WO2015119486A1 - 전기 화학 소자 - Google Patents
전기 화학 소자 Download PDFInfo
- Publication number
- WO2015119486A1 WO2015119486A1 PCT/KR2015/001352 KR2015001352W WO2015119486A1 WO 2015119486 A1 WO2015119486 A1 WO 2015119486A1 KR 2015001352 W KR2015001352 W KR 2015001352W WO 2015119486 A1 WO2015119486 A1 WO 2015119486A1
- Authority
- WO
- WIPO (PCT)
- Prior art keywords
- volume
- case
- electrolyte
- electrochemical device
- free space
- Prior art date
Links
Images
Classifications
-
- 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
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/058—Construction or manufacture
-
- 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
- H01M10/04—Construction or manufacture in general
- H01M10/049—Processes for forming or storing electrodes in the battery container
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/058—Construction or manufacture
- H01M10/0587—Construction or manufacture of accumulators having only wound construction elements, i.e. wound positive electrodes, wound negative electrodes and wound separators
-
- 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
- H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
- H01M4/50—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of manganese
- H01M4/505—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of manganese of mixed oxides or hydroxides containing manganese for inserting or intercalating light metals, e.g. LiMn2O4 or LiMn2OxFy
-
- 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
- H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
- H01M4/52—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron
- H01M4/525—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron of mixed oxides or hydroxides containing iron, cobalt or nickel for inserting or intercalating light metals, e.g. LiNiO2, LiCoO2 or LiCoOxFy
-
- 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
- H01M4/58—Selection of substances as active materials, active masses, active liquids of inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy; of polyanionic structures, e.g. phosphates, silicates or borates
- H01M4/583—Carbonaceous material, e.g. graphite-intercalation compounds or CFx
- H01M4/587—Carbonaceous material, e.g. graphite-intercalation compounds or CFx for inserting or intercalating light metals
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P70/00—Climate change mitigation technologies in the production process for final industrial or consumer products
- Y02P70/50—Manufacturing or production processes characterised by the final manufactured product
Definitions
- the present invention relates to an electrochemical device, and more particularly, the gas generated by the oxidation reaction of the electrolyte due to the high voltage reduces the reaction area of the electrode surface, further increases the side reactions, and can solve the problem of accelerating capacity deterioration. It is to provide a chemical device.
- Lithium secondary batteries for example, lithium ion batteries
- nickel hydride batteries and other secondary batteries are becoming increasingly important as power supplies for in-vehicle power supplies or portable terminals such as notebook computers.
- a lithium secondary battery capable of attaining a high energy density at a light weight can be preferably used as a high output power supply for a vehicle, which is expected to increase demand in the future.
- US Pat. No. 7223502 proposes a technique for reducing gas generation using an electrolyte containing a carboxylic acid ester having a unsaturated bond and a compound of a sulfone group. have.
- Korean Patent Publication No. 2011-0083970 also discloses a technique of using an electrolyte having a compound containing difluorotoluene having a low oxidation potential to improve the swelling phenomenon of the battery due to decomposition of the electrolyte in a high voltage state. .
- Korean Patent Registration No. 0760763 relates to an electrolyte for a high voltage lithium secondary battery, and includes an halogenated biphenyl and dihalogenated toluene as an additive having an oxidation reaction potential of 4.6 to 5.0 V to secure stability during overcharging of a lithium secondary battery.
- the use of electrolytes has been proposed to prevent electrolyte decomposition.
- Japanese Patent Laid-Open No. 2005-135906 relates to a lithium secondary battery including a nonaqueous electrolyte having excellent charge and discharge characteristics, and proposes a technique of adding an overcharge preventing agent to stabilize the performance of the battery at high voltage.
- An object of the present invention is to provide an electrochemical device that can solve the problem of the gas generated by the oxidation reaction of the electrolyte due to the high voltage to reduce the reaction area of the electrode surface, further increase the side reaction, to accelerate the capacity degradation.
- An electrochemical device includes a case, an electrode assembly positioned inside the case, including an anode and a cathode, and a separator interposed between the anode and the cathode, and an electrolyte injected into the case.
- the volume EV of the free space according to Equation 2 to the entire volume CV of the inner space of the case according to Equation 1 is 0 to 45% by volume.
- volume of empty space inside the case total volume inside the case (AV)-volume of the electrode assembly (BV)
- volume of free space volume of empty space inside the case (CV)-volume of electrolyte (DV)
- the volume EV of the free space with respect to the entire volume CV of the empty space inside the case may be 5 to 30% by volume.
- the volume DV of the electrolyte may be 55 to 100% by volume based on the total volume CV of the empty space inside the case.
- the volume DV of the electrolyte may be 0.5 to 10 cm 3 .
- the electrochemical device was charged at 1 ° C. at 25 ° C. and discharged at 1 ° C., and 100 cycles of the charging and discharging were repeated at 1 cycle.
- the pressure inside the case may be 1.5 to 15 times the pressure inside the case when the volume EV of the free space exceeds 45% by volume.
- the electrochemical device is charged at 1 ° C. at 25 ° C., discharged at 1 ° C., and 100 cycles of the charging and discharging are performed at 1 cycle.
- the pressure inside the case may be 1 to 15 atmospheres.
- the positive electrode may be any one of a positive electrode active material selected from the group consisting of LiNi 1-y Mn y O 2 (O ⁇ y ⁇ 1), LiMn 2-z Ni z O 4 (0 ⁇ z ⁇ 2), and mixtures thereof. It may include.
- the negative electrode may include any one negative electrode active material selected from the group consisting of artificial graphite, natural graphite, graphitized carbon fiber, amorphous carbon, and mixtures thereof.
- the electrochemical device may be a high voltage electrochemical device of 3V or more.
- the electrochemical device may be a lithium secondary battery.
- an electrochemical device includes a case, an electrode assembly positioned inside the case, including an anode and a cathode, and a separator interposed between the anode and the cathode, and an electrolyte injected into the case. And a volume occupied by the gas generated in the electrochemical device at 25 ° C. and 1 atm pressure in a state of charging at 1 ° C. at 25 ° C., discharging at 1 ° C., and repeating 100 cycles of charging and discharging at 1 cycle. GV) is 1.5 to 15 times the volume (EV) of the free space.
- volume of empty space inside the case total volume inside the case (AV)-volume of the electrode assembly (BV)
- volume of free space volume of empty space inside the case (CV)-volume of electrolyte (DV)
- the volume EV of the free space according to Equation 2 with respect to the entire volume CV of the empty space inside the case according to Equation 1 may be 0 to 45% by volume.
- the volume EV of the free space with respect to the entire volume CV of the empty space inside the case may be 5 to 30% by volume.
- the volume DV of the electrolyte may be 55 to 100% by volume based on the total volume CV of the empty space inside the case.
- the volume DV of the electrolyte may be 0.5 to 10 cm 3 .
- the electrochemical device was charged at 1 ° C. at 25 ° C. and discharged at 1 ° C., and 100 cycles of the charging and discharging were repeated at 1 cycle.
- the pressure inside the case may be 1.5 to 15 times the pressure inside the case when the volume EV of the free space exceeds 45% by volume.
- the electrochemical device is charged at 1 ° C. at 25 ° C., discharged at 1 ° C., and 100 cycles of the charging and discharging are performed at 1 cycle.
- the pressure inside the case may be 1 to 15 atmospheres.
- the positive electrode may be any one of a positive electrode active material selected from the group consisting of LiNi 1-y Mn y O 2 (O ⁇ y ⁇ 1), LiMn 2-z Ni z O 4 (0 ⁇ z ⁇ 2), and mixtures thereof. It may include.
- the negative electrode may include any one negative electrode active material selected from the group consisting of artificial graphite, natural graphite, graphitized carbon fiber, amorphous carbon, and mixtures thereof.
- the electrochemical device of the present invention can solve the problem that the gas generated by the oxidation reaction of the electrolyte due to the high voltage reduces the reaction area of the electrode surface and further increases the side reactions, thereby accelerating capacity deterioration.
- FIG. 1 is an exploded perspective view of a rechargeable lithium battery according to another embodiment of the present invention.
- FIG. 2 is a diagram schematically illustrating capacity decay due to gas generation in a conventional lithium secondary battery.
- Figure 3 is a diagram showing the principle that the rate of capacity degradation is reduced in the present invention.
- Figure 4 is a graph showing the life characteristics of the lithium secondary battery prepared in Examples and Comparative Examples of the present invention.
- An electrochemical device includes a case, an electrode assembly positioned inside the case, including an anode and a cathode, and a separator interposed between the anode and the cathode, and an electrolyte injected into the case. do.
- the electrochemical device includes all devices that undergo an electrochemical reaction, and specific examples thereof include all kinds of primary and secondary batteries, fuel cells, solar cells, and capacitors such as supercapacitor devices.
- the lithium secondary battery may be classified into a lithium ion battery, a lithium ion polymer battery, and a lithium polymer battery according to the type of separator and electrolyte used, and may be classified into a cylindrical shape, a square shape, a coin type, a pouch type, and the like. Depending on the size, it can be divided into bulk type and thin film type.
- FIG. 1 is an exploded perspective view of a lithium secondary battery 1 according to another embodiment of the present invention.
- a separator 7 is disposed between the negative electrode 3, the positive electrode 5, the negative electrode 3, and the positive electrode 5 to form an electrode assembly 9. It can be prepared by placing in the case 15 and injecting an electrolyte (not shown) so that the negative electrode 3, the positive electrode 5 and the separator 7 is impregnated in the electrolyte.
- Conductive lead members 10 and 13 may be attached to the negative electrode 3 and the positive electrode 5, respectively, and the lead members 10 and 13 may be attached to the positive electrode 5, respectively. And a current generated in the negative electrode 3 to the positive electrode terminal and the negative electrode terminal.
- the negative electrode 3 may be prepared by mixing a negative electrode active material, a binder, and optionally a conductive agent to prepare a composition for forming a negative electrode active material layer, and then applying the same to a negative electrode current collector such as copper foil.
- the negative electrode active material a compound capable of reversible intercalation and deintercalation of lithium may be used.
- the negative electrode active material may be a carbonaceous material such as artificial graphite, natural graphite, graphitized carbon fiber, amorphous carbon, or the like.
- a metallic compound capable of alloying with lithium, or a composite including a metallic compound and a carbonaceous material may also be used as the negative electrode active material.
- the metal capable of alloying with lithium at least one of Si, Al, Sn, Pb, Zn, Bi, In, Mg, Ga, Cd, Si alloy, Sn alloy, and Al alloy may be used.
- a metal lithium thin film may be used as the negative electrode active material.
- the negative electrode active material any one selected from the group consisting of crystalline carbon, amorphous carbon, carbon composite, lithium metal, an alloy containing lithium, and mixtures thereof may be used in view of high stability.
- the binder adheres the electrode active material particles to each other, and also serves to adhere the electrode active material to the current collector well, and specific examples thereof include polyvinylidene fluoride (PVDF), polyvinyl alcohol, and carboxymethyl cellulose (CMC). , Starch, hydroxypropylcellulose, regenerated cellulose, polyvinylpyrrolidone, tetrafluoroethylene, polyethylene, polypropylene, ethylene-propylene-diene polymer (EPDM), sulfonated-EPDM, styrene-butadiene rubber , Fluororubbers and various copolymers thereof can be used.
- PVDF polyvinylidene fluoride
- CMC carboxymethyl cellulose
- Starch hydroxypropylcellulose, regenerated cellulose, polyvinylpyrrolidone, tetrafluoroethylene, polyethylene, polypropylene, ethylene-propylene-diene polymer (EPDM), sulfonated-EPDM
- solvent examples include dimethyl sulfoxide (DMSO), alcohol, N-methylpyrrolidone (NMP), acetone or water.
- the current collector may be any one metal selected from the group consisting of copper, aluminum, stainless steel, titanium, silver, palladium, nickel, alloys thereof, and combinations thereof, and the stainless steel may be carbon, nickel, titanium, or It may be surface treated with silver, and the alloy may preferably be an aluminum-cadmium alloy.
- a non-conductive polymer or a conductive polymer may be used which is surface-treated with calcined carbon, a conductive material.
- the conductive material is used to impart conductivity to the electrode, and any battery can be used as long as it is an electronic conductive material without causing chemical change in the battery.
- any battery can be used as long as it is an electronic conductive material without causing chemical change in the battery.
- Metal powder, metal fiber, etc. such as black, carbon fiber, copper, nickel, aluminum, silver, etc. can be used, and 1 type (s) or 1 or more types can be mixed and conductive materials, such as a polyphenylene derivative, can be used.
- the method of applying the current collector-coated composition for forming the negative electrode active material layer it may be selected from a known method or performed by a new suitable method in consideration of the properties of the material. For example, it is preferable to disperse the composition for forming the negative electrode active material layer on a current collector and then to uniformly disperse the same using a doctor blade or the like. In some cases, a method of distributing and dispersing in one process may be used. In addition, methods such as die casting, comma coating, and screen printing may be used.
- the positive electrode 5 is a mixture of a positive electrode active material, a conductive agent and a binder to prepare a composition for forming a positive electrode active material layer, and then the positive electrode current collector such as aluminum foil It can be prepared by rolling on the coating.
- a compound (lithiated intercalation compound) capable of reversible intercalation and deintercalation of lithium may be used.
- the electrolyte may include an organic solvent and a lithium salt.
- the organic solvent may be used without particular limitation as long as it can serve as a medium through which ions involved in the electrochemical reaction of the battery can move.
- the organic solvent may be an ester solvent, an ether solvent, a ketone solvent, an aromatic hydrocarbon solvent, an alkoxyalkane solvent, a carbonate solvent, or the like, and may be used alone or in combination of two or more thereof.
- ester solvent examples include methyl acetate, ethyl acetate, n-propyl acetate, dimethyl acetate, dimethyl acetate, methyl propionate, and ethyl prop.
- ether solvents include dibutyl ether, tetraglyme, 2-methyltetrahydrofuran, tetrahydrofuran, and the like.
- ketone solvent examples include cyclohexanone.
- aromatic hydrocarbon-based organic solvent examples include benzene, fluorobenzene, chlorobenzene, iodobenzene, toluene, fluorotoluene, or xylene (xylene) etc. are mentioned.
- alkoxyalkane solvent examples include dimethoxy ethane or diethoxy ethane.
- the carbonate solvent examples include dimethyl carbonate (dimethyl carbonate, DMC), diethyl carbonate (DEC), dipropyl carbonate (dipropyl carbonate, DPC), methyl propyl carbonate (methyl propyl carbonate, MPC), ethyl propyl carbonate (ethyl propyl carbonate, EPC) , Methylethylcarbonate (MEC), ethylmethylcarbonate (EMC), ethylene carbonate (EC), propylene carbonate (PC), butylene carbonate (BC), or fluoro Ethylene carbonate (FEC) etc. are mentioned.
- a carbonate solvent is preferably used as the organic solvent, and among the carbonate solvents, a carbonate organic solvent having a high dielectric constant having a high ionic conductivity that can increase the charge / discharge performance of a battery, and the intrinsic It may be preferable to use a mixture of a low-viscosity carbonate-based organic solvent capable of appropriately adjusting the viscosity of the organic solvent.
- an organic solvent having a high dielectric constant selected from the group consisting of ethylene carbonate, propylene carbonate and mixtures thereof, and an organic solvent having a low viscosity selected from the group consisting of ethyl methyl carbonate, dimethyl carbonate, diethyl carbonate and mixtures thereof can be mixed and used.
- the high dielectric constant organic solvent and the low viscosity organic solvent may be mixed and used in a volume ratio of 2: 8 to 8: 2, and more specifically, ethylene carbonate or propylene carbonate; Ethyl methyl carbonate; And dimethyl carbonate or diethyl carbonate can be used by mixing in a volume ratio of 5: 1: 1 to 2: 5: 3, preferably can be used by mixing in a volume ratio of 3: 5: 2.
- the lithium salt may be used without particular limitation as long as it is a compound capable of providing lithium ions used in the lithium secondary battery 1.
- the lithium salt is LiPF 6 , LiClO 4 , LiAsF 6 , LiBF 4 , LiSbF 6 , LiAl0 4 , LiAlCl 4 , LiCF 3 SO 3 , LiC 4 F 9 SO 3 , LiN (C 2 F 5 SO 3 ) 2 , LiN (C 2 F 5 SO 2 ) 2 , LiN (CF 3 SO 2 ) 2 .
- LiPF 6 lithium hexafluorophosphate
- the lithium salt When the lithium salt is dissolved in the electrolyte, the lithium salt may function as a source of lithium ions in the lithium secondary battery 1 and may promote the movement of lithium ions between the positive electrode 5 and the negative electrode 3. Accordingly, the lithium salt is preferably included at a concentration of approximately 0.6 mol% to 2 mol% in the electrolyte. When the concentration of the lithium salt is less than 0.6 mol%, the conductivity of the electrolyte may be lowered and the performance of the electrolyte may be lowered. When the concentration of the lithium salt is higher than 2 mol%, the viscosity of the electrolyte may be increased, thereby reducing the mobility of lithium ions. In consideration of the conductivity of the electrolyte and the mobility of lithium ions, the lithium salt may be more preferably adjusted to about 0.7 mol% to 1.6 mol% in the electrolyte.
- the electrolyte further includes additives (hereinafter, referred to as 'other additives') that can be generally used in the electrolyte for the purpose of improving the life characteristics of the battery, suppressing battery capacity reduction, and improving the discharge capacity of the battery. can do.
- additives hereinafter, referred to as 'other additives'
- the other additives include vinylene carbonate (VC), metal fluoride (eg, LiF, RbF, TiF, AgF, AgF, BaF 2 , CaF 2 , CdF 2 , FeF 2 , HgF 2 , Hg 2 F 2 , MnF 2 , NiF 2 , PbF 2 , SnF 2 , SrF 2 , XeF 2 , ZnF 2 , AlF 3 , BF 3 , BiF 3 , CeF 3 , CrF 3 , DyF 3 , EuF 3 , GaF 3, GdF 3, FeF 3, HoF 3, InF 3, LaF 3, LuF 3, MnF 3, NdF 3, PrF 3, SbF 3, ScF 3, SmF 3, TbF 3, TiF 3, TmF 3, YF 3, YbF 3, TIF 3, CeF 4 , GeF 4, HfF 4, SiF 4, SnF 4, TiF 4, VF 4, ZrF4 4, NbF 5, SbF
- the separator 7 is a conventional porous polymer film conventionally used as a separator, such as ethylene homopolymer, propylene homopolymer, ethylene / butene copolymer, ethylene / hexene copolymer, ethylene / methacrylate copolymer, and the like.
- the porous polymer film made of the polyolefin-based polymer may be used alone or by laminating them, or a conventional porous nonwoven fabric, for example, a non-woven fabric made of high melting glass fiber, polyethylene terephthalate fiber, or the like may be used. It doesn't happen.
- the lithium secondary battery 1 has a volume EV of free space according to Equation 2 with respect to the entire volume CV of the empty space inside the case 15 according to Equation 1 0 to 45% by volume. It may be, preferably 5 to 30% by volume, more preferably 5 to 25% by volume.
- volume of empty space inside the case total volume inside the case (AV)-volume of the electrode assembly (BV)
- volume of free space volume of empty space inside the case (CV)-volume of electrolyte (DV)
- the volume CV of the empty space inside the case 15 is a volume excluding the volume BV occupied by the electrode assembly 9 from the total volume AV inside the case 15. It means the volume of space that can be injected.
- the volume CV of the empty space inside the case 15 may not only be the volume BV of the electrode assembly 9, but also may exclude a volume of a structure occupying a predetermined space inside the case 15.
- the volume CV of the internal empty space may be the same as excluding the volume of the structure occupying a predetermined space in the case 15.
- the volume (DV) of the electrolyte can be known through the injection amount of the electrolyte, but for a battery that is already manufactured, the weight of the electrolyte extracted through centrifugation or heating is evaporated to convert the weight difference before and after heating into a volume. It can be measured.
- the volume EV of the free space is the volume CV of the empty space inside the case 15 minus the volume DV of the electrolyte, that is, the empty space remaining after pouring the electrolyte.
- the volume DV of the electrolyte may be 55 to 100% by volume, preferably 70 to 95% by volume, and more preferably 75 to 95% based on the total volume CV of the empty space inside the case 15. Volume%. More specifically, the volume DV of the electrolyte may be 0.5 to 10 cm 3 .
- the lithium secondary battery 1 has the volume (EV) of the free space or the volume (EV) as described above, the gas generated by the oxidation reaction of the electrolyte due to the high voltage reduces the reaction area of the electrode surface, By further increasing side reactions, the problem of accelerating dose decay can be solved.
- the volume of the gas when pressure is applied while the volume is fixed, the volume of the gas is inversely proportional to the pressure when gas is generated therein. For example, if 10 ml of gas is produced under one atmosphere, assuming that the same mass of gas is generated, the volume of the gas is doubled to 5 ml under two atmospheres.
- the lithium secondary battery 1 applies this principle.
- the volume EV of the free space inside the case 15 varies according to the amount of electrolyte injected. If the amount of the electrolyte is large, the volume EV of the free space is reduced. If the amount of the electrolyte is small, the volume EV of the free space is large.
- the lithium secondary battery 1 has no problem in exhibiting the performance of the lithium secondary battery 1 even if the electrolyte is injected only in a content such that the positive electrode 5 and the negative electrode 3 are immersed due to its structural characteristics. . Therefore, in the case of the high-voltage lithium secondary battery 1, the electrolyte is injected only to the amount that the positive electrode 5 and the negative electrode 3 are locked, and the liquid is injected to the extent that the volume (EV) of the free space is little. In all cases, the mass of gas generated by electrolyte oxidation is the same.
- the gas generated due to the electrolyte oxidation reaction at a high voltage is pressurized as the amount of the electrolyte is increased, thereby reducing the volume of the generated gas.
- the rate at which the reaction area of the surface of the positive electrode 5 or the negative electrode 3 decreases is smaller than before pressing, thereby reducing the capacity decay rate.
- FIG. 2 is a diagram schematically illustrating capacity decay due to gas generation in a conventional lithium secondary battery
- FIG. 3 illustrates a principle in which capacity decay rate decreases when the volume EV of the free space is small as in the present invention. It is an illustration. 2 and 3, LNMO represents a positive electrode 5, Graphite represents a negative electrode 3, and electrolyte represents an electrolyte.
- the gas generated in the lithium secondary battery 1 is 25 ° C. in the state where the lithium secondary battery 1 is charged at 1 ° C. at 25 ° C. and discharged at 1 ° C., and 100 cycles are repeated with the charging and discharging as 1 cycle.
- the volume (GV) occupies at 1 atmosphere condition may be 1.5 to 15 times, preferably 2 to 10 times, and more preferably 3 to 10 times the volume (EV) of the free space.
- the generated gas does not affect the surface of the cathode 3 so that the surface coating layer This uniform and thin formation can reduce the rate of capacity degradation.
- the lithium secondary battery 1 was charged at 1 ° C. at 25 ° C. and discharged at 1 ° C., and 100 cycles of the charging and discharging were repeated at 1 cycle.
- the pressure inside the case 15 may be 1.5 to 15 times the pressure inside the case 15 when the volume EV of the free space exceeds 45% by volume, preferably 2 to 12 times. And more preferably 3 to 10 times. That is, when the volume (EV) of the free space is 0 to 45% by volume, as the generated gas is pressurized, the surface coating layer is uniformly and thinly formed because it does not affect the surface of the cathode 3, so that the capacity deterioration rate is increased. Can be reduced.
- the lithium secondary battery 1 was charged at 1 ° C. at 25 ° C. and discharged at 1 ° C., and the charging and discharging at 1 cycle was repeated 100 cycles, and the pressure inside the case 15 was 1 to 15 atm. May be, preferably 5 to 15 atmospheres, more preferably 7 to 15 atmospheres.
- the pressure inside the case 15 is within the range, the gas generated in the case 15 is pressurized so that the surface of the cathode 3 is not affected, and a surface coating layer is formed on the surface of the cathode 3. It can be formed uniformly and thinly to reduce the rate of capacity degradation.
- the anode 5 is any one selected from the group consisting of LiNi 1-y Mn y O 2 (O ⁇ y ⁇ 1), LiMn 2-z Ni z O 4 (0 ⁇ z ⁇ 2) and mixtures thereof.
- LNMO-based positive electrode active material the negative electrode 3 may include any one graphite-based negative active material selected from the group consisting of artificial graphite, natural graphite, graphitized carbon fiber, amorphous carbon, and mixtures thereof. Can be.
- the lithium secondary battery 1 may be a high voltage lithium secondary battery 1 having a voltage of 3 V or more, preferably 5 V or more.
- the lithium secondary battery 1 may be manufactured by a conventional method, and thus detailed description thereof will be omitted.
- the cylindrical lithium secondary battery 1 has been described as an example, but the technology of the present invention is not limited to the cylindrical lithium secondary battery 1, and may be any shape as long as it can operate as a battery.
- the natural graphite, the carbon black conductive material, and the PVdF binder were mixed in an N-methylpyrrolidone solvent to prepare a composition for forming a negative electrode active material layer, which was applied to a copper current collector to form a negative electrode active material layer.
- the LNMO positive electrode active material, the carbon black conductive material, and the PVdF binder were mixed in an N-methylpyrrolidone solvent to prepare a composition for forming a positive electrode active material layer, which was applied to an aluminum current collector to form a positive electrode active material layer.
- An electrode assembly is manufactured by interposing a membrane of porous polyethylene between the anode and the graphite-based cathode prepared as described above, and after placing the electrode assembly inside the case, a free space for the entire volume (CV) of the empty space inside the case.
- the lithium secondary battery was prepared by injecting an electrolyte such that the volume (EV) was 20% by volume.
- Example 2 In the same manner as in Example 1, except that the electrolyte was injected so that the volume (EV) of the free space with respect to the entire volume (CV) of the empty space inside the case was 46% by volume. In the same manner as the lithium secondary battery was prepared.
- the volume (EV) of the free space was 20% by volume with respect to the total volume (CV) of the empty space inside the case, and 80 volumes with respect to the total volume (CV) of the empty space inside the case. %,
- the lithium secondary battery was charged at 1 ° C. at 25 ° C., discharged at 1 ° C., and 100 cycles of the charging and discharging were repeated at a cycle of 25 ° C. and 1 atm.
- the volume GV occupied in the condition was 6 times the volume EV of the free space, and the pressure inside the case was 12 atm.
- the volume (EV) of the free space was 46% by volume with respect to the total volume (CV) of the interior empty space, and 54 volumes with respect to the total volume (CV) of the empty space inside the case. %,
- the lithium secondary battery was charged at 1 ° C. at 25 ° C., discharged at 1 ° C., and 100 cycles of the charging and discharging were repeated at a cycle of 25 ° C. and 1 atm.
- the volume GV occupied in the condition was 12 times with respect to 100 parts by volume of the volume EV of the free space, and the pressure inside the case was 6 atm.
- the life characteristics of the batteries were measured for the lithium secondary batteries prepared in Examples and Comparative Examples. Charging and discharging was carried out 200 cycles at 0.1 ° C / 0.1C charge / discharge conditions at 25 °C, each measured twice and the results are shown in Figure 4.
- the embodiment shows a large electrolyte content (large)
- the comparative example shows a small electrolyte content.
- the lithium secondary battery prepared in the example has a reduced capacity degradation compared to the lithium secondary battery prepared in the comparative example, thereby improving life characteristics.
- the present invention relates to an electrochemical device, which includes all devices that undergo an electrochemical reaction, and specific examples thereof include all kinds of primary, secondary, fuel, solar, or supercapacitor devices.
Abstract
Description
Claims (11)
- 케이스,상기 케이스 내부에 위치하며, 양극과 음극 및 상기 양극과 음극 사이에 개재된 세퍼레이터를 포함하는 전극 조립체, 그리고상기 케이스 내부에 주입된 전해질를 포함하며,하기 수학식 1에 따른 케이스 내부 빈 공간의 부피(CV) 전체에 대한 하기 수학식 2에 따른 자유 공간의 부피(EV)가 0 내지 45 부피%인 것인 전기 화학 소자:[수학식 1]케이스 내부 빈 공간의 부피(CV) = 케이스 내부의 전체 부피(AV) - 전극 조립체의 부피(BV)[수학식 2]자유 공간의 부피(EV) = 케이스 내부 빈 공간의 부피(CV) - 전해질의 부피(DV).
- 제1항에 있어서,상기 케이스 내부 빈 공간의 부피(CV) 전체에 대한 상기 자유 공간의 부피(EV)가 5 내지 30 부피%인 것인 전기 화학 소자.
- 제1항 또는 제2항에 있어서,상기 전해질의 부피(DV)는 상기 케이스 내부 빈 공간의 부피(CV) 전체에 대하여 55 내지 100 부피%인 것인 전기 화학 소자.
- 제1항 또는 제2항에 있어서,상기 전해질의 부피(DV)는 0.5 내지 10cm3인 것인 전기 화학 소자.
- 제1항에 있어서,상기 전기 화학 소자를 25℃에서 1C로 충전, 1C로 방전하고, 상기 충전 및 방전을 1 사이클로하여 100 사이클을 반복한 상태에서,상기 자유 공간의 부피(EV)가 0 내지 45 부피% 이상인 경우 상기 케이스 내부의 압력은 상기 자유 공간의 부피(EV)가 45 부피%를 초과하는 경우 상기 케이스 내부의 압력 대비 1.5 내지 15배인 것인 전기 화학 소자.
- 제1항 또는 제5항에 있어서,상기 전기 화학 소자를 25℃에서 1C로 충전, 1C로 방전하고, 상기 충전 및 방전을 1 사이클로하여 100 사이클을 반복한 상태에서,상기 케이스 내부의 압력은 1 내지 15 기압인 것인 전기 화학 소자.
- 제1항, 제2항 및 제5항 중 어느 한 항에 있어서,상기 양극은 LiNi1-yMnyO2(O<y<1), LiMn2-zNizO4(0<z<2) 및 이들의 혼합물로 이루어진 군에서 선택되는 어느 하나의 양극 활물질을 포함하는 것인 전기 화학 소자.
- 제1항, 제2항 및 제5항 중 어느 한 항에 있어서,상기 음극은 인조흑연, 천연흑연, 흑연화 탄소섬유, 비정질탄소, 및 이들의 혼합물로 이루어진 군에서 선택되는 어느 하나의 음극 활물질을 포함하는 것인 전기 화학 소자.
- 제1항, 제2항 및 제5항 중 어느 한 항에 있어서,상기 전기 화학 소자는 3V 이상의 고전압 전기 화학 소자인 것인 전기 화학 소자.
- 제1항, 제2항 및 제5항 중 어느 한 항에 있어서,상기 전기 화학 소자는 리튬 이차 전지인 것인 전기 화학 소자.
- 케이스,상기 케이스 내부에 위치하며, 양극과 음극 및 상기 양극과 음극 사이에 개재된 세퍼레이터를 포함하는 전극 조립체, 그리고상기 케이스 내부에 주입된 전해질을 포함하며,25℃에서 1C로 충전, 1C로 방전하고, 상기 충전 및 방전을 1 사이클로하여 100 사이클을 반복한 상태에서, 상기 전기 화학 소자 내부에서 발생한 가스가 25℃ 및 1 기압 조건에서 차지하는 부피(GV)는 하기 수학식 2에 따른 자유 공간의 부피(EV)에 대하여 1.5 내지 15배인 것인 전기 화학 소자.[수학식 1]케이스 내부 빈 공간의 부피(CV) = 케이스 내부의 전체 부피(AV) - 전극 조립체의 부피(BV)[수학식 2]자유 공간의 부피(EV) = 케이스 내부 빈 공간의 부피(CV) - 전해질의 부피(DV).
Priority Applications (3)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
US15/024,935 US20170170512A1 (en) | 2014-02-10 | 2015-02-10 | Electrochemical device |
JP2016529937A JP6403770B2 (ja) | 2014-02-10 | 2015-02-10 | 電気化学素子 |
CN201580002859.9A CN105794039B (zh) | 2014-02-10 | 2015-02-10 | 电化学元件 |
Applications Claiming Priority (4)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
KR1020140014862A KR20150094055A (ko) | 2014-02-10 | 2014-02-10 | 전기 화학 소자 |
KR10-2014-0014838 | 2014-02-10 | ||
KR1020140014838A KR101620512B1 (ko) | 2014-02-10 | 2014-02-10 | 전기 화학 소자 |
KR10-2014-0014862 | 2014-02-10 |
Publications (1)
Publication Number | Publication Date |
---|---|
WO2015119486A1 true WO2015119486A1 (ko) | 2015-08-13 |
Family
ID=53778223
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
PCT/KR2015/001352 WO2015119486A1 (ko) | 2014-02-10 | 2015-02-10 | 전기 화학 소자 |
Country Status (4)
Country | Link |
---|---|
US (1) | US20170170512A1 (ko) |
JP (1) | JP6403770B2 (ko) |
CN (1) | CN105794039B (ko) |
WO (1) | WO2015119486A1 (ko) |
Families Citing this family (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP6693473B2 (ja) * | 2017-05-23 | 2020-05-13 | トヨタ自動車株式会社 | フッ化物イオン電池 |
CN113871728A (zh) * | 2021-09-15 | 2021-12-31 | 湖南立方新能源科技有限责任公司 | 一种锂离子电池及其制备方法 |
CN114005961A (zh) * | 2021-10-15 | 2022-02-01 | 湖南立方新能源科技有限责任公司 | 一种负极补锂的锂离子电池的制备方法及其锂离子电池 |
CN115360438B (zh) * | 2022-10-20 | 2023-03-24 | 中创新航科技股份有限公司 | 一种电池 |
Citations (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP2000294294A (ja) * | 1999-04-02 | 2000-10-20 | Denso Corp | 非水電解液二次電池 |
JP2002203555A (ja) * | 2000-12-28 | 2002-07-19 | Sony Corp | 非水電解質二次電池 |
JP2002270225A (ja) * | 2001-03-09 | 2002-09-20 | Matsushita Electric Ind Co Ltd | リチウム二次電池 |
JP2003346906A (ja) * | 2002-05-29 | 2003-12-05 | Japan Storage Battery Co Ltd | 非水電解質二次電池 |
KR20120008467A (ko) * | 2010-07-16 | 2012-01-30 | 산요덴키가부시키가이샤 | 비수 전해질 2차 전지 |
Family Cites Families (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US847096A (en) * | 1906-05-11 | 1907-03-12 | Marshall E Mcbee | Fan-hanger. |
JPH10172601A (ja) * | 1996-12-06 | 1998-06-26 | Haibaru:Kk | 円筒形電池 |
JP5375816B2 (ja) * | 2003-02-27 | 2013-12-25 | 三菱化学株式会社 | 非水系電解液およびリチウム二次電池 |
US8680730B2 (en) * | 2010-07-01 | 2014-03-25 | Powertec Industrial Motors, Inc. | Low voltage high horsepower brushless motor assembly |
-
2015
- 2015-02-10 JP JP2016529937A patent/JP6403770B2/ja active Active
- 2015-02-10 US US15/024,935 patent/US20170170512A1/en not_active Abandoned
- 2015-02-10 WO PCT/KR2015/001352 patent/WO2015119486A1/ko active Application Filing
- 2015-02-10 CN CN201580002859.9A patent/CN105794039B/zh active Active
Patent Citations (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP2000294294A (ja) * | 1999-04-02 | 2000-10-20 | Denso Corp | 非水電解液二次電池 |
JP2002203555A (ja) * | 2000-12-28 | 2002-07-19 | Sony Corp | 非水電解質二次電池 |
JP2002270225A (ja) * | 2001-03-09 | 2002-09-20 | Matsushita Electric Ind Co Ltd | リチウム二次電池 |
JP2003346906A (ja) * | 2002-05-29 | 2003-12-05 | Japan Storage Battery Co Ltd | 非水電解質二次電池 |
KR20120008467A (ko) * | 2010-07-16 | 2012-01-30 | 산요덴키가부시키가이샤 | 비수 전해질 2차 전지 |
Also Published As
Publication number | Publication date |
---|---|
CN105794039B (zh) | 2018-09-25 |
JP2017511951A (ja) | 2017-04-27 |
CN105794039A (zh) | 2016-07-20 |
US20170170512A1 (en) | 2017-06-15 |
JP6403770B2 (ja) | 2018-10-10 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
WO2017104867A1 (ko) | 리튬 이차 전지용 음극 및 이를 포함하는 리튬 이차 전지 | |
WO2014129823A1 (ko) | 리튬 이차 전지용 전해액 첨가제, 상기 전해액 첨가제를 포함하는 비수성 전해액 및 리튬 이차 전지 | |
WO2016052850A1 (ko) | 리튬 이차 전지용 음극 활물질, 이의 제조 방법, 이를 포함하는 리튬 이차 전지용 음극, 및 리튬 이차 전지 | |
WO2014104710A1 (ko) | 비수성 전해액 및 이를 포함하는 리튬 이차 전지 | |
WO2016052910A1 (ko) | 리튬이차전지용 음극 활물질, 이의 제조 방법, 이를 포함하는 리튬이차전지용 음극, 및 리튬이차전지 | |
WO2014185750A1 (ko) | 비수성 전해액 및 이를 포함하는 리튬 이차전지 | |
WO2020153822A1 (ko) | 리튬 이차 전지 | |
WO2015119486A1 (ko) | 전기 화학 소자 | |
KR102003298B1 (ko) | 코어-쉘 실리콘 복합체, 이의 제조방법 및 이를 포함하는 리튬이차전지용 음극 활물질 | |
WO2016105176A1 (ko) | 전기 화학 소자 | |
WO2020159263A1 (ko) | 이차전지용 음극의 제조방법 | |
WO2019221410A1 (ko) | 전극 보호층을 포함하는 음극 및 이를 적용한 리튬 이차전지 | |
WO2011087205A2 (ko) | 리튬 이차전지용 비수 전해액 및 이를 구비한 리튬 이차전지 | |
KR102605446B1 (ko) | 비수전해액 및 리튬 이차전지 | |
WO2016208946A1 (ko) | 리튬 이차 전지용 전해질 및 이를 포함하는 리튬 이차 전지 | |
KR101584323B1 (ko) | 전극의 제조 방법, 이를 이용하여 제조된 전극, 상기 전극을 포함하는 전기 화학 소자 | |
WO2021033986A1 (ko) | 이차전지용 전해액 및 이를 포함하는 이차전지 | |
KR101747496B1 (ko) | 전기 화학 소자 | |
WO2019059653A1 (ko) | 이차전지용 양극 활물질 및 이를 포함하는 리튬 이차전지 | |
WO2024005410A1 (ko) | 주석염 또는 게르마늄염을 포함하는 비수계 전해질 및 이를 채용하는 이차전지 | |
WO2024085298A1 (ko) | 음극 및 리튬 이차전지 | |
WO2021096267A1 (ko) | 이차전지 | |
KR101620512B1 (ko) | 전기 화학 소자 | |
KR20170134156A (ko) | 이차전지용 비수전해액 및 리튬 이차전지 | |
WO2014084642A1 (ko) | 전해질 염 용해용 용매로 알킬메탄설포네이트를 사용하는 비수계 전해액을 포함하는 이차전지 |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
121 | Ep: the epo has been informed by wipo that ep was designated in this application |
Ref document number: 15745867 Country of ref document: EP Kind code of ref document: A1 |
|
WWE | Wipo information: entry into national phase |
Ref document number: 15024935 Country of ref document: US |
|
ENP | Entry into the national phase |
Ref document number: 2016529937 Country of ref document: JP Kind code of ref document: A |
|
NENP | Non-entry into the national phase |
Ref country code: DE |
|
122 | Ep: pct application non-entry in european phase |
Ref document number: 15745867 Country of ref document: EP Kind code of ref document: A1 |