[go: up one dir, main page]

WO2018190665A1 - Électrolyte solide polymère et batterie secondaire au lithium comprenant celui-ci - Google Patents

Électrolyte solide polymère et batterie secondaire au lithium comprenant celui-ci Download PDF

Info

Publication number
WO2018190665A1
WO2018190665A1 PCT/KR2018/004316 KR2018004316W WO2018190665A1 WO 2018190665 A1 WO2018190665 A1 WO 2018190665A1 KR 2018004316 W KR2018004316 W KR 2018004316W WO 2018190665 A1 WO2018190665 A1 WO 2018190665A1
Authority
WO
WIPO (PCT)
Prior art keywords
solid electrolyte
polymer solid
formula
polymer
lithium
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Ceased
Application number
PCT/KR2018/004316
Other languages
English (en)
Korean (ko)
Inventor
김승하
최영철
채종현
김경훈
이연주
김대일
김루시아
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
LG Chem Ltd
Original Assignee
LG Chem Ltd
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Priority claimed from KR1020180042604A external-priority patent/KR102160709B1/ko
Application filed by LG Chem Ltd filed Critical LG Chem Ltd
Priority to JP2019512775A priority Critical patent/JP6742651B2/ja
Priority to US16/330,795 priority patent/US10886563B2/en
Priority to CN201880004041.4A priority patent/CN109863634B/zh
Priority to EP18783779.4A priority patent/EP3512023B1/fr
Publication of WO2018190665A1 publication Critical patent/WO2018190665A1/fr
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

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
    • 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
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/42—Methods or arrangements for servicing or maintenance of secondary cells or secondary half-cells
    • 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 solid electrolyte and a lithium secondary battery comprising the same.
  • Lithium secondary batteries are used in various industries, such as automotive batteries, in small electronic devices such as smartphones, laptops, and tablet PCs. These developments are being made toward technology miniaturization, light weight, high performance, and high capacity.
  • the lithium secondary battery includes a negative electrode, a positive electrode and an electrolyte.
  • Lithium, carbon, and the like are used as a negative electrode active material of the lithium secondary battery, a transition metal oxide, a metal chalcogen compound, a conductive polymer, and the like are used as the positive electrode active material, and a liquid electrolyte, a solid electrolyte, and a polymer electrolyte are used as the electrolyte. have.
  • the polymer electrolyte is environmentally friendly because there is no problem such as leakage of liquid generated from the liquid electrolyte, and the thin film and the processing of the film form can be processed, and thus the structure of the device can be easily changed to any desired shape.
  • the polymer electrolyte is composed of a polymer, a lithium salt, a non-aqueous organic solvent (optional), and other additives.
  • the polymer electrolyte exhibits an ionic conductivity of about 10-8 S / cm at room temperature, so that performance is much lower than that of the non-aqueous liquid electrolyte. There was a problem.
  • the ion conductivity of the polymer electrolyte and the ion conductivity of the non-aqueous liquid electrolyte are It has been reported that similar up to 10-3 S / cm can be improved.
  • the present inventors have conducted various studies to develop a polymer solid electrolyte capable of attaining ionic conductivity and excellent interfacial stability at the same time, and as a result, the organic solvent having high HOOC (highest occupied molecular orbital) energy as an additive
  • the compound was selected, and the higher the HOMO energy of the organic compound, the better electrons escape from the electrolyte molecules, and the better the ion conductivity, and the easier the oxidation on the surface of the anode. It was confirmed that the protection could improve the oxidation stability of the anode interface.
  • an object of the present invention is to provide a polymer solid electrolyte for preparing a polymer solid electrolyte.
  • the present invention also provides a lithium secondary battery including the polymer solid electrolyte.
  • the present invention is a polymer solid electrolyte comprising a polymer for electrolyte electrolyte, lithium salt and additives
  • the additive is a polymer that is an organic compound having a high occupied molecular orbital (HOMO) energy of -8.5 eV or more It provides a solid electrolyte.
  • HOMO high occupied molecular orbital
  • the HOMO energy may be -7.6 eV or more.
  • the organic compound may be vinylene carbonate (VC); Fluoroethylene carbonate (FEC); Vinyl ethylene carbonate (VEC); Pyridine-boron trifluoride (PBT); Succinonitrile (SN); A compound represented by Formula 1; A compound represented by Formula 2; A compound represented by Formula 3; A compound represented by Formula 4; And it may be at least one selected from the group consisting of a compound represented by the formula (5):
  • the electrolyte polymer is polyethylene oxide (PEO), polyethylene carbonate (PEC), polypropylene carbonate (PPC), polyvinylidene fluoride (poly (vinylidene fluoride), PVDF), polyethylene glycol (poly (ethylene glycol), PEG), poly phenylene sulfide (poly phenylene sulfide (PPS)) and derivatives thereof may be one or more selected from the group consisting of.
  • the lithium salt is LiCl, LiBr, LiI, LiClO 4 , LiBF 4 , LiB 10 Cl 10 , LiPF 6 , LiAsF 6 , LiSbF 6 , LiAlCl 4 , LiSCN, Li (FSO 2 ) 2 N LiCF 3 CO 2 , LiCH 3 SO 3 , LiCF 3 SO 3 , LiN (SO 2 CF 3 ) 2 , LiTFSI, LiFSI, LiOH, LiOHH 2 O, LiBOB, LiN (SO 2 C 2 F 5 ) 2 , LiC 4 F 9 SO 3 , LiC (CF 3 SO 2 ) 3 , (CF 3 SO 2 ) 2 NLi, LiOH.H 2 O, LiB (C 2 O 4 ) 2 , lithium chloroborane, lower aliphatic lithium carbonate, lithium phenyl borate and lithium imide It may be one or more selected.
  • the lithium salt may be contained 10 to 30% by weight based on the total weight of the polymer solid electrolyte.
  • the polymer solid electrolyte may further include an organic solvent,
  • the organic solvent is 4-acetylmorpholine, 2-methylpyridine-1-oxide, 2-pyrrolidon, 2-pyrrolidon, 1- (2-hydroxyethyl ) -2-pyrrolidone (1- (2-hydroxyethyl) -2-pyrrolidinone), propylene carbonate (PC), ethylene carbonate (EC), 2-oxepanone, Butanone (butanone), 2-pentanone (2-pentanone) and methyl ethyl ketone (methyl ethyl ketone, MEK) may be one or more selected from the group consisting of.
  • the present invention provides a lithium secondary battery comprising the polymer solid electrolyte.
  • the polymer solid electrolyte according to the present invention can improve the performance of the lithium secondary battery by securing high ion conductivity and interfacial stability at the positive electrode.
  • FIG. 1 is a cross-sectional view showing a lithium secondary battery according to the present invention.
  • 2A to 2C are schematic diagrams of cells prepared for evaluating the extent to which electrolyte components reach the anode surface by molecular dynamics.
  • FIG. 3 is a graph showing a positive electrode surface distribution (Probi, first layer) of an electrode protective additive with respect to the degree of reaching the positive electrode surface during charging of a lithium secondary battery according to the polymer solid electrolyte prepared in Examples 1 to 5, respectively.
  • FIG. 4 is a graph illustrating a distribution diagram (Probi, first layer) of an electrode protective additive included in the surface of the positive electrode when the lithium secondary battery is charged, according to the polymer solid electrolytes prepared in Examples 5 to 10, respectively.
  • the polymer solid electrolyte according to the present invention includes an electrolyte polymer, a lithium salt, and an additive, and has excellent characteristics of reaching the anode as the additive, and also has a low oxidation potential and excellent film formation and adsorption characteristics on the surface of the anode. It may be an organic compound having a low oxidation potential.
  • the additive may be an electrode protective additive, and the oxidation potential of the organic compound may be defined by a high occupied molecular orbital (HOMO) energy level.
  • HOMO high occupied molecular orbital
  • HOMO energy level that can define the oxidation potential of the organic compound can be analyzed by the B3PW91 / 6-31 + G * level in the Gaussian 09 program.
  • the additive may be an organic compound having a HOMO energy of -8.5 eV or more, preferably -7.6 eV or more, more preferably -7.6 eV to -6.3 eV.
  • HOMO energy of the additive is less than the above range, it is not easy to form a film on the surface of the anode, the effect of improving the interface stability may be insignificant.
  • the higher the HOMO energy may be excellent in improving the surface stability, but if excessively high, such as greater than -6.3 eV, the thickness of the formed film may be thickened, rather the performance of the battery may be lowered.
  • the organic compound may be vinylene carbonate (VC); Fluoroethylene carbonate (FEC); Vinyl ethylene carbonate (VEC); Pyridine-boron trifluoride (PBT); Succinonitrile (SN); A compound represented by Formula 1; A compound represented by Formula 2; A compound represented by Formula 3; A compound represented by Formula 4; And it may be at least one selected from the group consisting of a compound represented by the formula (5):
  • VC vinylene carbonate
  • FEC fluoroethylene carbonate
  • VEC vinyl ethylene carbonate
  • PBT pyridine-boron trifluoride
  • succinonitrile succinonitrile
  • SN, VC, FEC, VEC, and PBT represented by Chemical Formula 6 of the organic compound may have HOMO energy of ⁇ 8.5 eV or more, preferably ⁇ 8.5 eV to ⁇ 7.3 eV, and are represented by Chemical Formulas 1 to 5 HOMO energy of the organic compound may be -7.6 eV or more, preferably -7.6 eV to -6.3 eV.
  • the content of the organic compound may be 0.1 to 20% by weight, preferably 5 to 15% by weight, and more preferably 8 to 13% by weight, based on the total weight of the polymer solid electrolyte. If it is less than the above range, it is difficult to form a film at the anode, so that stability at the anode interface may be lowered, and if it is more than the above range, ion conductivity may be lowered.
  • the electrolyte polymer is polyethylene oxide (PEO), polyethylene carbonate (PEC), polypropylene carbonate (PPC), polyvinylidene fluoride (poly (vinylidene fluoride) ), PVDF), polyethylene glycol (poly (ethylene glycol), PEG), poly phenylene sulfide (poly phenylene sulfide (PPS)) and derivatives thereof may be one or more selected from the group consisting of.
  • the electrolyte polymer may be polyethylene (poly (ethylene oxide), PEO).
  • the content of the electrolyte polymer may be 10 to 30% by weight, preferably 15 to 25% by weight, more preferably 18 to 23% by weight based on the total weight of the polymer solid electrolyte. If it is less than the above range, the life of the battery may be reduced, and if it is above the above range, the ionic conductivity may be reduced.
  • the lithium salt used as an ion supply compound in the polymer solid electrolyte of the present invention may improve lithium ion conductivity, and according to one embodiment of the present invention, the ion supply compound may be a lithium salt.
  • lithium salt examples include LiCl, LiBr, LiI, LiClO 4 , LiBF 4 , LiB 10 Cl 10 , LiPF 6 , LiAsF 6 , LiSbF 6 , LiAlCl 4 , LiSCN, Li (FSO 2 ) 2 N LiCF 3 CO 2 , LiCH 3 SO 3 , LiCF 3 SO 3 , LiN (SO 2 CF 3 ) 2 , LiTFSI, LiFSI, LiOH, LiOHH 2 O, LiBOB, LiN (SO 2 C 2 F 5 ) 2 , LiC 4 F 9 SO 3 , LiC (CF 3 SO 2 ) 3 , (CF 3 SO 2 ) 2 NLi, LiOH.H 2 O, LiB (C 2 O 4 ) 2 , chloroborane lithium, lower aliphatic carbonate, lithium 4 phenyl borate, lithium
  • One kind of lithium salt selected from the group consisting of imides and combinations thereof may be used.
  • the lithium salt is contained in 10 to 30% by weight, preferably 15 to 25% by weight, more preferably 17 to 23% by weight in the total polymer solid electrolyte. If the content of the lithium salt is less than the above range, it is not easy to secure the lithium ion conductivity, and on the contrary, if the lithium salt exceeds the above range, there is no significant increase in effect, and thus it is uneconomical, so it is appropriately selected within the above range.
  • organic solvent used in the preparation of the polymer solid electrolyte of the present invention a solvent capable of dissolving an ion conductive compound may be used.
  • organic solvent a polar aprotic solvent and a hydrogen bond acceptor (H-bond) may be used.
  • the polar proton solvent is 4-acetylmorpholine (4-acetylmorpholine), 2-methylpyridine-1-oxide, 2-pyrrolidone ( 2-pyrrolidon), 1- (2-hydroxyethyl) -2-pyrrolidone (1- (2-hydroxyethyl) -2-pyrrolidinone), and the hydrogen bond acceptor (H-bond Acceptor solvents are propylene carbonate (PC), ethylene carbonate (EC), 2-oxepanone, butanone, 2-pentanone and methyl It may be one or more selected from the group consisting of ethyl ketone (methyl ethyl ketone, MEK).
  • the content of the solvent is limited in consideration of the viscosity of the finally obtained polymer solid electrolyte. That is, the higher the content of the solvent, the higher the viscosity of the final composition obtained, so that the manufacturing process of the polymer solid electrolyte membrane is not easy. On the contrary, the lower the viscosity, the lower the viscosity, and thus the workability may be lowered.
  • the solution viscosity at 30 ° C. of the polymer solid electrolyte of the present invention is not particularly limited, but is preferably 200 to 1,000 cP, preferably 300 to 800 cP or less, and more preferably 500 to 700 cP. have. This viscosity control allows to secure the viscosity to increase the film processability in manufacturing the polymer solid electrolyte membrane.
  • the polymer solid electrolyte performs a film manufacturing process as is known to form a polymer solid electrolyte membrane.
  • molding methods such as the solution casting method (solution casting method), the melt extrusion method, the calender method, or the compression molding method, are mentioned, for example.
  • a solution cast method (solution casting method) or a melt extrusion method is preferable.
  • a solution cast method (solution casting method) may be used for film production.
  • the solution cast method is performed by coating a polymer solid electrolyte.
  • the polymer solid electrolyte may be directly coated on either the positive electrode or the negative electrode, or may be coated on a separate substrate and separated therefrom, thereby laminating the positive electrode and the negative electrode.
  • the substrate may be a glass substrate or a plastic substrate.
  • the plastic substrate include polyethylene terephthalate, polyethylene naphthalate, polypropylene, polyethylene, cellulose triacetate, cellulose diacetate, poly (meth) acrylic acid alkyl ester, poly (meth) acrylic acid ester copolymer, polyvinyl chloride, polyvinyl alcohol
  • various plastic films such as polycarbonate, polystyrene, cellophane, polyvinylidene chloride copolymer, polyamide, polyimide, vinyl chloride / vinyl acetate copolymer, polytetrafluoroethylene, and polytrifluoroethylene. have.
  • the composite material which consists of these 2 or more types can also be used,
  • the polyethylene terephthalate film excellent in the light transmittance is especially preferable.
  • the thickness of the support is preferably 5 to 150 ⁇ m, more preferably 10 to 50 ⁇ m.
  • the coating may be, for example, spin coating, dip coating, solvent casting, slot die coating, spray coating. Roll coating, extrusion coating, curtain coating, die coating, wire bar coating or knife coating may be used.
  • the coating process may be performed at 500 to 4000 rpm, or divided into two stages.
  • a device having a thickness gap of 10 to 200 ⁇ m may be used.
  • when performing the spray coating can be carried out by spraying with a spraying number of 5 to 100 times through a spray pressure of 0.5 to 20 MPa. The design of these processes and the selection of parameters can be controlled by one of ordinary skill in the art.
  • After the coating may additionally perform a film drying step.
  • the drying is different depending on each component or type of organic solvent, and the content ratio, it is preferable to perform at 30 to 15 minutes at 60 to 100 °C.
  • the drying may be performed by one of hot air drying, electromagnetic wave drying, vacuum drying, spray drying, drum drying, and lyophilization, and preferably hot air drying.
  • the thickness of the polymer solid electrolyte membrane is finally formed to the thickness of the membrane to be prepared, and if necessary, the coating-drying or coating step is performed at least once.
  • melt extrusion may be used for film production.
  • melt extrusion method examples include a T-die method and an inflation method. Molding temperature becomes like this. Preferably it is 150-350 degreeC, More preferably, it is 200-300 degreeC.
  • a T die When forming a film by the said T die method, a T die can be attached to the front-end
  • the hot melt may be subjected to a first hot melt, a filtration filter, and a second hot melt in sequence.
  • the hot melt temperature during the melt extrusion may be 170 °C to 320 °C, preferably 200 °C to 300 °C.
  • After melt extrusion from the T die it can be cooled and solidified using at least one or more metal drums maintained at 70 ° C to 140 ° C. When using a drum (casting roll) in this way, you may extrude on the temperature conditions mentioned above or below.
  • the polymer solid electrolyte presented above can be applied to a lithium secondary battery due to high lithium ion conductivity and physical properties such as interfacial stability at the surface of the positive electrode.
  • the polymer solid electrolyte of the present invention has a low oxidation potential in the cured ion-conducting compound and has a form in which an organic compound that easily reaches the anode is dispersed, and the electrode is formed by the organic compound that easily reaches the anode.
  • the film is easily formed and adsorbed on the surface of the anode, and thus has excellent interfacial stability with excellent physical properties compared to polymers such as polyethylene oxide or polypropylene oxide.
  • the voltage stability of the lithium secondary battery may be further improved by solving problems (heat generation, explosion, film degradation, etc.) generated during operation of the lithium secondary battery due to heat resistance, durability, chemical resistance, and flame resistance.
  • the polymer solid electrolyte proposed in the present invention is applied to a lithium secondary battery, but may be preferably used as the polymer solid electrolyte.
  • the lithium secondary battery 10 includes a positive electrode 11, a negative electrode 15, and an electrolyte interposed therebetween, wherein the polymer solid electrolyte 13 is used as the electrolyte, which is presented above.
  • the polymer solid electrolyte 13 is used as the electrolyte, which is presented above.
  • One polymer solid electrolyte is used.
  • the polymer solid electrolyte 13 described above exhibits high lithium ion conductivity while satisfying all of the characteristics such as electrochemically stable potential difference, low electrical conductivity, and high temperature stability, and is preferably used as an electrolyte of a battery.
  • the electrolyte 13 may further include a material used for this purpose in order to further increase the lithium ion conductivity.
  • the polymer solid electrolyte 13 further includes an inorganic solid electrolyte or an organic solid electrolyte.
  • the inorganic solid electrolyte is a ceramic-based material, a crystalline or amorphous and crystalline materials can be used, Thio-LISICON (Li 3. 25 Ge 0 .25 P 0.
  • the inorganic solid electrolyte such as a
  • organic solid electrolyte examples include polymer-based materials such as polyethylene derivatives, polyethylene oxide derivatives, polypropylene oxide derivatives, phosphate ester polymers, polyedgetion lysine, polyester sulfides, polyvinyl alcohol, and polyvinylidene fluoride. What mixed lithium salt can be used. At this time, these may be used alone or in combination of at least one or more.
  • the specific application method to the polymer solid electrolyte 13 is not particularly limited in the present invention, and may be selected or selected by a method known by those skilled in the art.
  • the lithium secondary battery 10 in which the polymer solid electrolyte 13 is applicable as an electrolyte is not limited to the positive electrode 11 or the negative electrode 15, and in particular, a lithium-air battery, a lithium oxide battery, and a lithium-sulfur battery that operate at a high temperature. It is applicable to a lithium metal battery, an all-solid-state battery, and the like.
  • Oxides, sulfides or halides may be used, and more specifically, TiS 2 , ZrS 2 , RuO 2 , Co 3 O 4 , Mo 6 S 8 , V 2 O 5, etc. may be used, but is not limited thereto. no.
  • Such a positive electrode active material may be formed on a positive electrode current collector.
  • the positive electrode current collector is not particularly limited as long as it has high conductivity without causing chemical change in the battery.
  • carbon on the surface of aluminum or stainless steel, The surface-treated with nickel, titanium, silver, etc. can be used.
  • the positive electrode current collector may use various forms such as a film, a sheet, a foil, a net, a porous body, a foam, and a nonwoven fabric having fine irregularities formed on a surface thereof so as to increase the adhesion with the positive electrode active material.
  • the negative electrode 15 has a negative electrode mixture layer having a negative electrode active material formed on the negative electrode current collector, or uses a negative electrode mixture layer (for example, lithium foil) alone.
  • the type of the negative electrode current collector or the negative electrode mixture layer is not particularly limited in the present invention, and a known material may be used.
  • the negative electrode current collector is not particularly limited as long as it has conductivity without causing chemical change in the battery, and for example, carbon on the surface of copper, stainless steel, aluminum, nickel, titanium, calcined carbon, copper or stainless steel , Surface-treated with nickel, titanium, silver, or the like, aluminum-cadmium alloy, or the like can be used.
  • the negative electrode current collector like the positive electrode current collector, may be used in various forms such as a film, a sheet, a foil, a net, a porous body, a foam, a nonwoven fabric having fine irregularities formed on a surface thereof.
  • the negative electrode active material is one selected from the group consisting of crystalline artificial graphite, crystalline natural graphite, amorphous hard carbon, low crystalline soft carbon, carbon black, acetylene black, Ketjen black, super-P, graphene, fibrous carbon Carbon-based material, Si-based material, LixFe 2 O 3 (0 ⁇ x ⁇ 1), Li x WO 2 (0 ⁇ x ⁇ 1), 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) Metal composite oxides; Lithium metal; Lithium alloys; Silicon-based alloys; Tin-based alloys; SnO, SnO 2 , PbO, PbO 2 , Pb 2 O 3 , Pb 3 O 4 , Sb 2 O 3 , Sb 2 O 4 ,
  • the negative electrode active material is SnxMe 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, Metal composite oxides such as halogen, 0 ⁇ x ⁇ 1, 1 ⁇ y ⁇ 3, 1 ⁇ z ⁇ 8); SnO, SnO 2 , 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 2 , Bi 2 O 3 , Bi 2 O 4 and An oxide such as Bi 2 O 5 may be used, and a carbon-based negative active material such as crystalline carbon, amorphous carbon or a carbon composite may be used alone or in combination of two or more thereof.
  • a carbon-based negative active material such as crystalline carbon, amorphous carbon or a carbon composite may be used alone or in combination
  • the electrode mixture layer may further include a binder resin, a conductive material, a filler and other additives.
  • the binder resin is used for bonding the electrode active material and the conductive material and the current collector.
  • binder resins include polyvinylidene fluoride (PVDF), polyvinyl alcohol, carboxymethyl cellulose (CMC), starch, hydroxypropyl cellulose, regenerated cellulose, polyvinylpyrrolidone, tetra Fluoroethylene, 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-butadiene rubber
  • fluorine rubber various copolymers thereof, and the like.
  • the said conductive material is used in order to improve the electroconductivity of an electrode active material further.
  • 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 carbon black, acetylene black, ketjen black, channel black, furnace black, lamp black and summer black; Conductive fibers such as carbon fibers and metal fibers; Metal powders such as carbon fluoride powder, aluminum powder and nickel powder; Conductive whiskers such as zinc oxide and potassium titanate; Conductive metal oxides such as titanium oxide; Polyphenylene derivatives and the like can be used.
  • the filler is optionally used as a component for inhibiting the expansion of the electrode, and is not particularly limited as long as it is a fibrous material without causing chemical change in the battery.
  • the filler include olefinic polymers such as polyethylene and polypropylene; Fibrous materials, such as glass fiber and carbon fiber, are used.
  • the shape of the lithium secondary battery 10 as described above is not particularly limited, and may be, for example, jelly-roll type, stack type, stack-fold type (including stack-Z-fold type), or lamination-stack type. It may preferably be stack-foldable.
  • the electrode assembly After fabricating an electrode assembly in which the negative electrode 15, the polymer solid electrolyte 13, and the positive electrode 11 are sequentially stacked, the electrode assembly is placed in a battery case, sealed by a cap plate and a gasket, and assembled to form a lithium secondary battery. To prepare.
  • the lithium secondary battery 10 may be classified into various batteries such as lithium-sulfur battery, lithium-air battery, lithium-oxide battery, lithium all-solid battery, and the like according to the shape of the cylinder and the square according to the cathode / cathode material used. It can be classified into coin type, pouch type, etc., and can be divided into bulk type and thin film type according to the size. Since the structure and manufacturing method of these batteries are well known in the art, detailed description thereof will be omitted.
  • various batteries such as lithium-sulfur battery, lithium-air battery, lithium-oxide battery, lithium all-solid battery, and the like according to the shape of the cylinder and the square according to the cathode / cathode material used. It can be classified into coin type, pouch type, etc., and can be divided into bulk type and thin film type according to the size. Since the structure and manufacturing method of these batteries are well known in the art, detailed description thereof will be omitted.
  • the lithium secondary battery 10 may be used as a power source for devices requiring high capacity and high rate characteristics.
  • the device include a power tool moving by being driven by an electric motor; Electric vehicles including electric vehicles (EVs), hybrid electric vehicles (HEVs), plug-in hybrid electric vehicles (PHEVs), and the like; Electric two-wheeled vehicles including electric bicycles (E-bikes) and electric scooters; Electric golf carts; Power storage systems and the like, but is not limited thereto.
  • Example 1 to Example 10 Preparation of Polymer Solid Electrolyte Using Electrode Protective Additives
  • the polymer solid electrolyte includes a PEO polymer and a polymer solid electrolyte composition was prepared by adding an electrode protective additive as described in Table 1 below.
  • the content of the electrode protective additive is 10% by weight based on the total weight of the polymer solid electrolyte composition to prepare a polymer solid electrolyte composition.
  • Examples 1 to 10 were prepared in consideration of one LiTFSI lithium salt per ethylene oxide (ethylene oxide) monomer in PEO, a polymer solid electrolyte.
  • the temperature in the electrolyte was based on a room temperature of 25 °C.
  • a polymer solid electrolyte was prepared in the same manner as in Example 1 without using an electrode protective additive.
  • electrolyte components such as anions, electrolyte solutions, and additives of lithium salts contained in the electrolyte are distributed on the surface of the cathode during charging
  • the anion and electrolyte solution of the lithium salt are charged on the surface of the cathode during charging.
  • the distribution of electrolyte components, such as additives, can be calculated and compared to evaluate the extent to which these materials reach the surface of the anode.
  • 2A to 2C are schematic diagrams of cells prepared for evaluating the extent to which electrolyte components reach the anode surface by molecular dynamics.
  • FIG. 2A two layers of graphite (G +, G-) are disposed as electrodes at both ends to simulate the electrode, so that anion (PF 6 ⁇ ), an electrolytic solution (EC & EMC), and an additive of lithium salt are added.
  • the cell 100 is constructed by fixing it so as not to escape (Vatamanu et al, JPCC , 2012, 1114).
  • the electrolyte is included in the cell 100, and then, under normal temperature (25 ° C.) and high temperature (60 ° C.), a potential (E field ) that is a voltage difference between the electrodes G1 and G2. ) Is set to 0.6 V / nm for molecular dynamics analysis.
  • the force field for molecular dynamics was applied to the general AMBER force field (GAFF) [4] (Wang et al. , J. Comp. Chem ., 2004, 1157), and OPLS (Optimized Potentials for Liquid Simulations) for lithium ions. (Jorgensen et al., JACS , 1996,11225) apply.
  • GFF AMBER force field
  • the number density of the components is calculated based on the surface of the anode (G +), and the actual area is used by using the area and density of the peak closest to the surface of the pole. Measure the number of objects reaching the anode surface and analyze the percentage of the total.
  • the potential (E) which is the voltage difference between the electrodes G + and G ⁇ , at room temperature (25 ° C.) and high temperature (60 ° C.) in the cell 100 prepared as shown in FIG. 2A.
  • the distribution (Pi, first layer) on the anode surface of each electrode protective additive was measured.
  • FIG 3 is a graph showing the distribution (Prob i, first layer ) of the electrode protective additive included in the positive electrode surface coating during charging the lithium secondary battery according to the polymer solid electrolyte prepared in Examples 1 to 5 as a percentage (%). .
  • the probability of distribution on the surface of the anode in the order of PBT ⁇ FEC ⁇ VEC ⁇ SN ⁇ VC was found to be high. It can be seen that the protective additive has a high tendency to reach the surface of the anode. In addition, the distribution on the surface of the anode of the additive for protecting the electrode appeared to have a similar tendency at room temperature (25 °C) and high temperature (60 °C). Ethylene carbonate (EC), gamma-butyrolactone (GBL) and cyclohexylbenzene (CHB) are measured by reference.
  • EC ethylene carbonate
  • GBL gamma-butyrolactone
  • CHB cyclohexylbenzene
  • FIG. 4 is a graph illustrating a distribution diagram (Prob i, first layer ) of an electrode protective additive included in the surface of the positive electrode when the lithium secondary battery is charged, according to the polymer solid electrolytes prepared in Examples 5 to 10, respectively.
  • HOMO energy levels were measured for the compounds of Formula 1 to Formula 5, which are the additives used in the experiment 5 to 10, respectively. HOMO energy levels were measured at B3PW91 / 6-31 + G * levels in the Gaussian 09 program. Ethylene carbonate (EC), gamma-butyrolactone (GBL) and cyclohexylbenzene (CHB) are measured by reference. EC, GBL and CHB are additives used in conventional non-aqueous liquid electrolytes.
  • the compounds of Formula 1 to Formula 5 (NSC-1 to NSC-5), which are additives used in Examples 5 to 10, are compared with EC and CHB, which are additives used in conventional non-aqueous liquid electrolytes. It can be seen that high.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Manufacturing & Machinery (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Electrochemistry (AREA)
  • General Chemical & Material Sciences (AREA)
  • Physics & Mathematics (AREA)
  • Condensed Matter Physics & Semiconductors (AREA)
  • Dispersion Chemistry (AREA)
  • General Physics & Mathematics (AREA)
  • Inorganic Chemistry (AREA)
  • Secondary Cells (AREA)

Abstract

La présente invention concerne un électrolyte solide polymère présentant des propriétés élevées de conductivité ionique et de stabilité interfaciale, et peut fournir une batterie secondaire au lithium présentant des performances améliorées puisque l'électrolyte solide polymère présente une excellente accessibilité à la surface d'une cathode et un additif présentant une caractéristique facilitant la formation de film au niveau de la cathode car un faible potentiel d'oxydation est inclus, de sorte qu'un film est facilement formé sur la surface de la cathode.
PCT/KR2018/004316 2017-04-14 2018-04-13 Électrolyte solide polymère et batterie secondaire au lithium comprenant celui-ci Ceased WO2018190665A1 (fr)

Priority Applications (4)

Application Number Priority Date Filing Date Title
JP2019512775A JP6742651B2 (ja) 2017-04-14 2018-04-13 高分子固体電解質及びこれを含むリチウム二次電池
US16/330,795 US10886563B2 (en) 2017-04-14 2018-04-13 Polymer solid electrolyte and lithium secondary battery comprising same
CN201880004041.4A CN109863634B (zh) 2017-04-14 2018-04-13 聚合物固体电解质和包含其的锂二次电池
EP18783779.4A EP3512023B1 (fr) 2017-04-14 2018-04-13 Électrolyte solide polymère et batterie secondaire au lithium comprenant celui-ci

Applications Claiming Priority (4)

Application Number Priority Date Filing Date Title
KR10-2017-0048292 2017-04-14
KR20170048292 2017-04-14
KR10-2018-0042604 2018-04-12
KR1020180042604A KR102160709B1 (ko) 2017-04-14 2018-04-12 고분자 고체 전해질 및 이를 포함하는 리튬 이차전지

Publications (1)

Publication Number Publication Date
WO2018190665A1 true WO2018190665A1 (fr) 2018-10-18

Family

ID=63792716

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/KR2018/004316 Ceased WO2018190665A1 (fr) 2017-04-14 2018-04-13 Électrolyte solide polymère et batterie secondaire au lithium comprenant celui-ci

Country Status (1)

Country Link
WO (1) WO2018190665A1 (fr)

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN112421097A (zh) * 2019-08-20 2021-02-26 中南大学 一种全固态锂电池及其制备方法
CN114207894A (zh) * 2019-06-06 2022-03-18 赢创运营有限公司 用于锂离子电池的原位聚合的聚合物电解质
EP3958366A4 (fr) * 2020-01-14 2022-08-10 LG Energy Solution, Ltd. Procédé de fabrication de batterie tout solide comprenant une membrane électrolytique hybride solide-liquide, et membrane électrolytique hybride solide-liquide

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2002319434A (ja) * 2001-04-20 2002-10-31 Sharp Corp リチウムポリマー二次電池
KR20100028928A (ko) * 2008-09-05 2010-03-15 한국화학연구원 고분자 전해질 및 이를 이용한 리튬 이차 전지
KR101462110B1 (ko) * 2013-04-24 2014-11-17 부산대학교 산학협력단 고분자 블렌드 및 무기 필러를 포함하는 고분자 복합체 전해질 및 이를 이용한 리튬 이차 전지
KR20170032713A (ko) * 2015-09-15 2017-03-23 주식회사 엘지화학 고분자, 이의 제조 방법, 그리고 이를 포함하는 고체 고분자 전해질, 전극, 세퍼레이터 및 리튬 이차 전지

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2002319434A (ja) * 2001-04-20 2002-10-31 Sharp Corp リチウムポリマー二次電池
KR20100028928A (ko) * 2008-09-05 2010-03-15 한국화학연구원 고분자 전해질 및 이를 이용한 리튬 이차 전지
KR101462110B1 (ko) * 2013-04-24 2014-11-17 부산대학교 산학협력단 고분자 블렌드 및 무기 필러를 포함하는 고분자 복합체 전해질 및 이를 이용한 리튬 이차 전지
KR20170032713A (ko) * 2015-09-15 2017-03-23 주식회사 엘지화학 고분자, 이의 제조 방법, 그리고 이를 포함하는 고체 고분자 전해질, 전극, 세퍼레이터 및 리튬 이차 전지

Non-Patent Citations (2)

* Cited by examiner, † Cited by third party
Title
OUATANI, L EI ET AL.: "The Effect of Vinylene Carbonate Additive on Surface Film Formation on Both Electrodes in Li-Ion Batteries", JOURNAL OF THE ELECTROCHEMICAL SOCIETY, vol. 156, no. 2, 2009, pages A103 - A113, XP002760483 *
See also references of EP3512023A4 *

Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN114207894A (zh) * 2019-06-06 2022-03-18 赢创运营有限公司 用于锂离子电池的原位聚合的聚合物电解质
US12412927B2 (en) 2019-06-06 2025-09-09 Evonik Operations Gmbh In-situ polymerized polymer electrolyte for lithium ion batteries
CN112421097A (zh) * 2019-08-20 2021-02-26 中南大学 一种全固态锂电池及其制备方法
EP3958366A4 (fr) * 2020-01-14 2022-08-10 LG Energy Solution, Ltd. Procédé de fabrication de batterie tout solide comprenant une membrane électrolytique hybride solide-liquide, et membrane électrolytique hybride solide-liquide
US12230755B2 (en) 2020-01-14 2025-02-18 Lg Energy Solution, Ltd. Method for manufacturing all-solid-state battery including solid-liquid hybrid electrolyte membrane, and solid-liquid hybrid electrolyte membrane

Similar Documents

Publication Publication Date Title
KR102160709B1 (ko) 고분자 고체 전해질 및 이를 포함하는 리튬 이차전지
WO2018034526A1 (fr) Anode comprenant de multiples couches de protection, et batterie secondaire au lithium la comprenant
WO2018012694A1 (fr) Pile rechargeable au lithium ayant du métal lithium formé sur la cathode et son procédé de fabrication
WO2019212314A1 (fr) Procédé de fabrication de batterie entièrement solide comprenant un électrolyte solide à base de polymère et batterie entièrement solide fabriquée par ce procédé
WO2018056650A1 (fr) Composite de lithium à base de lco à revêtement antipérovskite riche en lithium, procédé de préparation de celui-ci, et matériau actif d'électrode positive et batterie secondaire au lithium le comprenant
WO2019059637A2 (fr) Électrode négative pour accumulateur au lithium, son procédé de fabrication et accumulateur au lithium la comprenant
WO2018169247A2 (fr) Anode pour pile rechargeable au lithium, procédé de production associé et pile rechargeable au lithium comprenant ladite anode
WO2020185014A1 (fr) Électrode négative et batterie secondaire la comprenant
WO2019112167A1 (fr) Électrode négative destinée à une batterie au lithium-métal, et batterie lithium-métal comprenant une telle électrode négative
WO2018016737A1 (fr) Batterie secondaire au lithium comprenant un matériau actif de cathode pour la synthèse d'oxyde de cobalt et de lithium, et son procédé de fabrication
WO2020067792A1 (fr) Procédé de fabrication d'électrode comprenant un électrolyte solide polymère, et électrode fabriquée au moyen de celui-ci
WO2019098541A1 (fr) Matériau actif de cathode pour batterie secondaire, son procédé de fabrication, et batterie secondaire au lithium comprenant celui-ci
WO2019212315A1 (fr) Procédé de fabrication d'électrode comprenant un électrolyte solide à base de polymère, et électrode fabriquée par le procédé
WO2022154309A1 (fr) Procédé pour charger et décharger une batterie secondaire
WO2019004705A1 (fr) Procédé de production de suspension de cathode pour batterie secondaire au lithium, et cathode pour batterie secondaire au lithium ainsi obtenue
WO2019245284A1 (fr) Matériau actif de cathode pour batterie secondaire au lithium, et batterie secondaire au lithium
WO2019245286A1 (fr) Matériau actif de cathode pour batterie secondaire au lithium et batterie secondaire au lithium
WO2021101281A1 (fr) Procédé de préparation d'un matériau actif de cathode pour batterie rechargeable au lithium, et matériau actif de cathode préparé par le même procédé
WO2021045583A1 (fr) Procédé de pré-sodiation pré-lithiation d'anode, anode pré-lithiée et pré-sodiatée et batterie secondaire au lithium la comportant
WO2021045581A1 (fr) Procédé de pré-lithiation/pré-sodiation d'électrode négative, électrode négative pré-lithiée/pré-sodiatée et batterie secondaire au lithium la comprenant
WO2022270860A1 (fr) Anode pour batterie secondaire au lithium, son procédé de fabrication, et batterie secondaire au lithium la comprenant
WO2018190665A1 (fr) Électrolyte solide polymère et batterie secondaire au lithium comprenant celui-ci
WO2021060803A1 (fr) Système de batterie, son procédé d'utilisation, et bloc-batterie le comprenant
WO2021133027A1 (fr) Composition de liant pour anode, anode et batterie secondaire
WO2020185013A1 (fr) Batterie secondaire

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: 18783779

Country of ref document: EP

Kind code of ref document: A1

ENP Entry into the national phase

Ref document number: 2019512775

Country of ref document: JP

Kind code of ref document: A

ENP Entry into the national phase

Ref document number: 2018783779

Country of ref document: EP

Effective date: 20190410

NENP Non-entry into the national phase

Ref country code: DE