Patent Application
20210028488
This application claims priorities from Korean Patent Application No. 10-2018-0086460, filed on Jul. 25, 2018, all contents of which are incorporated herein by reference in its entirety.
The present invention relates to a polymer electrolyte excellent in mobility and ionic conductivity and a method for manufacturing the same.
For current portable electronic devices, a lithium ion secondary battery with high energy density is commonly used. The liquid electrolyte, which is mainly used in this case, has problems such as the risk of leakage and explosion. In order to protect them, a safety circuit device is required, and the weight of the battery is inevitably increased by being sealed with a metal sheath can to prevent the leakage. In addition, since the thickness of the battery becomes thick, there is a limitation in battery design. As electronic devices become thinner and flexible in the future, the lithium ion secondary battery, which currently uses liquid as an electrolyte, cannot meet all of the requirements such as miniaturization, light weight, and flexibility.
On the other hand, a lithium polymer battery has high average voltage and high energy density. Also, in addition to the properties of a lithium ion secondary battery with no memory effect, the lithium polymer battery can prevent leakage of the electrolyte to the outside of the battery, thereby improving the stability of the battery. Also, in the case of the lithium polymer battery, since the electrode and the separator are integrated, the surface resistance is reduced, thereby being advantageous for high efficiency charging and discharging with relatively low internal resistance. In addition, the electrolyte film can be thinned to make flexible devices and batteries of any shape, and since the metal sheath can is not used, the thickness of the battery may be thinner. Therefore, batteries for portable electronic devices such as mobile phones, notebook computers, and digital cameras, which are increasing in demand by the consumer for stability, miniaturization, and high capacity, are expected to be largely replaced by lithium polymer batteries from existing lithium ion batteries. Also, the lithium polymer battery is expected to be applied to a high capacity lithium secondary battery for a hybrid electric vehicle and the like, and thus is gaining popularity as a next-generation battery.
The most important difference of the lithium polymer battery compared to the lithium ion secondary battery using the liquid electrolyte is that the separator between the positive electrode and the negative electrode is made of a polymer, and this polymer separator can also act as an electrolyte. In the lithium polymer battery, ion conduction is achieved by internal ion transfer of a stable polymer electrolyte as in a solid phase.
The polymer electrolyte used in the lithium polymer battery is being studied roughly in two parts, an intrinsic solid polymer electrolyte and a gel-type polymer electrolyte, wherein in the case of the intrinsic solid polymer electrolyte, ions of dissociated salts by adding electrolytic salts to the polymer containing heteroatoms such as O, N, and S are moved by segmental movement of the polymer, and wherein in the case of the gel-type polymer electrolyte, ionic conductivity is obtained by impregnating a liquid electrolyte into the polymer film and immobilizing it with electrolytic salts.
Among them, in the case of gel-type polymer electrolyte, there is still a difficulty in securing the stability of the battery due to the occurrence of leakage of the existing liquid electrolyte at the time of use, and also there is a problem of the difficulty in the process for manufacturing the battery. The intrinsic solid polymer electrolyte has been studied continuously since the discovery by P. V. Wright in 1975 that sodium ions are conducted in poly(ethylene oxide) (PEO). The intrinsic solid polymer electrolyte has high chemical and electrochemical stability and has the advantage that a high capacity lithium metal electrode can be used, but it has a problem of very low ionic conductivity at room temperature.
The ionic conductivity in the intrinsic solid polymer electrolyte has been found to be closely related to the degree of local motion of the polymer chain, and thus several methods have been studied to lower the high crystallinity of the PEO-based polymer electrolyte so that dissociated ions move freely.
As one of the methods, studies have been conducted to graft a low molecular weight PEO as a side chain to a flexible polymer main chain having a very low Tg value. A siloxane polymer electrolyte having various lengths of PEO as branches at both sides were synthesized, and when the siloxane polymer has six PEO repeating chains, which does not exhibit crystallinity, it showed high ionic conductivity of 4.5×10−4 S/cm at room temperature.
In order to overcome and improve the problems of the conventional electrolyte, various studies have been conducted in terms of the material and shape of the electrolyte.
Korean Patent No. 1232607 relates to a polymer electrolyte membrane for a lithium secondary battery comprising an organic-inorganic hybrid copolymer, wherein the organic-inorganic hybrid copolymer can be polymerized by reversible addition fragmentation chain transfer polymerization (RAFT) to form a polymer electrolyte membrane.
In addition, Korean Laid-open Patent Publication No. 2017-0083387 relates to an electrolyte comprising a block copolymer, wherein the block copolymer can also be obtained by RAFT reaction.
The block copolymer is obtained by a reversible addition fragmentation chain transfer polymerization (RAFT) reaction and discloses the use of a monomer, a chain transfer agent, an ionic liquid, a lithium salt, and an initiator as raw materials.
As described above, in recent years, attempts have been made to improve the physical properties of a polymer electrolyte membrane using a reversible addition fragmentation chain transfer polymerization (RAFT). However, the low ionic conductivity and the mobility of the electrolyte membrane itself, which are problems of the polymer electrolyte membrane, still remain to be improved.
(Patent Document 1) Korean Patent No. 1232607.
(Patent Document 2) Korean Patent Publication No. 2017-0083387.
As a result of various studies to solve the above problems, the inventors of the present invention have manufactured a polymer electrolyte membrane using a reversible addition fragmentation chain transfer polymerization (RAFT) where the polymer electrolyte membrane is manufactured by using a RAFT agent containing a styrene functional group with C═C double bond and a Solvate ion liquid together. The polymer electrolyte membrane thus manufactured has excellent ionic conductivity and excellent mobility of the electrolyte membrane itself, and thus was found to be advantageous in improving the performance of the battery.
Therefore, it is an object of the present invention to provide a polymer electrolyte membrane having excellent mobility and ionic conductivity.
In addition, it is still another object of the present invention to provide a method of manufacturing the polymer electrolyte membrane as described above.
In order to achieve the above objects, the present invention provides a polymer electrolyte comprising a polymer comprising a monomer containing ethylene oxide (EO) repeating units; a reversible addition fragmentation chain transfer polymerization agent (RAFT agent) comprising styrene groups at both ends; and a solvate ionic liquid (SIL) containing a lithium salt and a glyme-based material or an amide-based material.
The polymer electrolyte may contain 40 to 60% by weight of the polymer comprising a monomer containing the ethylene oxide repeating units; 3 to 10% by weight of the RAFT agent; and 30 to 50% by weight of the solvate ionic liquid containing the lithium salt and the glyme-based material.
The monomer containing the ethylene oxide repeating units may be at least one selected from the group consisting of poly(ethylene glycol) methyl ether acrylate (PEGMEA) and poly (ethylene glycol) methyl methacrylate (PEGMEMA).
The RAFT agent may comprise styrene functional group having C═C double bonds at both ends.
The RAFT agent may be crosslinked with the polymer.
In the solvate ionic liquid, the molar ratio of the lithium salt and the glyme-based material may be 1:0.1 to 3, and the molar ratio of the lithium salt and the amide-based material may be 1:1 to 6.
The glyme-based material may be at least one selected from the group consisting of monoglyme, diglyme, triglyme, and tetraglyme.
The lithium salt may be at least one selected from the group consisting of LiSCN, LiN(CN)2, LiClO4, LiBF4, LiAsF6, LiPF6, LiCF3SO3, LiN(SO2F)2, Li(CF3SO2)3C, LiN(SO2CF3)2, LiN(SO2CF2CF3)2, LiSbF6, LiPF3(CF2CF3)3, LiPF3(C2F5)3, LiPF3(CF3)3, and LiB(C2O4)2.
The solvate ionic liquid may be impregnated inside the chain of the polymer or contained in a swollen form inside the chain of the polymer.
The polymer electrolyte may be a polymer electrolyte membrane in a network form.
The present invention also provides a method for manufacturing a polymer electrolyte comprising the steps of (S1) mixing a monomer containing ethylene oxide repeating units, a RAFT agent, a solvate ionic liquid (SIL) containing a lithium salt and a glyme-based material or an amide-based material, and an initiator; (S2) removing oxygen from the mixed solution obtained in step (S1) above; and (S3) applying the mixed solution, from which oxygen has been removed in step (S2) above, to the substrate and curing it.
In step (S1) above, 40 to 60% by weight of the monomer containing ethylene oxide repeating units; 3 to 10% by weight of the RAFT agent; 30 to 50% by weight of the solvate ionic liquid (SIL) containing the lithium salt and the glyme-based material; and 0.1 to 1% by weight of the initiator may be mixed.
In step (S3) above, the curing may be thermal-curing or photo-curing.
The present invention also provides a lithium secondary battery comprising the polymer electrolyte.
The polymer electrolyte according to the present invention can be manufactured in the form of a polymer membrane having a network form that has a homogeneous and low crosslinking degree by RAFT polymerization using a RAFT agent, and thus can improve the phenomenon of the decrease of the mobility of the polymer chain and can solve the problem of the occurrence of leakage in assembling the battery using the conventional polymer electrolyte.
In addition, in the manufacture of the polymer electrolyte, a RAFT agent, into which a styrene functional group with C═C double bond is introduced at both ends, can play a role as a crosslinker and as a chain transfer agent at the same time.
Also, in the manufacture of the polymer electrolyte, ionic conductivity can be improved by using the solvate ionic liquid.
Hereinafter, the present invention will be described in detail in order to facilitate understanding of the present invention.
The terms and words used in the present specification and claims should not be construed as being limited to ordinary or dictionary terms, and should be construed in a sense and concept consistent with the technical idea of the present invention, based on the principle that the inventor can properly define the concept of a term to describe his invention in the best way.
Polymer Electrolyte
The present invention relates to a polymer electrolyte prepared by a reversible addition fragmentation chain transfer polymerization (RAFT), which has a network form with homogeneous and low crosslinking degree and has high ionic conductivity.
The polymer electrolyte of the present invention comprises a polymer comprising a monomer containing ethylene oxide repeating units; a reversible addition fragmentation chain transfer polymerization agent (RAFT agent) into which a styrene group is introduced at both ends; and a solvate ionic liquid (SIL) containing a lithium salt and a glyme-based material or an amide-based material.
Specifically, the polymer electrolyte may comprise the SIL and a random copolymer comprising the repeating units having ethylene oxide and styrene.
The polymer comprising a monomer containing ethylene oxide repeating units may be contained in an amount of 40 to 60% by weight, preferably 43 to 57% by weight, and more preferably 45 to 55% by weight, based on the total weight of the polymer electrolyte. If the amount is less than the above range, leakage may occur. If the amount is more than the above range, the ionic conductivity of the polymer electrolyte may be lowered.
In the present invention, the RAFT agent may function as a crosslinker and a chain transfer agent in the manufacture of the polymer electrolyte, thereby enabling the formation of a polymer electrolyte membrane having a network form with homogeneous and low crosslinking degree.
Specifically, the RAFT agent may be comprised in the polymer electrolyte in a state crosslinked with the polymer containing ethylene oxide monomer, thereby enabling the formation of a polymer electrolyte membrane having a network form with homogeneous and low crosslinking degree.
The RAFT agent may be contained in an amount of 3 to 10% by weight, preferably 4 to 9% by weight, more preferably 5 to 8% by weight based on the total weight of the polymer electrolyte. If the amount is less than the above range, leakage may occur. If the amount is more than the above range, the ionic conductivity of the polymer electrolyte may be lowered.
Also, the RAFT agent may have a styrene functional group with C═C double bonds introduced at both ends. For example, the RAFT agent is at least one selected from the group consisting of 3,4-divinyl benzyl trithiocarbonate (DVBTC) represented by Formula 1 and trithiocarbonate represented by Formula 2:
In the present invention, the solvate ionic liquid (SIL) can function to improve the ionic conductivity of the polymer electrolyte.
The solvate ionic liquid may be impregnated inside the chain of the polymer containing the ethylene oxide repeating units or contained in a swollen form inside the chain of the polymer.
The solvate ionic liquid may be contained in an amount of 30 to 50% by weight, preferably 25 to 45% by weight, and more preferably 30 to 40% by weight, based on the total weight of the polymer electrolyte. If the amount is less than the above range, leakage may occur. If the amount is more than the above range, the ionic conductivity of the polymer electrolyte may be lowered.
In addition, the solvate ionic liquid may contain the lithium salt and the glyme-based material, or may contain the lithium salt and the amide-based material.
If the solvate ionic liquid contains the lithium salt and the glyme-based material, the molar ratio of the glyme-based material and the lithium salt is 1:0.1 to 3, preferably 1:0.1 to 2, and more preferably 1:1.5. If the molar ratio of the glyme-based material to the lithium salt is less than or greater than the above range, the solvate ionic liquid cannot be formed.
The glyme-based material may be at least one selected from the group consisting of monoglyme, diglyme, triglyme, and tetraglyme. The glyme-based material contains oxygen to coordinate lithium salts.
The lithium salt may be at least one selected from the group consisting of LiSCN, LiN(CN)2, LiClO4, LiBF4, LiAsF6, LiPF6, LiCF3SO3, LiN(SO2F)2, Li(CF3SO2)3C, LiN(SO2CF3)2, LiN(SO2CF2CF3)2, LiSbF6, LiPF3(CF2CF3)3, LiPF3(C2F5)3, LiPF3(CF3)3, and LiB(C2O4)2. Preferably, the lithium salt may be LiN(SO2F)2 or LiN(SO2CF3)2, which may be more advantageous in improving ionic conductivity and mechanical properties of the polymer electrolyte.
Referring to
In addition,
In addition, if the solvate ionic liquid contains the lithium salt and the amide-based material, the molar ratio of the lithium salt and the amide-based material may be 1:1 to 6, preferably 1:2 to 6, and more preferably 1:3 to 5. If the molar ratio of the amide-based material to the lithium salt is less than or greater than the above range, the solvate ionic liquid cannot be formed.
The amide-based material may be at least one selected from the group consisting of N-methylacetamide(NMAC), acetamide, N-methylpropionamide, N-ethylacetamide, propionamide, formamide, N-methylformamide, N-ethylformamide, N,N-dimethylformamide, N,N-diethylformamide, N, N-dimethylacetamide and N,N-diethylacetamide, and preferably may be N-methylacetamide.
The polymer electrolyte according to the present invention may be a polymer electrolyte membrane in a network form.
Specifically, since radical formation is slow and uniform RAFT polymerization is performed as compared with free radical polymerization, a polymer electrolyte membrane having a network form with a homogeneous and low crosslinking degree can be formed.
Manufacturing Method of Polymer Electrolyte
The present invention also relates to a method for manufacturing a polymer electrolyte having a network form with a homogeneous and low crosslinking degree and having high ionic conductivity, using RAFT polymerization.
The method for manufacturing the polymer electrolyte according to the present invention may comprise the steps of (S1) mixing a monomer containing ethylene oxide repeating units, a RAFT agent, a solvate ionic liquid (SIL) containing a lithium salt and a glyme-based material or an amide-based material, and an initiator; (S2) removing oxygen from the mixed solution obtained in step (S1) above; and (S3) applying the mixed solution, from which oxygen has been removed in step (S2) above, to the substrate and curing it.
Hereinafter, a method for manufacturing the polymer electrolyte according to the present invention will be described in detail for each step.
Step (S1)
In step (S1), a monomer containing ethylene oxide repeating units; a RAFT agent; a solvate ionic liquid (SIL) containing a lithium salt and a glyme-based material or an amide-based material; and an initiator may be mixed.
The monomer containing the ethylene oxide repeating units may be at least one selected from the group consisting of poly(ethylene glycol) methyl ether acrylate (PEGMEA) and poly(ethylene glycol) methyl methacrylate (PEGMEMA), and preferably may be PEGMEA.
The monomer containing the ethylene oxide repeating units may be mixed in an amount of 40 to 60% by weight, preferably 43 to 57% by weight, and more preferably 45 to 55% by weight, based on the total weight of the four mixed materials, i.e. the monomer containing ethylene oxide repeating units, the RAFT agent, the solvate ionic liquid containing the lithium salt and the glyme-based material, and the initiator. If the amount is less than the above range, leakage may occur. If the amount is more than the above range, the ionic conductivity of the polymer electrolyte may be lowered.
The functions, specific types, proper weight to be used when mixing, critical significance and characteristics of the RAFT agent and solvate ionic liquid are as described above.
The initiator may allow the RAFT polymerization reaction to commence.
The initiator may be at least one selected from the group consisting of azobis(isobutyronitrile) (AIBN), benzoyl peroxide, acetyl peroxide, dilauryl peroxide, di-tert-butylperoxide, t-butyl peroxy-2-ethyl-hexanoate, cumyl hydroperoxide, hydrogen peroxide, 2,2-azobis(2-cyanobutane), 2,2-azobis(methylbutyronitrile) and azobisdimethyl valeronitrile (AMVN), and preferably, may be azobis(isobutyronitrile) (AIBN).
The initiator may be mixed in an amount of 0.1 to 1% by weight, preferably 0.1 to 0.8% by weight, and more preferably 0.1 to 0.5% by weight, based on the total weight of the four mixed materials, i.e. the monomer containing ethylene oxide repeating units, the RAFT agent, the solvate ionic liquid containing the lithium salt and the glyme-based material, and the initiator. If the amount is less than the above range, the RAFT polymerization reaction may not be initiated, and even if the amount exceeds the above range, it does not cause the RAFT polymerization reaction to initiate more smoothly, so there is no benefit from exceeding the above range.
Step (S2)
In step (S2), oxygen can be removed from the mixed solution obtained in step (S1). Since oxygen plays a role of eliminating the radicals necessary for the polymerization reaction, it is preferable to remove oxygen from the mixed solution.
The method of removing oxygen may be a bubbling method or a freeze-pump-thaw method, and preferably oxygen may be removed by nitrogen bubbling.
Step (S3)
In step (S3), the mixed solution from which oxygen is removed in step (S2) may be applied on the substrate and cured.
The method of applying the oxygen-removed mixed solution onto the substrate may be selected from the group consisting of spraying method, screen printing method, doctor blade method, and slot die method. There is no particular limitation as long as it is a method of applying a solution on a substrate, which can be used in the art.
After the application, the polymer electrolyte formed on the substrate, specifically, the polymer electrolyte membrane may be peeled off.
The substrate may preferably be a release film.
The release film is not particularly limited as long as it is a release film used in the art, and for example, the release film formed by polyester resins such as polyethylene terephthalate, polybutylene terephthalate, polyethylene naphthalate and polybutylene naphthalate; polyimide resin; acrylic resin; styrene resins such as polystyrene and acrylonitrile-styrene; polycarbonate resin; polylactic acid resin; polyurethane resin; polyolefin resins such as polyethylene, polypropylene, and ethylene-propylene copolymer; vinyl resins such as polyvinyl chloride and polyvinylidene chloride; polyamide resins; sulfonic resin; polyether-ether ketone resin; allylate-based resin; or a mixture thereof may be used.
The curing may be thermal-curing or photo-curing. The thermal-curing may be performed by heating to a temperature of 50 to 80° C., preferably 55 to 75° C., and more preferably to 70° C. If the above-mentioned thermal-curing temperature is lower than the above-mentioned range, the polymer electrolyte cannot be obtained because the curing is not performed as much as desired. If the thermal-curing temperature is higher than the above range, the physical properties of the polymer electrolyte itself may be denatured. The photo-curing may be UV curing.
Lithium Secondary Battery
The present invention also relates to a lithium secondary battery comprising the polymer electrolyte as described above.
The lithium secondary battery according to the present invention comprises a positive electrode, a negative electrode, and an electrolyte interposed therebetween, wherein the electrolyte may be the polymer electrolyte as described above.
The polymer electrolyte exhibits high lithium ion conductivity while satisfying both electrochemically excellent voltage stability and cation transportation rate, and thus can be preferably used as an electrolyte of the battery to improve the performance of the battery.
In addition, in order to further increase the lithium ion conductivity, the electrolyte may further comprise a substance used for this purpose.
If desired, the polymer electrolyte further comprises an inorganic solid electrolyte or an organic solid electrolyte. The inorganic solid electrolyte may be a ceramic material, which is a crystalline material or an amorphous material, and may be inorganic solid electrolytes such as thio-LISICON (Li3.25Ge0.25P0.75S4), Li2S—SiS2, LiI—Li2S—SiS2, LiI—Li2S—P2S5, LiI—Li2S—P2O5, LiI—Li3PO4—P2S5, Li2S—P2S5, Li3PS4, Li7P3Si11, Li2O—B2O3, Li2O—B2O3—P2O5, Li2O—V2O5—SiO2, Li2O—B2O3, Li3PO4, Li2O—Li2WO4—B2O3, LiPON, LiBON, Li2O—SiO2, LiI, Li3N, Li5La3Ta2O12, Li7La3Zr2O12, Li6BaLa2Ta2O12, Li3PO(4−3/2w)Nw (wherein w<1), Li3.6Si0.6P0.4O4.
Examples of the organic solid electrolyte may be organic solid electrolytes prepared by mixing lithium salt to polymeric materials such as polyethylene derivatives, polyethylene oxide derivatives, polypropylene oxide derivatives, phosphate ester polymers, poly agitation lysine, polyester sulfide, polyvinyl alcohol, and polyvinylidene fluoride. In this case, these may be used alone or in combination of at least one.
The specific application method of the polymer electrolyte is not particularly limited in the present invention, and can be selected from methods known to those skilled in the art.
The lithium secondary battery to which the polymer electrolyte can be applied as an electrolyte has no limitations on positive or negative electrodes, and especially is applicable to lithium-air battery, lithium oxide battery, lithium-sulfur battery, lithium metal battery, and all-solid-state battery which operate at high temperature.
The positive electrode of the lithium secondary battery may comprise, but is not limited to, a layered compound such as lithium cobalt oxide(LiCoO2) and lithium nickel oxide (LiNiO2), or a compound substituted by one or more transition metals; lithium manganese oxide such as LiMnO3, LiMn2O3, LiMnO2 represented by chemical formula of Li1+xMn2−xO4 (0≤x≤0.33); lithium copper oxide (Li2CuO2); vanadium oxide such as LiV3O8, LiFe3O4, V2O5, Cu2V2O7; Ni-site lithium nickel oxide represented by chemical formula of LiNi1−xMxO2 (M=Co, Mn, Al, Cu, Fe, Mg, B or Ga; 0.01≤x≤0.3); lithium manganese composite oxide represented by chemical formula of LiMn2−xMxO2 (M=Co, Ni, Fe, Cr, Zn or Ta; 0.01≤x≤0.1) or Li2Mn3MO8 (M=Fe, Co, Ni, Cu or Zn); lithium manganese complex oxide of spinel structure represented by LiNixMn2−xO4; LiMn2O4 in which a portion of Li in the chemical formula is replaced by an alkaline earth metal ion; disulfide compound; chalcogenide such as Fe2(MoO4)3, Cu2Mo6S8, FeS, CoS and MiS, oxides, sulfides or halides of scandium, ruthenium, titanium, vanadium, molybdenum, chromium, manganese, iron, cobalt, nickel, copper, zinc and the like, and more specifically may comprise TiS2, ZrS2, RuO2, Co3O4, Mo6S8, V2O5 or the like.
This positive electrode active material can 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. For example, stainless steel, aluminum, nickel, titanium, sintered carbon; aluminum or stainless steel surface-treated with carbon, nickel, titanium, silver or the like may be used as the positive electrode current collector. At this time, the positive electrode current collector may be formed in various forms such as film having fine irregularities on its surface, sheet, foil, net, porous body, foam, or nonwoven fabric to enhance the bonding force with the positive electrode active material.
In addition, the negative electrode is manufactured by forming a negative electrode mixture layer with a negative electrode active material on the negative electrode current collector, or may be a negative electrode mixture layer (for example, lithium foil) alone.
At this time, the types of the negative electrode current collector and the negative electrode mixture layer are not particularly limited in the present invention, and known materials can be used.
In addition, the negative electrode current collector is not particularly limited as long as it has electrical conductivity without causing a chemical change in the battery. For example, copper, stainless steel, aluminum, nickel, titanium, sintered carbon, copper or stainless steel surface-treated with carbon, nickel, titanium, silver or the like; aluminum-cadmium alloy or the like may be used as the negative electrode current collector. Also, as with the positive electrode current collector, the shape of the negative electrode current collector can be various forms such as a film having fine irregularities on its surface, sheet, foil, net, porous body, foam, nonwoven fabric and the like.
In addition, the negative electrode active material may comprises, but is not limited to, at least one carbon-based material 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, and fibrous carbon, Si-based material, metal composite oxides such as LixFe2O3(0≤x≤1), LixWO2(0≤x≤1), SnxMe1-xMe′yOz (Me:Mn, Fe, Pb, Ge; Me′:Al, B, P, Si, elements of groups 1, 2, and of the periodic table, halogen; 0<x≤1; 1≤y≤3; 1≤z≤8); lithium metal; lithium alloy; silicon-based alloy; tin-based alloy; metal oxide such as SnO, SnO2, PbO, PbO2, Pb2O3, Pb3O4, Sb2O3, Sb2O4, Sb2O5, GeO, GeO2, Bi2O3, Bi2O4, Bi2O5; an electrical conductivity polymer such as polyacetylene; Li—Co—Ni based material; titanium oxide; lithium titanium oxide.
In addition, the negative electrode active material may be metal composite oxides such as SnxMe1-xMe′yOz (Me:Mn, Fe, Pb, Ge; Me′:Al, B, P, Si, elements of groups 1, 2, and 3 of the periodic table, halogen; 0<x≤1; 1≤y≤3; 1≤z≤8); oxides such as SnO, SnO2, PbO, PbO2, Pb2O3, Pb3O4, Sb2O3, Sb2O4, Sb2O5, GeO, GeO22, Bi2O3, Bi2O4, and Bi2O5, and carbon-based negative electrode active materials such as crystalline carbon, amorphous carbon, or carbon composite may be used alone or in combination of two or more.
At this time, the electrode material mixture layer may further include a binder resin, an electrically conductive material, a filler, and other additives.
The binder resin is used for the bonding of the electrode active material and the electrically conductive material and for the bonding to the current collector. Examples of such binder resins may comprise polyvinylidene fluoride (PVDF), polyvinyl alcohol, carboxymethylcellulose (CMC), starch, hydroxypropyl cellulose, regenerated cellulose, polyvinyl pyrrolidone, tetrafluoroethylene, polyethylene, polypropylene, ethylene-propylene-diene polymer (EPDM), sulfonated-EPDM, styrene-butadiene rubber, fluorine rubber, and various copolymers thereof.
The electrically conductive material is used to further improve the electrical conductivity of the electrode active material. The electrically conductive material is not particularly limited as long as it has electrical conductivity without causing chemical changes in the battery, and for example, graphite such as natural graphite or artificial graphite; carbon blacks such as carbon black, acetylene black, Ketjen black, channel black, furnace black, lamp black, and thermal black; electrically conductive fibers such as carbon fiber and metal fiber; metal powders such as carbon fluoride, aluminum and nickel powder; electrically conductive whiskers such as zinc oxide and potassium titanate; electrically conductive metal oxides such as titanium oxide; polyphenylene derivative can be used.
The filler is selectively used as a component for suppressing the expansion of the electrode and is not specifically limited as long as it is a fibrous material without causing chemical change in the battery, and for example, includes olefin-based polymers such as polyethylene and polypropylene; and fibrous materials such as glass fiber and carbon fiber.
The shape of the lithium secondary battery as described above is not particularly limited and may be, for example, a jelly-roll type, a stack type, a stack-folding type (comprising a stack-Z-folding type), or a lamination-stacking type, and preferably a stack-folding type.
The electrode assembly in which the negative electrode, polymer electrolyte, and the positive electrode are sequentially stacked is prepared, and the electrode assembly is inserted into the battery case, and then sealed with cap plate and gasket to obtain the lithium secondary battery.
In this case, the lithium secondary battery can be classified into various types of batteries such as lithium-sulfur battery, lithium-air battery, lithium-oxide battery, and lithium all-solid-state battery depending on the type of positive electrode/negative electrode materials used, can be classified into cylindrical, rectangular, coin-shaped, pouch type depending on the type, and can be divided into bulk type and thin film type depending on the size. The structure and preparing method of these batteries are well known in the art, and thus detailed description thereof is omitted.
The lithium secondary battery according to the present invention can be used as a power source for devices requiring high capacity and high rate characteristics, etc. Specific examples of the device may comprise, but are not limited to, a power tool that is powered by a battery powered motor; electric cars comprising an electric vehicle (EV), a hybrid electric vehicle (HEV), a plug-in hybrid electric vehicle (PHEV), and the like; an electric motorcycle comprising an electric bike (E-bike) and an electric scooter (Escooter); an electric golf cart; and a power storage system.
Hereinafter, preferred examples of the present invention will be described in order to facilitate understanding of the present invention. It will be apparent to those skilled in the art, however, that the following examples are illustrative of the present invention and that various changes and modifications can be made within the scope and spirit of the present invention. Such variations and modifications are within the scope of the appended claims.
In the following examples and comparative examples, polymer electrolytes were manufactured according to the composition as set forth in Table 1 below.
(1) Synthesis of RAFT Agent
3,4-divinylbenzyl trithiocarbonate (DVBTC), a RAFT agent, was synthesized according to Reaction Scheme 1 below.
In a 250 mL round bottom flask, carbon disulfide (CS2, Sigma-Aldrich, 3.81 g) and potassium carbonate (K2CO3, DaeJungWhaGeum, 7.26 g) were dissolved in 100 mL of dimethylformamide (DMF, Sigma-Aldrich, 100 mL) and stirring was continued for 30 minutes to obtain a solution.
To the obtained solution, 3,4-vinylbenzyl chloride (VBC, Sigma-Aldrich, 7.63 g) was added dropwise and the reaction was carried out at 40° C. for 24 hours while stirring.
The solution with undergoing the reaction was placed in an excess amount of deionized water (DI water) stored in the refrigerator to terminate the reaction.
The reaction terminated solution was mixed with 300 mL of ethyl acetate (EtAC, Sigma-Aldrich), and then the yellow reactant of the EtAC layer was collected using a separation funnel, and residual water was removed using magnesium sulfate (MgSO4).
Thereafter, the reactant was separated by filtration, the EtAc was removed using a rotary evaporator, and then the residual solvent was removed by vacuum drying (room temperature, 24 hours).
Additional purification was carried out through a silica gel column to obtain 3,4-divinylbenzyl trithiocarbonate (DVBTC) (RAFT agent) in the form of a yellow oil.
(2) Identification of Synthetic Material
Referring to
(1) Synthesis of SIL (Li[NMAC][TFSI])
After mixing N-methylacetamide (NMAC, Sigma-Aldrich) and bis(trifluoromethane)sulfonimide lithium salt (LiTFSI, Sigma-Aldrich) vacuum-dried at 100° C. for 24 hours in a ratio of 50.46% by weight and 49.54% by weight, respectively, the mixture was stirred in a glove box at room temperature for 4 hours to synthesize the solvate ionic liquid (Li[NMAC][TFSI], 1.9M) represented by the following Formula 3.
(2) Confirmation of Physical Properties of Synthesized SIL (Li[NMAC][TFSI])
(2-1) Phase Identification of SIL (Li[NMAC][TFSI])
As a result of visual observation of the synthesized SIL (Li[NMAC][TFSI]), it was confirmed that NMAC existing in crystal form at 25° C. exists in the form of LiTFSI and ionic liquid, and changes to a liquid phase in SIL.
(2-2) Confirmation of Thermal Stability
A Differential Scanning calorimeter (DSC) was measured to confirm the thermal stability of synthesized SIL (Li[NMAC][TFSI]).
Referring to
(2-3) Confirmation of Flame Retardancy
Experiments were conducted to confirm the flame retardancy of the synthesized SIL (Li[NMAC][TFSI]).
Referring to
(1) Mixing of Raw Materials
Poly(ethylene glycol) methyl ether acrylate (PEGMEA, Sigma-Aldrich, Mn: 480) as a monomer; DVBTC synthesized in Preparation Example 1 as a RAFT agent; SIL synthesized to include NMAC and LiTFSI according to the same method as Preparation Example 2; and azobis(isobutyronitrile) (AIBN) as an initiator according to the composition shown in Table 1 were weighed in a reaction vial of 20 mL to have a total of 2 g, and mixed using a vortex for 1 minute, so that the initiator could be completely dissolved, to prepare a mixed solution. At this time, the SIL was synthesized according to the same method as Preparation Example 2, wherein the SIL is synthesized so as to satisfy the composition ratio as set forth in Table 1
(2) Removal of Oxygen
The mixed solution was bubbled with nitrogen for 2 minutes to remove residual oxygen from the mixed solution.
(3) Curing
The mixed solution from which the residual oxygen was removed was applied onto a release film (polyester film (SKC, SH71S, 100 μm)) using a pipette and thermal-cured.
The thermal-curing method was performed in two steps as described below.
After the curing was completed, the polymer electrolyte membrane was peeled from the release film.
In Example 1, the polymerization reaction in the manufacture of the polymer electrolyte is as shown in the following Reaction Scheme 2. In the following Reaction Scheme 2, the polymerized polymer electrolyte is shown as a schematic representation of the crosslinked form of PEGMEA (-) and RAFT agent (---).
The same procedure as in Example 1 was carried out, except that a polymer electrolyte was manufactured according to the composition as shown in Table 1 above using a photo-curing method. At this time, the SIL was synthesized according to the same method as Preparation Example 2, except that the SIL was synthesized so as to satisfy the composition ratio as shown in Table 1 above.
The photo-curing method was performed in two steps as described below.
The same procedure as in Example 2 was carried out, except that a polymer electrolyte was manufactured according to the composition as described in Table 1 above. At this time, the SIL was synthesized according to the same method as Preparation Example 2, except that the SIL was synthesized so as to satisfy the composition ratio as described in Table 1 above.
The same procedure as in Example 1 was carried out, except that a polymer electrolyte was manufactured by photo-curing method using 2-(dodecylthiocarbonothioylthio)-2-methylpropionic acid (Sigma-Aldrich) as a RAFT agent, which is not crosslinkable. At this time, the SIL was synthesized according to the same method as Preparation Example 2, except that the SIL was synthesized so as to satisfy the composition ratio as described in Table 1 above.
In Comparative Example 1, the reaction in the manufacture of the polymer electrolyte is as shown in Reaction Scheme 3 below.
Poly(ethylene oxide) having molecular weight of 1,000,000 (PEO, Sigma-Aldrich), NMAC, and LiTFSI were dissolved in acetonitrile (Sigma-Aldrich) to have a solid content of 10% by weight, and then solution casting was performed to prepare a polymer electrolyte membrane. At this time, the SIL was synthesized according to the same method as Preparation Example 2, except that the SIL was synthesized so as to satisfy the composition ratio as described in Table 1 above.
The ionic conductivity, voltage stability, and cation transportation rate of the polymer electrolytes prepared in examples and comparative examples were measured and evaluated as follows.
(1) Ionic Conductivity (σ)
After manufacturing a coin cell in the form of Steel Use Stainless (SUS)/polymer electrolyte/SUS, the ionic conductivity was measured by using a potentiostat, wherein the ionic conductivity was measured by applying a voltage of 10 mV in the range of 1 Hz to 5 MHz at 25° C.
The form of the polymer electrolyte was visually observed, and the results are shown in Table 2 below.
Referring to Table 2 above, it can be seen that the polymer electrolytes of Examples 1 to 3 exhibit superior ionic conductivity as compared to Comparative Examples 1 and 2.
In addition, it can be seen that since the polymer electrolytes of Examples 1 to 3 have the form of a free-standing film in which the film itself can be handled, the polymer electrolyte membranes of network form are formed. On the other hand, it was confirmed that in Comparative Example 1, the polymer electrolyte manufactured by using a non-crosslinkable RAFT agent was manufactured in the form of a non-crosslinked viscous liquid.
Referring to
(2) Voltage Stability
After manufacturing a coin cell in the form of Li metal/polymer electrolyte/SUS, the voltage stability was measured by using a potentiostat, wherein the voltage stability was measured at a scan rate of 5 mV/s in the range of −0.5 to 8V.
Referring to
(3) Cation Transportation Rate
After manufacturing a coin cell in the form of Li metal/polymer electrolyte/Li metal, the cation transportation rate was obtained by applying a voltage of 10 mV and measuring the current change over 20 hours. The cation transportation rate (tLi+) was calculated by the ratio of the steady state current (IS) and the initial current amount (I0) according to the following Equation (1).
According to Equation 1, the cation transportation rate of the polymer electrolyte prepared in Example 3 is 0.39.
While the present invention has been described with reference to exemplary examples and drawings, the present invention is not limited thereto. It will be understood by those skilled in the art that various changes in form and details may be made therein without departing from the spirit and scope of the present invention as defined by the appended claims.
| Number | Date | Country | Kind |
|---|---|---|---|
| 10-2018-0086460 | Jul 2018 | KR | national |
| Filing Document | Filing Date | Country | Kind |
|---|---|---|---|
| PCT/KR2019/008106 | 7/3/2019 | WO | 00 |
