리프로필렌글리콜, 폴리프로필렌옥사이드, 폴리에틸렌숙시네이트, 폴리에틸렌아디페이트, 폴리에틸렌이민, 폴리에피클로로히드린, 폴리β-프로피오락톤, 폴리N-프로필아지리딘, 폴리에틸렌글리콜디아크릴레이트, 폴리프로필렌글리콜디아크릴레이트, 폴리에틸렌글리콜디메타크릴레이트 및 폴리프로필렌글리콜디메타크릴레이트로 이루어진 군으로부터 선택된 하나 이상을 포함하는 것을 특징으로 하는 리튬 이차전지용 음극.
- 제1항에 있어서,상기 탄소나노튜브-전기 전도성 고분자의 복합재료는 전기 전도성 고분자 100중량부에 대하여 탄소나노튜브 0.5~20중량부를 포함하는 것을 특징으로 하는 리튬 이차전지용 음극.
- 제1항에 있어서,상기 전기 전도성 고분자는 폴리아닐린, 폴리에틸렌디옥시티오펜, 폴리페닐렌비닐렌, 폴리아세틸렌, 폴리(p-페닐렌), 폴리티오펜, 폴리(3-알킬티오펜), 폴리(3-알콕시티오펜), 폴리(크라운에테르티오펜), 폴리피롤, 폴리(디알킬-2,2'-비피리딘), 폴리피리딘, 폴리알킬피리딘, 폴리(2,2'-비피리딘), 폴리(디알킬-2,2'-비피리딘), 폴리피리미딘, 폴리디하이드로페난트렌, 폴리퀴놀린, 폴리이소퀴놀린, 폴리(1,2,3-벤조티아디아졸), 폴리(벤즈이미다졸), 폴리(퀴녹살린), 폴리(2,3-디아릴퀴녹살린), 폴리(1,5-나프티리딘), 폴리(1,3-시클로헥사디엔), 폴리(안트라퀴논), 폴리(Z-메틸안트라퀴논), 폴리(페로센), 폴리(6,6'-비퀴놀린), 폴리페닐렌설파이드, 폴리페닐렌비닐렌, 폴리인돌, 폴리피렌. 폴리카바졸, 폴리아줄렌, 폴리아제핀, 폴리플루오렌, 폴리나프탈렌 및 폴리3,4-에틸렌디옥시티오펜-폴리스티렌설포네이트로 이루어진 군으로부터 선택된 하나 이상을 포함하는 것을 특징으로 하는 리튬 이차전지용 음극.
- 리튬 금속층;상기 리튬 금속층 상에 형성된 임시 보호 금속층; 및상기 임시 보호 금속층 상에 형성된 다층 구조의 보호층;을 구비하되,상기 임시 보호 금속은 리튬 금속과 합금을 형성할 수 있거나 또는 리튬 금속으로 확산될 수 있으며,상기 보호층은 탄소나노튜브-이온 전도성 고분자의 복합재료를 포함하는 제1보호층; 및탄소나노튜브-전기 전도성 고분자의 복합재료를 포함하는 제2보호층;을 포함하는 것을 특징으로 하는 리튬 이차전지용 음극.
- 제9항에 있어서,상기 임시 보호 금속은 구리, 마그네슘, 알루미늄, 은, 금, 납, 카드뮴, 비스무스, 인듐, 게르마늄, 갈륨, 아연, 주석 및 백금으로 이루어진 군으로부터 선택된 하나 이상을 포함하는 것을 특징으로 하는 리튬 이차전지용 음극.
- 제1항 내지 제10항 중 어느 한 항의 음극을 포함하는 리튬 이차전지.
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EP17841708.5A EP3413380B1 (en) | 2016-08-19 | 2017-08-18 | Anode comprising multiple protective layers, and lithium secondary battery comprising same |
JP2018544515A JP6685542B2 (ja) | 2016-08-19 | 2017-08-18 | 多重保護層を含む負極及びこれを含むリチウム二次電池 |
CN201780016255.9A CN108713267B (zh) | 2016-08-19 | 2017-08-18 | 包含多重保护层的负极和包括该负极的锂二次电池 |
US16/079,665 US10497930B2 (en) | 2016-08-19 | 2017-08-18 | Anode comprising multiple protective layers, and lithium secondary battery comprising same |
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JP2019175568A (ja) * | 2018-03-27 | 2019-10-10 | 本田技研工業株式会社 | リチウムイオン二次電池 |
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CN108713267B (zh) | 2021-05-11 |
EP3413380A4 (en) | 2019-06-05 |
JP2019506715A (ja) | 2019-03-07 |
CN108713267A (zh) | 2018-10-26 |
EP3413380B1 (en) | 2020-05-13 |
EP3413380A1 (en) | 2018-12-12 |
US10497930B2 (en) | 2019-12-03 |
JP6685542B2 (ja) | 2020-04-22 |
KR102140122B1 (ko) | 2020-07-31 |
US20190058185A1 (en) | 2019-02-21 |
KR20180020599A (ko) | 2018-02-28 |
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