WO2019151724A1 - Batterie secondaire au lithium présentant de meilleures caractéristiques de stockage à haute température - Google Patents

Batterie secondaire au lithium présentant de meilleures caractéristiques de stockage à haute température Download PDF

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Publication number
WO2019151724A1
WO2019151724A1 PCT/KR2019/001127 KR2019001127W WO2019151724A1 WO 2019151724 A1 WO2019151724 A1 WO 2019151724A1 KR 2019001127 W KR2019001127 W KR 2019001127W WO 2019151724 A1 WO2019151724 A1 WO 2019151724A1
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Prior art keywords
lithium
secondary battery
lithium secondary
additive
organic solvent
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PCT/KR2019/001127
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English (en)
Korean (ko)
Inventor
임영민
이철행
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주식회사 엘지화학
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Priority claimed from KR1020190009127A external-priority patent/KR102301670B1/ko
Application filed by 주식회사 엘지화학 filed Critical 주식회사 엘지화학
Priority to CN201980003760.9A priority Critical patent/CN111052488B/zh
Priority to PL19747419T priority patent/PL3651254T3/pl
Priority to JP2020524328A priority patent/JP7038967B2/ja
Priority to US16/635,371 priority patent/US11476459B2/en
Priority to EP19747419.0A priority patent/EP3651254B1/fr
Publication of WO2019151724A1 publication Critical patent/WO2019151724A1/fr

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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • 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
    • 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
    • H01M10/056—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes
    • H01M10/0564—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes the electrolyte being constituted of organic materials only
    • H01M10/0566—Liquid materials
    • H01M10/0567—Liquid materials characterised by the additives
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/056—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes
    • H01M10/0564—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes the electrolyte being constituted of organic materials only
    • H01M10/0566—Liquid materials
    • H01M10/0568—Liquid materials characterised by the solutes
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/056—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes
    • H01M10/0564—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes the electrolyte being constituted of organic materials only
    • H01M10/0566—Liquid materials
    • H01M10/0569—Liquid materials characterised by the solvents
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/10—Energy storage using batteries

Definitions

  • the present invention relates to a lithium secondary battery having improved high temperature storage characteristics.
  • the lithium secondary battery currently applied is composed of a negative electrode capable of occluding and releasing lithium ions, a positive electrode made of a lithium-containing transition metal oxide, and the like, and a non-aqueous electrolyte in which lithium salt is dissolved in a carbonate-based organic solvent.
  • charging and discharging are possible by transferring energy while repeating a phenomenon in which lithium ions from the positive electrode are inserted into the negative electrode by charge and are detached again during discharge.
  • the electrolyte additive components and organic solvents are decomposed in the region of 0.5 V to 3.5 V to form a film on the surface of the negative electrode, and lithium ions generated from the positive electrode move to the negative electrode. And react with the electrolyte to produce compounds such as Li 2 CO 3 , Li 2 O, LiOH. These compounds form a kind of passivation layer on the surface of the cathode, which is called a solid electrolyte interface (SEI) film.
  • SEI solid electrolyte interface
  • the SEI film formed at the beginning of charging serves as a protective film for stabilizing a battery by inhibiting decomposition of a carbonate-based electrolyte solution at the negative electrode surface.
  • the SEI film produced only by the organic solvent and the lithium salt is somewhat insufficient to serve as a continuous protective film, so that the charging and discharging of the battery is continuously progressed or increased electrochemical energy, especially at high temperature storage in a full charge state. It can be disintegrated slowly by heat energy. Due to the collapse of the SEI film, side reactions in which the exposed surface of the negative electrode active material and the electrolyte solvent are decomposed continuously occur, thereby deteriorating battery characteristics such as a decrease in battery capacity, a decrease in lifespan, and an increase in resistance.
  • a non-aqueous electrolyte that can form a solid coating on the surface of the electrode, to provide a lithium secondary battery that can ensure the capacity characteristics even at high temperature storage.
  • the anode includes a cathode active material represented by the formula (1),
  • the non-aqueous electrolyte includes a non-aqueous organic solvent, lithium salt and additives,
  • the additive provides a lithium secondary battery that is a mixed additive containing lithium difluorophosphate (LiDFP), tetravinylsilane (TVS) and a sultone compound in a weight ratio of 1: 0.05: 0.1 to 1: 1: 1.5.
  • LiDFP lithium difluorophosphate
  • TVS tetravinylsilane
  • sultone compound in a weight ratio of 1: 0.05: 0.1 to 1: 1: 1.5.
  • the cathode active material may be a lithium transition metal oxide represented by Chemical Formula 1a.
  • the cathode active material may include Li (Ni 0.8 Co 0.1 Mn 0.1 ) O 2 .
  • the non-aqueous organic solvent included in the non-aqueous electrolyte may include a cyclic carbonate organic solvent and a linear carbonate organic solvent.
  • the cyclic carbonate organic solvent: the linear carbonate organic solvent may be included in a weight ratio of 1: 1 to 1: 4.
  • the weight ratio of the lithium difluorophosphate, tetravinylsilane and sultone-based compound may be 1: 0.07: 0.3 to 1: 0.7: 1, specifically 1: 0.1: 0.5 to 1: 0.5: 0.8.
  • the sultone compound may be at least one selected from the group consisting of 1,3-propanesultone, 1,4-butane sultone, and 1,3-propenesultone, and specifically, may be 1,3-propanesultone. .
  • the content of the additive may be 0.1 wt% to 7 wt%, specifically 0.1 wt% to 5 wt%, based on the total weight of the nonaqueous electrolyte.
  • the non-aqueous electrolyte is vinylene carbonate, ethylene sulfate (Ethylene Sulfate; Esa), trimethylene sulfate (TMS), methyl trimethylene sulfate (MTMS), lithium difluoro (bisoxalato) )
  • At least one additional additive selected from the group consisting of phosphate, lithium difluorophosphate, lithium oxalyldifluoroborate, succinonitrile and LiBF 4 .
  • a non-aqueous electrolyte capable of forming a rigid film on the surface of the anode containing a transition metal oxide containing high content nickel (Ni) during the initial charging, it is possible to secure a high energy density to improve the output characteristics
  • a lithium secondary battery having improved stability may be manufactured by suppressing a resistance increase rate and a thickness increase rate.
  • the anode includes a cathode active material represented by the formula (1),
  • the non-aqueous electrolyte includes a non-aqueous organic solvent, lithium salt and additives,
  • the additive provides a lithium secondary battery that is a mixed additive containing lithium difluorophosphate (LiDFP), tetravinylsilane (TVS) and a sultone compound in a weight ratio of 1: 0.05: 0.1 to 1: 1: 1.5. .
  • LiDFP lithium difluorophosphate
  • TVS tetravinylsilane
  • sultone compound in a weight ratio of 1: 0.05: 0.1 to 1: 1: 1.5. .
  • a separator may be sequentially stacked between the positive electrode, the negative electrode, and the positive electrode and the negative electrode to form an electrode assembly, and may be manufactured by injecting an electrolyte in which lithium salt is dissolved.
  • the constituting positive electrode, negative electrode and separator may be manufactured and applied according to conventional methods known in the art.
  • the positive electrode may be prepared by forming a positive electrode mixture layer on the positive electrode current collector.
  • the positive electrode current collector is not particularly limited as long as it has conductivity without causing chemical changes in the battery.
  • the positive electrode current collector may be formed of stainless steel, aluminum, nickel, titanium, calcined carbon, or carbon on the surface of aluminum or stainless steel. Surface treated with nickel, titanium, silver, or the like may be used.
  • the cathode mixture layer may be formed by coating a cathode slurry including a cathode active material, a binder, a conductive material, a solvent, and the like on a cathode current collector, followed by drying and rolling.
  • the cathode active material may include a transition metal oxide represented by Chemical Formula 1 having a high capacity, specifically, a lithium transition metal oxide represented by Chemical Formula 1a to increase energy density.
  • Lithium secondary battery of the present invention by providing a positive electrode containing a transition metal oxide containing a high content nickel (Hi-Ni) as a positive electrode active material Ni content of more than 0.65 as shown in Formula 1, to ensure a high energy density
  • a positive electrode active material Ni content of more than 0.65 as shown in Formula 1, to ensure a high energy density
  • the output characteristic of a lithium secondary battery can be improved.
  • the cathode active material may include Li (Ni 0.8 Mn 0.1 Co 0.1 ) O 2 as a representative example.
  • the nickel transition metal having a d-orbit should have an octahedral structure when coordinating bonds in an environment such as a high temperature according to a change in the oxidation number of Ni contained in the positive electrode active material, but the order of the energy levels is reversed by external energy supply,
  • the distorted octahedron is formed by the heterogeneous reaction in which the oxidation number is varied, resulting in the deformation and collapse of the crystal structure of the positive electrode active material.
  • the secondary reaction of the positive electrode active material and the electrolyte during high temperature storage causes another side reaction in which the transition metal, in particular nickel metal, is eluted from the positive electrode active material, deterioration of overall performance of the secondary battery due to electrolyte depletion and structural collapse of the positive electrode active material. do.
  • the lithium secondary battery of the present invention forms a solid ion conductive film on the surface of the positive electrode by applying a non-aqueous electrolyte containing a specific composition of the transition metal oxide represented by Formula 1 together with the positive electrode including the positive electrode active material It is possible to suppress the cation mixing of Li + 1 ions and Ni + 2 ions and to effectively suppress side reactions between the positive electrode and the electrolyte and dissolution of metals, thereby alleviating structural instability of the high capacity electrode. Therefore, since a sufficient amount of nickel transition metal for securing the capacity of the lithium secondary battery can be ensured, it is possible to prevent the output characteristics from being lowered by increasing the energy density.
  • the positive electrode active material is a compound capable of reversible intercalation and deintercalation of lithium in addition to the lithium-nickel-manganese-cobalt oxide having a nickel content of more than 0.65, for example, lithium-manganese oxide (eg , LiMnO 2 or LiMn 2 O 4, etc.), lithium-cobalt oxides (eg, LiCoO 2, etc.), lithium-nickel oxides (eg, LiNiO 2, etc.), lithium-nickel-manganese oxides (eg, For example, LiNi 1-Y Mn Y O 2 (here, 0 ⁇ Y ⁇ 1) or LiMn 2-z Ni z O 4 (here, 0 ⁇ Z ⁇ 2) and the like, lithium-nickel-cobalt oxide (Eg, LiNi 1-Y1 Co Y1 O 2 (here, 0 ⁇ Y1 ⁇ 1), etc.), lithium-manganese-cobalt based oxides (eg , Li
  • the cathode active material may be LiCoO 2 , LiMnO 2 , LiNiO 2 , or lithium nickel cobalt aluminum oxide having a nickel content of 0.65 or less (eg, Li (Ni 1/3 Mn 1/3 Co 1/3 ) O 2 , Li (Ni 0.6 Mn 0.2 Co 0.2 ) O 2 , or Li (Ni 0.5 Mn 0.3 Co 0.2 ) O 2 ) or the like.
  • the cathode active material may be included in an amount of 80 wt% to 99.5 wt%, specifically 85 wt% to 95 wt%, based on the total weight of solids in the cathode slurry. If the content of the positive electrode active material is less than 80% by weight, the energy density may be lowered and the capacity may be lowered.
  • the binder one of the positive electrode slurry components, is a component that assists in bonding the active material, the conductive material, and the like to the current collector, and is generally added in an amount of 1 wt% to 30 wt% based on the total weight of solids in the positive electrode slurry. do.
  • binders examples include polyvinylidene fluoride, polyvinyl alcohol, carboxymethyl cellulose (CMC), starch, hydroxypropyl cellulose, regenerated cellulose, polyvinylpyrrolidone, tetrafluoroethylene, Polyethylene, polypropylene, ethylene-propylene-diene monomer, styrene-butadiene rubber, fluororubber, various copolymers, and the like.
  • the conductive material which is one of the positive electrode slurry components is not particularly limited as long as it has conductivity without causing chemical change in the battery.
  • the conductive material is typically added in an amount of 1% to 30% by weight based on the total weight of solids in the positive electrode slurry.
  • the average particle diameter (D 50 ) of the conductive material may be 10 ⁇ m or less, specifically 0.01 ⁇ m to 10 ⁇ m, and more specifically 0.01 ⁇ m to 1 ⁇ m. In this case, when the average particle diameter of the conductive material exceeds 10 ⁇ m, dispersibility is poor, and thus the conductivity improving effect due to the addition of graphite powder is not preferable.
  • the solvent may include an organic solvent such as N-methyl-2-pyrrolidone (NMP), and may be used in an amount that becomes a desirable viscosity when including the positive electrode active material and optionally a binder and a conductive material.
  • NMP N-methyl-2-pyrrolidone
  • the solvent may be included so that the solid content concentration in the positive electrode slurry including the positive electrode active material, and optionally the binder and the conductive material is 10% to 60% by weight, preferably 20% to 50% by weight.
  • the negative electrode may be prepared by forming a negative electrode mixture layer on the negative electrode current collector.
  • the negative electrode current collector generally has a thickness of 3 to 500 ⁇ m.
  • a negative electrode current collector is not particularly limited as long as it has high conductivity without causing chemical change in the battery.
  • copper, stainless steel, aluminum, nickel, titanium, calcined carbon, copper or stainless steel Surface-treated with carbon, nickel, titanium, silver, and the like on the surface, aluminum-cadmium alloy and the like can be used.
  • fine concavities and convexities may be formed on the surface to enhance the bonding strength of the negative electrode active material, and may be used in various forms such as a film, a sheet, a foil, a net, a porous body, a foam, and a nonwoven fabric.
  • the negative electrode mixture layer may be formed by coating a negative electrode slurry including a negative electrode active material, a binder, a conductive material, a solvent, and the like on a negative electrode current collector, followed by drying and rolling.
  • the negative electrode active material may be lithium metal, a carbon material capable of reversibly intercalating / deintercalating lithium ions, a metal or an alloy of these metals with lithium, a metal composite oxide, a material capable of doping and undoping lithium, And at least one selected from the group consisting of transition metal oxides.
  • any carbon-based negative electrode active material generally used in a lithium ion secondary battery may be used without particular limitation.
  • Examples thereof include crystalline carbon, Amorphous carbons or these may be used together.
  • Examples of the crystalline carbon include graphite such as amorphous, plate, flake, spherical or fibrous natural graphite or artificial graphite, and examples of the amorphous carbon include soft carbon (soft carbon) Or hard carbon, mesophase pitch carbide, calcined coke, or the like.
  • the metals or alloys of these metals with lithium include Cu, Ni, Na, K, Rb, Cs, Fr, Be, Mg, Ca, Sr, Si, Sb, Pb, In, Zn, Ba, Ra, Ge, Al And a metal selected from the group consisting of Sn or an alloy of these metals with lithium may be used.
  • the metal complex oxide may include PbO, PbO 2 , Pb 2 O 3 , Pb 3 O 4 , Sb 2 O 3 , Sb 2 O 4 , Sb 2 O 5 , GeO, GeO 2 , Bi 2 O 3 , Bi 2 O 4 , Bi 2 O 5 , Li x Fe 2 O 3 (0 ⁇ x ⁇ 1), Li x WO 2 (0 ⁇ x ⁇ 1), and Sn x Me 1-x Me ' y O z (Me: Mn, Fe Me ': Al, B, P, Si, Group 1, Group 2, Group 3 elements of the periodic table, halogen; 0 ⁇ x ⁇ 1;1 ⁇ y ⁇ 3; 1 ⁇ z ⁇ 8 Any one selected from the group can be used.
  • Examples of the material capable of doping and undoping lithium include Si, SiO x (0 ⁇ x ⁇ 2), Si—Y alloys (wherein Y is an alkali metal, an alkaline earth metal, a Group 13 element, a Group 14 element, a transition metal, Is an element selected from the group consisting of rare earth elements and combinations thereof, not Si), Sn, SnO 2 , Sn-Y (Y is an alkali metal, alkaline earth metal, group 13 element, group 14 element, transition metal, rare earth) An element selected from the group consisting of elements and combinations thereof, and not Sn; and at least one of these and SiO 2 may be mixed and used.
  • transition metal oxide examples include lithium-containing titanium composite oxide (LTO), vanadium oxide, lithium vanadium oxide, and the like.
  • the negative electrode active material may be included in an amount of 80 wt% to 99 wt% based on the total weight of solids in the negative electrode slurry.
  • the binder which is one of the negative electrode slurry components, is a component that assists in bonding between the conductive material, the active material, and the current collector, and is generally added in an amount of 1 wt% to 30 wt% based on the total weight of solids in the negative electrode slurry.
  • binders examples include polyvinylidene fluoride, polyvinyl alcohol, carboxymethyl cellulose (CMC), starch, hydroxypropyl cellulose, regenerated cellulose, polyvinylpyrrolidone, tetrafluoroethylene, Polyethylene, polypropylene, ethylene-propylene-diene polymer, styrene-butadiene rubber, fluorine rubber, various copolymers thereof, and the like.
  • the conductive material is a component for further improving the conductivity of the negative electrode active material, and may be added in an amount of 1 wt% to 20 wt% based on the total weight of solids in the negative electrode slurry.
  • the conductive material is not particularly limited as long as it has conductivity without causing chemical change in the battery.
  • carbon black, acetylene black, ketjen black, channel black, furnace black, lamp black, or thermal black may be used.
  • Carbon powder such as natural graphite, artificial graphite, or graphite with very advanced crystal structure
  • 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 solvent may include an organic solvent such as water or NMP or alcohol, and may be used in an amount that becomes a desirable viscosity when including the negative electrode active material and optionally a binder and a conductive material.
  • concentration of the solids in the negative electrode slurry including the negative electrode active material and optionally the binder and the conductive material may be 50 wt% to 75 wt%, preferably 50 wt% to 70 wt%.
  • the separator serves to block internal short circuits of both electrodes and to impregnate the electrolyte, and to prepare a separator composition by mixing a polymer resin, a filler, and a solvent, and then coating and drying the separator composition directly on the electrode. After forming or by casting and drying the separator composition on the support, the separator film peeled from the support may be formed by laminating on the electrode.
  • the separator is a porous polymer film commonly used, for example, a porous polymer made of a polyolefin-based polymer such as ethylene homopolymer, propylene homopolymer, ethylene / butene copolymer, ethylene / hexene copolymer and ethylene / methacrylate copolymer.
  • the polymer film may be used alone or in a stack thereof, or a conventional porous nonwoven fabric, for example, a non-woven fabric made of high melting point glass fiber, polyethylene terephthalate fiber, or the like may be used, but is not limited thereto.
  • the pore diameter of the porous separator is generally 0.01 to 50 ⁇ m, porosity may be 5 to 95%.
  • the thickness of the porous separator may generally be in the range of 5 to 300 ⁇ m.
  • the lithium secondary battery according to an embodiment of the present invention may include a non-aqueous electrolyte containing (i) a non-aqueous organic solvent, (ii) a lithium salt and (iii) an additive.
  • the non-aqueous organic solvent which is one of the non-aqueous electrolyte components, preferably minimizes decomposition by an oxidation reaction during charging and discharging of a secondary battery, and uses a carbonate-based solvent to exhibit desired properties with an additive.
  • a cyclic carbonate organic solvent having a high dielectric constant and a linear carbonate organic solvent having a low dielectric constant may be mixed and applied.
  • the cyclic carbonate organic solvent the linear carbonate organic solvent may be included in a weight ratio of 1: 1 to 1: 4, specifically 1: 2 to 1: 4 weight ratio.
  • the content ratio of the linear carbonate organic solvent is less than 1 weight ratio with respect to 1 weight of the cyclic carbonate organic solvent, since the content of the cyclic carbonate having a high viscosity is high, the movement of Li + is not easy and the initial resistance is increased, thereby increasing the output characteristics. This can be degraded. In particular, a large amount of gas may be generated during high temperature storage.
  • the content of the linear carbonate-based organic solvent exceeds 4 weight ratio, the content of the cyclic carbonate-based organic solvent forming the SEI film is lowered, the initial SEI film formation effect and the SEI film regeneration during the driving life is lowered, the cycle characteristics are lowered Can be.
  • cyclic carbonate organic solvents include ethylene carbonate (EC), propylene carbonate (PC), 1,2-butylene carbonate, 2,3-butylene carbonate, and 1,2-pentylene At least one selected from the group consisting of carbonate, 2,3-pentylene carbonate, vinylene carbonate, and fluoroethylene carbonate (FEC).
  • linear carbonate organic solvent examples include dimethyl carbonate (dimethyl carbonate, DMC), diethyl carbonate (DEC), dipropyl carbonate, ethyl methyl carbonate (EMC), methylpropyl carbonate and ethylpropyl carbonate. At least one selected from the group consisting of may be used, but is not limited thereto.
  • non-aqueous organic solvent may further include a linear ester organic solvent in order to improve the output and high temperature characteristics.
  • linear carbonate-based organic solvent linear ester-based organic solvent may be included in a 1: 0.2 to 1: 1 weight ratio.
  • the linear ester organic solvent When the linear ester organic solvent is included in the content range, the effect of the output characteristics and the high temperature storage characteristics of the secondary battery can be improved.
  • linear ester organic solvents include at least one selected from the group consisting of methyl acetate, ethyl acetate, propyl acetate, methyl propionate, ethyl propionate, propyl propionate and butyl propionate. It is not limited to these.
  • the non-aqueous organic solvent may further include a cyclic ester organic solvent.
  • the cyclic ester organic solvent may be included in less than 1: 1 weight ratio with respect to the linear ester organic solvent.
  • cyclic ester compound examples include at least one selected from the group consisting of ⁇ -butyrolactone, ⁇ -valerolactone, ⁇ -caprolactone, ⁇ -valerolactone, and ⁇ -caprolactone.
  • Lithium salt which is one of the non-aqueous electrolyte components may be used without limitation those conventionally used in the electrolyte for lithium secondary batteries, for example, include Li + as a cation, F ⁇ , Cl ⁇ , Br ⁇ , I as an anion.
  • the lithium salt is LiCl, LiBr, LiI, LiBF 4 , LiClO 4 , LiB 10 Cl 10 , LiAlCl 4 , LiAlO 4 , LiPF 6 , LiCF 3 SO 3 , LiCH 3 CO 2 , LiCF 3 CO 2 , LiAsF 6 , LiSbF 6 , LiCH 3 SO 3 , LiFSI (Lithium bis (fluorosulfonyl) imide, LiN (SO 2 F) 2 ), LiBETI (lithium bisperfluoroethanesulfonimide, LiN (SO 2 CF 2 CF 3 ) 2 and LiTFSI (lithium (bis) trifluoromethanesulfonimide , LiN (SO 2 CF 3 ) 2 ) It may include a single material or a mixture of two or more selected from the group consisting of, In addition to these lithium salts commonly used in the electrolyte of the lithium secondary battery can be used without limitation.
  • the lithium salt may be included in a concentration of 0.01M to 2M, specifically 0.01M to 1M in the non-aqueous electrolyte.
  • the concentration of the lithium salt is less than 0.01 M, the effect of improving the low temperature output of the lithium secondary battery and improving the cycle characteristics during high temperature storage is insignificant, and when the concentration of the lithium salt exceeds 2 M, the viscosity of the non-aqueous electrolyte may increase and the electrolyte impregnation may be deteriorated. have.
  • the non-aqueous electrolyte may include a mixed additive in which lithium difluorophosphate, tetravinylsilane, and sultone compound are mixed.
  • the SEI film dissociates or the electrolyte decomposes and depletes under high temperature storage and / or in an extreme environment, the anode and / or cathode are exposed to cause side reactions with the electrolyte, resulting in structural collapse of the anode and / or cathode. Can be.
  • the present invention by providing a non-aqueous electrolyte containing the mixed additives, it is possible to form a more robust ion conductive film on the surface of the positive electrode and the negative electrode, thereby ensuring output characteristics and at the same time to prevent side reactions between the electrode and the electrolyte at high temperature
  • a lithium secondary battery having improved storage characteristics and high temperature cycle characteristics can be manufactured.
  • the weight ratio of the lithium difluorophosphate, tetravinylsilane and sultone-based compound is 1: 0.05: 0.1 to 1: 1: 1.5, specifically 1: 0.07: 0.3 to 1: 0.7: 1, more specifically 1: 0.1: 0.5 to 1: 0.5: 0.8.
  • the lithium difluorophosphate which is one of the additive components of the non-aqueous electrolyte, is a component for implementing long-term life characteristics improvement effect of the secondary battery, and is electrochemically decomposed at the surface of the anode and the cathode to help form an ion conductive film. Since it is possible to suppress the elution of the metal from the positive electrode and prevent side reaction between the electrode and the electrolyte, it is possible to implement the effect of improving the high temperature storage characteristics and cycle life characteristics of the secondary battery.
  • the lithium difluorophosphate is preferably included in less than 2% by weight based on the total weight of the non-aqueous electrolyte.
  • the lithium difluorophosphate content is 2% by weight or more, it is present as a precipitate without dissolving in the non-aqueous organic solvent, thereby increasing the resistance of the battery or excessive side reactions in the electrolyte during charging and discharging.
  • the cycle life of the secondary battery may be reduced.
  • the tetravinylsilane which is one of the additive components, is a component for improving stability during high temperature storage of a secondary battery, and when it is included, a solid ion conductive membrane may be formed through physical adsorption and electrochemical reaction on the surface of the positive electrode and the negative electrode. Because of this, it is possible to suppress side reactions of the electrolyte and increase in resistance caused therefrom during high temperature storage.
  • the tetravinylsilane may be included in a weight ratio of 0.05 or more and 1 or less with respect to 1 weight of lithium difluorophosphate, and when included in this range, may not only reduce gas generation and stabilize the SEI film formation, but also secondary It is possible to prevent the battery from increasing in resistance, thereby preventing the cycle life characteristic from deteriorating.
  • the sultone compound which is one of the additive components, is a component for improving high temperature stability, and when it is included, a stable protective film that does not crack upon high temperature storage in addition to the SEI film.
  • the negative electrode coated with the protective film can suppress the generation of non-aqueous solvent by the negative electrode active material during high temperature storage even when a carbon material highly crystallized by active such as natural graphite or artificial graphite is used for the negative electrode. have.
  • the protective film does not interfere with the normal reaction of charge and discharge of the battery. Therefore, performances such as cycle life, capacity and resistance can be improved at room temperature and high temperature of the secondary battery.
  • Such sultone compounds include 1,3-propane sultone (PS), 1,4-butane sultone and 1,3-propene sultone (PPS). At least one selected from the group consisting of, specifically may be at least one or more of 1,3-propane sultone (PS) and 1,3-propene sultone (PPS), More specifically, it may include 1,3-propane sultone.
  • the sultone-based compound may be included in a weight ratio of 0.1 or more and 1.5 or less with respect to 1 weight of lithium difluorophosphate, when included in this range can ensure the stabilization effect of the SEI membrane without increasing the resistance, by inhibiting the side reaction of the electrolyte secondary battery It is possible to improve the high temperature storage characteristics and cycle life characteristics of the.
  • the sultone-based compound may be included up to 4% by weight, specifically 3% by weight or less, based on the total weight of the nonaqueous electrolyte.
  • the total content of the sultone compound in the non-aqueous electrolyte exceeds 4% by weight, an excessively thick film may be formed to increase resistance and deteriorate output.
  • the mixed additive is 0.1 wt% to 7 wt%, specifically 0.1 wt% to 5 wt%, more specifically 0.1 wt% based on the total weight of the non-aqueous electrolyte % To 3.5% by weight may be included.
  • the content of the additive When the content of the additive is less than 0.1% by weight, the effect of improving the low temperature output, the high temperature storage characteristics, and the high temperature life characteristics of the battery is insignificant, and when the content of the additive exceeds 7% by weight, it is charged and discharged by excess additives. Side reactions may occur. In particular, since the additives are not sufficiently decomposed at high temperatures when added in excess, and remain unreacted or precipitated in the electrolyte at room temperature, the resulting resistance may increase, thereby reducing cycle life characteristics of the secondary battery. have.
  • the lithium secondary battery according to an embodiment of the present invention is prevented from being decomposed in a high-power environment to cause negative electrode collapse, or low temperature, high rate discharge characteristics, high temperature stability, overcharge prevention, and the effect of inhibiting battery expansion at high temperature.
  • it may further comprise additional additives in the non-aqueous electrolyte as needed.
  • additives include vinylene carbonate, vinylethylene carbonate, ethylene sulfate (Ethylene Sulfate; Esa), trimethylene sulfate (TMS), methyl trimethylene sulfate (MTMS), lithium difluoro (bis) Or at least one selected from the group consisting of oxalato) phosphate, lithium difluorophosphate, lithium oxalyldifluoroborate, succinonitrile (SN) and LiBF 4 .
  • vinylene carbonate, vinylethylene carbonate or succinonitrile may form a stable SEI film on the surface of the negative electrode together with lithium difluorophosphate during the initial activation process of the secondary battery.
  • the LiBF 4 may suppress the generation of gas that may be generated due to decomposition of the electrolyte during high temperature storage, thereby improving the high temperature stability of the secondary battery.
  • the additional additives may be included in a mixture of two or more kinds, based on the total weight of the non-aqueous electrolyte containing the mixed additive, 0.01 to 5% by weight, specifically 0.01 to 3% by weight, more specifically 0.05 to 3% by weight It may be included as.
  • the amount of the additional additive is less than 0.01% by weight, the effect of improving the low temperature output, the high temperature storage characteristics and the high temperature life characteristics of the battery is insignificant, and when the content of the additional additive exceeds 5% by weight, the battery is charged and discharged. There is a possibility of excessive side reactions in the electrolytic solution.
  • the SEI film-forming additives may not be sufficiently decomposed at high temperatures when added in excess, and thus may remain unreacted or precipitated in the electrolyte at room temperature. Accordingly, a side reaction may occur in which the lifespan or resistance characteristics of the secondary battery are reduced.
  • the lithium secondary battery of the present invention is a non-aqueous electrolyte including a positive electrode containing a transition metal oxide containing high content nickel (Ni) as a positive electrode active material and a mixed additive in which three compounds are mixed in a specific ratio.
  • the external shape of the lithium secondary battery of the present invention is not particularly limited, but may be variously applied, such as cylindrical, square, pouch type, or coin type, depending on the purpose of performing the same.
  • Lithium secondary battery according to an embodiment of the present invention may be a pouch-type secondary battery.
  • LiDFP lithium difluorophosphate
  • TVS tetravinylsilane
  • PS 1,3-propanesultone
  • a positive electrode active material Li (Ni 0.8 Mn 0.1 Co 0.1 ) O 2
  • a conductive material carbon black
  • a binder polyvinylidene fluoride
  • NMP N-methyl-2-pyrrolidone
  • a negative electrode active material artificial graphite
  • a conductive material carbon black
  • a binder polyvinylidene fluoride
  • NMP N-methyl-2-pyrrolidone
  • a coin-type battery was manufactured by a conventional method of sequentially stacking the prepared positive electrode, the polyethylene porous film, and the negative electrode, and then, a non-aqueous electrolyte was injected to prepare a lithium secondary battery (battery capacity 340 mAh). .
  • a lithium secondary battery was prepared (see Table 1 below).
  • a non-aqueous electrolyte and a lithium secondary battery including the same were prepared in the same manner as in Example 1, except that 3 g of vinylene carbonate (VC) was included in 97 g of the non-aqueous organic solvent. 1).
  • VC vinylene carbonate
  • a non-aqueous electrolyte and a lithium secondary battery including the same were prepared in the same manner as in Example 1, except that 2.0 g of LiBF 4 was included in the non-aqueous organic solvent (see Table 1 below). .
  • a lithium secondary battery including the positive electrode and the same was manufactured in the same manner as in Example 1, except that LiCoO 2 was used instead of Li (Ni 0.8 Mn 0.1 Co 0.1 ) O 2 as the cathode active material (see Table 1 below). ).
  • the lithium secondary batteries prepared in Examples 1 to 6 and each of the secondary batteries prepared in Comparative Examples 1 to 9 were each 1C up to 4.25V / 55mA at 25 ° C. under constant current / constant voltage (CC / CV) conditions. And then discharged at 2C to 2.5V under constant current (CC) conditions.
  • CC constant current
  • Initial discharge capacity was measured using PNE-0506 charger / discharger (manufacturer: PNE solution, 5V, 6A).
  • PNE solution 5V, 6A
  • a pulse of 2.5 C was applied for 10 seconds to calculate the initial resistance through the difference between the voltage before the pulse and the voltage after the application.
  • each secondary battery was left at 60 ° C. for 10 weeks.
  • the discharge capacity retention rate after high temperature storage was calculated by substituting the measured initial discharge capacity and the discharge capacity measured after storage for 10 weeks at high temperature in the following Equation (1), and the results are shown in Table 1 below.
  • the resistance after 10 weeks of storage at high temperature was calculated by applying a voltage drop appearing in a state of discharging a pulse for 10 seconds at 50 ° C. at 50% of SOC and substituting this into Equation 2 below to increase the resistance (%). After the calculation, it is shown in Table 1 below. At this time, the voltage drop was measured using a PNE-0506 charger (manufacturer: PNE solution, 5V, 6A).
  • Discharge capacity retention rate (%) (discharge capacity / initial discharge capacity after high temperature storage for 10 weeks) ⁇ 100
  • each of the secondary batteries was subjected to constant current / constant voltage (CC) at 25 ° C. / CV) was charged to 1C up to 4.25V / 55mA and then discharged to 2C up to 2.5V under constant current (CC) conditions.
  • CC constant current / constant voltage
  • each secondary battery was left at 60 ° C. for 10 weeks, and after cooling at room temperature, the thickness change after high temperature storage was measured using a plate thickness meter (Mitsutoyo ( ⁇ )).
  • the thickness increase rate (%) was calculated using the initial thickness measured as described above and the thickness change rate after high temperature storage, and the results are shown in Table 1 below.
  • the lithium secondary batteries prepared in Examples 1 to 6 and the lithium secondary batteries prepared in Comparative Examples 1 to 9 were each 1C up to 4.25V / 55mA at 25 ° C. under constant current / constant voltage (CC / CV) conditions. After charging, the battery was discharged at 2 C up to 3.0 V under constant current conditions. Initial discharge capacity was measured using PNE-0506 charger / discharger (manufacturer: PNE solution, 5V, 6A).
  • the battery was charged with 0.33 C CC up to 4.20 V under constant current-constant voltage (CC-CV) charging conditions at 45 ° C., followed by 0.05 C current cut, and discharged with 0.33 C up to 2.50 V under CC conditions.
  • 500 cycles of charge-discharge were performed using the said charge-discharge as 1 cycle.
  • Discharge capacity after 500 cycles was measured at 45 degreeC using PNE-0506 charger / discharger (manufacturer: PNE solution, 5V, 6A).
  • EC ethylene carbonate
  • EMC ethylmethyl carbonate
  • LiDFP lithium difluorophosphate
  • TVS tetravinylsilane
  • PS 1,3-propanesultone
  • VC vinylene carbonate
  • the secondary batteries prepared in Examples 1 to 6 have a capacity retention (%) of 84.2% or more after 10 weeks of storage at high temperature (60 ° C.), Comparative Examples 1 to 4 and Comparative Examples. It can be seen that compared to the secondary battery manufactured in 6 to Comparative Example 9.
  • the secondary batteries prepared in Examples 1 to 6 have a resistance increase rate of 18.3% or less, and a battery thickness increase rate of 18.7% or less even after 10 weeks of storage at high temperature (60 ° C.), Comparative Examples 1 to 4 and Comparative Examples. It can be seen that the improvement compared to the secondary battery manufactured in 6 to Comparative Example 9.
  • the secondary batteries prepared in Examples 1 to 6 have a discharge capacity retention (%) of 83.9% or more after 500 cycles at a high temperature, and the secondary batteries prepared in Comparative Examples 1 to 4 and Comparative Examples 6 to 9 It can be seen that better.

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Abstract

La présente invention concerne une batterie secondaire au lithium comprenant : une électrode positive; une électrode négative; un séparateur placé entre l'électrode positive et l'électrode négative; et un électrolyte non aqueux, l'électrode positive contenant un matériau actif d'électrode positive représenté par la formule chimique 1 ci-dessous, l'électrolyte non aqueux contenant un solvant organique non aqueux, un sel de lithium et un additif, l'additif étant un additif mélangé contenant difluorophosphate de lithium, tétra-vinylsilane, et un composé à base de sultone selon un rapport pondéral de 1 : 0,05 : 0,1 à 1:1:1,5. [Formule chimique 1] Li(NiaCobMnc)O2 Dans la formule chimique 1, 0,65<a≤0,9, 0,05≤b<0,2, 0,05≤c<0,2, et a+b+c=1.
PCT/KR2019/001127 2018-01-30 2019-01-25 Batterie secondaire au lithium présentant de meilleures caractéristiques de stockage à haute température WO2019151724A1 (fr)

Priority Applications (5)

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CN201980003760.9A CN111052488B (zh) 2018-01-30 2019-01-25 高温存储特性改善的锂二次电池
PL19747419T PL3651254T3 (pl) 2018-01-30 2019-01-25 Akumulator litowy o ulepszonej charakterystyce przechowywania w wysokiej temperaturze
JP2020524328A JP7038967B2 (ja) 2018-01-30 2019-01-25 高温貯蔵特性が向上されたリチウム二次電池
US16/635,371 US11476459B2 (en) 2018-01-30 2019-01-25 Lithium secondary battery having improved high-temperature storage characteristics
EP19747419.0A EP3651254B1 (fr) 2018-01-30 2019-01-25 Batterie secondaire au lithium présentant de meilleures caractéristiques de stockage à haute température

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WO2022133019A1 (fr) * 2020-12-18 2022-06-23 Phillips 66 Company Additifs d'électrolyte in situ pour batteries

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WO2022133019A1 (fr) * 2020-12-18 2022-06-23 Phillips 66 Company Additifs d'électrolyte in situ pour batteries
WO2022133021A1 (fr) * 2020-12-18 2022-06-23 Phillips 66 Company Additifs d'électrolyte ex-situ pour batteries

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