WO2019059705A2 - Électrolyte polymère et son procédé de préparation - Google Patents

Électrolyte polymère et son procédé de préparation Download PDF

Info

Publication number
WO2019059705A2
WO2019059705A2 PCT/KR2018/011231 KR2018011231W WO2019059705A2 WO 2019059705 A2 WO2019059705 A2 WO 2019059705A2 KR 2018011231 W KR2018011231 W KR 2018011231W WO 2019059705 A2 WO2019059705 A2 WO 2019059705A2
Authority
WO
WIPO (PCT)
Prior art keywords
polymer
peo
compound
lithium
seo
Prior art date
Application number
PCT/KR2018/011231
Other languages
English (en)
Korean (ko)
Other versions
WO2019059705A3 (fr
Inventor
김대일
박문정
채종현
이연주
김루시아
정하영
조규하
Original Assignee
주식회사 엘지화학
포항공과대학교 산학협력단
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 KR1020180093721A external-priority patent/KR102229457B1/ko
Application filed by 주식회사 엘지화학, 포항공과대학교 산학협력단 filed Critical 주식회사 엘지화학
Priority to PL18859540.9T priority Critical patent/PL3595070T3/pl
Priority to US16/487,725 priority patent/US11387489B2/en
Priority to ES18859540T priority patent/ES2965482T3/es
Priority to JP2019565146A priority patent/JP7101707B2/ja
Priority to EP18859540.9A priority patent/EP3595070B1/fr
Priority to CN201880014509.8A priority patent/CN110402516B/zh
Publication of WO2019059705A2 publication Critical patent/WO2019059705A2/fr
Publication of WO2019059705A3 publication Critical patent/WO2019059705A3/fr

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
    • 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 and a method for producing the same, and more particularly, to a polymer electrolyte improved in the number of lithium cation transport and a method for producing the same.
  • the safety of a battery is improved in the order of liquid electrolyte ⁇ gel polymer electrolyte > solid electrolyte, while battery performance is known to decrease.
  • Electrolytes for electrochemical devices such as batteries and electric double layer capacitors using electrochemical reactions have been mainly used as liquid electrolytes, especially ion conductive organic liquid electrolytes in which salts are dissolved in non-aqueous organic solvents.
  • ion conductive organic liquid electrolytes in which salts are dissolved in non-aqueous organic solvents.
  • the electrode material is degenerated and the organic solvent is volatilized, and there is a problem in safety such as combustion due to the ambient temperature and the temperature rise of the battery itself.
  • the electrolyte used in the lithium secondary battery is in a liquid state, and there is a risk of flammability in a high temperature environment, which may be a considerable burden to the application of electric vehicles.
  • organic electrolytic solutions whose solvents are flammable are used, problems of not only leakage but also ignition and combustion accidents are always accompanied. For this reason, it has been studied to use an ionic liquid, a gel-like electrolyte, or a polymer electrolyte in the electrolytic solution. Therefore, this problem can be solved by replacing the liquid lithium electrolyte with a solid electrolyte. So far, various solid electrolytes have been researched and developed.
  • Solid electrolytes are mainly made of flame retardant materials, and are stable at high temperatures because they are made of nonvolatile materials with high stability.
  • the solid electrolyte serves as a separator, a conventional separator is not necessary and a thin film process may be possible.
  • the most ideal form is a secondary battery which is not only safe but also excellent in stability and reliability as a high-solid type using an inorganic solid in an electrolyte.
  • a large capacity (energy density) it is also possible to adopt a laminated structure.
  • the composite electrolyte of polyethylene oxide (PEO) and lithium salt, which is one of the electrolytes used in the lithium ion battery, is advantageous in that it has higher stability than the conventional liquid electrolyte.
  • PEO used in this electrolyte is a polymer having a high crystallinity, and therefore, there is a problem that when the polymer is crystallized at a melting point (about 50 ° C) of the polymer, the ion conductivity becomes extremely low.
  • a polymer having a liquid state at room temperature is frequently used because the molecular weight of PEO is extremely low.
  • this is not a fundamental study for relaxing crystallization characteristics of PEO.
  • Non-Patent Document 1 Ito, K .; Nishina, N .; Ohno, H. J. Mater. Chem. 1997, 7, 1357-1362.
  • Non-Patent Document 2 Jo, G .; Anh, H .; Park, M. J. ACS Macro Lett. 2013, 2, 990-995.
  • a PEO-based polymer electrolyte including a lithium salt has excellent room temperature ionic conductivity at room temperature and a lithium cation transport number is improved through a polymer having a new functional group.
  • the present invention provides a polymer electrolyte membrane comprising: a poly (ethylene oxide) (PEO) polymer; And lithium salts; Wherein the end of the polyethylene oxide polymer is substituted with a sulfur compound functional group, a nitrogen compound functional group or a phosphorus compound functional group.
  • a polymer electrolyte membrane comprising: a poly (ethylene oxide) (PEO) polymer; And lithium salts; Wherein the end of the polyethylene oxide polymer is substituted with a sulfur compound functional group, a nitrogen compound functional group or a phosphorus compound functional group.
  • the present invention also provides a method for preparing a polyethylene oxide polymer, comprising the steps of: (a) adding a sulfur compound, a nitrogen compound or a phosphorus compound to a poly (ethylene oxide) (PEO) polymer to modify the terminal of the polyethylene oxide polymer; And (b) adding a lithium salt to the polymer electrolyte.
  • a sulfur compound, a nitrogen compound or a phosphorus compound to a poly (ethylene oxide) (PEO) polymer to modify the terminal of the polyethylene oxide polymer
  • PEO poly (ethylene oxide)
  • the present invention also relates to a solid electrolyte comprising an anode, a cathode and a solid polymer electrolyte interposed therebetween, wherein the solid polymer electrolyte is selected from the group consisting of polyethylene oxide (PEO) -based polymer; And a lithium salt, wherein the end of the polyethylene oxide polymer is a polymer electrolyte substituted with a nitrogen compound functional group or a phosphorus compound functional group.
  • PEO polyethylene oxide
  • the crystallinity of the polymer can be reduced by synthesizing a polymer having various terminal functional groups introduced therein without changing the molecular weight of the PEO. Therefore, And can have excellent ionic conductivity.
  • the number of lithium cation transport can be improved by controlling the molecular attraction between the terminal functional group and the lithium salt, thereby improving the discharge capacity and the charge / discharge rate.
  • Example 1 is a graph showing the results of NMR data measurement of Examples 1 to 3 and Comparative Example 1 of the present invention.
  • FIG. 2 is a graph showing 31 P NMR results of measuring the hydrolysis efficiency of Examples 2 to 3 of the present invention.
  • Example 3 is a graph showing the results of gel permeation chromatography analysis of Examples 1 to 3 and Comparative Example 1 of the present invention.
  • DSC differential scanning calorimetry
  • Example 5 is a graph showing the results of analyzing ionic conductivities of Examples 1 to 3 and Comparative Example 1 of the present invention.
  • Fig. 6 is a graph showing correction of the results of analyzing ionic conductivities of Examples 1 to 3 and Comparative Example 1 of the present invention.
  • Example 7 is a graph showing the results of measurement of electrode polarization in Examples 1 to 3 and Comparative Example 1 of the present invention.
  • Example 11 is a graph showing FT-IR measurement results obtained by doping a polymer with LiTFSI salt in Example 1 and Example 1 of the present invention.
  • Example 12 is a graph showing FT-IR measurement results obtained after doping LiTFSI salt into the polymer of Example 3 and Example 3 of the present invention.
  • Example 13 is a graph showing Examples 1 to 3 and Comparative Example 1 of the present invention and FT-IR measurement results obtained after doping with LiTFSI salt thereof.
  • Figure 14 shows the synthesis route of the PS-b-PEO block copolymer with terminal substitution via thiol-ene click chemistry.
  • Figure 16 shows SAXS data at 60 ⁇ ⁇ for SEO-h, SEO-c, SEO-2h, and SEO-2c.
  • the filled inverse triangle represents bragg peaks q * , 2 q * of SEO-c.
  • the open inverted triangles are bragg peaks in SEO-2h and SEO-2c q * , q * , q * , q * , q * , and q * .
  • Interfacial changes by end groups are shown in the figure.
  • DSC data showing the degree of crystallinity of the SEO samples with terminal substitutions were inserted.
  • 18 is a graph showing ion conduction characteristics by doping a lithium salt-doped sample into a terminal group-substituted sample.
  • the present invention relates to a novel polymer capable of reducing the crystallinity of a polymer by synthesizing a polymer having various terminal functional groups introduced therein without changing the molecular weight of PEO, and includes a polymer such as polyethylene oxide (PEO) -based polymer; And a lithium salt,
  • PEO polyethylene oxide
  • the end of the polyethylene oxide polymer is substituted with a sulfur compound functional group, a nitrogen compound or a phosphorus compound.
  • the polymer electrolyte of the present invention can induce various interactions between a functional group introduced into a polymer and a lithium salt by introducing a sulfur compound, a nitrogen compound or a phosphorus compound as a functional group at the terminal of the polyethylene oxide polymer, .
  • the nitrogen compound functional group to be introduced into the terminal of the polyethylene oxide polymer includes nitrile, amine, pyridine, imidazole and the like. Diethyl phosphonate, or phosphonic acid.
  • polymer in which a nitrogen compound or a phosphorus compound is introduced as a functional group at the terminal of the polyethylene oxide polymer may be represented by any one of the following Chemical Formulas 1 to 3.
  • n is an integer of from 10 to 120, and R is an alkyl chain having from 1 to 4 carbon atoms.
  • the polymer electrolyte of the present invention can be produced by synthesizing a polymer having various terminal functional groups introduced therein without changing the molecular weight of polyethylene oxide (PEO) To about 80%.
  • PEO polyethylene oxide
  • sulfur compound functional group introduced into the terminal of the polyethylene oxide polymer in the present invention those having a functional group represented by the following general formula (4) can be used.
  • R is a carboxyl group having 1 to 4 carbon atoms, a diol group, or a dicarbonyl group
  • -R may be selected from one or more functional groups represented by the following formulas (5) to (5).
  • the polyethylene oxide polymer when the terminal of the polyethylene oxide polymer is substituted with a sulfur compound, the polyethylene oxide polymer may be a block copolymer composed of a polyethylene oxide block and a hydrophobic block, for example, a polystyrene block.
  • the block copolymer may be represented by the following formula (6)
  • R is a carboxyl group, a diol group, or a dicarboxyl group having 1 to 4 carbon atoms
  • R1 is alkyl of 1-8 carbon atoms
  • the molecular weight of the block copolymer is 20 kg / mol or less, preferably 2 to 20 kg / mol, and the molecular weight of each block is 1 to 10 kg / mol.
  • the block copolymer is represented by the following chemical formula (7), and the functional group -R may be represented by the chemical formula (5).
  • b means a block copolymer
  • the molecular weight of the block copolymer is 2 to 20 kg / mol.
  • the block copolymer may be doped with a metal salt, preferably a lithium salt.
  • the block copolymer may have a gyroid, a lamellar, or an amorphous structure.
  • polymer electrolyte of the present invention can be used as a solid electrolyte for all solid-state batteries.
  • Solid electrolytes are mainly made of flame retardant materials, and are stable at high temperatures because they are made of nonvolatile materials with high stability.
  • the solid electrolyte serves as a separator, a conventional separator is not necessary and a thin film process may be possible.
  • the most ideal form is a secondary battery which is not only safe but also excellent in stability and reliability as a high-solid type using an inorganic solid in an electrolyte.
  • a large capacity (energy density) it is also possible to adopt a laminated structure.
  • the polymer electrolyte of the present invention has improved ionic conductivity as described later, it is preferable to be applied to all solid ion batteries.
  • the present invention intends to improve the ionic conductivity and lithium cation transport property by introducing a lithium salt into the polymer as described above to prepare a composite electrolyte.
  • the present invention dope a lithium salt to a polyethylene oxide-based polymer.
  • the lithium salt is not particularly limited but preferably LiCl, LiBr, LiI, LiClO 4 , LiBF 4 , LiB 10 Cl 10 , LiPF 6 , LiCF 3 SO 3 , LiCF 3 CO 2 , LiAsF 6 , LiSbF 6 , LiAlCl 4, CH 3 SO 3 Li, CF 3 SO 3 Li, LiSCN, LiC (CF 3 SO 2) 3, (CF 3 SO 2) 2 NLi, (FSO 2) 2 NLi, chloroborane lithium, lower aliphatic carboxylic acid lithium , Lithium 4-phenylborate, imide, and bis (trifluoromethane sulfonyl) imide (LiTFSI).
  • the polymer electrolyte of the present invention can reduce the crystallinity of a polymer by synthesizing a polymer having various terminal functional groups introduced therein without changing the molecular weight of polyethylene oxide (PEO), so that the molecular weight of the polymer electrolyte is preferably 1 to 20 kg / mol .
  • PEO polyethylene oxide
  • the polymer electrolyte of the present invention may have a value of [Li +] / [EO] of 0.02 to 0.08, which is a ratio of [Li +] of the lithium salt to that of the polymer [EO] in order to ensure practical performance of the lithium battery. have.
  • concentration of [EO] of the polymer and the [Li +] concentration of the lithium salt are within the above range, the electrolyte has appropriate conductivity and viscosity, and therefore, excellent electrolyte performance can be exhibited and lithium ions can be effectively transferred.
  • the polymer electrolyte of the present invention has an excellent ion transport property with a number of lithium cation transporting number of 0.5 or more.
  • a sulfur compound, a nitrogen compound or a phosphorus compound is added to a poly (ethylene oxide) (PEO) polymer to modify the terminal of the polyethylene oxide polymer,
  • PEO poly (ethylene oxide)
  • the end of the oxide polymer may be substituted with a sulfur compound functional group, a nitrogen compound functional group or a phosphorus compound functional group.
  • the polymer electrolyte of the present invention can induce various interactions between a functional group introduced into a polymer and a lithium salt by introducing a sulfur compound, a nitrogen compound or a phosphorus compound as a functional group at the terminal of the polyethylene oxide polymer, .
  • the method of adding the sulfur compound, the nitrogen compound or the phosphorus compound can be added in a manner conventionally used in the industry without particular limitation.
  • the nitrogen compound functional group to be introduced into the terminal of the polyethylene oxide polymer includes nitrile, amine, pyridine, imidazole and the like. Diethyl phosphonate, or phosphonic acid.
  • step (a) specific examples of the polymer in which a nitrogen compound or a phosphorus compound is introduced as a functional group at the terminal of the polyethylene oxide polymer may be represented by any one of the following Chemical Formulas 1 to 3.
  • n is an integer of from 10 to 120, and R is an alkyl chain having from 1 to 4 carbon atoms.
  • the polyethylene oxide polymer when the terminal of the polyethylene oxide polymer is substituted with a sulfur compound, the polyethylene oxide polymer may be a block copolymer composed of a polyethylene oxide block and a hydrophobic block, for example, a polystyrene block.
  • the end of the polyethylene oxide block is modified by the following formula (8);
  • R < 2 > is alkyl having 1 to 6 carbon atoms
  • R is a carboxyl group, a diol group or a dicarboxyl group having 1 to 4 carbon atoms
  • the terminal of the polyethylene oxide polymer may be substituted with a sulfur compound.
  • the polymer electrolyte of the present invention can be produced by synthesizing a polymer having various terminal functional groups introduced therein without changing the molecular weight of polyethylene oxide (PEO) To about 80%.
  • PEO polyethylene oxide
  • the present invention also provides a method for preparing a composite electrolyte by introducing a lithium salt into the polymer modified in the step (a) through a step of adding a lithium salt in step (b) to improve ionic conductivity and lithium cation transport property do.
  • the present invention can be doped with a lithium salt to a polyethylene oxide-based polymer.
  • the lithium salt is not particularly limited but preferably LiCl, LiBr, LiI, LiClO 4 , LiBF 4 , LiB 10 Cl 10 , LiPF 6 , LiCF 3 SO 3 , LiCF 3 CO 2 , LiAsF 6 , LiSbF 6 , LiAlCl 4, CH 3 SO 3 Li, CF 3 SO 3 Li, LiSCN, LiC (CF 3 SO 2) 3, (CF 3 SO 2) 2 NLi, (FSO 2) 2 NLi, chloroborane lithium, lower aliphatic carboxylic acid lithium , Lithium 4-phenylborate, imide, and bis (trifluoromethane sulfonyl) imide (LiTFSI).
  • the polymer electrolyte of the present invention can reduce the crystallinity of a polymer by synthesizing a polymer having various terminal functional groups introduced therein without changing the molecular weight of polyethylene oxide (PEO), so that the molecular weight of the polymer electrolyte is preferably 1 to 20 kg / mol .
  • PEO polyethylene oxide
  • the polymer electrolyte of the present invention may have a value of [Li +] / [EO] of 0.02 to 0.08, which is a ratio of [Li +] of the lithium salt to that of the polymer [EO] in order to ensure practical performance of the lithium battery. have.
  • concentration of [EO] of the polymer and the [Li +] concentration of the lithium salt are within the above range, the electrolyte has appropriate conductivity and viscosity, and therefore, excellent electrolyte performance can be exhibited and lithium ions can be effectively transferred.
  • the polymer electrolyte of the present invention has an excellent ion transport property with a number of lithium cation transporting number of 0.5 or more.
  • the present invention also relates to a solid electrolyte comprising an anode, a cathode and a solid polymer electrolyte interposed therebetween, wherein the solid polymer electrolyte is selected from the group consisting of polyethylene oxide (PEO) -based polymer; And a lithium salt, wherein the end of the polyethylene oxide polymer is a polymer electrolyte substituted with a nitrogen compound functional group or a phosphorus compound functional group.
  • PEO polyethylene oxide
  • the electrode active material may be a cathode active material when the electrode is a positive electrode, or a negative active material when it is a negative electrode.
  • each of the electrode active materials can be any active material applied to conventional electrodes, and is not particularly limited in the present invention.
  • the cathode active material may be varied depending on the use of the lithium secondary battery, and a known material is used for the specific composition. For example, any one selected from the group consisting of a lithium-phosphoric acid-iron compound, a lithium cobalt oxide, a lithium manganese oxide, a lithium copper oxide, a lithium nickel oxide and a lithium manganese composite oxide, and a lithium-nickel-manganese- Of lithium transition metal oxides.
  • M is at least one selected from metals of Groups 2 to 12
  • X is at least one selected from the group consisting of F, S and N
  • the negative electrode active material may be selected from the group consisting of lithium metal, lithium alloy, lithium metal composite oxide, lithium-containing titanium composite oxide (LTO), and combinations thereof.
  • the lithium alloy may be an alloy of lithium and at least one metal selected from Na, K, Rb, Cs, Fr, Be, Mg, Ca, Sr, Ba, Ra, Al and Sn.
  • a conductive material or a polymer electrolyte may be further added to the active material, and examples of the conductive material include nickel powder, cobalt oxide, titanium oxide, carbon, and the like.
  • the carbon include any one selected from the group consisting of Ketjen black, acetylene black, furnace black, graphite, carbon fiber and fullerene, or one or more of them.
  • the preparation of the entire solid battery is carried out by a dry compression process in which an electrode and a solid electrolyte are prepared in a powder state and then put into a predetermined mold and pressed, or a slurry composition including an active material, a solvent and a binder, ≪ / RTI > slurry coating process.
  • a dry compression process in which an electrode and a solid electrolyte are prepared in a powder state and then put into a predetermined mold and pressed, or a slurry composition including an active material, a solvent and a binder, ≪ / RTI > slurry coating process.
  • a solid electrolyte is disposed between an anode and a cathode, and the cell is assembled by compression molding. After the assembled cells are installed in the casing, they are sealed by heat compression or the like. Laminate packs made of aluminum, stainless steel or the like, and cylindrical or square metal containers are very suitable for the exterior material.
  • the method of coating the electrode slurry on the current collector includes a method of uniformly dispersing the electrode slurry on the current collector using a doctor blade or the like, a method of die casting, a comma coating, , Screen printing, and the like.
  • the electrode slurry may be bonded to the current collector by pressing on a separate substrate and then laminating. At this time, the thickness of the coating to be finally coated can be controlled by adjusting the concentration of the slurry solution, the number of times of coating, and the like.
  • the drying process is a process for removing the solvent and moisture in the slurry to dry the slurry coated on the metal current collector, and may be changed depending on the solvent used. For example, it is carried out in a vacuum oven at 50 to 200 ° C.
  • the drying method include a drying method by hot air, hot air, low-humidity air, vacuum drying, and irradiation with (circle) infrared rays or electron beams.
  • the drying time is not particularly limited, but is usually in the range of 30 seconds to 24 hours.
  • the process may further include a cooling process, and the cooling process may be slow cooling to room temperature so that the recrystallized structure of the binder is well formed.
  • a rolling process may be performed to increase the capacity density of the electrode after the drying process and to increase the adhesion between the current collector and the active materials, thereby compressing the electrode to a desired thickness by passing the electrode between the two heated rolls.
  • the rolling process is not particularly limited in the present invention, and a known rolling process is possible. For example, between rotating rolls or using a flat press machine.
  • the calculated amount of LiTFSI is mixed with the polymer using a methanol / benzene cosolvent and then stirred at room temperature for one day.
  • the solvent in the argon environment is slowly evaporated to dryness and then completely dried in vacuum for one week. All sample preparation and drying procedures were performed in a glove box in an argon environment equipped with an oxygen and moisture sensor, vacuum oven to avoid water absorption by the sample.
  • the DSC thermogram of all synthesized polymer samples was measured using TA Instruments (model Q20). About 5 mg of the sample was placed in an aluminum pan in a glove box filled with argon, and an empty aluminum pan was used as a reference. Thermodynamic properties of between -65 ° C and 120 ° C were measured for 5 ° C / min and 10 ° C / min temperature rise / cooling rates.
  • the dynamic storage modulus and loss modulus were measured using an Anton Paar MCR 302 rheometer.
  • the rheometer was fitted with an 8 mm parallel plate and the sample was adjusted to 0.5 mm. All measurements were taken at a strain of 0.1% in a linear viscoelastic regime. Experiments were carried out at a frequency ranging from 0.1 to 100 rad / s at a temperature of 50 ° C. The temperature and the cooling rate were fixed at 0.5 rad / s and 1 o C / min.
  • Test condition 5 Conductivity measurement
  • the salt-doped samples were measured for through-plane conductivity using a potentiostat (VersaSTAT 3, Princeton Applied Research) in a glove box in an argon environment. Two electrode cells (consisting of a stainless steel blocking electrode and a 1 cm x 1 cm platinum working / counter electrode) were used and the sample thickness was 200 mm.
  • Samples doped with salt were placed between two lithium electrodes to conduct polarization experiments.
  • the temperature of the sample was set at 60 ° C, and the polarization current (DV) was observed at 1 V while maintaining the voltage at 0.1 V. All procedures were performed in a glove box in an argon environment.
  • Infrared spectroscopy was performed using a Bruker Vertex 70 FT-IR spectrophotometer at a constant temperature of 22 ° C. Powder samples (high molecular weight) were averaged 32 times in reflection mode (frequency resolution 1 cm -1 ) and liquid samples (low molecular weight) were averaged 16 times in transmission mode. (Frequency resolution 4 cm -1 )
  • Ethylene oxide monomer was refined by CaH 2 for one day and n-butyllithium for 30 minutes with stirring repeatedly twice.
  • Methanol was purified using magnesium and THF to be used as a solvent was purified using benzophenone kethyl.
  • Methanol (0.04 mL, 1 mmol) and t-Bu-P 4 (1 mL, 1 mmol) are added to purified 100 mL THF and degassed to give a vacuum.
  • the distilled ethylene oxide (5 mL, 100 mmol) is distilled and the reaction is carried out at room temperature for 3 days. The reaction is terminated by adding 0.1 mL of acetic acid. After completion of the reaction, purification was carried out using hexane.
  • reaction product (4 g, 2 mmol) was dissolved in 80 mL of anhydrous toluene, thioglycerol (8.6 g, 80 mmol) and AIBN (1.3 mg, 8 mmol) The reaction proceeds at 80 DEG C for 1.5 hours. The solvent was removed from the reaction mixture using a rotary evaporator, and the residue was purified using ether
  • the PEO-CN polymer of Example 1 in which the nitrile functional group was introduced, had an extremely high substitution efficiency of 99% or more as a result of 1 H NMR measurement (using AV300, Bruker) of Examples 1 to 3 and Comparative Example 1 there was.
  • the PEO-PE polymer of Example 2 having diethylphosphonate functional group had a high substitution efficiency of 87%, and the phosphonic acid functional group of Example 3 synthesized by hydrolysis thereof was PEO having a hydrolysis efficiency of 100% -PA < / RTI > polymer was synthesized. In the case of such a hydrolysis efficiency, it was also confirmed by the 31 P NMR in FIG. 2 that it was 100%.
  • PDI Polydispersity Index
  • DSC Differential scanning calorimeter
  • Example 3 which hydrolyzed the phosphonic acid functional group to form PEO, the crystallinity was only 42% I could see that I had. It was found that introduction of terminal functional groups has a great influence on the crystallinity of PEO and it can be a method of improving the room temperature conductivity of the polymer electrolyte.
  • PA shows hydrogen bond between strong OH functional groups when compared with PEO. This is because the absolute number of OH is about 1.7 times more, and the hydrogen bonding network between phosphonic acids is formed more efficiently.
  • the phosphonic acid functional group forms a strong hydrogen bond with the TFSI anion, and the OH peak at about 3400 cm -1 shifts to about 3200 cm -1 .
  • Example 1 PEO-CN
  • Example 2 PEO-PE
  • Example 3 PEO-PA
  • Comparative Example 1 PEO
  • the terminal is an allyl group ( allyl group) to Substituted polyethylene Oxide Synthesis (synthesis of SEO-ene)
  • PS-b-PEO block copolymers substituted with different kinds and numbers of end groups were synthesized.
  • thiolating agents thioglycolic acid, mercaptosuccinic acid, thioglycerol.
  • PEO-h, PEO-ene, PEO-c PEO-2h and PEO-2c were synthesized by a similar reaction to the PEO homopolymer (5.0 kg / mol). All samples with terminal substitutions for PEO have an increase in molecular weight of less than 0.19 kg / mol.
  • FIG. 16 shows SAXS data at 60 DEG C of the prepared samples.
  • This result implies the formation of an ordered lamellar structure.
  • the scattering intensity increases markedly at low q values, which is considered to be the effect of the formation of the structure by the introduction of -COOH at the terminal.
  • Figure 17b directly compares the modulus and viscoelastic properties of SEO-2c and PEO-2c.
  • PEO-2c showed a reaction of viscoelastic solid (G '(w) ⁇ G "(w) ⁇ w 1/4 ) -2c is PEO-2c more showed a higher modulus greater than or equal to 10 3 times, dependent on the frequency was about (G '(w) ⁇ w 0.12, G "(w) ⁇ w 0.03).
  • the results show that the characteristics of the cube and elastic behavior are exhibited by the glassy state of the PS block.
  • the glass transition temperature is -65 o C (SEO-h) , -45 o C (SEO-c), -44 o C (SEO-2h), and -37 o C (SEO-2c)
  • the improvement in conductivity is a very interesting result.
  • SEO-2h and SEO-2c are three to seven times more robust than SEO-h.
  • the structure of SEO-c, SEO-2h, and SEO-2c is maintained, and SEO-h increases the segregation strength between PS and PEO including salt to form a lamellar structure .
  • FIG. 18b shows the T Li + value at 60 ° C.
  • SEO-h showed a T Li + value of 0.25, which is consistent with the values of typical PEO and lithium salt composite electrolyte membranes reported in the literature.
  • the introduction of carboxylic acid into the terminal group did not improve T Li + , but when a diol group was introduced T Li + was nearly doubled (0.48).
  • FIG. 18B shows results of sample polarization experiments in which -OH and - (OH) 2 were introduced at the terminals. The mechanism of such a result will be discussed in the next chapter.
  • DSC data confirmed that all samples were amorphous. Samples with carboxylic acid termini exhibited the lowest conduction characteristics, which are believed to be due to slow segmental motion due to internal dipole-dipole interactions. The notable point is that SEO-2h has higher conductivity than SEO-h at higher temperatures. Even if the salt concentration was increased, T Li + was improved by a factor of two in the case of the diol group, and the other samples were very high at about 0.2.
  • Potential barriers obtained by fitting the conductivity data to the Vogel-Tammann-Fulcher (VTF) equation are 974 K, 1181 K, 1380 K for SEO-h, SEO-c, SEO- , And 1227K.
  • FT-IR spectroscopy was used for in-depth study of inter- and intramolecular interactions in PEO.
  • Samples were prepared by replacing terminal groups with low molecular weight PEO (0.55 kg / mol) to emphasize the end group signals. This increased the concentration of the terminal group to 8 mol%.
  • the synthesized polymers were liquid phase, filled between CaF 2 window and observed FT-IR spectrum. The CH stretching peak near 2900 cm -1 was used as the internal standard.
  • PEO-c and PEO-2c samples also showed peaks due to OH stretching. However, a very broad, low-intensity peak was observed in the region of 3000-3700-cm -1 , which means that the carboxylic acid at the terminal is actively hydrogen bonding with the ether oxygen in the chain.
  • PEO-c and PEO-2c are visible at 1850-1600 cm -1
  • PEO-c showed three peaks while PEO-2c showed one peak. This difference was due to the hydrogen bonding and the quadrupole formation by forming a dimer with the fact that -COOH at the terminal of PEO-c was adjacent to the PEO- (Quadrupole interactions). In contrast, PEO-2c did not interact well with steric hindrance.
  • FIG. 19d shows the data of PEO-2h, and a broad and red-shifted band due to OH stretching can be observed.
  • OH stretching can be observed at 3332 cm -1 and 3542 cm -1 .
  • FIG. 20A shows PEO-h having crystallinity and PEO-c forming dimer and PEO-2h having intramolecular hydrogen bonding.
  • lithium Fig. 20b
  • lithium ion primarily coordinates with ether oxygen in the main chain of PEO, and the terminal group and the anion of the lithium salt undergo hydrogen bonding.
  • Samples with diol groups at the ends showed higher conduction characteristics and lithium ion transport rates than samples with dicarboxylic acid at the ends, since they did not undergo quadrupole interactions.
  • the lithium ion transport rate was greatly improved by hydrogen bonding with the anion of the lithium salt.
  • the method of controlling the density of the end groups proposed in this study can solve the low lithium ion transport rate which is a fundamental disadvantage of the electrolyte membrane doped with PEO and can be utilized in the production of the solid polymer electrolyte membrane to develop the next generation energy storage device Is expected to make a major contribution to

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)
  • Conductive Materials (AREA)
  • Secondary Cells (AREA)
  • Processes Of Treating Macromolecular Substances (AREA)
  • Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)

Abstract

La présente invention concerne un électrolyte polymère comprenant un polymère de poly(oxyde d'éthylène) (PEO) ; et un sel de lithium, une extrémité du polymère de poly(oxyde d'éthylène) étant substituée par un groupe fonctionnel d'un composé d'azote ou un groupe fonctionnel d'un composé de phosphore, et son procédé de préparation.
PCT/KR2018/011231 2017-09-21 2018-09-21 Électrolyte polymère et son procédé de préparation WO2019059705A2 (fr)

Priority Applications (6)

Application Number Priority Date Filing Date Title
PL18859540.9T PL3595070T3 (pl) 2017-09-21 2018-09-21 Elektrolit polimerowy i sposób jego wytwarzania
US16/487,725 US11387489B2 (en) 2017-09-21 2018-09-21 Polymer electrolyte and preparation method therefor
ES18859540T ES2965482T3 (es) 2017-09-21 2018-09-21 Electrolito polimérico y método de preparación para el mismo
JP2019565146A JP7101707B2 (ja) 2017-09-21 2018-09-21 高分子電解質及びこの製造方法
EP18859540.9A EP3595070B1 (fr) 2017-09-21 2018-09-21 Électrolyte polymère et son procédé de préparation
CN201880014509.8A CN110402516B (zh) 2017-09-21 2018-09-21 聚合物电解质和其制备方法

Applications Claiming Priority (4)

Application Number Priority Date Filing Date Title
KR20170121709 2017-09-21
KR10-2017-0121709 2017-09-21
KR10-2018-0093721 2018-08-10
KR1020180093721A KR102229457B1 (ko) 2017-09-21 2018-08-10 고분자 전해질 및 이의 제조방법

Publications (2)

Publication Number Publication Date
WO2019059705A2 true WO2019059705A2 (fr) 2019-03-28
WO2019059705A3 WO2019059705A3 (fr) 2019-05-09

Family

ID=65811563

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/KR2018/011231 WO2019059705A2 (fr) 2017-09-21 2018-09-21 Électrolyte polymère et son procédé de préparation

Country Status (1)

Country Link
WO (1) WO2019059705A2 (fr)

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN113381060A (zh) * 2021-06-21 2021-09-10 浙江大学 一种全固态复合电解质及其制备方法和应用
CN114940762A (zh) * 2022-05-18 2022-08-26 深圳市贝特瑞新能源技术研究院有限公司 聚合物及其制备方法、聚合物电解质、锂离子电池

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
KR20170029527A (ko) 2014-07-02 2017-03-15 토요잉크Sc홀딩스주식회사 열 경화성 수지 조성물, 폴리아미드, 접착성 시트, 경화물 및 프린트 배선판
KR20170121709A (ko) 2016-04-25 2017-11-02 뉴 시코 모터 컴퍼니 리미티드 렌즈 구동 장치, 카메라 장치 및 전자기기
KR20180093721A (ko) 2017-02-14 2018-08-22 삼성전자주식회사 디스플레이 장치와 방법 및 광고 서버

Family Cites Families (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5102751A (en) * 1990-02-07 1992-04-07 Sri International Plasticizers useful for enhancing ionic conductivity of solid polymer electrolytes
WO2011132717A1 (fr) * 2010-04-22 2011-10-27 日油株式会社 Electrolyte non aqueux pour dispositif électrique et son emploi dans une batterie auxiliaire
KR101639839B1 (ko) * 2013-10-08 2016-07-25 포항공과대학교 산학협력단 말단 기능기를 이용한 고분자 전해질의 모폴리지 제어 및 전도도 향상 방법
KR101930478B1 (ko) * 2017-03-08 2018-12-18 주식회사 엘지화학 말단화학을 통한 고분자 전해질 막의 이온 전도도, 기계적 물성 및 모폴로지 제어방법

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
KR20170029527A (ko) 2014-07-02 2017-03-15 토요잉크Sc홀딩스주식회사 열 경화성 수지 조성물, 폴리아미드, 접착성 시트, 경화물 및 프린트 배선판
KR20170121709A (ko) 2016-04-25 2017-11-02 뉴 시코 모터 컴퍼니 리미티드 렌즈 구동 장치, 카메라 장치 및 전자기기
KR20180093721A (ko) 2017-02-14 2018-08-22 삼성전자주식회사 디스플레이 장치와 방법 및 광고 서버

Non-Patent Citations (3)

* Cited by examiner, † Cited by third party
Title
ITO, K.NISHINA, N.OHNO, H. J., MATER. CHEM., vol. 7, 1997, pages 1357 - 1362
JO, G.ANH, H.PARK, M. J., ACS MACRO LETT, vol. 2, 2013, pages 990 - 995
See also references of EP3595070A4

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN113381060A (zh) * 2021-06-21 2021-09-10 浙江大学 一种全固态复合电解质及其制备方法和应用
CN114940762A (zh) * 2022-05-18 2022-08-26 深圳市贝特瑞新能源技术研究院有限公司 聚合物及其制备方法、聚合物电解质、锂离子电池

Also Published As

Publication number Publication date
WO2019059705A3 (fr) 2019-05-09

Similar Documents

Publication Publication Date Title
WO2015056907A1 (fr) Membrane de séparation et batterie au lithium-soufre comprenant cette dernière
WO2017196105A1 (fr) Électrode négative de protection pour batterie lithium-métal et batterie lithium-métal la comprenant
KR102229457B1 (ko) 고분자 전해질 및 이의 제조방법
WO2020067779A1 (fr) Électrolyte non aqueux et batterie secondaire au lithium le comprenant
WO2020055017A1 (fr) Composite soufre-carbone, procédé pour le produire, et accumulateur au lithium l'incluant
WO2020055110A1 (fr) Composition d'électrolyte thermodurcissable pour batterie secondaire au lithium, électrolyte polymérique en gel préparé avec ladite composition et batterie secondaire au lithium le comportant
WO2019108032A1 (fr) Composition d'électrolyte polymérique en gel et batterie secondaire au lithium la comprenant
WO2020060295A1 (fr) Composition pour électrolyte polymère en gel et batterie rechargeable au lithium comprenant un électrolyte polymère en gel formé à partir de cette dernière
WO2019059705A2 (fr) Électrolyte polymère et son procédé de préparation
WO2020036336A1 (fr) Électrolyte pour batterie secondaire au lithium
WO2022211589A1 (fr) Matériau actif de cathode composite, cathode et batterie au lithium utilisant celui-ci, et son procédé de préparation
WO2020060293A1 (fr) Composition pour électrolyte polymère en gel et accumulateur au lithium comprenant un électrolyte polymère en gel ainsi formé
WO2020022777A1 (fr) Électrolyte polymérique et procédé de production associé
WO2018012877A1 (fr) Polymère, et électrolyte et batterie au lithium comprenant chacun celui-ci
WO2022055307A1 (fr) Composition de précurseur pour électrolyte polymère, et électrolyte polymère en gel formé à partir de celle-ci
WO2021225359A1 (fr) Électrolyte solide à base de polymère ayant une résistance mécanique améliorée, son procédé de préparation et batterie secondaire au lithium comprenant un électrolyte solide
WO2020055122A1 (fr) Composition d'électrolyte thermodurcissable pour batterie secondaire au lithium, électrolyte en gel polymérique préparé avec ladite composition et batterie secondaire au lithium le comportant
WO2022158749A1 (fr) Additif pour électrolyte de batterie au lithium, électrolyte organique le comprenant et batterie au lithium comprenant un électrolyte
WO2022231394A1 (fr) Monomère pour addition d'électrolyte polymère réticulé et membrane électrolytique polymère réticulée le comprenant pour une batterie au lithium-ion
WO2022169186A1 (fr) Composition pour la préparation d'électrolyte solide, électrolyte solide l'utilisant et batterie rechargeable au lithium
WO2020209511A1 (fr) Plastifiant à base d'oxyde d'éthylène-propylène multiramifié pour électrolyte polymère tout solide et composition d'électrolyte polymère tout solide le comprenant
WO2024010179A1 (fr) Polymère de polystyrène comprenant un groupe bifonctionnel, membrane électrolytique polymère le comprenant, et dispositif électronique
WO2023059063A1 (fr) Composé dérivé de la furodioxine saturée et utilisation associée comme additif pour batterie secondaire
WO2023090665A1 (fr) Nouvel additif pour solution électrolytique non aqueuse et batterie secondaire au lithium le comprenant
WO2023027541A1 (fr) Électrolyte pour batterie secondaire au lithium et batterie secondaire au lithium le comprenant

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: 18859540

Country of ref document: EP

Kind code of ref document: A2

ENP Entry into the national phase

Ref document number: 2019565146

Country of ref document: JP

Kind code of ref document: A

ENP Entry into the national phase

Ref document number: 2018859540

Country of ref document: EP

Effective date: 20191008

NENP Non-entry into the national phase

Ref country code: DE