WO2018080259A1 - Électrolyte polymère pour accumulateur et accumulateur le comprenant - Google Patents

Électrolyte polymère pour accumulateur et accumulateur le comprenant Download PDF

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Publication number
WO2018080259A1
WO2018080259A1 PCT/KR2017/012077 KR2017012077W WO2018080259A1 WO 2018080259 A1 WO2018080259 A1 WO 2018080259A1 KR 2017012077 W KR2017012077 W KR 2017012077W WO 2018080259 A1 WO2018080259 A1 WO 2018080259A1
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polymer electrolyte
formula
secondary battery
repeating unit
polymer
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PCT/KR2017/012077
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English (en)
Korean (ko)
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박솔지
안경호
김영제
장용진
한중진
이철행
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주식회사 엘지화학
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Priority claimed from KR1020170140768A external-priority patent/KR102094466B1/ko
Application filed by 주식회사 엘지화학 filed Critical 주식회사 엘지화학
Priority to US16/067,964 priority Critical patent/US10749210B2/en
Priority to EP17866152.6A priority patent/EP3382785B1/fr
Priority to CN201780006910.2A priority patent/CN108701862B/zh
Publication of WO2018080259A1 publication Critical patent/WO2018080259A1/fr

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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/056—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
    • H01M10/0565—Polymeric materials, e.g. gel-type or solid-type
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G81/00—Macromolecular compounds obtained by interreacting polymers in the absence of monomers, e.g. block polymers
    • 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
    • H01M10/0569—Liquid materials characterised by the solvents
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M2300/00—Electrolytes
    • H01M2300/0017—Non-aqueous electrolytes
    • H01M2300/002—Inorganic electrolyte
    • H01M2300/0022—Room temperature molten salts
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M2300/00—Electrolytes
    • H01M2300/0017—Non-aqueous electrolytes
    • H01M2300/0065—Solid electrolytes
    • H01M2300/0082—Organic polymers
    • 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 polymer electrolyte for a secondary battery and a secondary battery comprising the same.
  • Lithium secondary batteries can be divided into lithium ion batteries using liquid electrolytes and lithium polymer batteries using polymer electrolytes, depending on the electrolyte applied.
  • Lithium ion batteries have the advantage of high capacity, but there is a risk of leakage and explosion due to the use of a liquid electrolyte containing lithium salts.
  • the lithium polymer battery uses a solid polymer electrolyte or a gel polymer electrolyte containing an electrolyte as a polymer electrolyte
  • the lithium polymer battery has improved stability and flexibility, and thus may be developed in various forms such as a small size or a thin film type.
  • the gel polymer electrolyte can reduce the number of parts used in the battery manufacturing of the lithium secondary battery can be expected to reduce the cost.
  • polyethylene oxide which has been widely used as a polymer electrolyte, is excellent in dissociating ionic conductive metal salts in spite of being in a solid state. That is, since the cation of the alkali metal salt is stabilized while coordinating with the oxygen atoms present in the polyethylene oxide to form a complex, it is possible to exist in a stable ionic state without a solvent.
  • the polyethylene oxide has a semi-crystalline structure at room temperature, so the crystal structure prevents the dissociation of the metal salt dissociated, resulting in a decrease in energy characteristics such as low ion conductivity values of about 1.0 ⁇ 10 -8 S / cm at room temperature. There is this. Therefore, the level is not suitable for commercialization.
  • hybrid polymer electrolytes or gel polymer electrolytes having an ion conductivity of 1.0 ⁇ 10 ⁇ 4 S / cm or more have been studied by adding a liquid electrolyte of several times to as many as ten times as large as the polymer matrix.
  • Such a gel polymer electrolyte is a copolymer of a polyacrylonitrile (EIC Lab. Inc.), a vinyl chloride, vinyl acetate, acrylonitrile, styrene and a monomer of a heterogeneous monomer selected from a monomer of methyl acrylate (Panasonic Corp. ); Copolymers of high polar monomers such as vinyl chloride, methyl methacrylate, vinyl alcohol and acrylic acid, and low polar monomers such as styrene and butadiene (Nippon Telegraph &Telephone); There are polymethyl methacrylate copolymers and terpolymers (Samsung General Chemistry) having high affinity with the electrolyte solution.
  • the conventional polymer electrolyte it is difficult to manufacture so that both mechanical strength and lithium ion conductivity have excellent effects.
  • a first object of the present invention is to provide a polymer electrolyte for secondary batteries having a high ion conductivity.
  • a second technical object of the present invention is to provide a lithium secondary battery having improved cycle life characteristics and oxidation safety by including the polymer electrolyte for secondary batteries.
  • a polymer electrolyte for a secondary battery including a polymer including at least one or more repeating units of the repeating unit B represented by Formula 2 below.
  • R and R 5 are C or S
  • R 9 is -C (CF 3 ) 2- ,
  • R 3 is -S (CF 2) 2 SO 3 - and Li +,
  • R 4 is Wherein, R 10 is —C (CF 3 ) 2 —,
  • R 8 is ego
  • p, p ', q, q', r and s are 0 or 1
  • N, m, n 'and m' are each the number of moles of the repeating unit
  • n ': m' The molar ratio of n ': m' is 95: 5-5:95.
  • the molar ratio of n: m may be 40:60 to 60:40
  • the molar ratio of n ': m' in Formula 2 may be 40:60 to 60:40.
  • the weight average molecular weight (Mw) of the polymer including the repeating unit represented by Formula 1 or Formula 2 may be 5,000 g / mol to 2,000,000 g / mol, respectively.
  • the repeating unit represented by Formula 1 may be at least one selected from the group consisting of those represented by Formulas 1a to 1c.
  • n1: m1 is the number of moles of the repeating unit
  • n1: m1 The molar ratio of n1: m1 is 95: 5-5: 95.
  • n2: m2 is the number of moles of the repeating unit
  • n2: m2 The molar ratio of n2: m2 is 95: 5-5: 95.
  • n3: m3 is the number of moles of the repeating unit
  • n3: m3 The molar ratio of n3: m3 is 95: 5-5: 95.
  • repeating unit represented by Formula 2 may be represented by the following formula (2a).
  • n'1: m'1 is the number of moles of the repeating unit
  • n'1: m'1 The molar ratio of n'1: m'1 is 95: 5-5: 95.
  • the secondary battery polymer electrolyte may be a free-standing solid polymer electrolyte or a gel polymer electrolyte.
  • the gel polymer electrolyte may further include an electrolyte solution containing a lithium salt and an organic solvent.
  • the gel polymer electrolyte may further include an ionic liquid.
  • anode cathode; And a polymer electrolyte formed on at least one surface of the positive electrode and the negative electrode.
  • the polymer electrolyte provides a lithium secondary battery including the polymer electrolyte for a secondary battery of the present invention.
  • the lithium secondary battery may further include a separator, in which case the polymer electrolyte may be formed on at least one surface of at least one of the positive electrode, the negative electrode, and the separator.
  • the movement effect of lithium ions is improved to have high ion conductivity.
  • Polymer electrolytes can be prepared. In addition, by including this, it is possible to manufacture a lithium secondary battery with improved cycle life characteristics and oxidation safety.
  • a polymer electrolyte for a secondary battery including a polymer including at least one or more units of the repeating unit B represented by Formula 2 below.
  • R and R 5 are C or S
  • R 9 is -C (CF 3 ) 2- ,
  • R 3 is -S (CF 2) 2 SO 3 - and Li +,
  • R 4 is Wherein, R 10 is —C (CF 3 ) 2 —,
  • R 8 is ego
  • p, p ', q, q', r and s are 0 or 1
  • N, m, n 'and m' are each the number of moles of the repeating unit
  • n ': m' The molar ratio of n ': m' is 95: 5-5:95.
  • the molar ratio of n: m may be 40:60 to 60:40
  • the molar ratio of n ': m' in Formula 2 may be 40:60 to 60:40.
  • n, m, n 'and m' in the repeating unit represented by Formula 1 or Formula 2 independently means the number of moles of the repeating unit
  • m and n 'and m' may be arranged alternately, in graft form or randomly, with or without rules.
  • the molar ratio of n: m may be 40:60 to 60:40, more specifically 50:50.
  • the mole ratio of n ': m' may be 40:60 to 60:40, more specifically 50:50.
  • the weight average molecular weight (Mw) of the polymer including the repeating unit represented by Formula 1 or Formula 2 may each independently be 5,000 g / mol to 2,000,000 g / mol, specifically 500,000 g / mol to 1,000,000 g / mol. .
  • the weight average molecular weight of the unit When the weight average molecular weight of the unit is in the above range, the stability of the electrolyte is excellent and the chemical and physical properties are excellent.
  • the weight average molecular weight (Mw) of the repeating unit (A) represented by Formula 1 or Formula 2 may be measured using gel permeation chromatography (GPC). For example, after preparing a sample sample of a certain concentration, the GPC measurement system alliance 4 instrument is stabilized.
  • the repeating unit represented by Formula 1 may be at least one or more selected from the group consisting of those represented by the following formulas (1a to 1c). .
  • n1: m1 is the number of moles of the repeating unit
  • n1: m1 The molar ratio of n1: m1 is 95: 5-5: 95.
  • n2: m2 is the number of moles of the repeating unit
  • n2: m2 The molar ratio of n2: m2 is 95: 5-5: 95.
  • n3: m3 is the number of moles of the repeating unit
  • n3: m3 The molar ratio of n3: m3 is 95: 5-5: 95.
  • repeating unit represented by Formula 2 may be represented by the following formula (2a).
  • n'1: m'1 is the number of moles of the repeating unit
  • n'1: m'1 The molar ratio of n'1: m'1 is 95: 5-5: 95.
  • the polymer electrolyte of the present invention may be a free-standing solid polymer electrolyte including a polymer including a repeating unit represented by Formula 1 or Formula 2.
  • the polymer electrolyte of the present invention is the self-supporting solid polymer electrolyte
  • Li + ion source is present in the polymer including the repeating unit represented by Formula 1 and the repeating unit represented by Formula 2
  • the battery may be driven in the form of an all solid-ion battery.
  • the self-supporting solid polymer electrolyte of the present invention may be formed according to a conventional solution casting method known in the art. That is, at least one or more of the repeating units represented by Chemical Formula 1 or 2 is prepared in the form of a coating solution by dissolving in an organic solvent, and then cast on a support substrate (casting film) and dried to form a film ) Can be formed.
  • the supporting substrate may include a glass substrate, PET (polyethylene terephthalate), Teflon, FEP film, or the like.
  • a volatile organic solvent having a low boiling point may be used to facilitate removal.
  • examples thereof include N, N'-dimethylacetamide and N-methyl-2-pyrroli.
  • NMP pig
  • DMSO dimethyl sulfoxide
  • DMF N-dimethylformamide
  • acetonitrile acetonirile
  • the amount of the organic solvent is not particularly limited as long as it can be easily removed after dissolving the polymer including the repeating unit represented by the formula (1) or (2) by applying a uniform thickness.
  • the amount of the organic solvent exceeds 10,000 parts by weight, it is difficult to remove the organic solvent in a short time, and it is difficult to sufficiently secure the mechanical properties, thin film thickness, and ion conductivity effects of the polymer electrolyte due to the remaining of the organic solvent. .
  • the amount of the organic solvent is less than 100 parts by weight, it is difficult to dissolve the repeating unit represented by the formula (1) or (2), the uniformity of the film may be lowered during the molding of the polymer electrolyte.
  • the general polymer electrolyte has a disadvantage of having low ion conductivity because the resistance in the battery is greater than that of the liquid electrolyte, and thus the movement speed of lithium ions is slow.
  • the polymer comprising a repeating unit represented by the formula (1) or (2) of the present invention is in the form of a conjugated polymer (conjugated polymer), by containing both lithium ions (Li + ) and sulfonate groups in the polymer structure, In addition to suppressing side reactions of lithium ions (Li + ), decomposition of salts, and the like by the stationary phase, lithium ions can be freed (free Li + ) to improve lithium ion transfer effects.
  • the polymer electrolyte including the polymer including at least one unit of the repeating unit A and the repeating unit B represented by the general formula (2) of the present invention not only excellent mechanical properties can be secured, With high ionic conductivity, good thermal, chemical, and oxidative stability can be achieved.
  • the polymer electrolyte of the present invention may be a gel polymer electrolyte in which a lithium salt-containing electrolyte is used together to impart an ion transfer characteristic effect.
  • the gel polymer electrolyte (or the solid-liquid mixed electrolyte) of the present invention may include a solid polymer electrolyte including a polymer including a repeating unit represented by Formula 1 or Formula 2 of the present invention in an electrode assembly in a battery case.
  • the lithium salt-containing electrolyte solution can be injected by dissolving the solid polymer electrolyte membrane without melting the solid polymer electrolyte membrane, thereby forming the solid polymer electrolyte by swelling.
  • the anion wherein the lithium salt comprises a Li + cation are F -, Cl -, Br - , I -, NO 3 -, N (CN) 2 -, BF 4 -, ClO 4 -, AlO 4 -, AlCl 4 -, PF 6 -, SbF 6 -, AsF 6 -, BF 2 C 2 O 4 -, B (C 2 O 4) 2 -, (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 -, C 4 F 9 SO 3 -, CF 3 CF 2 SO 3 - , (FSO 2) 2 N - , CF 3 CF 2 (CF 3) 2 CO -, (CF 3 SO 2) 2 N -, (SF 5) 3 C -, (CF 3 SO 2) 3 C -, CF 3 C -,
  • the said lithium salt can also be used 1 type or in mixture of 2 or more types as needed.
  • the lithium salt may be appropriately changed within a conventionally usable range, but may be included at a concentration of 0.5M to 5M in the polymer electrolyte in order to obtain an effect of forming an anti-corrosion coating on the surface of the electrode.
  • the organic solvent may use both a low boiling point volatile organic solvent or a high boiling point nonvolatile organic solvent, specifically, propylene carbonate (PC), ethylene carbonate (EC), butylene carbonate (BC), dimethyl carbonate ( DMC), diethyl carbonate (DEC), ethyl methyl carbonate (EMC), fluoroethylene carbonate (FEC), gamma-butyrolactone (GBL), 1,2-dimethoxyethane, tetrahydroxyfuran, 2-methyl Tetrahydrofuran (THF), dimethyl sulfoxide, 1,3-dioxolon (DOL), 1,4-dioxane (4-dioxane), formamide, dimethylformamide, dioxolon, acetonitrile, nitromethane Methyl formate, methyl acetate (MA), ethyl acetate (EA), methyl propionate (MP), ethyl propionate (EP), propylene carbon
  • the organic solvent may not be easily blown, and a non-volatile organic solvent having a high boiling point such as tetraglyme may be additionally used to swell the polymer electrolyte and maintain the gel polymer electrolyte.
  • a non-volatile organic solvent having a high boiling point such as tetraglyme may be additionally used to swell the polymer electrolyte and maintain the gel polymer electrolyte.
  • the amount of the organic solvent is not particularly limited, but may be used in a range capable of sufficiently securing the uniformity of the membrane when forming the gel polymer electrolyte, and sufficiently securing mechanical properties, thin film thickness, and ion conductivity effects.
  • the gel polymer electrolyte of the present invention may further include an ionic liquid as needed.
  • an ionic liquid can be used after additionally pouring the lithium salt-containing electrolyte solution.
  • the ionic liquid in the ion conductivity high ingredient is impregnated into or alone with the electrolyte in the polymer electrolyte by improving movement (Li + flux) of lithium ions in the polymer electrolyte, on the negative electrode surface Li + ion plating or
  • the phenomenon of stripping can be made uniform, and the production of lithium dendrites can be suppressed, and the flame retardant property can bring safety when applied inside the battery.
  • Such ionic liquids include, for example, diethylmethylammonium trifluoromethanesulfonate, dimethylpropylammonium trifluoromethanesulfonate, N, N-diethyl-N-methyl-N- (2-methoxyethyl) ammonium Bis (trifluoromethanesulfonyl) imide, N-methyl-N-propylpiperidium bis (trifluoromethanesulfonyl) imide, N-butyl-N-methyl pyrrolidium bis (trifluoromethanesulfonyl ) Imide and methylpropylpiperidiumtrifluoro methanesulfonylimide.
  • the ionic liquid may be included in an amount of 50 wt% or less, specifically 0.01 wt% to 50 wt%, and more specifically 0.01 wt% to 20 wt%, based on the total weight of the polymer electrolyte.
  • lithium dendrite may be formed on the surface of the lithium negative electrode have.
  • It includes a positive electrode, a negative electrode and a polymer electrolyte formed on at least one surface of the positive electrode and the negative electrode,
  • the polymer electrolyte provides a lithium secondary battery comprising the polymer electrolyte of the present invention.
  • the polymer electrolyte may include a freestanding solid polymer electrolyte or a gel polymer electrolyte.
  • the lithium secondary battery of the present invention may be manufactured in the following steps.
  • the positive electrode may be prepared by forming a positive electrode mixture layer on the positive electrode current collector.
  • the cathode mixture layer may be prepared by coating a cathode active material slurry including a cathode active material, a binder, a conductive material, a solvent, and the like, followed by drying and rolling.
  • 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 positive electrode active material is a compound capable of reversible intercalation and deintercalation of lithium, and may specifically include a lithium composite metal oxide containing lithium and one or more metals such as cobalt, manganese, nickel or aluminum. have. More specifically, the lithium composite metal oxide is a lithium-manganese oxide (eg, LiMnO 2 , LiMn 2 O 4, etc.), lithium-cobalt oxide (eg, LiCoO 2, etc.), lithium-nickel oxide (for example, LiNiO 2 and the like), lithium-nickel-manganese-based oxide (for example, LiNi 1-Y Mn Y O 2 (where, 0 ⁇ Y ⁇ 1), LiMn 2-z Ni z O 4 ( here, 0 ⁇ Z ⁇ 2) and the like), lithium-nickel-cobalt oxide (e.g., LiNi 1-Y1 Co Y1 O 2 (here, 0 ⁇ Y1 ⁇ 1) and the like), lithium-manganese-cobal
  • the lithium composite metal oxide may be LiCoO 2 , LiMnO 2 , LiNiO 2 , or lithium nickel manganese cobalt oxide (for example, Li (Ni 1/3 Mn 1/3 Co 1). / 3) O 2, Li ( Ni 0.6 Mn 0.2 Co 0.2) O 2, Li (Ni 0.5 Mn 0.3 Co 0.2 ) O 2 , Li (Ni 0.7 Mn 0.15 Co 0.15 ) O 2, and Li (Ni 0.8 Mn 0.1 Co 0.1 ) O 2 , or the like, or lithium nickel cobalt aluminum oxide (eg, Li (Ni 0.8 Co 0.15 Al 0.05 ) O 2 , and the like.
  • Li ( Ni 0.6 Mn 0.2 Co 0.2) O 2 Li (Ni 0.5 Mn 0.3 Co 0.2 ) O 2 , Li (Ni 0.7 Mn 0.15 Co 0.15 ) O 2
  • the cathode active material may be included in an amount of 40 wt% to 90 wt%, specifically 40 wt% to 75 wt%, based on the total weight of solids in the cathode active material slurry.
  • the binder is a component that assists the bonding between the active material and the conductive material and the current collector, and is generally added in an amount of 1 to 30 wt% based on the total weight of solids in the cathode active material slurry.
  • binders include polyvinylidene fluoride (PVDF), polyvinyl alcohol, carboxymethyl cellulose (CMC), starch, hydroxypropyl cellulose, regenerated cellulose, polyvinylpyrrolidone, tetrafluoro Low ethylene, polyethylene, polypropylene, ethylene-propylene-diene terpolymer (EPDM), sulfonated EPDM, styrene-butadiene rubber, fluorine rubber, various copolymers, and the like.
  • PVDF polyvinylidene fluoride
  • CMC carboxymethyl cellulose
  • EPDM ethylene-propylene-diene terpolymer
  • EPDM sulfonated EPDM
  • the conductive material is typically added in an amount of 1 wt% to 30 wt% based on the total weight of solids in the cathode active material 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 Graphite powders 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 whiskeys 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 conductive material is Chevron Chemical Company, Denka Singapore Private Limited, Gulf Oil Company, etc., Ketjenblack, EC series (Armak Company) Armak Company), Vulcan XC-72 (Cabot Company), and Super P (manufactured by Timcal) can also be used.
  • 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 concentration of the solids in the slurry including the positive electrode active material and optionally the binder and the conductive material may be 10 wt% to 60 wt%, preferably 20 wt% to 50 wt%.
  • the negative electrode may be prepared by forming a negative electrode mixture layer on the negative electrode current collector.
  • the negative electrode mixture layer may be formed by coating a negative electrode active material 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 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 active material may be lithium metal, a carbon material capable of reversibly intercalating / deintercalating lithium ions, a metal or an alloy of these metals and lithium, a metal complex oxide, and may dope and undo lithium. At least one selected from the group consisting of materials, and transition metal oxide 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, Pb, Ge; 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) may 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) element and an element selected from the group consisting of, Sn and the like are not), and may also use a mixture of at least one of these with SiO 2.
  • transition metal oxide examples include lithium-containing titanium composite oxide (LTO), vanadium oxide, lithium vanadium oxide, and the like.
  • the negative active material may be included in an amount of 80 wt% to 99 wt% based on the total weight of solids in the slurry of the negative electrode active material.
  • the binder is a component that assists the bonding between the conductive material, the active material and the current collector, and is typically added in an amount of 1 to 30 wt% based on the total weight of solids in the slurry of the negative electrode active material.
  • binders include polyvinylidene fluoride (PVDF), polyvinyl alcohol, carboxymethyl cellulose (CMC), starch, hydroxypropyl cellulose, regenerated cellulose, polyvinylpyrrolidone, tetrafluoro Low ethylene, polyethylene, polypropylene, ethylene-propylene-diene polymer (EPDM), sulfonated-EPDM, styrene-butadiene rubber, fluorine rubber, various copolymers thereof, and the like.
  • PVDF polyvinylidene fluoride
  • CMC carboxymethyl cellulose
  • EPDM ethylene-propylene-diene polymer
  • sulfonated-EPDM styrene-buta
  • 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 to 20 wt% based on the total weight of solids in the negative electrode active material slurry.
  • a conductive material is not particularly limited as long as it has conductivity without causing chemical change in the battery, and examples thereof include graphite such as natural graphite and artificial graphite; Carbon blacks such as acetylene black, Ketjen black, channel black, furnace black, lamp black and thermal black; Conductive fibers such as carbon fibers and metal fibers; Metal powders such as carbon fluoride powder, aluminum powder and nickel powder; Conductive whiskeys 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, alcohol, etc., 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 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 65 wt%.
  • the lithium secondary battery of the present invention may further include a separator as necessary.
  • the separator serves to block internal short circuits of both electrodes and to impregnate an electrolyte, to prepare a separator composition by mixing a polymer resin, a filler, and a solvent, and then directly coating and separating the separator composition on an electrode to separate the separator film.
  • the separator film separated 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 range from 5 to 300 ⁇ m.
  • the polymer electrolyte of the present invention is disposed on at least one surface of at least one of the positive electrode and the negative electrode or on at least one surface of the positive electrode, the negative electrode and the separator.
  • the polymer electrolyte is prepared in the form of a film using a polymer including a repeating unit represented by Chemical Formula 1 or Chemical Formula 2, and then at least one of a cathode, an anode, and a separator manufactured.
  • Intercalation (introduction) on one side or 2 dissolving a polymer containing a repeating unit represented by Formula 1 or Formula 2 in an organic solvent to prepare a coating solution, and then the coating solution is prepared in the negative electrode, the positive electrode and the separator After apply
  • the solid polymer electrolyte membrane may be formed on at least one surface of the cathode, the anode, and the separator by the above method, and then the liquid electrolyte may be additionally injected to swell the solid polymer electrolyte to form a gel polymer electrolyte (solid-liquid mixed electrolyte).
  • the liquid electrolyte may be additionally injected to swell the solid polymer electrolyte to form a gel polymer electrolyte (solid-liquid mixed electrolyte).
  • the thickness of the polymer electrolyte in the form of a membrane is preferably a thin membrane in consideration of ion conductivity, but specifically, may be 0.5 ⁇ m to 300 ⁇ m.
  • the thickness of the electrolyte membrane is less than 0.5 ⁇ m, the strength of the membrane is remarkably reduced, so that it is difficult to apply the electrolyte membrane.
  • the thickness of the electrolyte membrane exceeds 300 ⁇ m, protons (Li + ), which are ion transporters, are difficult to pass, Since the volume per performance is increased, it is difficult to manufacture a secondary battery having a high energy density.
  • a polymer electrolyte including a polymer including at least one or more repeating units of the repeating unit A represented by Formula 1 and the repeating unit B represented by Formula 2 is introduced into a component of a lithium secondary battery.
  • a polymer electrolyte including a polymer including at least one or more repeating units of the repeating unit A represented by Formula 1 and the repeating unit B represented by Formula 2 is introduced into a component of a lithium secondary battery.
  • the positive electrode active material slurry was applied to the surface of the aluminum (Al) thin film having a thickness of 20 ⁇ m to a thickness of 10 ⁇ m and dried to prepare a positive electrode plate having a positive electrode mixture layer.
  • Lithium metal was coated on the Cu thin film, and then rolled to prepare a negative electrode plate having a thickness of 20 ⁇ m.
  • An electrode assembly is manufactured between a cathode and a cathode including a polymer electrolyte through a polyolefin-based separator (thickness: 20 ⁇ m), and the electrode assembly is accommodated in a pouch-type battery case to store a 4.2V class lithium secondary battery (Full). cell) was prepared.
  • Mw weight average molecular weight
  • a 4.2V-class lithium secondary battery was manufactured in the same manner as in Example 1, except that a 4.2V-class secondary cell including a gel polymer electrolyte was manufactured.
  • a 4.2V class lithium secondary battery was manufactured in the same manner as in Example 2, except that a 4.2V class secondary battery including a gel polymer electrolyte was manufactured.
  • a 4.2V class lithium secondary battery was manufactured in the same manner as in Example 3, except that the 4.2V secondary battery including the gel polymer electrolyte was manufactured.
  • a 4.2V class lithium secondary battery was manufactured in the same manner as in Example 4, except that the 4.2V secondary battery including the gel polymer electrolyte was manufactured.
  • Example 5 In preparing the secondary battery of Example 5, 4.2V class lithium secondary battery was prepared in the same manner as in Example 5, except that 20% ionic liquid (EMIM-FSI) was additionally added after the non-aqueous electrolyte solution. Prepared.
  • EMIM-FSI 20% ionic liquid
  • Example 8 In preparing the secondary battery of Example 8, 4.2V class lithium secondary battery was prepared in the same manner as in Example 8, except that 20% ionic liquid (EMIM-FSI) was additionally injected after the nonaqueous electrolyte solution. Prepared.
  • EMIM-FSI 20% ionic liquid
  • Example 1 In preparing the polymer electrolyte in Example 1, except that a linear polyethylene glycol copolymer was used instead of the polymer including the repeating unit represented by Formula 1a, the solid polymer electrolyte and the same method as in Example 1 A lithium secondary battery including the same was prepared.
  • the positive electrode mixture was applied to the surface of the aluminum (Al) thin film having a thickness of 20 ⁇ m to a thickness of 10 ⁇ m and dried to prepare a positive electrode plate.
  • Lithium metal was coated on the Cu thin film, and then rolled to prepare a negative electrode plate having a thickness of 20 ⁇ m.
  • a lithium secondary battery was manufactured in the same manner as in Comparative Example 1, except that a 4.2V secondary battery including a gel polymer electrolyte was manufactured.
  • Cycle capacity retention rate (%) which is the ratio of the discharge capacity at the 50th cycle to the initial capacity, was measured, and the values are shown in FIGS. 1 and 1 below, respectively.
  • Cycle capacity retention rate (%) which is the ratio of the discharge capacity at the 50th cycle to the initial capacity, was measured, and the values are shown in Table 2, respectively.
  • the gel polymer electrolytes prepared in Examples 5 to 8 and 10 and the gel polymer electrolytes prepared in Comparative Examples 4 and 5 were injected into a band-shaped conductive glass substrate or lithium-copper foil, followed by thermosetting to polymerize, After drying sufficiently, the AC impedance of the band-type or sandwich-type electrode value was measured under an argon atmosphere, and the ionic conductivity was measured by analyzing the measured value with a frequency response analyzer, and analyzing the complex impedance. Shown in
  • the band-shaped electrode was attached to a masking tape having a width of about 1 mm to the conductive glass (ITO) at intervals of 2 cm, placed in an etching solution, etched, washed, and dried to prepare a cell.
  • the ion conductivity was measured in the frequency band 100MHz ⁇ 0.1Hz using VMP3 measuring equipment and 4294A.
  • the gel prepared in Comparative Example 4 Ion conductivity of the polymer electrolyte is 3 ⁇ 10 -6 S / cm, the ion conductivity of the gel polymer electrolyte prepared in Comparative Example 5 is 6 ⁇ 10 -5 S / cm, prepared in Examples 5 to 8 and Example 10 It can be seen that the gel polymer electrolyte is significantly lowered.
  • the lithium secondary batteries prepared in Examples 1 to 9 and the secondary batteries prepared in Comparative Examples 1 and 2 were subjected to linear sweep voltammetry (LSV) or cyclic voltammetry up to 7V. Electrochemical (oxidation) safety was measured at 60 ° C. The results are shown in Table 4 below.
  • the electrolyte specimen was prepared through ASTM standard D638 (Type V specimens), the tensile strength was measured at a tensile rate of 5mm per minute at 25 °C, about 30% relative humidity through Lloyd LR-10K. The results are shown in Table 5 below.
  • the solid polymer electrolytes prepared in Examples 1 to 4 have a tensile strength of 6 kPa or more, compared to the solid polymer electrolyte prepared in Comparative Example 3 (0.1 kPa). Can be.

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Abstract

La présente invention concerne un électrolyte polymère pour accumulateur, offrant une conductivité ionique élevée, et un accumulateur lithium le comprenant.
PCT/KR2017/012077 2016-10-31 2017-10-30 Électrolyte polymère pour accumulateur et accumulateur le comprenant WO2018080259A1 (fr)

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US16/067,964 US10749210B2 (en) 2016-10-31 2017-10-30 Polymer electrolyte for secondary battery and secondary battery including the same
EP17866152.6A EP3382785B1 (fr) 2016-10-31 2017-10-30 Électrolyte polymère pour accumulateur et accumulateur l'incluant
CN201780006910.2A CN108701862B (zh) 2016-10-31 2017-10-30 用于二次电池的聚合物电解质以及包含其的二次电池

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KR20160143353 2016-10-31
KR10-2016-0143353 2016-10-31
KR1020170140768A KR102094466B1 (ko) 2016-10-31 2017-10-27 이차전지용 고분자 전해질 및 이를 포함하는 이차전지
KR10-2017-0140768 2017-10-27

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Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN112567557A (zh) * 2018-09-21 2021-03-26 株式会社Lg化学 用于凝胶聚合物电解质的组合物和包括由该组合物形成的凝胶聚合物电解质的锂二次电池
CN113299986A (zh) * 2021-05-24 2021-08-24 东莞新能安科技有限公司 电解质膜及包含其的电化学装置和电子设备

Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20090163692A1 (en) * 2007-12-21 2009-06-25 General Electric Company Aromatic polyethers
KR20150045361A (ko) * 2013-10-18 2015-04-28 주식회사 엘지화학 분리막 및 그를 포함하는 리튬-황 전지
WO2016012669A1 (fr) * 2014-07-23 2016-01-28 Cdp Innovation Nouveaux polymeres contenant des sels de lithium ou de sodium de sulfonamides, leurs procedes de preparation et leurs utilisations comme electrolytes pour batteries
KR20160024411A (ko) * 2014-08-25 2016-03-07 삼성전자주식회사 리튬 전지용 고분자 전해질 및 이를 구비한 리튬 전지
KR20160037616A (ko) * 2014-09-29 2016-04-06 주식회사 엘지화학 리튬이온전달소재 및 이의 제조 방법

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20090163692A1 (en) * 2007-12-21 2009-06-25 General Electric Company Aromatic polyethers
KR20150045361A (ko) * 2013-10-18 2015-04-28 주식회사 엘지화학 분리막 및 그를 포함하는 리튬-황 전지
WO2016012669A1 (fr) * 2014-07-23 2016-01-28 Cdp Innovation Nouveaux polymeres contenant des sels de lithium ou de sodium de sulfonamides, leurs procedes de preparation et leurs utilisations comme electrolytes pour batteries
KR20160024411A (ko) * 2014-08-25 2016-03-07 삼성전자주식회사 리튬 전지용 고분자 전해질 및 이를 구비한 리튬 전지
KR20160037616A (ko) * 2014-09-29 2016-04-06 주식회사 엘지화학 리튬이온전달소재 및 이의 제조 방법

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN112567557A (zh) * 2018-09-21 2021-03-26 株式会社Lg化学 用于凝胶聚合物电解质的组合物和包括由该组合物形成的凝胶聚合物电解质的锂二次电池
CN112567557B (zh) * 2018-09-21 2024-04-16 株式会社Lg新能源 用于凝胶聚合物电解质的组合物和包括由该组合物形成的凝胶聚合物电解质的锂二次电池
CN113299986A (zh) * 2021-05-24 2021-08-24 东莞新能安科技有限公司 电解质膜及包含其的电化学装置和电子设备

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