KR20120114716A - Polymer composite electrolytes for lithium rechargeable batteries and method of making the same - Google Patents
Polymer composite electrolytes for lithium rechargeable batteries and method of making the same Download PDFInfo
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Abstract
본 발명은 리튬 이차전지용 전해질에 관한 것으로서, 더욱 상세하게는, 리튬이 도핑된 플라스틱 결정 이온전도체(Plastic crystal electrolytes)와 고분자 매트릭스를 혼합한 고분자 복합 전해질에 관한 것이다. 본 발명에 의하면, 고분자 매트릭스와, 리튬염이 도핑된 플라스틱 결정을 포함하는 리튬 이차전지용 고분자 복합 전해질이 제공된다. 또한, 본 발명에 의하면, 플라스틱 결정과 리튬염을 혼합한 후 가열하여 용액을 만드는 단계와, 상기 용액에 광가교 모노머를 혼합하는 단계와, 광가교 진행하는 단계를 포함하는 리튬 이차전지용 고분자 복합 전해질의 제조방법이 제공된다.The present invention relates to an electrolyte for a lithium secondary battery, and more particularly, to a polymer composite electrolyte in which lithium-doped plastic crystal electrolytes and a polymer matrix are mixed. According to the present invention, there is provided a polymer composite electrolyte for a lithium secondary battery comprising a polymer matrix and plastic crystals doped with lithium salts. In addition, according to the present invention, a polymer composite electrolyte for a lithium secondary battery, comprising the steps of making a solution by mixing the plastic crystals and lithium salt and then heating, mixing a photocrosslinking monomer in the solution, and performing a photocrosslinking Provided is a method for preparing.
Description
본 발명은 리튬 이차전지용 전해질에 관한 것으로서, 더욱 상세하게는, 고분자 매트릭스와 그 내부에 함입되는 리튬이 도핑된 플라스틱 결정을 포함하는 고분자 복합 전해질에 관한 것이다.The present invention relates to an electrolyte for a lithium secondary battery, and more particularly, to a polymer composite electrolyte comprising a polymer matrix and plastic crystals doped with lithium embedded therein.
노트북 컴퓨터, 캠코더 등의 휴대용 전자정보 기기와 이동전화, PCS, TRS, GPS 등 무선통신기기의 보급이 활발해짐에 따라 더욱 큰 용량의 전지가 요구된다. 이러한 이동 기기를 위한 전지로서 충전할 수 있는 이차전지가 사용되며, 그 중 리튬 전지는 에너지 밀도가 높다는 점에서 많이 사용되고 있다.As portable electronic information devices such as notebook computers and camcorders, and wireless communication devices such as mobile phones, PCS, TRS, and GPS become more popular, a larger capacity battery is required. A rechargeable battery that can be charged as a battery for such a mobile device is used, and lithium batteries are widely used in view of high energy density.
이러한 리튬 이차전지에서 각종 유기 용매가 전해액으로 사용되고 있다. 그러나 유기 용매를 전해액으로 사용하는 이차전지는 전해액이 누출되는 문제, 장기 보존성이 나쁘다는 문제, 안전성 문제, 유연성이 없다는 점 등 다양한 문제가 있다.In such a lithium secondary battery, various organic solvents are used as electrolytes. However, secondary batteries using organic solvents as electrolytes have various problems such as leakage of electrolytes, poor long-term storage, safety, and inflexibility.
이를 개선하기 위해서 고체 고분자 전해질에 대한 연구가 진행되고 있다. 고체 고분자 전해질은 일반적으로 전해질 누출 염려가 없으며 유연하여 원하는 모양으로 가공하기가 용이하다는 장점이 있다.In order to improve this, research into a solid polymer electrolyte is being conducted. Solid polymer electrolytes are generally free of electrolyte leakage and have the advantage of being flexible and easy to process into desired shapes.
고체 고분자 전해질에는 다량의 액체 전해질을 고분자에 함침시켜 겔화하여 얻어지는 겔형 고체 전해질과, 고분자 내에 존재하는 극성분자가 알칼리 금속 양이온에 배위 결합하여 착체를 형성하여 고분자 내에서 염이 해리된 상태로 고분자 속을 이동하여 전기 전도성을 띠는 본질형 고체 전해질로 구분되는데, 이 중 본질형 고체 전해질 그 중에서도 특히 폴리에틸렌 옥사이드(poly(ethylene oxide); PEO)계 전해질을 일반적으로 많이 사용한다. 이런 PEO계 고체 고분자 전해질은 화학적, 전기화학적 안정성이 높고, 특히 고용량의 리튬 금속 전극이 사용가능하다는 장점이 있으나 수용액 또는 겔 상태의 전해질에 비하여 상온에서 상대적으로 낮은 이온전도도를 가지는 단점이 있다. 이러한 문제점을 해결하기 위하여 액상의 가소제 및 TiO2, Al2O3, SiO2 그리고 활성 실리카와 같은 충전제를 첨가하여 사용한다. 이러한 방법 중 가소제를 첨가하는 방법은 고체 고분자 전해질의 이온전도도의 향상을 가져오나, 전해질의 기계적 물성이 저하되고, 양극과 반응하는 문제점이 있다.In the solid polymer electrolyte, a gel-type solid electrolyte obtained by impregnating a polymer with a large amount of liquid electrolyte and a polar molecule present in the polymer coordinate with an alkali metal cation to form a complex to dissociate salt in the polymer. It is divided into an intrinsic solid electrolyte having an electrical conductivity by moving, and among these, an intrinsic solid electrolyte, in particular, a polyethylene (poly (ethylene oxide); PEO) electrolyte is generally used. The PEO-based solid polymer electrolyte has a high chemical and electrochemical stability, and particularly has the advantage that a high capacity lithium metal electrode can be used. In order to solve this problem, a liquid plasticizer and fillers such as TiO 2 , Al 2 O 3 , SiO 2 and activated silica are added and used. Among these methods, the method of adding a plasticizer results in the improvement of the ionic conductivity of the solid polymer electrolyte, but the mechanical properties of the electrolyte are deteriorated and there is a problem of reacting with the positive electrode.
최근에는 리튬이 도핑된 유기 플라스틱 결정을 고체 전해질로 사용하고자 하는 시도가 있다. 공개특허 제10-2010-016393호와 제10-2008-0033421호에는 리튬 염으로 도핑된 유기 플라스틱 결정 이온전도체를 포함하는 전해질과 전기화학장치가 개시되어 있다.Recently, there have been attempts to use lithium-doped organic plastic crystals as solid electrolytes. Korean Patent Publication Nos. 10-2010-016393 and 10-2008-0033421 disclose an electrolyte and an electrochemical device including an organic plastic crystal ion conductor doped with a lithium salt.
상술한 리튬이 도핑된 유기 플라스틱 결정 고체 전해질은 다음과 같은 문제가 있었다. 대표적인 유기 플라스틱 결정인 숙시노니트릴(succinonitrile)은 -40℃ ~ 58℃ 사이에서 결정 플라스틱 상으로 유지되며, 그 이상의 온도에서는 액상이 된다. 유기 플라스틱 결정의 융점은 리튬 염이 도핑되면 더욱 낮아진다. 경우에 따라서는 상온에서도 액상으로 상변이가 일어난다. The lithium-doped organic plastic crystalline solid electrolyte has the following problems. Succinonitrile, a representative organic plastic crystal, is maintained in the crystalline plastic phase between −40 ° C. and 58 ° C. and becomes liquid at higher temperatures. The melting point of the organic plastic crystal becomes even lower when the lithium salt is doped. In some cases, phase transition occurs in the liquid phase even at room temperature.
따라서 리튬이 도핑된 유기 플라스틱 결정 이온전도체는 이차전지의 사용온도에서 결정 플라스틱 상에서 액상으로 변할 수 있어, 안전성이 떨어있다. 액상이 되면 전해질이 누출될 염려도 있다. 또한, 유연성이 적다는 문제가 있었다. Therefore, the lithium-doped organic plastic crystalline ion conductor may change into a liquid phase on the crystalline plastic at the use temperature of the secondary battery, resulting in poor safety. If the liquid phase, the electrolyte may leak. In addition, there was a problem of low flexibility.
본 발명은 상술한 문제점을 해결하기 위한 것으로서, 전기적 및 기계적 물성이 향상된 리튬 이차전지용 고분자 복합 전해질을 제공하는 것을 목적으로 한다.The present invention is to solve the above problems, an object of the present invention is to provide a polymer composite electrolyte for lithium secondary battery with improved electrical and mechanical properties.
또한, 전기적 및 기계적 물성이 향상된 리튬 이차전지용 고분자 복합 전해질의 제조방법을 제공하는 것을 다른 목적으로 한다. In addition, another object of the present invention is to provide a method for preparing a polymer composite electrolyte for a lithium secondary battery with improved electrical and mechanical properties.
본 발명을 상술한 목적을 달성하기 위해서, 고분자 매트릭스와, 상기 고분자 매트릭스에 함입되는 리튬염이 도핑된 플라스틱 결정을 포함하는 리튬 이차전지용 고분자 복합 전해질을 제공한다.In order to achieve the above object of the present invention, there is provided a polymer composite electrolyte for a lithium secondary battery comprising a polymer matrix and a plastic crystal doped with a lithium salt contained in the polymer matrix.
상기 플라스틱 결정은 숙시노니트릴(succinonitrile)인 것이 바람직하다.The plastic crystal is preferably succinonitrile.
상기 고분자 매트릭스는 폴리에틸렌, 폴리프로필렌, 셀룰로오스, 셀룰로오스 아세테이트, 셀룰로오스 아세테이트 부틸레이트, 셀룰로오스아세테이트 프로피오네이트, 폴리비닐피롤리돈-비닐아세테이트, 폴리[비스(2-(2-메톡시에톡시에톡시))포스파젠], 폴리에틸렌이미드, 폴리에틸렌옥사이드, 폴리에틸렌숙시네이트, 폴레에틸렌설파이드, 폴리(옥시메틸렌-올리고-옥시에틸렌), 폴리프로필렌옥사이드, 폴리비닐아세테이트, 폴리아크릴로니트릴, 폴리(아크릴로니트릴-코-메틸아크릴레이트), 폴리메틸메타크릴레이트, 폴리(메틸메타크릴레이드-코-에틸아크릴레이트), 폴리비닐클로라이드, 폴리(비닐리덴클로라이드-코-아크릴로니트릴), 폴리비닐리덴디플루오라이드, 폴리(비닐리덴플루오라이드-코-헥사플루오로프로필렌), 및 이들의 혼합물로 구성되는 군에서 선택되는 것이 바람직하다.The polymer matrix is polyethylene, polypropylene, cellulose, cellulose acetate, cellulose acetate butyrate, cellulose acetate propionate, polyvinylpyrrolidone-vinylacetate, poly [bis (2- (2-methoxyethoxyethoxy) ) Phosphazene], polyethyleneimide, polyethylene oxide, polyethylene succinate, polyethylene sulfide, poly (oxymethylene-oligo-oxyethylene), polypropylene oxide, polyvinylacetate, polyacrylonitrile, poly (acrylonitrile- Co-methylacrylate), polymethylmethacrylate, poly (methylmethacrylate-co-ethylacrylate), polyvinylchloride, poly (vinylidenechloride-co-acrylonitrile), polyvinylidenedifluoride , Poly (vinylidene fluoride-co-hexafluoropropylene), and mixtures thereof It is preferably selected from the group.
상기 리튬염은 리튬 비스-트리플루오로메탄설포닐이미드(Li(CF3SO2)2N, LiTFSI), 리튬 비스-퍼플루오로에틸설포닐이미드(Li(C2F5SO2)2N), 리튬 테트라플루오로보레이트(LiBF4), 리튬 헥사프루오로포스페이트(LiPF6), 리튬 티오시아네이트(LiSCN), 리튬 트리플레이트(LiCF3SO3), 리튬 테트라플루오로알루미네이트(LiAlF4), 리튬 퍼콜레이트(LiClO4) 및 이들의 혼합물로 구성되는 군에서 선택되는 것이 바람직하다. The lithium salt is lithium bis-trifluoromethanesulfonylimide (Li (CF 3 SO 2 ) 2 N, LiTFSI), lithium bis-perfluoroethylsulfonylimide (Li (C 2 F 5 SO 2 ) 2 N), lithium phosphate tetrafluoroborate (LiBF 4), lithium hexafluoro program Luo (LiPF 6), lithium thiocyanate (LiSCN), lithium triflate (LiCF 3 SO 3), aluminum lithium tetrafluoroborate carbonate ( LiAlF 4 ), lithium percholate (LiClO 4 ) and mixtures thereof are preferred.
또한, 본 발명에 의하면, 플라스틱 결정과 리튬염을 혼합한 후 가열하여 용액을 만드는 단계와, 상기 용액에 광가교 모노머를 혼합하는 단계와, 광가교를 진행하는 단계를 포함하는 리튬 이차전지용 고분자 복합 전해질의 제조방법이 제공된다.In addition, according to the present invention, a polymer composite for lithium secondary battery comprising the step of making a solution by mixing the plastic crystal and lithium salt and heating, mixing the photo-crosslinking monomer in the solution, and the step of performing photo-crosslinking A method for producing an electrolyte is provided.
본 발명에 따르면 고분자 매트릭스에 리튬이 도핑된 플라스틱 결정을 함입함으로써 전기적, 기계적 물성이 우수한 리튬 이차전지용 고분자 복합 전해질을 얻을 수 있다. 또한, 본 발명에 따른 고분자 복합 전해질은 플라스틱 결정 이온전도체가 액상이 되어 누출될 염려가 없다. According to the present invention, by incorporating lithium-doped plastic crystals into the polymer matrix, a polymer composite electrolyte for lithium secondary batteries having excellent electrical and mechanical properties can be obtained. In addition, the polymer composite electrolyte according to the present invention has no fear of leakage due to the liquid phase of the plastic crystal ion conductor.
이하, 본 발명을 상세히 설명하고자 한다.Hereinafter, the present invention will be described in detail.
본 발명은 고분자 매트릭스와, 고분자 매트릭스에 함입되는 리튬염이 도핑된 플라스틱 결정을 포함하는 리튬 이차전지용 고분자 복합 전해질을 제공한다. The present invention provides a polymer composite electrolyte for a lithium secondary battery comprising a polymer matrix and plastic crystals doped with lithium salts embedded in the polymer matrix.
고분자 매트릭스는 폴리에틸렌, 폴리프로필렌, 셀룰로오스, 셀룰로오스 아세테이트, 셀룰로오스 아세테이트 부틸레이트, 셀룰로오스아세테이트 프로피오네이트, 폴리비닐피롤리돈-비닐아세테이트, 폴리[비스(2-(2-메톡시에톡시에톡시))포스파젠], 폴리에틸렌이미드, 폴리에틸렌옥사이드, 폴리에틸렌숙시네이트, 폴레에틸렌설파이드, 폴리(옥시메틸렌-올리고-옥시에틸렌), 폴리프로필렌옥사이드, 폴리비닐아세테이트, 폴리아크릴로니트릴, 폴리(아크릴로니트릴-코-메틸아크릴레이트), 폴리메틸메타크릴레이트, 폴리(메틸메타크릴레이드-코-에틸아크릴레이트), 폴리비닐클로라이드, 폴리(비닐리덴클로라이드-코-아크릴로니트릴), 폴리비닐리덴디플루오라이드, 폴리(비닐리덴플루오라이드-코-헥사플루오로프로필렌), 및 이들의 혼합물로 구성되는 군에서 선택된다. 고분자 매트릭스는 원료가 되는 모노머에 자외선을 조사하여 광가교를 통해서 합성할 수 있다. The polymer matrix is polyethylene, polypropylene, cellulose, cellulose acetate, cellulose acetate butyrate, cellulose acetate propionate, polyvinylpyrrolidone-vinylacetate, poly [bis (2- (2-methoxyethoxyethoxy)) Phosphazene], polyethyleneimide, polyethylene oxide, polyethylene succinate, polyethylene sulfide, poly (oxymethylene-oligo-oxyethylene), polypropylene oxide, polyvinylacetate, polyacrylonitrile, poly (acrylonitrile-co -Methyl acrylate), polymethyl methacrylate, poly (methyl methacrylate-co-ethyl acrylate), polyvinyl chloride, poly (vinylidene chloride-co-acrylonitrile), polyvinylidene difluoride, Poly (vinylidene fluoride-co-hexafluoropropylene), and mixtures thereof It is selected. The polymer matrix can be synthesized by photocrosslinking by irradiating ultraviolet light to the monomer as a raw material.
리튬염은 리튬 비스-트리플루오로메탄설포닐이미드(Li(CF3SO2)2N, LiTFSI라 약칭), 리튬 비스-퍼플루오로에틸설포닐이미드(Li(C2F5SO2)2N), 리튬 테트라플루오로보레이트(LiBF4), 리튬 헥사프루오로포스페이트(LiPF6), 리튬 티오시아네이트(LiSCN), 리튬 트리플레이트(LiCF3SO3), 리튬 테트라플루오로알루미네이트(LiAlF4), 리튬 퍼콜레이트(LiClO4) 및 이들의 혼합물로 구성되는 군에서 선택된다.Lithium salts include lithium bis-trifluoromethanesulfonylimide (Li (CF 3 SO 2 ) 2 N, abbreviated LiTFSI), lithium bis-perfluoroethylsulfonylimide (Li (C 2 F 5 SO 2 ) 2 N), lithium tetrafluoroborate (LiBF 4 ), lithium hexafluoroophosphate (LiPF 6 ), lithium thiocyanate (LiSCN), lithium triflate (LiCF 3 SO 3 ), lithium tetrafluoroaluminate (LiAlF 4 ), lithium percholate (LiClO 4 ), and mixtures thereof.
플라스틱 결정은 장거리 병진(translation) 질서를 유지하면서 회전 및/또는 배향 무질서를 나타내는 준구형 또는 원반 유사 분자에 의해 주로 형성된다. 이 유형의 "무질서"의 결과는 고 확산성 및 가소성으로서 이는 플라스틱 결정이 고분자 물질과 유사한 기계적 특성을 갖도록 한다. 플라스틱 결정은 숙시노니트릴(succinonitrile)인 것이 바람직하다. 숙신니트릴은 -40℃ 내지 58℃의 온도에서 플라스틱 결정 형성을 나타내며, 리튬염이 도핑되면 용융 온도가 내려간다. Plastic crystals are mainly formed by quasi-spherical or disc-like molecules that exhibit rotational and / or orientation disorders while maintaining long distance translation order. The result of this type of "disorder" is high diffusivity and plasticity, which allows plastic crystals to have mechanical properties similar to polymeric materials. The plastic crystal is preferably succinonitrile. Succinitrile exhibits plastic crystal formation at temperatures between -40 [deg.] C. and 58 [deg.] C. and when the lithium salt is doped, the melting temperature drops.
본 발명의 고분자 복합 전해질은 다음과 같은 방법으로 제조한다. 우선, 플라스틱 결정에 리튬염을 혼합한 후 30 내지 60℃로 30분 정도 가열하여 용액을 만든다. 다음, 이 용액에 고분자 매트릭스를 형성할 수 있는 모노머를 혼합한다. 모노머는 10 내지 20중량%를 첨가한다. 다음, 모노머까지 혼합된 용액을 원하는 형상의 틀에 투입한 후 자외선을 10~30초 정도 조사하여 고분자 매트릭스를 합성한다. 고분자 매트릭스의 합성이 완료되면, 리튬염이 도핑된 플라스틱 결정이 고분자 매트릭스 내에 고르게 분포하는 고분자 복합 전해질을 얻을 수 있다.The polymer composite electrolyte of the present invention is prepared by the following method. First, a lithium salt is mixed with plastic crystals and then heated to 30 to 60 ° C for about 30 minutes to form a solution. Next, the monomer which can form a polymer matrix is mixed with this solution. The monomer is added 10 to 20% by weight. Next, the solution mixed up to the monomer is put in a mold of a desired shape, and then irradiated with ultraviolet light for about 10 to 30 seconds to synthesize a polymer matrix. When the synthesis of the polymer matrix is completed, a polymer composite electrolyte in which lithium salt-doped plastic crystals are evenly distributed in the polymer matrix may be obtained.
이하, 실시예를 통하여 본 발명을 더욱 상세히 설명하고자 한다.Hereinafter, the present invention will be described in more detail with reference to Examples.
본 실시예는 본 발명을 보다 구체적으로 설명하기 위한 것이며, 본 발명의 범위가 이들 실시예에 한정되는 것은 아니다.This embodiment is intended to illustrate the present invention in more detail, and the scope of the present invention is not limited to these examples.
<실시예><Examples>
먼저, 갈색 유리병에 숙시노니트릴(succinonitrile) 0.9665g과 리튬 비스-트리플루오로메탄설포닐이미드(Li(CF3SO2)2N, LiTFSI) 0.3588g을 넣어 1M의 용액을 만들고, 50℃에서 30분간 가열을 한다. First, a solution of 1M was prepared by adding 0.9665 g of succinonitrile and 0.3588 g of lithium bis-trifluoromethanesulfonylimide (Li (CF 3 SO 2 ) 2 N, LiTFSI) in a brown glass bottle. Heat at 30 ° C.
숙시노니트릴(succinonitrile)과 리튬 비스-트리플루오로메탄설포닐이미드(Li(CF3SO2)2N, LiTFSI)는 각각 고체 상태이지만 두 물질이 섞이면 액체 상태로 상변이가 일어난다. Succinonitrile and lithium bis-trifluoromethanesulfonylimide (Li (CF 3 SO 2 ) 2 N, LiTFSI) are each in the solid state, but when the two materials are mixed, a phase change occurs in the liquid state.
갈색 유리병을 사용하는 이유는 광가교 모노머를 함께 혼합할 것이기 때문에 빛의 투과를 막기 위함이다. The reason for using the brown glass bottle is to prevent the transmission of light since the light crosslinking monomers will be mixed together.
용액을 충분히 혼합시키고 난 뒤 광가교 모노머인 PEGDA(Poly(ethylene glycol) diacrylate)를 0.2339g 넣어준다. 이때 먼저 만든 용액과 광가교 모노머 PEGDA의 무게 비율을 약 85/15이다. After mixing the solution sufficiently, add 0.2339 g of PEGDA (Poly (ethylene glycol) diacrylate), a photocrosslinking monomer. At this time, the weight ratio of the first solution and the photocrosslinking monomer PEGDA is about 85/15.
그리고 반응의 진행을 위한 개시제(2-hydroxy-2-methyl-1-phenyl-1-propaneone)를 0.0023g 넣어준다. 개시제의 비율은 광가교 모노머 양의 1중량%이다. 이렇게 다 섞은 혼합물에 마그네틱 바를 넣고 30분간 혼합시켜준다.And 0.0023g of the initiator (2-hydroxy-2-methyl-1-phenyl-1-propaneone) for the progress of the reaction is added. The proportion of initiator is 1% by weight of the photocrosslinking monomer amount. Add the magnetic bar to the mixture and mix for 30 minutes.
혼합이 끝난 용액을 2x2㎝ 크기의 틀에 주사기를 이용하여 적당히 넣은 다음 20초간 자외선을 조사하여 광가교를 진행하면 폴리에틸렌 옥사이드(poly(ethylene oxide); PEO) 결합이 형성되면서, 플라스틱 결정 고분자 복합 전해질이 제조된다. 용액은 틀 위로 많이 떠오르지 않을 만큼만 넣어준다. 제조된 막을 분리막 펀칭기를 이용하여 셀 제작이 가능한 크기로 자른다. 이때 제조된 막의 지름은 1.88cm이다. After mixing the solution into a 2x2cm frame by using a syringe, the light is crosslinked by irradiation with ultraviolet light for 20 seconds to form a polyethylene oxide (poly (ethylene oxide); PEO) bond. Is manufactured. Add enough solution so that it doesn't float on the mold. The prepared membrane is cut into a size capable of cell fabrication using a membrane puncher. In this case, the diameter of the prepared membrane is 1.88 cm.
이상, 본 발명을 바람직한 실시예를 들어 상세하게 설명하였으나, 본 발명은 상기 실시예에 한정되지 않으며, 본 발명의 기술적 사상 내에서 당 분야에서 통상의 지식을 가진 자에 의하여 여러 가지 많은 변형이 가능함은 명백하다. In the above, the present invention has been described in detail with reference to preferred embodiments, but the present invention is not limited to the above embodiments, and various modifications can be made by those skilled in the art within the technical idea of the present invention. Is obvious.
Claims (7)
상기 플라스틱 결정은 숙시노니트릴(succinonitrile)인 리튬 이차전지용 고분자 복합 전해질.The method of claim 1,
The plastic crystal is succinonitrile (succinonitrile) polymer composite electrolyte for a lithium secondary battery.
상기 고분자 매트릭스는 폴리에틸렌, 폴리프로필렌, 셀룰로오스, 셀룰로오스 아세테이트, 셀룰로오스 아세테이트 부틸레이트, 셀룰로오스아세테이트 프로피오네이트, 폴리비닐피롤리돈-비닐아세테이트, 폴리[비스(2-(2-메톡시에톡시에톡시))포스파젠], 폴리에틸렌이미드, 폴리에틸렌옥사이드, 폴리에틸렌숙시네이트, 폴레에틸렌설파이드, 폴리(옥시메틸렌-올리고-옥시에틸렌), 폴리프로필렌옥사이드, 폴리비닐아세테이트, 폴리아크릴로니트릴, 폴리(아크릴로니트릴-코-메틸아크릴레이트), 폴리메틸메타크릴레이트, 폴리(메틸메타크릴레이드-코-에틸아크릴레이트), 폴리비닐클로라이드, 폴리(비닐리덴클로라이드-코-아크릴로니트릴), 폴리비닐리덴디플루오라이드, 폴리(비닐리덴플루오라이드-코-헥사플루오로프로필렌), 및 이들의 혼합물로 구성되는 군에서 선택되는 리튬 이차전지용 고분자 복합 전해질.The method of claim 1,
The polymer matrix is polyethylene, polypropylene, cellulose, cellulose acetate, cellulose acetate butyrate, cellulose acetate propionate, polyvinylpyrrolidone-vinylacetate, poly [bis (2- (2-methoxyethoxyethoxy) ) Phosphazene], polyethyleneimide, polyethylene oxide, polyethylene succinate, polyethylene sulfide, poly (oxymethylene-oligo-oxyethylene), polypropylene oxide, polyvinylacetate, polyacrylonitrile, poly (acrylonitrile- Co-methylacrylate), polymethylmethacrylate, poly (methylmethacrylate-co-ethylacrylate), polyvinylchloride, poly (vinylidenechloride-co-acrylonitrile), polyvinylidenedifluoride , Poly (vinylidene fluoride-co-hexafluoropropylene), and mixtures thereof Polymer composite electrolyte for a lithium secondary battery selected from the group.
상기 리튬염은 리튬 비스-트리플루오로메탄설포닐이미드(Li(CF3SO2)2N, LiTFSI), 리튬 비스-퍼플루오로에틸설포닐이미드(Li(C2F5SO2)2N), 리튬 테트라플루오로보레이트(LiBF4), 리튬 헥사프루오로포스페이트(LiPF6), 리튬 티오시아네이트(LiSCN), 리튬 트리플레이트(LiCF3SO3), 리튬 테트라플루오로알루미네이트(LiAlF4), 리튬 퍼콜레이트(LiClO4) 및 이들의 혼합물로 구성되는 군에서 선택되는 리튬 이차전지용 고분자 복합 전해질.The method of claim 1,
The lithium salt is lithium bis-trifluoromethanesulfonylimide (Li (CF 3 SO 2 ) 2 N, LiTFSI), lithium bis-perfluoroethylsulfonylimide (Li (C 2 F 5 SO 2 ) 2 N), lithium phosphate tetrafluoroborate (LiBF 4), lithium hexafluoro program Luo (LiPF 6), lithium thiocyanate (LiSCN), lithium triflate (LiCF 3 SO 3), aluminum lithium tetrafluoroborate carbonate ( LiAlF 4 ), lithium percholate (LiClO 4 ) and a polymer composite electrolyte for a lithium secondary battery selected from the group consisting of these.
상기 용액에 광가교 모노머를 혼합하는 단계와,
광가교를 진행하는 단계를 포함하는 리튬 이차전지용 고분자 복합 전해질의 제조방법.Mixing the plastic crystal and the lithium salt and heating to form a solution,
Mixing a photocrosslinking monomer in the solution;
Method for producing a polymer composite electrolyte for a lithium secondary battery comprising the step of performing optical crosslinking.
상기 플라스틱 결정은 숙시노니트릴인 리튬 이차전지용 고분자 복합 전해질의 제조방법.The method of claim 5,
The plastic crystal is succinonitrile, the method for producing a polymer composite electrolyte for a lithium secondary battery.
상기 리튬염은 리튬 비스-트리플루오로메탄설포닐이미드(Li(CF3SO2)2N, LiTFSI), 리튬 비스-퍼플루오로에틸설포닐이미드(Li(C2F5SO2)2N), 리튬 테트라플루오로보레이트(LiBF4), 리튬 헥사프루오로포스페이트(LiPF6), 리튬 티오시아네이트(LiSCN), 리튬 트리플레이트(LiCF3SO3), 리튬 테트라플루오로알루미네이트(LiAlF4), 리튬 퍼콜레이트(LiClO4) 및 이들의 혼합물로 구성되는 군에서 선택되는 리튬 이차전지용 고분자 복합 전해질의 제조방법.The method of claim 5,
The lithium salt is lithium bis-trifluoromethanesulfonylimide (Li (CF 3 SO 2 ) 2 N, LiTFSI), lithium bis-perfluoroethylsulfonylimide (Li (C 2 F 5 SO 2 ) 2 N), lithium phosphate tetrafluoroborate (LiBF 4), lithium hexafluoro program Luo (LiPF 6), lithium thiocyanate (LiSCN), lithium triflate (LiCF 3 SO 3), aluminum lithium tetrafluoroborate carbonate ( LiAlF 4 ), lithium percholate (LiClO 4 ) and a method for producing a polymer composite electrolyte for a lithium secondary battery selected from the group consisting of these.
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| US12125978B2 (en) | 2018-11-19 | 2024-10-22 | Shanghai Zijian Chemical Technology Co., Ltd | Boron-containing plastic crystal polymer and preparation method therefor and application thereof |
| CN112563568A (en) * | 2020-11-13 | 2021-03-26 | 上海空间电源研究所 | Preparation method of all-solid-state battery interface layer and all-solid-state battery |
| US20220200060A1 (en) * | 2020-12-18 | 2022-06-23 | Vesselin Bojidarov NAYDENOV | Synthetic proton-conductive additives for battery electrolytes |
| US12431544B2 (en) * | 2020-12-18 | 2025-09-30 | Vesselin Bojidarov NAYDENOV | Synthetic proton-conductive additives for battery electrolytes |
| CN114551996A (en) * | 2022-01-14 | 2022-05-27 | 福州大学 | Cyclophosphnitrile modified flame-retardant polymer electrolyte and preparation method thereof |
| CN114551996B (en) * | 2022-01-14 | 2023-07-18 | 福州大学 | A kind of cyclophosphazene modified flame retardant polymer electrolyte and preparation method thereof |
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